U.S. patent application number 11/385773 was filed with the patent office on 2006-07-27 for process for the preparation of alkylarylsulfonates.
This patent application is currently assigned to BASF Aktiengesellschaft. Invention is credited to Heiko Maas, Thomas Narbeshuber, Michael Roper.
Application Number | 20060167308 11/385773 |
Document ID | / |
Family ID | 7652598 |
Filed Date | 2006-07-27 |
United States Patent
Application |
20060167308 |
Kind Code |
A1 |
Maas; Heiko ; et
al. |
July 27, 2006 |
Process for the preparation of alkylarylsulfonates
Abstract
The invention relates to a process for the preparation of
alkylarylsulfonates by a) reaction of a C.sub.4-olefin mixture over
a metathesis catalyst for the preparation of an olefin mixture
comprising 2-pentene and/or 3-hexene, and optional removal of
2-pentene and/or 3-hexene, b) dimerization of the 2-pentene and/or
3-hexene obtained in stage a) over a dimerization catalyst to give
a mixture containing C.sub.10-12-olefins, and optional removal of
the C.sub.10-12-olefins, c) reaction of the C.sub.10-12-olefin
mixtures obtained in stage b) with an aromatic hydrocarbon in the
presence of an alkylating catalyst to form alkylaromatic compounds,
where, prior to the reaction, additional linear olefins may be
added, d) sulfonation of the alkylaromatic compounds obtained in
stage c), and neutralization to give alkylarylsulfonates, where,
prior to the sulfonation, linear alkylbenzenes may additionally be
added, e) optional mixing of the alkylarylsulfonates obtained in
stage d) with linear alkylarylsulfonates.
Inventors: |
Maas; Heiko; (Mannheim,
DE) ; Narbeshuber; Thomas; (Ibbenbueren, DE) ;
Roper; Michael; (Wachenheim, DE) |
Correspondence
Address: |
OBLON, SPIVAK, MCCLELLAND, MAIER & NEUSTADT, P.C.
1940 DUKE STREET
ALEXANDRIA
VA
22314
US
|
Assignee: |
BASF Aktiengesellschaft
Ludwigshafen
DE
|
Family ID: |
7652598 |
Appl. No.: |
11/385773 |
Filed: |
March 22, 2006 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10343835 |
Feb 10, 2003 |
7060852 |
|
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PCT/EP01/09297 |
Aug 10, 2001 |
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11385773 |
Mar 22, 2006 |
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Current U.S.
Class: |
562/122 |
Current CPC
Class: |
C07C 2/66 20130101; C07C
2/08 20130101; C07C 6/04 20130101; C07C 303/32 20130101; C07C
303/32 20130101; C07C 6/04 20130101; C07C 6/04 20130101; C07C 11/02
20130101; C07C 303/06 20130101; C07C 11/107 20130101; C07C 309/31
20130101; C07C 309/31 20130101; C07C 15/107 20130101; C07C 11/10
20130101; C07C 11/02 20130101; C07C 303/06 20130101; C07C 2/08
20130101; C07C 2/66 20130101; C07C 6/04 20130101; C11D 11/04
20130101; C11D 1/22 20130101 |
Class at
Publication: |
562/122 |
International
Class: |
C07C 309/00 20060101
C07C309/00 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 11, 2000 |
DE |
100 39 995.9 |
Claims
1-11. (canceled)
12. A mixture of alkyaromatic compounds obtained by a process
comprising: a) reacting a C.sub.4-olefin mixture over a metathesis
catalyst for the preparation of an olefin composition comprising
2-pentene, 3-hexene or mixtures thereof, and optional removal of
2-pentene, 3 hexene, or mixtures thereof, b) dimerizing the
2-pentene, 3-hexene or mixtures thereof obtained in stage a) over a
dimerization catalyst to give a mixture containing
C.sub.10-12-olefins, and optional removal of the
C.sub.10-12-olefins, c) reacting the mixture containing
C.sub.10-12-olefins or the C.sub.10-12-olefins obtained in stage
b), or optionally a separated C.sub.10-12 fraction, with an
aromatic hydrocarbon in the presence of an alkylating catalyst to
form alkylaromatic compounds, wherein, in the C.sub.10-12-olefins,
the proportion of monosubstitution products is in the range from 40
to 75% by weight, and the proportion of double-branched products is
in the range from 5 to 25% by weight.
13. The mixture as claimed in claim 12, wherein the metathesis
catalyst in stage a) is selected from compounds of a metal of
transition groups VIb, VIIb or VIII of the Periodic Table of the
Elements.
14. The mixture as claimed in claim 12, wherein, in stage b), a
dimerization catalyst is used, which contains at least one element
from transition group VIII of the Periodic Table of the Elements,
and the catalyst composition and the reaction conditions are
chosen, such that a dimer mixture is obtained, which contains less
than 10% by weight of compounds which have a structural element of
the formula I (vinylidene group) ##STR5## wherein A.sup.1 and
A.sup.2 are aliphatic hydrocarbon radicals.
15. The mixture as claimed in claim 12, wherein the olefins
obtained in stage b), have a proportion of unbranched olefins of
less than 25% by weight.
16. The Mixture as claimed in claim 12, wherein at least 80% of the
olefins obtained in stage b), have one branch, or two branches on
adjacent carbon atoms, in the range from 1/4 to 3/4 of the number
of carbon atoms in the main chain of the molecule.
17. The mixture as claimed in claim 12, wherein, in stage c), the
alkylating catalyst that is used, leads to alkylaromatic compounds
which have an alkyl group that has 1 to 3 carbon atoms with an H/C
index of 1, wherein the H/C index defines the number of protons per
carbon atom in the alkyl group.
18. A mixture of alkylarylsufonates obtained by a process
comprising: a) reacting a C.sub.4-olefin mixture over a metathesis
catalyst for the preparation of an olefin composition comprising
2-pentene, 3-hexene or mixtures thereof, and optional removal of
2-pentene, 3 hexene, or mixtures thereof, b) dimerizing the
2-pentene, 3-hexene or mixtures thereof obtained in stage a) over a
dimerization catalyst to give a mixture containing
C.sub.10-12-olefins, and optional removal of the
C.sub.10-12-olefins, c) reacting the mixture containing
C.sub.10-12-olefins or the C.sub.10-12-olefins obtained in stage
b), or optionally a separated C.sub.10-12 fraction, with an
aromatic hydrocarbon in the presence of an alkylating catalyst to
form alkylaromatic compounds, d) sulfonating the alkylaromatic
compounds obtained in stage c), and neutralizing the resultant
mixture to give alkylarylsulfonates, and wherein, in the
C.sub.10-12-olefins, the proportion of monosubstitution products is
in the range from 40 to 75% by weight, and the proportion of
double-branched products is in the range from 5 to 25% by
weight.
19. The mixture as claimed in claim 18, wherein the metathesis
catalyst in stage a) is selected from compounds of a metal of
transition groups VIb, VIIb or VIII of the Periodic Table of the
Elements.
20. The mixture as claimed in claim 18, wherein, in stage b), a
dimerization catalyst is used, which contains at least one element
from transition group VIII of the Periodic Table of the Elements,
and the catalyst composition and the reaction conditions are
chosen, such that a dimer mixture is obtained, which contains less
than 10% by weight of compounds which have a structural element of
the formula I (vinylidene group) ##STR6## wherein A.sup.1 and
A.sup.2 are aliphatic hydrocarbon radicals.
21. The mixture as claimed in claim 18, wherein the olefins
obtained in stage b), have a proportion of unbranched olefins of
less than 25% by weight.
22. The mixture as claimed in claim 18, wherein at least 80% of the
olefins obtained in stage b), have one branch, or two branches on
adjacent carbon atoms, in the range from 1/4 to 3/4 of the number
of carbon atoms in the main chain of the molecule.
23. The mixture as claimed in claim 18, wherein, in stage c), the
alkylating catalyst that is used, leads to alkylaromatic compounds
which have an alkyl group that has 1 to 3 carbon atoms with an H/C
index of 1, wherein the H/C index defines the number of protons per
carbon atom in the alkyl group.
24. A detergent or cleaner comprising, the mixture of
alkylarylsulfonates as claimed in claim 8, and one or more
customary ingredients.
25. The detergent or cleaner as claimed in claim 24, wherein the
one or more customary ingredients comprise at least one member
selected from bleaches, bleach activators, bleach stabilizers,
inorganic builders, anionic surfactants, nonionic surfactants,
organic cobuilders, antiredeposition agents, soil release polymers,
color-transfer inhibitors or enzymes.
26. The detergent or cleaner as claimed in claim 24, further
comprising one or more auxiliaries, one or more adjuvants, water or
combinations thereof.
27. The detergent or cleaner as claimed in claim 24, wherein the
customary ingredients comprise: 0.5 to 50% by weight of at least
one anionic and/or nonionic surfactant, 0.5 to 60% by weight of at
least one inorganic builder, 0 to 20% by weight of at least one
organic cobuilder, 2 to 35% by weight of an inorganic bleach, 0.1
to 20% by weight of a bleach activator, optionally mixed with other
bleach activators, 0 to 1% by weight of a bleach catalyst, 0 to 5%
by weight of a polymeric color-transfer inhibitor, 0 to 1.5% by
weight of a protease, 0 to 1.5% by weight of a lipase, 0 to 1.5% by
weight of a soil release polymer, and customary auxiliaries,
adjuvants and water.
Description
[0001] The present invention relates to a process for the
preparation of alkylarylsulfonates, to alkylarylsulfonates
obtainable by the process, and to alkylaryls obtainable in the
process as intermediate, to the use of the alkylarylsulfonates as
surfactants, preferably in detergents and cleaners, and to
detergents and cleaners comprising these alkylarylsulfonates.
[0002] Alkylbenzenesulfonates (ABS) have been used for a long time
as surfactants in detergents and cleaners. Following the use
initially of surfactants based on tetrapropylene, which, however,
had poor biodegradability, alkylbenzenesulfonates which are as
linear as possible (LAS) have since been prepared and used.
However, linear alkylbenzenesulfonates do not have adequate
property profiles in all areas of application.
[0003] First, for example, it would be advantageous to improve
their low-temperature washing properties or their properties in
hard water. Likewise desirable is the ready ability to be
formulated, derived from the viscosity of the sulfonates and their
solubility. These improved properties are obtained by slightly
branched compounds or mixtures of slightly branched compounds with
linear compounds, although it is imperative to achieve the correct
degree of branching and/or the correct degree of mixing. Too much
branching adversely affects the biodegradability of the products.
Products which are too linear have a negative effect on the
viscosity and the solubility of the sulfonates.
[0004] Moreover, the proportion of terminal phenylalkanes
(2-phenylalkanes and 3-phenylalkanes) relative to internal
phenylalkanes (4-, 5-, 6- etc. phenylalkanes) plays a role for the
product properties. A 2-phenyl fraction of about 30% and a 2- and
3-phenyl fraction of about 50% can be advantageous with regard to
product quality (solubility, viscosity, washing properties).
[0005] Surfactants with very high 2- and 3-phenyl contents can have
the considerable disadvantage that the processability of the
products suffers as a result of a sharp increase in the viscosity
of the sulfonates.
[0006] Moreover, the solubility behavior may not be optimum. Thus,
for example, the Krafft point of a solution of LAS with very high
or very low 2- or 3-phenyl fractions is up to 10-20.degree. C.
higher than in the case of the optimal choice of the 2- and
3-phenyl fraction.
[0007] The process according to the invention offers the essential
advantage that, as a result of the combination of metathesis and
dimerization, a unique olefin mixture is obtained which, following
alkylation of an aromatic, sulfonation and neutralization, produces
a surfactant notable for its combination of excellent application
properties (solubility, viscosity, stability against water
hardness, washing properties, biodegradability). With regard to the
biodegradability of alkylarylsulfonates, compounds which are
adsorbed less strongly to clarification sludge than traditional LAS
are particularly advantageous.
[0008] For this reason, alkylbenzenesulfonates which are branched
to a certain degree have been developed.
[0009] For example, U.S. Pat. No. 3,442,964 describes the
dimerization of C.sub.5-8-hydrocarbons in the presence of a
cracking catalyst coated with a transition metal, giving
predominantly olefins having two or more branches. These olefins
are subsequently alkylated with benzene to give a nonlinear
alkylbenzene. For example, a mixture of hexenes is dimerized over a
silicon dioxide-aluminum oxide cracking catalyst and then alkylated
using HF as catalyst.
[0010] WO 88/07030 relates to olefins, alkylbenzenes and
alkylbenzenesulfonates which can be used in detergents and
cleaners. In the process, propene is dimerized to give hexene,
which in turn is dimerized to give largely linear dodecene
isomers.
[0011] Benzene is then alkylated in the presence of aluminum
halides and hydrofluoric acid.
[0012] U.S. Pat. No. 5,026,933 describes the dimerization of
propene or butene to give monoolefins, where at least 20% of
C.sub.12-olefins which have a degree of branching of from 0.8 to
2.0 methyl groups/alkyl chain and have only methyl groups as
branches. Aromatic hydrocarbons are alkylated over a
shape-selective catalyst, preferably dealuminated MOR.
[0013] WO 99/05241 relates to cleaners which comprise branched
alkylarylsulfonates as surfactants. The alkylarylsulfonates are
obtained by dimerization of olefins to give vinylidine olefins, and
subsequent alkylation of benzene over a shape-selective catalyst,
such as MOR or BEA. This is followed by sulfonation.
[0014] The olefins hitherto used for the alkylation partly have too
high or too low a degree of branching or do not produce an optimal
ratio of terminal to internal phenylalkanes. Alternatively, they
are prepared from costly starting materials, such as, for example,
propene or alpha-olefins, and sometimes the proportion of the
olefin fractions which is of interest for the preparation of
surfactants is only about 20%. This leads to costly work-up
steps.
[0015] The object of the present invention is to provide a process
for the preparation of alkylarylsulfonates which are at least
partially branched and thus have advantageous properties for use in
detergents and cleaners compared with known compounds. In
particular, they should have a suitable profile of properties of
biodegradability, insensitivity toward water hardness, solubility
and viscosity during the preparation and during use. In addition,
the alkylarylsulfonates should be preparable in a cost-effective
manner.
[0016] We have found that this object is achieved according to the
invention by a process for the preparation of alkylarylsulfonates
by [0017] a) reaction of a C.sub.4-olefin mixture over a metathesis
catalyst for the preparation of an olefin mixture comprising
2-pentene and/or 3-hexene, and optional removal of 2-pentene and/or
3-hexene, [0018] b) dimerization of the 2-pentene and/or 3-hexene
obtained in stage a) over a dimerization catalyst to give a mixture
containing C.sub.10-12-olefins, and optional removal of the
C.sub.10-12-olefins, [0019] c) reaction of the C.sub.10-12-olefin
mixtures obtained in stage b) with an aromatic hydrocarbon in the
presence of alkylating catalyst to form alkylaromatic compounds,
where, prior to the reaction, additional linear olefins may be
added, [0020] d) sulfonation of the alkylaromatic compounds
obtained in stage c), and neutralization to give
alkylarylsulfonates, where, prior to the sulfonation, linear
alkylbenzenes may additionally be added, [0021] e) optional mixing
of the alkylarylsulfonates obtained in stage d) with linear
alkylarylsulfonates.
[0022] The combination of a metathesis of C.sub.4-olefins with a
subsequent dimerization and alkylation of aromatic hydrocarbons
permits the use of cost-effective starting materials and of
preparation processes which make the desired products accessible in
high yields.
[0023] According to the invention, it has been found that the
metathesis of C.sub.4-olefins produces products which can be
dimerized to give slightly branched C.sub.10-12-olefin mixtures.
These mixtures can be used advantageously in the alkylation of
aromatic hydrocarbons, giving products which, following sulfonation
and neutralization, result in surfactants which have excellent
properties, in particular with regard to the sensitivity toward
hardness-forming ions, the solubility of the sulfonates, the
viscosity of the sulfonates and their washing properties. Moreover,
the present process is extremely cost-effective since the product
streams can be designed flexibly such that no byproducts are
produced. Starting from a C.sub.4-stream, the metathesis according
to the invention produces linear, internal olefins which are then
converted into branched olefins via the dimerization step.
[0024] Stage a) of the process according to the invention is the
reaction of a C.sub.4-olefin mixture over a metathesis catalyst for
the preparation of an olefin mixture comprising 2-pentene and/or
3-hexene, and optional removal of 2-pentene and/or 3-hexene. The
metathesis can be carried out, for example, as described in WO
00/39058 or DE-A-100 13 253.
[0025] The olefin metathesis (disproportionation) is, in its
simplest form, the reversible, metal-catalyzed transalkylidenation
of olefins by rupture or reformation of C.dbd.C double bonds
according to the following equation: ##STR1##
[0026] In the specific case of the metathesis of acyclic olefins, a
distinction is made between self-metathesis in which an olefin is
converted into a mixture of two olefins of differing molar masses
(for example: propene.fwdarw.ethene+2-butene), and cross- or
cometathesis, which is a reaction of two different olefins
(propene+1-butene.fwdarw.ethene+2-pentene). If one of the reactants
is ethene, this is generally referred to as ethenolysis.
[0027] Suitable metathesis catalysts are, in principle, homogeneous
and heterogeneous transition metal compounds, in particular those
of transition groups VI to VIII of the Periodic Table of the
Elements, and homogeneous and heterogeneous catalyst systems in
which these compounds are present.
[0028] Various metathesis processes starting from C.sub.4 streams
can be used according to the invention.
[0029] DE-A-199 32 060 relates to a process for the preparation of
C.sub.5/C.sub.6-olefins by reaction of a feed stream which
comprises 1-butene, 2-butene and isobutene to give a mixture of
C.sub.2-6-olefins. In this process, propene, in particular, is
obtained from butenes. In addition, hexene and methylpentene are
discharged as products. No ethene is added in the metathesis. If
desired, ethene formed in the metathesis is returned to the
reactor.
[0030] The preferred process for the preparation of optionally
propene and hexene from a raffinate II feed stream comprising
olefinic C.sub.4-hydrocarbons comprises [0031] a) carrying out a
metathesis reaction in the presence of a metathesis catalyst which
comprises at least one compound of a metal of transition group VIb,
VIIb or VIII of the Periodic Table of the Elements, in the course
of which, butenes present in the feed stream are reacted with
ethene to give a mixture comprising ethene, propene, butenes,
2-pentene, 3-hexene and butanes, where, based on the butenes, up to
0.6 mol equivalents of ethene may be used, [0032] b) first
separating the product stream thus obtained by distillation into
optionally a low-boiling fraction A comprising
C.sub.2-C.sub.3-olefins, and into a high-boiling fraction
comprising C.sub.4-C.sub.6-olefins and butanes, [0033] c) then
separating the low-boiling fraction A optionally obtained from b)
by distillation into a fraction comprising ethene and a fraction
comprising propene, where the fraction comprising ethene is
returned to the process step a), and the fraction comprising
propene is discharged as product, [0034] d) then separating the
high-boiling fraction obtained from b) by distillation into a
low-boiling fraction B comprising butenes and butanes, an
intermediate-boiling fraction C comprising 2-pentene, and a
high-boiling fraction D comprising 3-hexene, [0035] e) where the
fractions B and optionally C are completely or partly returned to
the process step a), and the fraction D and optionally C are
discharged as product.
[0036] The individual streams and fractions can comprise said
compounds or consist thereof. In cases where they consist of the
streams or compounds, the presence of relatively small amounts of
other hydrocarbons is not ruled out.
[0037] In this process, in a single-stage reaction procedure, a
fraction consisting of C.sub.4-olefins, preferably n-butenes and
butanes, is reacted in a metathesis reaction optionally with
variable amounts of ethene over a homogeneous or, preferably,
heterogeneous metathesis catalyst to give a product mixture of
(inert) butanes, unreacted 1-butene, 2-butene, and the metathesis
products ethene, propene, 2-pentene and 3-hexene. The desired
products 2-pentene and/or 3-hexene are discharged, and the products
which remain and unreacted compounds are completely or partly
returned to the metathesis. They are preferably returned as
completely as possible with only small amounts being discharged in
order to avoid accumulation. Ideally, there is no accumulation and
all compounds apart from 3-hexene are returned to the
metathesis.
[0038] According to the invention, up to 0.6, preferably up to 0.5,
molar equivalents of ethene, based on the butenes in the C.sub.4
feed stream, are used. Thus, only small amounts of ethene compared
with the prior art are used.
[0039] If no additional ethene is introduced, only up to at most
about 1.5%, based on the reaction products, of ethene form, which
is recirculated, see DE-A-199 32 060. According to the invention,
it is also possible to use larger amounts of ethene, the amounts
used being significantly lower than in the known processes for the
preparation of propene.
[0040] In addition, the maximum possible amounts of C.sub.4
products and optionally C.sub.5 products present in the reactor
discharge are recirculated according to the invention. This applies
in particular to the recirculation of unreacted 1-butene and
2-butene, and optionally of 2-pentene formed.
[0041] If small amounts of isobutene are still present in the
C.sub.4 feed stream, small amounts of branched hydrocarbons may
also be formed.
[0042] The amount of branched C.sub.5- and C.sub.6-hydrocarbons
which may additionally be formed in the metathesis product is
dependent on the isobutene content in the C.sub.4 feed and is
preferably kept as low as possible (<3%).
[0043] In order to illustrate the process according to the
invention in more detail in a plurality of variations, the reaction
which takes place in the metathesis reactor is divided into three
important individual reactions: ##STR2##
[0044] Depending on the respective demand for the target products
propene and 3-hexene (the designation 3-hexene includes any isomers
formed), and/or 2-pentene, the external mass balance of the process
can be influenced in a targeted way by means of variable use of
ethene and by shifting the equilibrium by recirculation of certain
substreams. Thus, for example, the yield of 3-hexene is increased
by suppressing the cross-metathesis of 1-butene with 2-butene by
recirculation of 2-pentene to the metathesis step, so that no or
extremely little 1-butene is consumed here. During the
self-metathesis of 1-butene to 3-hexene, which then preferably
proceeds, ethene is additionally formed, which reacts in a
subsequent reaction with 2-butene to give the desired product
propene.
[0045] Olefin mixtures which comprise 1-butene and 2-butene and
optionally isobutene are obtained, inter alia, as C.sub.4 fraction
in various cracking processes, such as steam cracking or fluid
catalytic cracking. As an alternative, it is possible to use butene
mixtures as are produced during the dehydrogenation of butanes or
by dimerization of ethene. Butanes present in the C.sub.4 fraction
have inert behavior. Dienes, alkynes or enynes are removed using
customary methods such as extraction or selective hydrogenation
prior to the metathesis step according to the present
invention.
[0046] The butene content of the C.sub.4 fraction used in the
process is 1 to 100% by weight, preferably 60 to 90% by weight. The
butene content is here based on 1-butene, 2-butene and
isobutene.
[0047] Preference is given to using a C.sub.4 fraction produced
during steam cracking or fluid catalytic cracking or during the
dehydrogenation of butane.
[0048] Here, the C.sub.4 fraction used is preferably raffinate II,
the C.sub.4 stream being freed from undesirable impurities by
appropriate treatment over adsorber guard beds, preferably over
high-surface-area aluminum oxides or molecular sieves, prior to the
metathesis reaction.
[0049] The low-boiling fraction A optionally obtained from step b),
which comprises C.sub.2-C.sub.3-olefins, is separated by
distillation into a fraction comprising ethene and a fraction
comprising propene. The fraction comprising ethene is then
recirculated to process step a), i.e. the metathesis, and the
fraction comprising propene is discharged as product.
[0050] In step d, the separation into low-boiling fraction B,
intermediate-boiling fraction C and high-boiling fraction D can,
for example, be carried out in a dividing wall column. Here, the
low-boiling fraction B is obtained at the top, the
intermediate-boiling fraction C is obtained via a middle outlet and
the high-boiling fraction D is obtained as bottoms.
[0051] In order to be able to better handle the differing amounts
of products produced in the flexibly controlled process, it is,
however, advantageous to carry out a two-stage separation of the
high-boiling fraction obtained from b). Preferably, the
high-boiling fraction obtained from b) is firstly separated by
distillation into a low-boiling fraction B comprising butenes and
butanes, and a high-boiling fraction comprising 2-pentene and
3-hexene. The high-boiling fraction is then separated by
distillation into fractions C and D. The two embodiments are
explained in more detail in FIGS. 1 and 2.
[0052] The metathesis reaction is here preferably carried out in
the presence of heterogeneous metathesis catalysts which are not or
only slightly isomerization-active and are selected from the class
of transition metal compounds of metals of group VIb, VIb or VIII
of the Periodic Table of the Elements applied to inorganic
supports.
[0053] The preferred metathesis catalyst used is rhenium oxide on a
support, preferably on .gamma.-aluminum oxide or on
Al.sub.2O.sub.3/B.sub.2O.sub.3/SiO.sub.2 mixed supports.
[0054] In particular, the catalyst used is
Re.sub.2O.sub.7/.gamma.-Al.sub.2O.sub.3 with a rhenium oxide
content of from 1 to 20% by weight, preferably 3 to 15% by weight,
particularly preferably 6 to 12% by weight.
[0055] The metathesis is, when carried out in a liquid phase,
preferably carried out at a temperature of from 0 to 150.degree.
C., particularly preferably 20 to 80.degree. C., and at a pressure
of from 2 to 200 bar, particularly preferably 5 to 30 bar.
[0056] If the metathesis is carried out in the gas phase, the
temperature is preferably 20 to 300.degree. C., particularly
preferably 50 to 200.degree. C. The pressure in this case is
preferably 1 to 20 bar, particularly preferably 1 to 5 bar.
[0057] The preparation of C.sub.5/C.sub.6-olefins and optionally
propene from steam cracker or refinery C.sub.4 streams may comprise
the substeps (1) to (4): [0058] (1) removal of butadiene and
acetylenic compounds by optional extraction of butadiene with a
butadiene-selective solvent and subsequently /or selective
hydrogenation of butadienes and acetylenic impurities present in
crude C.sub.4 fraction to give a reaction product which comprises
n-butenes and isobutene and essentially no butadienes and
acetylenic compounds, [0059] (2) removal of isobutene by reaction
of the reaction product obtained in the previous stage with an
alcohol in the presence of an acidic catalyst to give an ether,
removal of the ether and the alcohol, which can be carried out
simultaneously with or after the etherification, to give a reaction
product which comprises n-butenes and optionally oxygen-containing
impurities, it being possible to discharge the ether formed or
back-cleave it to obtain pure isobutene, and to follow the
etherification step by a distillation step for the removal of
isobutene, where, optionally, introduced C.sub.3--, i-C.sub.4-- and
C.sub.5-hydrocarbons can also be removed by distillation during the
work-up of the ether, or oligomerization or polymerization of
isobutene from the reaction product obtained in the previous stage
in the presence of an acidic catalyst whose acid strength is
suitable for the selective removal of isobutene as oligoisobutene
or polyisobutene, to give a stream containing 0 to 15% of residual
isobutene, [0060] (3) removal of the oxygen-containing impurities
from the product of the preceding steps over appropriately selected
adsorber materials, [0061] (4) metathesis reaction of the resulting
raffinate II stream as described.
[0062] The substep of selective hydrogenation of butadiene and
acetylenic impurities present in crude C.sub.4 fraction is
preferably carried out in two stages by bringing the crude C.sub.4
fraction in the liquid phase into contact with a catalyst which
comprises at least one metal selected from the group consisting of
nickel, palladium and platinum on a support, preferably palladium
on aluminum oxide, at a temperature of from 20 to 200.degree. C., a
pressure of from 1 to 50 bar, a volume flow rate of from 0.5 to 30
m.sup.3 of fresh feed per m.sup.3 of catalyst per hour and a ratio
of recycle to feed stream of from 0 to 30 with a molar ratio of
hydrogen to diolefins of from 0.5 to 50, to give a reaction product
in which, apart from isobutene, the n-butenes 1-butene and 2-butene
are present in a molar ratio of from 2:1 to 1:10, preferably from
2:1 to 1:3, and essentially no diolefins and acetylenic compounds
are present. For a maximum yield of hexene, 1-butene is preferably
present in excess, and for a high protein yield, 2-butene is
preferably present in excess. This means that the overall molar
ratio in the first case can be 2:1 to 1:1 and in the second case
1:1 to 1:3.
[0063] The substep of butadiene extraction from crude C.sub.4
fraction is preferably carried out using a butadiene-selective
solvent selected from the class of polar-aprotic solvents, such as
acetone, furfural, acetonitrile, dimethylacetamide,
dimethylformamide and N-methylpyrrolidone, to give a reaction
product in which, following subsequent selective
hydrogenation/isomerization, the n-butenes 1-butene and 2-butene
are present in a molar ratio 2:1 to 1:10, preferably from 2:1 to
1:3.
[0064] The substep of isobutene etherification is preferably
carried out in a three-stage reactor cascade using methanol or
isobutanol, preferably isobutanol, in the presence of an acidic ion
exchanger, in which the stream to be etherified flows through
flooded fixed-bed catalysts from top to bottom, the rector inlet
temperature being 0 to 60.degree. C., preferably 10 to 50.degree.
C., the outlet temperature being 25 to 85.degree.C., preferably 35
to 75.degree. C., the pressure being 2 to 50 bar, preferably 3 to
20 bar, and the ratio of isobutanol to isobutene being 0.8 to 2.0,
preferably 1.0 to 1.5, and the overall conversion corresponding to
the equilibrium conversion.
[0065] The substep of isobutene removal is preferably carried out
by oligomerization or polymerization of isobutene starting from the
reaction mixture obtained after the above-described stages of
butadiene extraction and/or selective hydrogenation, in the
presence of a catalyst selected from the class of homogeneous and
heterogeneous Broensted or Lewis acids, see DE-A-100 13 253.
Selective Hydrogenation of Crude C.sub.4 Fraction
[0066] Alkynes, alkynenes and alkadienes are undesired substances
in many industrial syntheses owing to their tendency to polymerize
or their pronounced tendency to form complexes with transition
metals. They sometimes have a very strong adverse effect on the
catalysts used in these reactions.
[0067] The C.sub.4 stream of a steam cracker contains a high
proportion of polyunsaturated compounds such as 1,3-butadiene,
1-butyne (ethylacetylene) and butenyne (vinylacetylene). Depending
on the downstream processing present, the polyunsaturated compounds
are either extracted (butadiene extraction) or are selectively
hydrogenated. In the former case, the residual content of
polyunsaturated compounds is typically 0.05 to 0.3% by weight, and
in the latter case is typically 0.1 to 4.0% by weight. Since the
residual amounts of polyunsaturated compounds likewise interfere in
the further processing, a further concentration by selective
hydrogenation to values <10 ppm is necessary. In order to obtain
the highest possible proportion of the desired butenes,
over-hydrogenation to butanes must be kept as low as possible.
Alternative: Extraction of Butadiene from Crude C.sub.4
Fraction
[0068] The preferred method of isolating butadiene is based on the
physical principle of extractive distillation. The addition of
selective organic solvents lowers the volatility of specific
components of a mixture, in this case butadiene. For this reason,
these remain with the solvent in the bottom of the distillation
column, while the accompanying substances which were not previously
able to be separated off by distillation can be taken off at the
top. Solvents used for the extractive distillation are mainly
acetone, furfural, acetonitrile, dimethylacetaminde,
dimethylformamide (DMF) and N-methylpyrrolidone (NMP). Extractive
distillations are particularly suitable for butadiene-rich C.sub.4
cracker fractions having a relatively high proportion of alkynes,
including methylacetylene, ethylacetylene and vinylacetylene, and
methylallene.
[0069] The simplified principle of solvent extraction from crude
C.sub.4 fraction can be described as follows: the completely
vaporized C.sub.4 fraction is fed to an extraction column at its
lower end. The solvent (DMF, NMP) flows from the top in the
opposite direction to the gas mixture and on its way downwards
becomes laden with the more soluble butadiene and small amounts of
butenes. At the lower end of the extraction column, part of the
pure butadiene which has been isolated is fed in in order to drive
out the butenes as far as possible. The butenes leave the
separation column at the top. In a further column, referred to as a
degasser, the butadiene is freed from the solvent by boiling out
and is subsequently purified by distillation.
[0070] The reaction product from an extractive butadiene
distillation is usually fed to the second stage of a selective
hydrogenation in order to reduce the residual butadiene content to
values of <10 ppm.
[0071] The C.sub.4 stream remaining after butadiene has been
separated off is referred to as C.sub.4 raffinate or raffinate I
and comprises mainly the components isobutene, 1-butene, 2-butenes,
and n- and isobutanes.
Separating off Isobutene from Raffinate I
[0072] In the further separation of the C.sub.4 stream, isobutene
is preferably isolated next since it differs from the other C.sub.4
components by virtue of its branching and its higher reactivity.
Apart from the possibility of a shape-selective molecular sieve
separation, by means of which isobutene can be isolated in a purity
of 99% and n-butenes and butane adsorbed on the molecular sieve
pores can be desorbed again using a higher-boiling hydrocarbon this
is carried out in the first instance by distillation using a
so-called deisobutenizer, by means of which isobutene is separated
off together with 1-butene and isobutene at the top, and 2-butenes
and n-butane together with residual amounts of iso- and 1-butene
remain in the bottoms, or extractively by reaction of isobutene
with alcohols over acidic ion exchangers. Methanol (.fwdarw.MTBE)
or isobutanol (IBTBE) are preferably used for this purpose.
[0073] The preparation of MTBE from methanol and isobutene is
carried out at 30 to 100.degree. C. and at a pressure slightly
above atmospheric pressure in the liquid phase over acidic ion
exchangers. The process is carried out either in two reactors or in
a two-stage shaft reactor in order to achieve virtually complete
isobutene conversion (>99%). The pressure-dependant azeotrope
formation between methanol and MTBE requires a multistage pressure
distillation to isolate pure MTBE, or is achieved by relatively new
technology using methanol adsorption on adsorber resins. All other
components of the C.sub.4 fraction remain unchanged. Since small
proportions of diolefins and acetylenes can shorten the life of the
ion exchanger as a result of polymer formation, preference is given
to using bifunctional PD-containing ion exchangers, in the case of
which, in the presence of small amounts of hydrogen, only diolefins
and acetylenes are hydrogenated. The etherification of the
isobutene remains uninfluenced by this.
[0074] MTBE serves primarily to increase the octane number of
gasoline. MTBE and IBTBE can alternatively be back-cleaved in the
gas phase at 150 to 300.degree. C. over acidic oxides to obtain
pure isobutene.
[0075] A further possibility for separating off isobutene from
raffinate I consists in the direct synthesis of
oligo/polyisobutene. In this way it is possible, over acidic
homogeneous and heterogeneous catalysts, such as e.g. tungsten
trioxide and titanium dioxide, and at isobutene conversions up to
95%, to obtain a product stream which has a residual isobutene
content of a maximum of 5%.
Feed Purification of the Raffinate II Stream over Adsorber
Materials
[0076] To improve the operation life of catalysts used for the
subsequent metathesis step, it is necessary, as described above, to
use a feed purification (guard bed) for removing catalyst poisons,
such as, for example, water, oxygen-containing compounds, sulfur or
sulfur compounds or organic halides.
[0077] Processes for adsorption or adsorptive purification are
described, for example, in W. Kast, Adsorption aus der Gasphase,
VCH, Weinheim (1988). The use of zeolitic adsorbents is described
in D. W. Breck, Zeolite Molecular Sieves, Wiley, New York
(1974).
[0078] The removal of, specifically, acetaldehyde from C.sub.3-- to
C.sub.15-hydrocarbons in the liquid phase can be carried out as in
EP-A-0 582 901.
Selective Hydrogenation of Crude C.sub.4 Fraction
[0079] Butadiene (1,2- and 1,3-butadiene) and alkynes or alkenynes
present in the C.sub.4 fraction are firstly selectively
hydrogenated in a two-stage process from the crude C.sub.4 fraction
originating from a steam cracker or a refinery. According to one
embodiment, the C.sub.4 stream originating from the refinery can
also be fed directly to the second step of the selective
hydrogenation.
[0080] The first step of the hydrogenation is preferably carried
out over a catalyst which comprises 0.1 to 0.5% by weight of
palladium on aluminum oxide as support. The reaction is carried out
in the gas/liquid phase in a fixed bed (downflow mode) with a
liquid cycle. The hydrogenation is carried out at a temperature in
the range from 40 to 80.degree. C. and at a pressure of from 10 to
30 bar, a molar ratio of hydrogen to butadiene of from 10 to 50 and
an LHSV of up to 15 m.sup.3 of fresh feed per m.sup.3 of catalyst
per hour and a ratio of recycle to feed steam of from 5 to 20.
[0081] The second step of the hydrogenation is preferably carried
out over a catalyst which comprises 0.1 to 0.5% by weight of
palladium on aluminum oxide as support. The reaction is carried out
in the gas/liquid phase over a fixed bed (downflow mode) with a
liquid cycle. The hydrogenation is carried out at a temperature in
the range from 50 to 90.degree. C. and at a pressure from 10 to 30
bar, a molar ratio of hydrogen to butadiene of from 1.0 to 10 and
an LHSV of from 5 to 20 m.sup.3 of fresh feed per m.sup.3 of
catalyst per hour and a ratio of recycle to feed stream of from 0
to 15.
[0082] The resulting reaction product is referred to as raffinate I
and, in addition to isobutene, has 1-butene and 2-butene in a molar
ratio of from 2:1 to 1:10, preferably from 2:1 to 1:3.
Alternative: Separating off Butadiene from Crude C.sub.4 Fraction
by Extraction
[0083] The extraction of butadiene from crude C.sub.4 fraction is
carried out using N-methylpyrrolidone.
[0084] According to one embodiment of the invention, the reaction
product of the extraction is fed to the second stage of the
selective hydrogenation described above in order to remove residual
amounts of butadiene, the desired ratio of 1-butene to 2-butene
being set in this selective hydrogenation step.
Separating off Isobutene by Means of Etherification with
Alcohols
[0085] In the etherification stage, isobutene is reacted with
alcohols, preferably with isobutanol, over an acidic catalyst,
preferably over an acidic ion exchanger, to give ethers, preferably
isobutyl tert-butyl ether. According to one embodiment of the
invention, the reaction is carried out in a three-stage reactor
cascade, in which the reaction mixture flows through flooded
fixed-bed catalysts from top to bottom. In the first reactor the
inlet temperature is 0 to 60.degree. C., preferably 10 to
50.degree. C.; the outlet temperature is between 25 and 85.degree.
C., preferably between 35 and 75.degree. C., and the pressure is 2
to 50 bar, preferably 3 to 20 bar. At a ratio of isobutanol to
isobutene of from 0.8 to 2.0, preferably 1.0 to 1.5, the conversion
is between 70 and 90%.
[0086] In the second reactor the inlet temperature is 0 to
60.degree. C., preferably 10 to 50.degree. C.; the outlet
temperature is between 25 and 85.degree. C., preferably between 35
and 75.degree. C., and the pressure is 2 to 50 bar, preferably 3 to
20 bar. The overall conversion over the two stages increases to 85
to 99%, preferably 90 to 97%.
[0087] In the third and largest reactor, equilibrium conversion is
achieved at equal inlet and outlet temperatures of from 0 to
60.degree. C., preferably 10 to 50.degree. C. The etherification
and removal of the ether formed is followed by ether cleavage: the
endothermic reaction is carried out over acidic catalysts,
preferably over acidic heterogeneous catalysts, for example
phosphoric acid on an SiO.sub.2 support, at an inlet temperature of
from 150 to 300.degree. C., preferably at 200 to 250.degree. C.,
and an outlet temperature of from 100 to 250.degree. C., preferably
at 130 to 220.degree. C.
[0088] If an FCC C.sub.4 fraction is used, it is to be expected
that propane in amounts of around 1% by weight, isobutene in
amounts of around 30 to 40% by weight, and C.sub.5 hydrocarbons in
amounts of around 3 to. 10% by weight will be introduced, which may
adversely affect the subsequent process sequence. The work-up of
the ether accordingly provides the opportunity of separating off
the components mentioned by distillation.
[0089] The resulting reaction product, referred to as raffinate II,
has a residual isobutene content of from 0.1 to 3% by weight.
[0090] If larger amounts of isobutene are present in the product,
for example when FCC C.sub.4 fractions are used or when isobutene
is separated off by acid-catalyzed polymerization to polyisobutene
(partial conversion), the raffinate stream which remains can,
according to one embodiment of the invention, be worked up by
distillation prior to further processing.
Purification of the Raffinate II Stream over Adsorber Materials
[0091] The raffinate II stream obtained after the
etherification/polymerization (or distillation) is purified over at
least one guard bed consisting of high surface-area aluminum
oxides, silica gels, alumino-silicates or molecular sieves. The
guard bed serves here to dry the C.sub.4 stream and to remove
substances which may act as catalyst poisons in the subsequent
metathesis step. The preferred adsorber materials are Selexsorb CD
and CDO and also 3 .ANG. and NaX molecular sieves (13X). The
purification is carried out in drying towers at temperatures and
pressures which are chosen such that all components are present in
the liquid phase. Optionally, the purification step is used to
preheat the feed for the subsequent metathesis step.
[0092] The raffinate II stream which remains is virtually free from
water, oxygen-containing compounds, organic chlorides and sulfur
compounds.
[0093] When the etherification step is carried out with methanol
for preparing MTBE, the formation of dimethyl ether as secondary
component may make it necessary to combine two or more purification
steps or to connect them in series.
[0094] Preferred metathesis catalysts are heterogeneous rhenium
catalysts known from the literature, such as ReO.sub.7 on
.gamma.-Al.sub.2O.sub.3 or on mixed supports, such as e.g.
SiO.sub.2/Al.sub.2O.sub.3, B.sub.2O.sub.3/SiO.sub.2/Al.sub.2O.sub.3
or Fe.sub.2O.sub.3/Al.sub.2O.sub.3 having different metal contents.
The rhenium oxide content is, regardless of the support chosen,
between 1 and 20%, preferably between 3 and 10%.
[0095] The catalysts are used in freshly calcined form and require
no further activation (e.g. by means of alkylating agents).
Deactivated catalyst can be regenerated a number of times by
burning off carbon residues at temperatures above 400.degree. C. in
a stream of air and cooling under an inert gas atmosphere.
[0096] A comparison of the heterogeneous catalysts shows that
Re.sub.2O.sub.7/Al.sub.2O.sub.3 is active even under very mild
reaction conditions (T=20 to 80.degree. C.), while
MO.sub.3/SiO.sub.2 (M=Mo, W) develops activity only at temperatures
above 100 to 150.degree. C. and, consequently, C.dbd.C double bond
isomerization can occur as secondary reactions.
[0097] Mention may also be made of: [0098] WO.sub.3/SiO.sub.2,
prepared from (C.sub.5H.sub.5)W(CO).sub.3Cl and SiO.sub.2 in J.
Mol. Catal. 1995, 95, 75-83; [0099] 3-component system consisting
of [Mo(NO).sub.2(OR).sub.2]n, SnEt4 and AlCl.sub.3 in J. Mol.
Catal. 1991, 64, 171-178 and J. Mol. Catal 1989, 57, 207-220;
[0100] nitrodomolybdenum (VI) complexes from highly active
precatalysts in J. Organomet. Chem. 1982, 229, C.sub.19-C.sub.23;
[0101] heterogeneous SiO.sub.2-supported MoO.sub.3 and WO.sub.3
catalysts in J. Chem. Soc., Faraday Trans./1982, 78, 2583-2592;
[0102] supported Mo catalysts in J. Chem. Soc., Faraday
Trans./1981, 77, 1763-1777; [0103] active tungsten catalyst
precursor in J. Am. Chem. Soc. 1980, 102(21), 6572-6574; [0104]
acetonitrile(pentacarbonyl)tungsten in J. Catal. 1975, 38, 482-484;
[0105] trichloro(nitrosyl)molybdenum(II) as catalyst precursor in
Z. Chem. 1974, 14, 284-285, [0106]
W(CO).sub.5PPH.sub.3/EtAlCl.sub.2 in J. Catal. 1974, 34, 196-202;
[0107] WCl.sub.6/n-BuLi in J. Catal 1973, 28, 300-303; [0108]
WCl.sub.6/n-BuLi in J. Catal. 1972, 26, 455-458;
[0109] FR 2 726 563: O.sub.3ReO[Al(OR)(L)xO]nReO.sub.3 where
R.dbd.C.sub.1-C.sub.40-hydrocarbon, n=1-10, x=0 or 1 and L
=solvent,
[0110] EP-A-191 0 675, EP-A-129 0 474, BE 899897: catalyst systems
comprising tungsten, 2-substituted phenoxide radicals and 4 other
ligands, including a halogen, alkyl or carbene group,
[0111] FR 2 499 083: catalyst system comprising a tungsten,
molybdenum or rhenium oxo transition metal complex with a Lewis
acid,
[0112] U.S. Pat. No. 4,060,468: catalyst system comprising a
tungsten salt, an oxygen-containing aromatic compound, e.g.
2,6-dichlorophenol and, if desired, molecular oxygen,
[0113] BE 776,564: catalyst system comprising a transition metal
salt, an organometallic compound and an amine.
[0114] To improve the cycle time of the catalysts used, especially
of the supported catalysts, it is advisable to purify the feed over
adsorber beds (guard beds). The guard bed serves here to dry the
C.sub.4 stream and to remove substances which may act as catalyst
poisons in the subsequent metathesis step. The preferred adsorber
materials are Selexsorb CD and CDO and 3 .ANG. and NaX molecular
sieves (13X). The purification is carried out in drying towers at
temperatures and pressures which are preferably chosen such that
all of the components are present in the liquid phase. Optionally,
the purification step is used for preheating the feed for the
subsequent methathesis step. It may be advantageous to combine two
or more purification steps with one another or to connect them in
series.
[0115] Pressure and temperature in the metathesis step is chosen
such that all reactants are present in the liquid phase (usually=0
to 150.degree. C., preferably 20 to 80.degree. C.; p=2 to 200 bar).
Alternatively, it may, however, be advantageous, particularly in
the case of feed streams having a relatively high isobutene
content, to carry out the reaction in the gas phase and/or to use a
catalyst which has lower acidity.
[0116] The reaction is generally complete after from 1 s to 1 h,
preferably after 30 s to 30 min. It may be carried out continuously
or batchwise in reactors such as pressurized-gas vessels, flow
tubes or reactive distillation apparatuses, with preference being
given to flow tubes.
Stage b)
[0117] In stage b), the 2-pentene and/or 3-hexene obtained in stage
a) is dimerized over a dimerization catalyst to give a
C.sub.10-12-olefin mixture. The C.sub.10-12-olefins obtained are
optionally separated off.
[0118] During the dimerization of the olefins or olefin mixtures
obtained in the metathesis step, dimerization products are obtained
which, with regard to the further processing to give alkyl
aromatics, have particularly favorable components and particularly
advantageous compositions if
[0119] a dimerization catalyst is used which contains at least one
element from transition group VIII of the Periodic Table of the
Elements,
[0120] and the catalyst composition and the reaction conditions are
chosen such that a dimer mixture is obtained which contains less
than 10% by weight of compounds which have a structural element of
the formula I (vinylidene group) ##STR3##
[0121] in which A.sup.1 and A.sup.2 are aliphatic hydrocarbon
radicals.
[0122] For the dimerization, preference is given to using the
internal, linear pentenes and hexenes present in the metathesis
product. Particular preference is given to using 3-hexene.
[0123] The dimerization may be carried out with homogenous or
heterogeneous catalysis. Preference is given to the heterogeneous
procedure since here, firstly, catalyst removal is simplified and
the process is thus more economical and, secondly, no
environmentally harmful wastewaters are produced, as are usually
formed during the removal of dissolved catalysts, for example by
hydrolysis. A further advantage of the heterogeneous process is
that the dimerization product does not contain halogens, in
particular chlorine or fluorine. Homogeneously soluble catalysts
generally contain halide-containing ligands, or they are used in
combination with halogen-containing cocatalysts. Halogen may be
incorporated from such catalyst systems into the dimerization
products, which considerably impairs both the product quality and
also the further processing.
[0124] For the heterogeneous catalysis, combinations of oxides of
metals from transition group VIII with aluminum oxide on support
materials of silicon oxides and titanium oxides, as are known, for
example, from DE-A-43 39 713, are expediently used. The
heterogeneous catalyst can be used in a fixed bed--then preferably
in coarse form as 1 to 1.5 mm chips--or in suspended form (particle
size 0.05 to 0.5 mm). The dimerization is, in the case of the
heterogeneous procedure, expediently carried out at temperatures
from 80 to 200.degree. C., preferably from 100 to 180.degree. C.,
under the pressure prevailing at the reaction temperature,
optionally also under a protective gas at a pressure above
atmospheric, in a closed system. To achieve optimal conversions,
the reaction mixture is circulated a number of times, a certain
proportion of the circulating product being continuously discharged
and replaced with starting material.
[0125] The dimerization according to the invention produces
mixtures of monounsaturated hydrocarbons, the components of which
predominantly have a chain length twice that of the starting
olefins.
[0126] Within the scope of the above details, the dimerization
catalysts and the reaction conditions are preferably chosen such
that at least 80% of the components of the dimerization mixture
have one branch, or two branches on adjacent carbon atoms, in the
range from 1/4 to 3/4, preferably from 1/3 to 2/3, of the chain
length of their main chain.
[0127] A very characteristic feature of the olefin mixtures
prepared according to the invention is their high
proportion--generally greater than 75%, in particular greater than
80%--of components with branches, and the low proportion--generally
below 25%, in particular below 20%--of unbranched olefins. A
further characteristic is that, at the branching sites of the main
chain, predominantly groups having (y-4) and (y-5) carbon atoms are
bonded, where y is the number of carbon atoms of the monomer used
for the dimerization. The value (y-5)=0 means that no side chain is
present.
[0128] In the case of the C.sub.12-olefin mixtures prepared
according to the invention, the main chain preferably carries
methyl or ethyl groups at the branching points.
[0129] The position of the methyl and ethyl groups on the main
chain is likewise characteristic: in the case of mono-substitution,
the methyl or ethyl groups are in the position P=(n/2)-m of the
main chain, where n is the length of the main chain and m is the
number of carbon atoms in the side groups, and in the case of
disubstitution products, one substituent is in the position P and
the other is on the adjacent carbon atom P+1. The proportions of
monosubstitution products (single branching) in the olefin mixture
prepared according to the invention are characteristically in total
in the range from 40 to 75% by weight, and the proportions of
double-branched components are in the range from 5 to 25% by
weight.
[0130] The olefin mixtures obtainable by the above process (cf. WO
00/39058) are valuable intermediates particularly for the
preparation, described below, of branched alkylaromatics for the
preparation of surfactants.
Stage c)
[0131] In stage c), the C.sub.10-12-olefin mixture obtained in
stage b) is reacted with an aromatic hydrocarbon in the presence of
an alkylation catalyst to form alkylaromatic compounds.
[0132] Here, preference is given to using an alkylation catalyst
which leads to alkylaromatic compounds which have, in the alkyl
radical, one to three carbon atoms with an H/C index of 1.
[0133] The alkylation can in principle be carried out in the
presence of any alkylation catalysts.
[0134] Although AlCl.sub.3 and HF can in principle be used,
heterogeneous or shape-selective catalysts offer advantages. For
reasons of plant safety and environmental protection, preference is
nowadays given to solid catalysts, which include, for example, the
fluorinated Si/Al catalyst used in the DETAL process, a number of
shape-selective catalysts or supported metal oxide catalysts, and
phyllosilicates and clays.
[0135] Regardless of the large influence of the feedstock used, in
choosing the catalyst it is important to minimize compounds formed
by the catalyst which are notable for the fact that they include in
the alkyl radical carbon atoms with an H/C index of 0. Furthermore,
compounds should be formed which, on average, have in the alkyl
radical 1 to 3 carbon atoms with an H/C index of 1. This may, in
particular, be achieved through the choice of suitable catalysts
which, on the one hand, as a result of their geometry, suppress the
formation of the undesired products but, on the other hand, permit
an adequate rate of reaction.
[0136] The H/C index defines the number of protons per carbon atom
in the alkyl radical.
[0137] Moreover, in choosing the catalysts, their tendency with
regard to deactivation must be taken into consideration.
One-dimensional pore systems in most cases have the disadvantage of
rapid blocking of the pores as a result of degradation or formative
products from the process. Catalysts with polydimensional pore
systems are therefore to be preferred.
[0138] The catalysts used can be of natural or synthetic origin,
the properties of which can be adjusted by methods known in the
literature (e.g. ion exchange, steaming, blocking of acidic
centers, washing out of extra lattice species, etc.) to a certain
extent. It is important for the present invention that the
catalysts at least in part have acidic character.
[0139] Depending on the type of application, the catalysts are
either in the form of powders or in the form of moldings. The
linkages of the matrices of the moldings ensure adequate mechanical
stability, although free access by the molecules to the active
constituents of the catalysts is to be ensured by sufficient
porosity of the matrix. The preparation of such moldings is known
in the literature and is detailed under the prior art.
[0140] Possible catalysts for the alkylation (nonexhaustive list)
are: AlCl.sub.3, AlCl.sub.3/support (WO 96/26787), HF,
H.sub.2SO.sub.4, ionic liquids (e.g. WO 98/50153), perfluorinated
ion exchangers or NAFION/silica (e.g. WO 99/06145), F--Si/Al (U.S.
Pat. No. 5,344,997) Beta (e.g. WO 98/09929, U.S. Pat. No.
5,877,370, U.S. Pat. No. 4,301,316, U.S. Pat. No. 4,301,317)
faujasite (CN 1169889), phyllosilicates, clays (EP 711600),
fluorinated mordenite (WO 00/23405), mordenite (EP 466558), ZSM 12,
ZSM-20, ZSM-38, mazzite, zeolite L, cancrinite, gmellinite,
offretite, MCM-22, etc.
[0141] Preference is given to shape-selective 12-ring zeolites.
Preferred Reaction Method
[0142] The alkylation is carried out by allowing the aromatic
compounds (the aromatic compound mixture) and the olefin (mixture)
to react in a suitable reaction zone by bringing them into contact
with the catalyst, working up the reaction mixture after the
reaction and thus obtaining the desired products.
[0143] Suitable reaction zones are, for example, tubular reactors
or stirred-tank reactors. If the catalyst is in solid form, then it
can be used either as a slurry, as a fixed bed or as a fluidized
bed.
[0144] Where a fixed-bed reactor is used, the reactants can be
introduced either in cocurrent or in countercurrent. Realization as
a catalytic distillation is also possible.
[0145] The reactants are either in the liquid and/or in the gaseous
state.
[0146] The reaction temperature is chosen such that, on the one
hand, as complete as possible a conversion of the olefin takes
place and, on the other hand, the fewest possible by-products
arise. The choice of temperature also depends decisively on the
catalyst chosen. Reaction temperatures between 50.degree. C. and
500.degree. C. (preferably 80 to 350.degree. C., particularly
preferably 80-250.degree. C.) can also be used.
[0147] The pressure of the reaction depends on the procedure chosen
(reactor type) and is between 0.1 and 100 bar, and the space
velocity (WHSV) is chosen between 0.1 and 100.
[0148] The reactants can optionally be diluted with inert
substances. Inert substances are preferably paraffins.
[0149] The ratio of aromatic compound: olefin is usually set
between 1:1 and 100:1 (preferably 2:1-20:1).
Aromatic Feed Substances
[0150] All aromatic hydrocarbons of the formula Ar--R are possible,
where Ar is a monocyclic or bicyclic aromatic hydrocarbon radical,
and R is chosen from H, C.sub.1-5, preferably C.sub.1-3-alkyl, OH,
OR etc., preferably H or C.sub.1-3-alkyl. Preference is given to
benzene and toluene.
Stage d)
[0151] In stage d), the alkylaromatic compounds obtained in stage
c) are sulfonated and neutralized to give alkylarylsulfonates.
[0152] The alkylaryls are converted into alkylarylsulfonates by
[0153] 1) sulfonation (e.g. with SO.sub.3, oleum, chlorosulfonic
acid, etc., preferably with SO.sub.3) and [0154] 2) neutralization
(e.g. with Na, K, NH.sub.4, Mg compounds, preferably with Na
compounds).
[0155] Sulfonation and neutralization are adequately described in
the literature and are carried out in accordance with the prior
art. The sulfonation is preferably carried out in a falling-film
reactor, but can also be carried out in a stirred-tank reactor. The
sulfonation with SO.sub.3 is to be preferred over the sulfonation
with oleum.
Mixtures
[0156] The compounds prepared by processes described above are
further processed (preferably) either as such, or are mixed
beforehand with other alkylaryls and then passed to the further
processing step. In order to simplify this process, it may also be
sensible to mix the raw materials which are used for the
preparation of the other alkylaryls mentioned above directly with
the raw materials of the present process, and then to carry out the
process according to the invention. Thus, the mixing of slightly
branched olefin streams from the process according to the invention
with linear olefins, for example, is sensible. Mixtures of the
alkylaryl-sulfonic acids or of the alkylarylsulfonates can also be
used. The mixings are always undertaken with regard to optimization
of the product quality of the surfactants prepared from the
alkylaryl.
[0157] An exemplary overview of alkylation, sulfonation,
neutralization is given, for example, in "Alkkylaryl-sulfonates:
History, Manufacture, Analysis and Environmental Properties" in
Surf. Sci. Ser. 56 (1996) Chapter 2, Marcel Dekker, New York, and
references contained therein.
Stage e)
[0158] In stage e), the alkylarylsulfonates present in stage d) are
additionally mixed with linear alkylaryl-sulfonates.
[0159] The invention also relates to alkylarylsulfonates obtainable
by a process as described above.
[0160] The alkylarylsulfonates according to the invention are
preferably used as surfactants, in particular in detergents and
cleaners. The invention also relates to a detergent or cleaner
comprising, in addition to customary ingredients,
alkylarylsulfonates as described above.
[0161] Nonexhaustive examples of customary ingredients of
detergents and cleaners according to the invention are listed
below.
Bleach
[0162] Examples are alkali metal perborates or alkali metal
carbonate perhydrates, in particular the sodium salts.
[0163] One example of an organic peracid which can be used is
peracetic acid, which is preferably used in commercial textile
washing or commercial cleaning.
[0164] Bleach or textile detergent compositions which can be used
advantageously comprise C.sub.1-12-percarboxylic acids,
C.sub.8-16-dipercarboxylic acids, imidopercarboxylic acids or
aryldipercarboxylic acids. Preferred examples of acids which can be
used are peracetic acid, linear or branched octane-, nonane-,
decane- or dodecane-monoper-acids, decane- and dodecane-diperacid,
mono- and diperphthalic acids, -isophthalic acids and -terephthalic
acids, phthalimidopercaproic acid and terephthaloyldipercaproic
acid. It is likewise possible to use polymeric peracids, for
example those which contain the acrylic acid basic building blocks
in which a peroxy function is present. The percarboxylic acids may
be used as free acids or as salts of the acids, preferably alkali
metal or alkaline earth metal salts.
Bleach Activator
[0165] Bleach catalysts are, for example, quaternized imines and
sulfonimines, as described, for example, in U.S. Pat. No.
5,360,568, U.S. Pat. No. 5,360,569 and EP-A-0 453 003, and also
manganese complexes as described, for example, in WO-A 94/21777.
Further metal-containing bleach catalysts which may be used are
described in EP-A-0 458 397, EP-A-0 458 398, EP-A-0 549 272.
[0166] Bleach activators are, for example, compounds from the
classes of substance below: polyacylated sugars or sugar
derivatives having C.sub.1-10-acyl radicals, preferably acetyl,
propionyl, octanoyl, nonanoyl or benzoyl radicals, particularly
preferably acetyl radicals, can be used as bleach activators. As
sugars or sugar derivatives, it is possible to use mono- or
disaccharides, and reduced or oxidized derivatives thereof,
preferably glucose, mannose, fructose, sucrose, xylose of lactose.
Particularly suitable bleach activators of this class of substance
are, for example, pentacetylglucose, xylose tetraacetate,
1-benzoyl-2,3,4,6-tetraacetylglucose and
1-octanoyl-2,3,4,6-tetraacetylglucose.
[0167] A further class of substance which can be used comprises the
acyloxybenzenesulfonic acids and alkali metal and alkaline earth
metal salts thereof, it being possible to use C.sub.1-14-acyl
radicals. Preference is given to acetyl, propionyl, octanoyl,
nonanoyl and benzoyl radicals, in particular acetyl radicals and
nonanoyl radicals. Particularly suitable bleach activators from
this class of substance are acetyloxybenzenesulfonic acid. They are
preferably used in the form of their sodium salts.
[0168] It is also possible to use O-acyl oxime esters, such as, for
example, O-acetylacetone oxime, O-benzoyl-acetone oxime,
bis(propylamino) carbonate, bis(cyclo-hexylimino) carbonate.
Examples of acylated oximes which can be used according to the
invention are described, for example, in EP-A-0 028 432. Oxime
esters which can be used according to the invention are described,
for example, EP-A-0 267 046.
[0169] It is likewise possible to use N-acylcaprolactams, such as,
for example, N-acetylcaprolactam, N-benzoylcapro-lactam,
N-octanoylcaprolactam, carbonylbiscaprolactam.
[0170] It is also possible to use [0171] N-diacylated and
N,N-tetraacylated amines, e.g.
N,N,N',N'-tetraacetylmethylenediamine and -ethylenediamine (TADE),
N,N-diacetylaniline, N,N-diacetyl-p-toluidine or 1,3-diacylated
hydantoins, such as 1,3-diactyl-5,5-dimethyl-hydantoin; [0172]
N-alkyl-N-sulfonylcarboxamides, e.g. N-methyl-N-mesylacetamide or
N-methyl-N-mesylbenzamide; [0173] N-acylated cyclic hydrazides,
acylated triazoles or urazoles, e.g. monoacetylmaleic hydrazide;
[0174] O,N,N-trisubstituted hydroxylamines, e.g.
O-benzoyl-N,N-succinylhydroxylamine,
O-acetyl-N,N-succinylhydroxylamine or
O,N,N-triacetylhydroxyl-amine; [0175] N,N'-diacylsulfurylamides,
e.g. N,N'-dimethyl-N,N'-diacetylsulfurylamide or
N,N'-diethyl-N,N'-di-propionylsulfurylamide; [0176] triacyl
cyanurate, e.g. triacetyl cyanurate or tribenzoyl cyanurate; [0177]
carboxylic anhydrides, e.g. benzoic anhydride, m-chlorobenzoic
anhydride or phthalic anhydride; [0178]
1,3-diacyl-4,5-diacyloxyimidazolines, e.g.
1,3-diacetyl-4,5-diacetoxyimidazoline; [0179] tetraacetylglycoluril
and tetrapropionylglycoluril; [0180] diacylated
2,5-diketopiperazines, e.g. 1,4-diacetyl-2,5-diketopiperazine;
[0181] acylation products of propylenediurea and
2,2,-di-methylpropylenediurea, e.g. tetraacetylpropylene-diurea;
[0182] .alpha.-acyloxypolyacylmalonamides, e.g.
.alpha.-acetoxy-N,N'-diacetylmalonamide; [0183]
diacyldioxohexahydro-1,3,5-triazines, e.g.
1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine.
[0184] It is likewise possible to use 1-alkyl- or
1-aryl-(4H)-3,1-benzoxazin-4-ones, as are described, for example,
in EP-B1-0 332 294 and EP-B 0 502 013. In particular, it is
possible to use 2-phenyl-(4H)-3,1-benzoxazin-4-one and
2-methyl-(4H)-3,1-benzoxazin-4-one.
[0185] It is also possible to use cationic nitriles, as described,
for example, in EP 303 520 and EP 458 391 Al. Examples of suitable
cationic nitriles are the methosulfates or tosylates of
trimethylammoniumacetonitrile,
N,N-dimethyl-N-octyl-ammoniumacetonitrile,
2-(trimethylammonium)propio-nitrile,
2-(trimethylammonium)-2-methylpropionitrile,
N-methylpiperazinium-N,N'-diacetonitrile and
N-methyl-morpholiniumacetonitrile.
[0186] Particularly suitable crystalline bleach activators are
tetraacetylethylenediamine (TAED), NOBS, isoNOBS,
carbonylbiscaprolactam, benzoylcaprolactam, bis(2-propylimino)
carbonate, bis(cyclohexylimino) carbonate, O-benzoylacetone oxime
and 1-phenyl-(4H)-3,1-benzoxazin-4-one, anthranil, phenylanthranil,
N-methylnorpholinoacetonitrile, N-octanoylcaprolactam (OCL) and
N-methylpiperazine-N,N'-diacetonitrile, and liquid or poorly
crystallizing bleach activators in a form formulated as a solid
product.
Bleach Stabilizer
[0187] These are additives which are able to adsorb, bind or
complex traces of heavy metal. Examples of additives with a
bleach-stabilizing action which can be used according to the
invention are polyanionic compounds, such as polyphosphates,
polycarboxylates, polyhydroxy-polycarboxylates, soluble silicates
in the form of completely or partially neutralized alkali metal or
alkaline earth metal salts, in particular in the form of neutral Na
or Mg salts, which are relatively weak bleach stabilizers. Strong
bleach stabilizers which can be used according to the invention
are, for example, complexing agents, such as
ethylenediarninetetraacetate (EDTA), nitrilotriacetic acid (NTA),
methylglycine-diacetic acid (MGDA), .beta.-alaninediacetic acid
(ADA), ethylenediamine-N,N'-disuccinate (EDDS) and phosphonates,
such as ethylenediaminetetramethylene-phosphonate,
diethylenetriaminepentamethylene-phosphonate or
hydroxyethylidene-1,1-diphosphonic acid in the form of the acids or
as partially or completely neutralized alkali metal salts. The
complexing agents are preferably used in the form of their Na
salts.
[0188] The detergents according to the invention preferably
comprise at least one bleach stabilizer, particularly preferably at
least one of the abovementioned strong bleach stabilizers.
[0189] In the field of textile washing, bleaching and household
cleaning and in the commercial sector, the bleach or textile
detergent compositions described may, in accordance with one
embodiment of the invention, comprise virtually all customary
constituents of detergents, bleaches and cleaners. In this way, it
is possible, for example, to formulate compositions which are
specifically suitable for textile treatment at low temperatures,
and also those which are suitable in a number of temperature ranges
up to and including the traditional range of the boil wash.
[0190] In addition to bleach compositions, the main constituents of
textile detergents and cleaners are builders, i.e. inorganic
builders and/or organic cobuilders, and surfactants, in particular
anionic and/or nonionic surfactants. In addition, it is also
possible for other customary auxiliaries and adjuncts, such as
extenders, complexing agents, phosphonates, dyes, corrosion
inhibitors, antiredeposition agents and/or soil release polymers,
color-transfer inhibitors, bleach catalysts, peroxide stabilizers,
electrolytes, optical brighteners, enzymes, perfume oils, foam
regulators and activating substances, to be present in these
compositions if this is advantageous.
Inorganic Builders (Builder Substances)
[0191] Suitable inorganic builder substances are all customary
inorganic builders, such as aluminosilicates, silicates, carbonates
and phosphates.
[0192] Examples of suitable inorganic builders are
alumino-silicates having ion-exchanging properties, such as, for
example, zeolites. Various types of zeolites are suitable, in
particular zeolite A, X, B, P, MAP and HS in their Na form or in
forms in which Na has partially been replaced by other cations such
Li, K, Ca, Mg or ammonium. Suitable zeolites are described, for
example, in EP-A 038 591, EP-A 021 491, EP-A 087 035, U.S. Pat. No.
4,604,224, GB-A 2 013 259, EP-A 522 726, EP-A 384 070 and WO-A
94/24 251.
[0193] Further suitable inorganic builders are, for example,
amorphous or crystalline silicates, such as, for example, amorphous
disilicates, crystalline disilicates, such as the phyllosilicate
SKS-6 (manufacturer: Hoechst). The silicates can be used in the
form of their alkali metal, alkaline earth metal or ammonium salts.
Preference is given to using Na, Li and Mg silicates.
Anionic Surfactants
[0194] Suitable anionic surfactants are the linear and/or slightly
branched alkylbenzenesulfonates (LAS) according to the
invention.
[0195] Further suitable anionic surfactants are, for example, fatty
alcohol sulfates of fatty alcohols having 8 to 22, preferably 10 to
18, carbon atoms, e.g. C.sub.9-- to C.sub.11-alcohol sulfates,
C.sub.12-- to C.sub.13-alcohol sulfates, cetyl sulfate, myristyl
sulfate, palmityl sulfate, stearyl sulfate and tallow fatty alcohol
sulfate.
[0196] Further suitable anionic surfactants are sulfated
ethoxylated C.sub.8-- to C.sub.22-alcohols (alkyl ether sulfates)
or soluble salts thereof. Compounds of this type are prepared, for
example, by firstly alkoxylating a C.sub.8-- to C.sub.22-alcohol,
preferably a C.sub.10-C.sub.18-alcohol, e.g. a fatty alcohol, and
then sulfating the alkoxylation product. For the alkoxylation,
preference is given to using ethylene oxide, in which case 2 to 50
mol, preferably 3 to 20 mol, of ethylene oxide are used per mole of
fatty alcohol. The alkoxylation of the alcohols can, however, also
be carried out using propylene oxide on its own and optionally
butylene oxide. Also suitable are those alkoxylated C.sub.8-- to
C.sub.22-alcohols which contain ethylene oxide and propylene oxide
or ethylene oxide and butylene oxide. The alkoxylated C.sub.8 to
C.sub.22-alcohols may contain the ethylene oxide, propylene oxide
and butylene oxide units in the form of blocks or in random
distribution.
[0197] Further suitable anionic surfactants are N-acylsarcosinates
having aliphatic saturated or unsaturated C.sub.8-- to
C.sub.25-acyl radicals, preferably C.sub.10-- to C.sub.20-acyl
radicals, e.g. N-oleoylsarcosinate.
[0198] The anionic surfactants are preferably added to the
detergent in the form of salts. Suitable cations in these salts are
alkali metal salts, such as sodium, potassium and lithium and
ammonium salts such as, for example, hydroxyethylammonium,
di(hydroxyethyl)ammonium and tri(hydroxyethyl)ammonium salts.
[0199] The detergents according to the invention preferably
comprise C.sub.10-- to C.sub.13-linear and/or slightly branched
alkylbenzenesulfonates (LAS).
Nonionic Surfactants
[0200] Suitable nonionic surfactants are, for example, alkoxylated
C.sub.8-- to C.sub.22-alcohols, such as fatty alcohol alkoxylates
or oxo alcohol alkoxylates. The alkoxylation can be carried out
with ethylene oxide, propylene oxide and/or butylene oxide.
Surfactants which can be used here are any alkoxylated alcohols
which contain at least two molecules of an abovementioned alkylene
oxide in added form. Block polymers of ethylene oxide, propylene
oxide and/or butylene oxide are also suitable here, or addition
products which contain said alkylene oxides in random distribution.
Per mole of alcohol, 2 to 50 mol, preferably 3 to 20 mol, of at
least one alkylene oxide are used. The alkylene oxide used is
preferably ethylene oxide. The alcohols preferably have 10 to 18
carbon atoms.
[0201] A further class of suitable nonionic surfactants are
alkylphenol ethoxylates having C.sub.6-C.sub.14-alkyl chains and 5
to 30 mol of ethylene oxide units.
[0202] Another class of nonionic surfactants are alkyl
polyglucosides having 8 to 22, preferably 10 to 18, carbon atoms in
the alkyl chain. These compounds contain at most 1 to 20,
preferably 1.1 to 5, glucoside units.
[0203] Another class of nonionic surfactants are N-alkyl-glucamides
of the structure II or III ##STR4##
[0204] in which R.sup.6 is C.sub.6-- to C.sub.22-alkyl, R.sup.7 is
H or C.sub.1-- to C.sub.4-alkyl and R.sup.8 is a polyhydroxyalkyl
radical having 5 to 12 carbon atoms and at least 3 hydroxyl groups.
Preferably, R.sub.6 is C.sub.10-- to C.sub.18-alkyl, R.sup.7 is
methyl and R.sup.8 is a C.sub.5-- or C.sub.6-radical. Such
compounds are obtained, for example, by the acylation of
reductively aminated sugars with acid chlorides of
C.sub.10-C.sub.18-carboxylic acids.
[0205] The detergents according to the invention preferably
comprise C.sub.10-C.sub.16-alcohols ethoxylated with 3-12 mol of
ethylene oxide, particularly preferably ethoxylated fatty alcohols
as nonionic surfactants.
Organic Cobuilders
[0206] Examples of suitable low molecular weight polycarboxylates
as organic cobuilders are:
[0207] C.sub.4-- to C.sub.20-di-, -tri- and -tetracarboxylic acids,
such as, for example, succinic acid, propanetricarboxylic acid,
butanetetracarboxylic acid, cyclopentanetetra- carboxylic acid and
alkyl- and alkenylsuccinic acids having C.sub.2-- to C.sub.16-alkyl
or -alkenyl radicals;
[0208] C.sub.4-- to C.sub.20-hydroxycarboxylic acids, such as, for
example, malic acid, tartaric acid, gluconic acid, glucaric acid,
citric acid, lactobionic acid and sucrose mono-, -di- and
-tricarboxylic acid;
[0209] aminopolycarboxylates, such as, for example,
nitrilo-triacetic acid, methylglycinediacetic acid, alaninediacetic
acid, ethylenediaminetetraacetic acid and serinediacetic acid;
[0210] salts of phosphonic acids, such as, for example,
hydroxyethanediphosphonic acid,
ethylenediaminetetra(methylenephosphonate) and
diethylenetriaminepenta-(methylenephosphonate).
[0211] Examples of suitable oligomeric or polymeric
polycarboxylates as organic cobuilders are:
[0212] oligomaleic acids, as described, for example, in EP-A-451
508 and EP-A-396 303;
[0213] co- and terpolymers of unsaturated
C.sub.4-C.sub.8-dicarboxylic acids, where, as comonomers,
monoethylenically unsaturated monomers [0214] from group (i) in
amounts of up to 95% by weight [0215] from group (ii) in amounts of
up to 60% by weight [0216] from group (iii) in amounts of up to 20%
by weight [0217] may be present in copolymerized form.
[0218] Examples of suitable unsaturated
C.sub.4-C.sub.8-dicarboxylic acids are, for example, maleic acid,
fumaric acid, itaconic acid and citraconic acid. Preference is
given to maleic acid.
[0219] The group (i) includes monoethylenically unsaturated
C.sub.3-C.sub.8-monocarboxylic acids, such as, for example, acrylic
acid, methacrylic acid, crotonic acid and vinyl acetic acid.
Preference is given to using acrylic acid and methacrylic acid from
group (i).
[0220] The group (ii) includes monoethylenically unsaturated
C.sub.2-C.sub.22-olefins, vinyl alkyl ethers having
C.sub.1-C.sub.8-alkyl groups, styrene, vinyl esters of
C.sub.1-C.sub.8 carboxylic acids, (meth)acrylamide and
vinylpyrrolidone. Preference is given to using
C.sub.2-C.sub.6-olefins, vinyl alkyl ethers having
C.sub.1-C.sub.4-alkyl groups, vinyl acetate and vinyl propionate
from group (ii).
[0221] The group (iii) includes (meth)acrylic esters of
C.sub.1-C.sub.8-alcohols, (meth)acrylonitrile, (meth)acrylamides of
C.sub.1-C.sub.8-amines, N-vinylformamide and vinylimidazole.
[0222] If the polymers of group (ii) contain vinyl esters in
copolymerized form, these may also be present partly or completely
in hydrolyzed form to give vinyl alcohol structural units. Suitable
co- and terpolymers are known, for example, from U.S. Pat. No. 3
887 806 and DE-A 43 13 909.
[0223] As copolymers of dicarboxylic acids, suitable organic
cobuilders are preferably:
[0224] copolymers of maleic acid and acrylic acid in the weight
ratio 10:90 to 95:5, particularly preferably those in the weight
ratio 30:70 to 90:10 having molar masses of from 10 000 to 150
000;
[0225] terpolymers of maleic acid, acrylic acid and a vinyl ester
of a C.sub.1-C.sub.3-carboxylic acid in the weight ratio 10(maleic
acid):90(acrylic acid+vinyl ester) to 95(maleic acid):5(acrylic
acid+vinyl ester), where the weight ratio of acrylic acid to vinyl
ester can vary in the range from 20:80 to 80:20, and particularly
preferably
[0226] terpolymers of maleic acid, acrylic acid and vinyl acetate
or vinyl propionate in the weight ratio 20(maleic acid):80(acrylic
acid+vinyl ester) to 90(maleic acid):10(acrylic acid+vinyl ester),
where the weight ratio of acrylic acid to the vinyl ester can vary
in the range from 30:70 to 70:30;
[0227] copolymers of maleic acid with C.sub.2-C.sub.8-olefins in
the molar ratio 40:60 to 80:20, where copolymers of maleic acid
with ethylene, propylene or isobutane in the molar ratio 50:50 are
particularly preferred.
[0228] Graft polymers of unsaturated carboxylic acids to low
molecular weight carbohydrates or hydrogenated carbohydrates, cf.
U.S. Pat. No. 5,227,446, DE-A-44 15 623, DE-A-43 13 909, are
likewise suitable as organic cobuilders.
[0229] Examples of suitable unsaturated carboxylic acids in this
connection are maleic acid, fumaric acid, itaconic acid, citraconic
acid, acrylic acid, methacrylic acid, crotonic acid and vinyl
acetic acid, and mixtures of acrylic acid and maleic acid which are
grafted on in amounts of from 40 to 95% by weight, based on the
component to be grafted.
[0230] For the modification, it is additionally possible for up to
30% by weight, based on the component to be grafted, of further
monoethylenically unsaturated monomers to be present in
copolymerized form. Suitable modifying monomers are the
abovementioned monomers of groups (ii) and (iii).
[0231] Suitable graft bases are degraded polysaccharides, such as,
for example, acidic or enzymatically degraded starches, inulins or
cellulose, reduced (hydrogenated or reductively aminated) degraded
polysaccharides, such as, for example, mannitol, sorbitol,
aminosorbitol and glucamine, and also polyalkylene glycols having
molar masses up to M.sub.w=5 000, such as, for example,
polyethylene glycols, ethylene oxide/propylene oxide or ethylene
oxide/butylene oxide block copolymers, random ethylene
oxide/propylene oxide or ethylene oxide/butylene oxide copolymers,
alkoxylated mono- or polybasic C.sub.1-C.sub.22-alcohols, cf. U.S.
Pat. No. 4,746,456.
[0232] From this group, preference is given to using grafted
degraded or degraded reduced starches and grafted polyethylene
oxides, in which case 20 to 80% by weight of monomers, based on the
graft component, are used in the graft polymerization. For the
grafting, preference is given to using a mixture of maleic acid and
acrylic acid in the weight ratio from 90:10 to 10:90.
[0233] Polyglyoxylic acids as organic cobuilders are described, for
example, in EP-B-001 004, U.S. Pat. No. 5,399,286, DE-A-41 06 355
and EP-A-656 914. The end-groups of the polyglyoxylic acids may
have different structures.
[0234] Polyamidocarboxylic acids and modified polyamidocarboxylic
acids as organic cobuilders are known, for example, from EP-A-454
126, EP-B-511 037, WO-A 94/01486 and EP-A-581 452.
[0235] As organic cobuilders, preference is also given to using
polyaspartic acid or cocondensates of aspartic acid with further
amino acids, C.sub.4-C.sub.25-mono- or -dicarboxylic acids and/or
C.sub.4-C.sub.25-mono- or -diamines. Particular preference is given
to using polyaspartic acids prepared in phosphorus-containing acids
and modified with C.sub.6-C.sub.22-mono- or -dicarboxylic acids or
with C.sub.6-C.sub.22-mono- or -diamines.
[0236] Condensation products of citric acid with hydroxycarboxylic
acids or polyhydroxy compounds as organic cobuilders are known, for
example, from WO-A 93/22362 and WO-A 92/16493. Such
carboxyl-containing condensates usually have molar masses up to 10
000, preferably up to 5 000.
Antiredeposition Agents and Soil Release Polymers
[0237] Suitable soil release polymers and/or antiredeposition
agents for detergents are, for example: polyesters of polyethylene
oxides with ethylene glycol and/or propylene glycol and aromatic
dicarboxylic acids or aromatic and aliphatic dicarboxylic
acids;
[0238] polyesters of polyethylene oxides terminally capped at one
end with di- and/or polyhydric alcohols and dicarboxylic acid.
[0239] Such polyesters are known, for example from U.S. Pat. No.
3,557,039, GB-A 1 154 730, EP-A-185 427, EP-A-241 984, EP-A-241
985, EP-A-272 033 and U.S. Pat. No. 5,142,020.
[0240] Further suitable soil release polymers are amphiphilic graft
or copolymers of vinyl and/or acrylic esters on polyalkylene oxides
(cf. U.S. Pat. No. 4,746,456, U.S. Pat. No. 4,846,995, DE-A-37 11
299, U.S. Pat. No. 4,904,408, U.S. Pat. No. 4,846,994 and U.S. Pat.
No. 4,849,126) or modified celluloses, such as, for example,
methylcellulose, hydroxypropylcellulose or
carboxymethylcellulose.
Color-Transfer Inhibitors
[0241] Examples of the color-transfer inhibitors used are homo- and
copolymers of vinylpyrrolidone, vinylimidazole, vinyloxazolidone
and 4-vinylpyridine N-oxide having molar masses of from 15 000 to
100 000, and crosslinked finely divided polymers based on these
monomers. The use mentioned here of such polymers is known, cf.
DE-B-22 32 353, DE-A-28 14 287, DE-A-28 14 329 and DE-A-43 16
023.
Enzymes
[0242] Suitable enzymes are, for example, proteases, amylases,
lipases and cellulases, in particular proteases. It is possible to
use two or more enzymes in combination.
[0243] In addition to use in detergents and cleaners for the
domestic washing of textiles, the detergent compositions which can
be used according to the invention can also be used in the sector
of commercial textile washing and of commercial cleaning. In this
field of use, peracetic acid is usually used as bleach, which is
added to the wash liquor as an aqueous solution.
Use in Textile Detergents
[0244] A typical pulverulent or granular heavy-duty detergent
according to the invention may, for example, have the following
composition: [0245] 0.5 to 50% by weight, preferably 5 to 30% by
weight, of at least one anionic and/or nonionic surfactant, [0246]
0.5 to 60% by weight, preferably 15 to 40% by weight, of at least
one inorganic builder, [0247] 0 to 20% by weight, preferably 0.5 to
8% by weight, of-at least one organic cobuilder, [0248] 2 to 35% by
weight, preferably 5 to 30% by weight, of an inorganic bleach,
[0249] 0.1 to 20% by weight, preferably 0.5 to 10% by weight, of a
bleach activator, optionally in a mixture with further bleach
activators, [0250] 0 to 1% by weight, preferably up to at most 0.5%
by weight, of a bleach catalyst, [0251] 0 to 5% by weight,
preferably 0 to 2.5% by weight, of a polymeric color-transfer
inhibitor, [0252] 0 to 1.5% by weight, preferably 0.1 to 1.0% by
weight, of protease, [0253] 0 to 1.5% by weight, preferably 0.1 to
1.0% by weight, of lipase, [0254] 0 to 1.5% by weight, preferably
0.2 to 1.0% by weight, of a soil release polymer, [0255] ad 100%
with customary auxiliaries and adjuncts and water.
[0256] Inorganic builders preferably used in detergents are sodium
carbonate, sodium hydrogen carbonate, zeolite A and P, and
amorphous and crystalline Na silicates.
[0257] Organic cobuilders preferably used in detergents are acrylic
acid/maleic copolymers, acrylic acid/maleic acid/vinyl ester
terpolymers and citric acid.
[0258] Inorganic bleaches preferably used in detergents are sodium
perborate and sodium carbonate perhydrate.
[0259] Anionic surfactants preferably used in detergents are the
novel linear and slightly branched alkylbenzenesulfonates (LAS),
fatty alcohol sulfates and soaps. Nonionic surfactants preferably
used in detergents are C.sub.11-C.sub.17-oxo alcohol ethoxylates
having 3-13 ethylene oxide units, C.sub.10-C.sub.16-fatty alcohol
ethoxylates having 3-13 ethylene oxide units, and ethoxylated fatty
alcohols or oxo alcohols additionally alkoxylated with 1-4
propylene oxide or butylene oxide units.
[0260] Enzymes preferably used in detergents are protease, lipase
and cellulase. Of the commercially available enzymes, amounts of
from 0.05 to 2.0% by weight, preferably 0.2 to 1.5% by weight, of
the formulated enzyme, are generally added to the detergent.
Suitable proteases are, for example, Savinase, Desazym and Esperase
(manufacturer: Novo Nordisk). A suitable lipase is, for example,
Lipolase (manufacturer: Novo Nordisk). A suitable cellulase is, for
example, Celluzym (manufacturer: Novo Nordisk).
[0261] Soil release polymers and antiredeposition agents preferably
used in detergents are graft polymers of vinyl acetate on
polyethylene oxide of molecular mass 2 500-8 000 in the weight
ratio 1.2:1 to 3.0:1, polyethylene terephthalates/oxyethylene
terephthalates of molar mass 3 000 to 25 000 from polyethylene
oxides of molar mass 750 to 5 000 with terephthalic acid and
ethylene oxide and a molar ratio of polyethylene terephthalate to
polyoxyethylene terephthalate of from 8:1 to 1:1, and block
polycondensates according to DE-A-44 03 866.
[0262] Color-transfer inhibitors preferably used in detergents are
soluble vinylpyrrolidone and vinylimidazole copolymers having molar
masses greater than 25 000, and finely divided crosslinked polymers
based on vinylimidazole.
[0263] The pulverulent or granular detergents according to the
invention can comprise up to 60% by weight of inorganic extenders.
Sodium sulfate is usually used for this purpose. However, the
detergents according to the invention preferably have a low content
of extenders and comprise only up to 20% by weight, particularly
preferably only up to 8% by weight, of extenders.
[0264] The detergents according to the invention can have various
bulk densities in the range from 300 to 1 200 g/l, in particular
500 to 950 g/l. Modern compact detergents generally have high bulk
densities and exhibit a granular structure.
[0265] The invention is described in more detail by reference to
the examples below.
EXAMPLE 1
[0266] A butadiene-free C.sub.4 fraction with a total butene
content of 84.2% by weight and a 1-butene to 2-butene molar ratio
of 1 to 1.06 is passed continuously at 40.degree. C. and 10 bar
over a tubular reactor fitted with Re.sub.2O.sub.7/Al.sub.2O.sub.3
heterogeneous catalyst. The space velocity in the example is 4 500
kg/m.sup.2 h. The reaction discharge is separated by distillation
and comprises the following components (data in percent by
mass):
[0267] ethene 1.15%; propene 18.9%, butanes 15.8%, 2-butenes 19.7%,
1-butene 13.3%, i-butene 1.0%, 2-pentene 19.4%, methylbutene 0.45%,
3-hexene 10.3%.
[0268] 2-Pentene and 3-hexene are isolated from the product by
distillation in purities of >99% by weight.
EXAMPLE 2
[0269] Continuous dimerization of 3-hexene in the fixed-bed
process
[0270] Catalyst: 50% NiO, 34% SiO.sub.2, 13% TiO.sub.2, 3%
Al.sub.2O.sub.3 (as in DE 43 39 713) used as 1-1.5 mm chips (100
ml), conditioned for 24 h at 160.degree. C. in N.sub.2
[0271] Reactor: isothermal, 16 mm O reactor
[0272] WHSV: 0.25 kg/l.h
[0273] Pressure: 20 to 25 bar
[0274] Temperature: 100 to 160.degree. C. TABLE-US-00001
Temperature 100 120 140 160 160 (.degree. C.) Pressure Feed- 20 20
20 25 25 Collective- C.sub.12 (bar) stock product distillate
Operating hours 12 19 36 60 107 Liquid produced 24 27 27 28 27
(g/h) Composition (% by weight) C.sub.6 99.9 68.5 52.7 43.6 57.0
73.2 n.d. 0.1 C.sub.7-C.sub.11 0.1 0.2 0.2 0.3 0.2 0.2 -- C.sub.12
25.9 38.6 44.0 35.6 23.6 99.9 C.sub.13+ 5.4 8.5 12.1 7.2 3.0 --
Conversion 31.4 47.2 56.4 42.9 26.7 C12 selectivity 82.5 81.8 78.2
83.0 88.4 (% by weight) S content in <1 n.d. n.d. n.d. n.d. n.d.
n.d. n.d. the liquid produced (ppm) The collective product was
distilled to a C.sub.12 purity of 99.9% by weight.
EXAMPLE 3
[0275] 2-Pentene from the raffinate II metathesis was dimerized
continuously as in example 2 over an Ni heterogeneous catalyst.
Fractional distillation of the product gave a decene fraction with
a purity of 99.5%.
EXAMPLE 4
[0276] A mixture of 2-pentene and 3-hexene from the raffinate II
methathesis was dimerized as in example 2 and example 3. Fractional
distillation of the product gave a decene/undecene/dodecene
fraction with a purity of 99.5%
EXAMPLE 5
[0277] The C.sub.12-olefin fraction from example 2 is alkylated
with benzene in the molar ratio 1:10. For this, the reaction
mixture is introduced into an autoclave (300 ml) which is equipped
with a stirrer and a catalyst basket. 25% by weight, based on the
mass of the olefin, of zeolite mordenith catalyst (MOR) are
introduced into the catalyst basket. The autoclave is sealed and
flushed twice with nitrogen (N.sub.2). The autoclave is then heated
to 180.degree. C. The reaction mixture is then reacted for 12 h,
then cooled, any catalyst particles are filtered from the reaction
mixture, and the reaction mixture is analyzed by means of gas
chromatography-mass spectrometry coupling. Excess benzene and
low-boiling components are distilled off, and the alkylaryl mixture
obtained is analyzed by means of gas chromatography-mass
spectrometry coupling and C.sup.13-NMR.
EXAMPLE 6
[0278] A 2 l four-necked flask fitted with magnetic stirrer,
thermometer, dropping funnel, gas inlet frit and gas outlet is
charged with 1 900 g of SO.sub.3-depleted oleum. This flask is
connected via the gas outlet to a 1I three-necked flask via a Viton
hose. This 1 l flask fitted with paddle stirrer, thermometer, gas
inlet frit and gas outlet is charged with the alkylbenzene mixture
from example 5.
[0279] The depleted oleum is brought to 120.degree. C. in the
SO.sub.3-developer, and the oleum (65% strength) is added via a
dropping funnel over the course of 30 minutes. Using a stream of
nitrogen of 80 l/h, the SO.sub.3 gas is stripped out and passed
into the alkylbenzene via a 6 mm inlet tube. The temperature of the
alkylbenzene/alkylbenzenesulfonic acid mixture increases slowly to
40.degree. C. and is maintained at 40.degree. C. using cooling
water. The residual gas is removed by suction using a water-jet
pump.
[0280] The molar ratio of SO.sub.3/alkylbenzene is 1.01:1.
[0281] After a postreaction time of 4 h, the alkylbenzene-sulfonic
acid formed is stabilized with 0.4% by weight of water and then
neutralized with NaOH to give the alkylbenzenesulfonate.
EXAMPLE 7
[0282] A mixture of the C.sub.10-/C.sub.11-/C.sub.12-olefin
fractions from example 4 is alkylated with benzene in the molar
ratio 1:10. For this, the reaction mixture is introduced into an
autoclave (300 ml) which is provided with a stirrer and a catalyst
basket. 25% by weight, based on the mass of the olefin, of zeolite
mordenite catalyst (MOR) are introduced into the catalyst basket.
The autoclave is sealed and flushed twice with nitrogen (N.sub.2).
The autoclave is then heated to 200.degree. C. The reaction mixture
is reacted for 12 h, then cooled, any catalyst particles are
filtered from the reaction mixture, and the reaction mixture is
analyzed by means of gas chromatography-mass spectrometry
coupling.
[0283] Excess benzene and low-boiling fractions are distilled off,
and the alkylaryl mixture obtained is analyzed by means of gas
chromatography-mass spectrometry coupling and C.sup.13-NMR.
EXAMPLE 8
[0284] The alkylbenzene mixture from example 7 is converted to the
alkylbenzenesulfonate analogously to the description in example
6.
EXAMPLE 9
[0285] A mixture of the C.sub.10-/C.sub.11-/C.sub.12-olefin
fractions from example 4 is alkylated with benzene in the molar
ratio 1:2. For this, the reaction mixture is introduced into an
autoclave (300 ml) which is provided with a stirrer and a catalyst
basket. 5% by weight, based on the mass of the olefin, of zeolite
ZSM-12 catalyst are introduced into the catalyst basket. The
autoclave is sealed and flushed twice with nitrogen (N.sub.2). The
autoclave is then heated to 180.degree. C. The reaction mixture is
reacted for 12 h, then cooled, any catalyst particles are filtered
from the reaction mixture, and the reaction mixture is analyzed by
means of gas chromatography-mass spectrometry coupling.
[0286] Excess benzene and low-boiling fractions are distilled off,
and the alkylaryl mixture obtained is analyzed by means of gas
chromatography-mass spectrometry coupling and C.sup.13-NMR.
EXAMPLE 10
[0287] The alkylbenzene mixture from example 9 is converted to the
alkylbenzenesulfonate analogously to the description in example
6.
EXAMPLE 11
[0288] A C.sub.12-olefin fraction from example 2 is alkylated with
benzene in the molar ratio 1:4. For this, the reaction mixture is
introduced into an autoclave (300 ml) which is provided with a
stirrer and a catalyst basket. 10% by weight, based on the mass of
the olefin, of zeolite beta (BEA) catalyst are introduced into the
catalyst basket. The autoclave is sealed and flushed twice with
nitrogen (N.sub.2). The autoclave is then heated to 180.degree. C.
The reaction mixture is reacted for 12 h, then cooled, any catalyst
particles are filtered from the reaction mixture, and the reaction
mixture is analyzed by means of gas chromatography-mass
spectrometry coupling.
[0289] Excess benzene and low-boiling fractions are distilled off,
and the resulting alkylaryl mixture is analyzed by means of gas
chromatography-mass spectrometry coupling and C.sup.13-NMR.
EXAMPLE 12
[0290] The alkylbenzene mixture from example 11 is converted to the
alkylbenzenesulfonate analogously to the description in example
6.
EXAMPLE 13
[0291] A mixture of the C.sub.10-/C.sub.11-/C.sub.12-olefin
fractions from example 4 is alkylated with benzene in the molar
ratio 1:4. For this, the reaction mixture is introduced into an
autoclave (300 ml) which is provided with a stirrer and a catalyst
basket. 10% by weight, based on the mass of the olefin, of zeolite
MCM-22 catalyst are introduced into the catalyst basket. The
autoclave is sealed and flushed twice with nitrogen (N.sub.2). The
autoclave is then heated to 200.degree. C. The reaction mixture is
reacted for 12 h, then cooled, any catalyst particles are filtered
from the reaction mixture, and the reaction mixture is analyzed by
means of gas chromatography-mass spectrometry coupling.
[0292] Excess benzene and low-boiling fractions are distilled off,
and the resulting alkylaryl mixture is analyzed by means of gas
chromatography-mass spectrometry coupling and C.sup.13-NMR.
EXAMPLE 14
[0293] 1 l/h of oleum (65%) in concentrated sulfuric acid is
introduced into a heated (120.degree. C.) 10 l four-necked flask
using a pump. 130 l/h of dry air are passed through the sulfuric
acid via a frit; this air strips out the SO.sub.3. The
SO.sub.3-enriched stream of air (about 4% of SO.sub.3) is brought
into contact with an alkylbenzene mixture from example 13 in a 2
m-long falling-film reactor, at approximately 40-50.degree. C.
(10-15.degree. C. double-jacket water cooling), and sulfonates this
mixture. The molar ratio of SO.sub.3/alkylbenzene is 1.01:1. The
reaction time in the falling-film reactor is approximately 10 sec.
The product is pumped to an afterripening container where it
remains for approximately 4-8 h. The sulfonic acid is then
stabilized with 0.4% by weight of water and neutralized with NaOH
to give the alkylbenzenesulfonate.
EXAMPLE 15
[0294] A C.sub.12-olefin fraction from example 2 is alkylated with
benzene in the molar ratio 1:10. Thus, the reaction mixture is
introduced into a four-necked flask (2 l), which is provided with a
stirrer, a thermometer, a reflux condenser with a gas offtake and a
dropping funnel. The flask is charged with benzene and AlCl.sub.3,
the temperature is increased to 80.degree. C., and the olefin
mixture is metered in slowly. The reaction mixture is afterreacted
for 1/2 h, then cooled, any catalyst particles are filtered from
the reaction mixture, and the reaction mixture is neutralized with
NaOH. Washing with water is then carried out, and the product is
dried.
[0295] Excess benzene and low-boiling fractions are distilled off,
and the resulting alkylaryl mixture is analyzed by means of gas
chromatography-mass spectrometry coupling and C.sup.13-NMR.
EXAMPLE 16
[0296] The alkylbenzene mixture from example 15 is converted to the
alkylbenzenesulfonate analogously to the description in example
6.
* * * * *