U.S. patent application number 10/467393 was filed with the patent office on 2004-03-18 for use of cardanol aldehyde resins as asphalt dispersants in crude oil.
Invention is credited to Feustel, Michael, Grundner, Heidi, Leinweber, Dirk, Wasmund, Elisabeth.
Application Number | 20040050752 10/467393 |
Document ID | / |
Family ID | 7673551 |
Filed Date | 2004-03-18 |
United States Patent
Application |
20040050752 |
Kind Code |
A1 |
Leinweber, Dirk ; et
al. |
March 18, 2004 |
Use of cardanol aldehyde resins as asphalt dispersants in crude
oil
Abstract
The invention relates to the use of resins, obtained by a
reaction of cardanol with a compound of formula (1), where
R1.dbd.H, COH, COOH, COOR2 or R2, R2.dbd.C1-C30 alkyl, C2-C30
alkenyl, C6-C18 aryl or C7-C30 alkaryl with a number average
molecular weight of 250 to 100,000 units, in amounts of 0.5 to
10,000 ppm relative to the oil, for the dispersion of asphalts in
crude oils or products derived therefrom.
Inventors: |
Leinweber, Dirk;
(Burghausen, DE) ; Feustel, Michael; (Kongernheim,
DE) ; Wasmund, Elisabeth; (Burgkirchen, DE) ;
Grundner, Heidi; (Garching/Alz, DE) |
Correspondence
Address: |
CLARIANT CORPORATION
INTELLECTUAL PROPERTY DEPARTMENT
4000 MONROE ROAD
CHARLOTTE
NC
28205
US
|
Family ID: |
7673551 |
Appl. No.: |
10/467393 |
Filed: |
August 7, 2003 |
PCT Filed: |
January 29, 2002 |
PCT NO: |
PCT/EP02/00882 |
Current U.S.
Class: |
208/48AA ;
208/48R |
Current CPC
Class: |
C09K 8/524 20130101;
C09K 23/017 20220101; C10L 1/2225 20130101; C10L 1/2437 20130101;
C10L 1/238 20130101; C09K 23/00 20220101; C09K 23/018 20220101;
C10L 1/1985 20130101; C10L 1/143 20130101; C10L 1/1981
20130101 |
Class at
Publication: |
208/048.0AA ;
208/048.00R |
International
Class: |
C10G 009/16 |
Foreign Application Data
Date |
Code |
Application Number |
Feb 10, 2001 |
DE |
101 06 144.7 |
Claims
1. The use of resins obtainable by reacting cardanol with a
compound of the formula (1) 5in which R.sup.1 is H, CHO, COOH,
COOR.sup.2 or R.sup.2, and R.sup.2 is C.sub.1-C.sub.30-alkyl,
C.sub.2-C.sub.30-alkenyl, C.sub.6-C.sub.18-aryl or
C.sub.7-C.sub.30-alkylaryl, and which have a number-average
molecular weight of from 250 to 100 000 units, in amounts of from
0.5 to 10 000 ppm, based on the oil, for dispersing asphaltenes in
crude oils or products derived therefrom.
2. The use as claimed in claim 1, where cardanol is reacted in a
mixture with alkylphenols of the formula (7) in the ratio 100:1 to
1:100 6in which R.sup.4 and OH may be in the ortho, meta or para
position relative to one another, and R.sup.4 is C.sub.1- to
C.sub.30-alkyl, C.sub.6- to C.sub.30-alkenyl, C.sub.6- to
C.sub.18-aryl or C.sub.7- to C.sub.30-alkylaryl.
3. The use as claimed in claim 1 and/or 2, where R.sup.1 is an
alkyl or alkenyl radical having 6 to 24 carbon atoms.
4. The use as claimed in one or more of claims 1 and/or 2, where
R.sup.1 is CHO.
5. The use as claimed in claim 4, where the resin obtained from the
reaction is esterified or etherified.
6. A process for dispersing asphaltenes in crude oils and products
derived therefrom, which comprises adding cardanol-aldehyde resins
as claimed in one or more of claims 1 to 5 in an amount of from 0.5
to 10 000 ppm.
7. The process as claimed in claim 6, wherein alkylphenol
formaldehyde resins, oxyalkylated amines, mono- or dialkylsulfonic
acids, petroleum acids, alkanesulfonic acids, wax dispersant or any
mixtures thereof are additionally used.
8. A crude oil or a product derived therefrom comprising an
asphaltene dispersant as claimed in one or more of claims 1 to 5.
Description
[0001] The present invention relates to the use of
cardanol-aldehyde resins as asphaltene dispersants in crude oils
and asphaltene-containing oils derived from these, and crude oils
and residual oils which comprise these resins.
[0002] Asphaltenes are constituents of crude oils. They contain a
large number of structures, particularly high molecular weight
condensed aromatic components with heteroatoms. In view of the
complexity of their chemistry, asphaltenes are described as the oil
fraction which is soluble in benzene but not in n-pentane.
[0003] In crude oil, asphaltenes are normally in the form of a
colloidal dispersion. This is stabilized by oil resins.
[0004] Asphaltenes can precipitate out during production, refinery,
transportation and storage of crude oil and products derived
therefrom, such as, for example, heavy fuel oil or marine oil.
Common causes for this precipitation are a drop in the temperature
or a change in the composition (e.g. evaporation of readily
volatile constituents). Asphaltenes can also precipitate out upon
flowing through porous media. Flooding with CO.sub.2 during the
recovery process can cause asphaltenes to flocculate or to
precipitate out.
[0005] Some oils comprise hydrocarbon waxes which precipitate out
at low temperatures. Interactions between the precipitation of wax
and asphaltenes can increase the overall amount of precipitated
substance or its rate of formation.
[0006] Precipitated asphaltenes cause problems during the
production and processing of crude oils. Asphaltenes settle out in
valves, pipes and conveyors. On hot surfaces, such as, for example,
heat exchangers, the carbonization of these precipitates can make
their removal very difficult. The precipitates reduce the
efficiency of plants and can, in the worst case, lead to complete
blockage and to a halt in production, which results in high
costs.
[0007] Heavy oils, which are often used for powering ships,
comprise considerable amounts of asphaltenes. The precipitation of
asphaltenes can lead both to poor combustion and also to
difficulties with regard to handling and storage of the fuel.
[0008] Bitumens, heavy oils and residues are sometimes diluted with
solvents in order to reduce the viscosity for transportation. If
asphaltenes precipitate out, then problems arise during
handling.
[0009] The precipitation of asphaltenes can be prevented or reduced
by small amounts of dispersants. These dispersants display one or
more of the following effects:
[0010] a) the amount of precipitate is reduced;
[0011] b) the precipitate is formed more slowly;
[0012] c) the precipitate is more finely divided; and
[0013] d) the tendency of the precipitate to deposit on surfaces is
reduced.
[0014] If precipitates of asphaltenes have already formed, they can
be removed through the use of solvents. The addition of a
dispersant can improve the effectiveness of these solvents.
[0015] A large number of asphaltene dispersants are already known.
CA-A-2 029 465 and CA-A-2 075 749 describe alkylphenol formaldehyde
resins in combination with hydrophilic-lipophilic vinyl polymers.
The asphaltene-dispersing properties of dodecylbenzenesulfonic acid
have been described in U.S. Pat. No. 4,414,035, and also by D. -L.
Chang and H. S. Fogler (SPE paper No. 25185, 1993) and by M. N.
Bouts et al. (J. Pet. Technol. 47, 782-7, 1995). Cardanol
formaldehyde resins have already been prepared as precursors for
crude oil emulsion breakers (U.S. Pat. No. 5,525,201), but were not
used as asphaltene dispersants.
[0016] The dispersants known to date can only partially solve the
problems caused by the precipitation of asphaltenes. Since oils
vary in their composition, individual dispersants can only operate
effectively within a limited range. Even small changes in the
composition of the oil sometimes have a great effect on the
dispersing properties for asphaltenes. For this reason, in some
cases the known dispersants are unsatisfactory and additional types
are required.
[0017] The object is therefore to provide novel asphaltene
dispersants which do not have the described disadvantages of the
dispersants known to date.
[0018] Surprisingly, it has been found that cardanol-aldehyde
resins can be used in order to prevent the precipitation and/or the
deposition of asphaltenes in crude oils and products derived
therefrom.
[0019] The invention therefore provides for the use of resins
obtainable by reacting cardanol with a compound of the formula (1)
1
[0020] in which
[0021] R.sup.1 is H, CHO, COOH, COOR.sup.2 or R.sup.2, and
[0022] R.sup.2 is C.sub.1-C.sub.30-alkyl, C.sub.2-C.sub.30-alkenyl,
C.sub.6-C.sub.18-aryl or C.sub.7-C.sub.30-alkylaryl, and which have
a number-average molecular weight of from 250 to 100 000 units, in
amounts of from 0.5 to 10 000 ppm, based on the oil, for dispersing
asphaltenes in crude oils or products derived therefrom.
[0023] The invention further provides crude oils and products
derived from these which comprise 0.5 to 10 000 ppm of the resins
defined above.
[0024] The invention further provides a process for dispersing
asphaltenes in crude oils and products derived therefrom by adding
0.5 to 10 000 ppm of the resins defined above to the oils.
[0025] The compounds according to the invention are, for example,
those of the formulae 2 to 5. 2
[0026] If glyoxal is used for the condensation, then the radical
R.sup.3 is initially OH. The resulting free OH group can
additionally also be esterified or etherified, so that R.sup.3 can
have the meaning O-alkyl, O-aryl, O-alkenyl, O-alkylaryl,
OCO-alkyl, OCO-aryl, OCO-alkenyl, OCO-alkylaryl. Corresponding
compounds prepared by subsequent etherification of the resins are
likewise covered by the subject-matter of the present invention.
The terms "alkyl", "alkenyl", "aryl" and "alkylaryl" are to be
understood as given for the definition of R.sup.2. R.sup.3 can also
have the same meaning as is given for R.sup.1 and R.sup.2.
[0027] Cardanol is a constituent of oil that is obtained from the
shell of cashew kernels. Its main constituent is an alkylphenol of
the formula 6 3
[0028] X is a hydrocarbon chain with about 15 carbon atoms and 1 to
3 double bonds, as disclosed, for example, in R. Ikeda et al.,
Macromol. Rapid Commun. 21, 496-499 (2000) and A. Mahannar, Journal
of Applied Polymer Science, 61, 2107-2111 (1996).
[0029] R.sup.2 is preferably an alkenyl or alkyl radical, a chain
length of from 6 to 24, particularly preferably 8 to 22,
specifically 12 to 18 carbon atoms. Alkyl and alkenyl radicals can
either be linear or branched.
[0030] If R.sup.2 is an alkylaryl radical, then alkylaryl is
preferably a radical, bonded by the aromatic ring, whose aromatic
ring preferably comprises 6 carbon atoms, and which carries, in the
ortho, meta or para position relative to the bond mentioned above,
an alkyl radical with a chain length of preferably 1 to 18,
particularly preferably 4 to 16, in particular 6 to 12, carbon
atoms.
[0031] Products derived from crude oils are, for example, heavy
fuel oil, marine oil or bitumen.
[0032] As well as resins based on pure cardanol, condensates of
mixtures of cardanol and alkylphenols of the formula (7) with
compounds according to formula 1 also act as asphaltene
dispersants, 4
[0033] in which R.sup.4 and OH may be in the ortho, meta or para
position relative to one another, and R.sup.4 is C.sub.1- to
C.sub.30-alkyl, C.sub.6- to C.sub.30-alkenyl, C.sub.6- to
C.sub.18-aryl or C.sub.7- to C.sub.13-alkylaryl. Particular
effectiveness is displayed by resins based on the
cardanol/alkylphenol mixtures with para-cresol, para-ethylphenol,
para-isopropylphenol, para-tert-butylphenol, para-isooctylphenol,
para-isononylphenol, para-isododecylphenol, para-phenylphenol and
para-cumylphenol in the ratios 1:100 to 100:1, preferably 1:10 to
10:1, particularly preferably 1:5 to 5:1, specifically 2:1 to 1:2,
in particular 1:1.
[0034] The resins according to the invention are generally prepared
by acid- or alkaline-catalyzed condensation of cardanol with the
corresponding aldehydes. The reaction temperature is generally
between 50 and 170.degree. C., preferably 120 to 165.degree. C. The
reaction is normally carried out at atmospheric pressure. The
catalyzing acids are, for example, HCl, H.sub.2SO.sub.4, sulfonic
acids or H.sub.3PO.sub.4, and the bases are NaOH, KOH or
triethylamine, which are used in amounts of from 0.1 to 50% by
weight, based on the weight of the reaction mixture. The
condensation generally requires 30 min to 6 hours. The molar ratio
between aldehyde and cardanol is generally from 0.5:1 to 4:1,
preferably from 0.8:1 to 1.8:1.
[0035] The dispersant according to the invention is used in a
concentration of from 0.5 to 10 000 ppm, preferably from 2 to 2000
ppm.
[0036] For easier dosing, the dispersant can be formulated as a
solution in an oil-miscible solvent, such as, for example, aromatic
hydrocarbons or mixtures of hydrocarbons and an aliphatic alcohol.
In addition to the dispersant according to the invention, it is
also possible to use alkylphenol-formaldehyde resins, oxyalkylated
amines, wax dispersants or any mixtures thereof. It is likewise
possible to use other organic acids with surfactant properties,
such as, for example, mono- or dialkylbenzenesulfonic acids,
petroleumsulfonic acids and alkanesulfonic acids as additional
components.
EXAMPLES
Example 1
Reaction of Cardanol with Formaldehyde
[0037] 100.0 g of cardanol (M=302), 100 ml of an aromatic solvent
and 1.1 g of alkylbenzenesulfonic acid (0.5 mol %) were initially
introduced into a 500 ml four-necked flask fitted with contact
thermometer, stirrer, dropping funnel and water separator. With
stirring and nitrogen blanketing, the reaction mixture was heated
to 120.degree. C. and, at this temperature, 26.8 g of aqueous
formaldehyde solution (37% strength) were slowly added dropwise.
When the addition was complete, the mixture was stirred for one
hour at 120.degree. C. and for one hour at 165.degree. C. and the
water of reaction which formed was removed by means of the
separator. The product was evaporated to dryness on a rotary
evaporator (yield: 107.2 g) and analyzed by means of GPC.
Example 2
Reaction of Cardanol with Glyoxal
[0038] 100.0 g of cardanol (M=302), 100 ml of an aromatic solvent
and 1.1 g of alkylbenzenesulfonic acid (0.5 mol %) were initially
introduced into a 500 ml four-necked flask fitted with contact
thermometer, stirrer, dropping funnel and water separator. With
stirring and nitrogen blanketing, the reaction mixture was heated
to 120.degree. C. and, at this temperature, 19.3 g of aqueous
glyoxal solution (50% strength) were slowly added dropwise. When
the addition was complete, the mixture was stirred for one hour at
120.degree. C. and for one hour at 165.degree. C., and the water of
reaction which formed was removed by means of the separator. The
product was evaporated to dryness on a rotary evaporator (yield:
102.8 g) and analyzed by means of GPC.
Example 3
Reaction of Cardanol with Glyoxalic Acid
[0039] 100.0 g of cardanol (M=302), 100 ml of an aromatic solvent
and 1.1 g of alkylbenzenesulfonic acid (0.5 mol %) were initially
introduced into a 500 ml four-necked flask fitted with contact
thermometer, stirrer, dropping funnel and water separator. With
stirring and nitrogen blanketing, the reaction mixture was heated
to 120.degree. C. and, at this temperature, 17.3 g of aqueous
glyoxalic acid solution (50% strength) were slowly added dropwise.
When the addition was complete, the mixture was stirred for one
hour at 120.degree. C. and for one hour at 165.degree. C., and the
water of reaction which formed was removed by means of the
separator. The product was evaporated to dryness on a rotary
evaporator (yield: 107.3 g) and analyzed by means of GPC.
Example 4
Reaction of Cardanol and Para-isononylphenol with Formaldehyde
[0040] 50.0 g of cardanol (M=302), 50.0 g of para-isononylphenol
(M=220), 100 ml of an aromatic solvent and 1.1 g of
alkylbenzenesulfonic acid (0.5 mol %) were initially introduced
into a 500 ml four-necked flask fitted with contact thermometer,
stirrer, dropping funnel and water separator. With stirring and
nitrogen blanketing, the reaction mixture was heated to 120.degree.
C. and, at this temperature, 23.2 g of aqueous formaldehyde
solution (37% strength) were slowly added dropwise. When the
addition was complete, the mixture was stirred for one hour at
120.degree. C. and for one hour at 165.degree. C. and the water of
reaction which formed was removed by means of the separator. The
product was evaporated to dryness on a rotary evaporator (yield:
104.9 g) and analyzed by means of GPC.
Example 5
Reaction of Cardanol and Para-Cumylphenol with Formaldehyde
[0041] 50.0 g of cardanol (M=302), 50.0 g of para-cumylphenol
(M=212), 100 ml of an aromatic solvent and 1.1 g of
alkylbenzenesulfonic acid (0.5 mol %) were initially introduced
into a 500 ml four-necked flask fitted with contact thermometer,
stirrer, dropping funnel and water separator. With stirring and
nitrogen blanketing, the reaction mixture was heated to 120.degree.
C. and, at this temperature, 22.8 g of aqueous formaldehyde
solution (37% strength) were slowly added dropwise. When the
addition was complete, the mixture was stirred for one hour at
120.degree. C. and for one hour at 165.degree. C. and the water of
reaction which formed was removed by means of the separator. The
product was evaporated to dryness on a rotary evaporator (yield:
104.9 g) and analyzed by means of GPC.
Example 6
Reaction of Cardanol with Dodecyl Glyoxalate
[0042] 100.0 g of cardanol (M=302) and 0.5 g of
alkylbenzenesulfonic acid (0.5 mol %) were dissolved in 100 g of an
aromatic solvent in a 1000 ml stirrable flask fitted with contact
thermometer, stirrer, dropping funnel and water separator. With
stirring and nitrogen blanketing, the reaction mixture was heated
to 120.degree. C. At 120.degree. C., 75.6 g of dodecyl glyoxalate
(M=242) in 100 g of an aromatic solvent were slowly added dropwise.
When the addition was complete, the mixture was after-reacted for
one hour at 120.degree. C. and for one hour at 165.degree. C. The
water of reaction which formed was removed by means of the water
separator. The product was evaporated to dryness on a rotary
evaporator (yield: 168.4 g) and analyzed by means of GPC.
[0043] Testing the Effectiveness of Asphaltene Dispersants
[0044] Principle of the Dispersion Test
[0045] Dispersion and precipitation of asphaltenes depends on the
nature of the hydrocarbon medium. Asphaltenes are soluble in
aromatic hydrocarbons, but not in aliphatic hydrocarbons. It is
thus possible to test dispersants by dissolving the oil or
extracted asphaltenes in an aromatic solvent and then adding an
aliphatic hydrocarbon in order to produce a precipitate. Since
asphaltenes are darker in color, the amount of precipitate can be
determined by means of a calorimetric measurement of the
supernatant liquid. The darker the supernatant liquid, the more
asphaltenes remain dispersed, i.e. the better the dispersant. This
test is described in CA-A-2 029 465. In our version of the test,
the precipitation medium is chosen so that the asphaltenes
precipitate out for the most part, but not completely. The
dispersion text is carried out according to steps a) to f):
[0046] a) A 25% strength oil solution in toluene is filtered in
order to remove impurities.
[0047] b) Initially introduce 9.5 ml of heptane as precipitating
agent for asphaltenes and 0.5 ml of toluene/dispersant mixture
(25:1) into a small graduated glass tube which easily holds 10 ml
and shake well. This corresponds to a dispersant concentration of
2000 ppm. The amount of dispersant can be varied as required. Pure
toluene is used for the blanks.
[0048] c) 0.1 ml of the filtered oil solution is then added to the
small glass tube and likewise shaken well.
[0049] d) Leave the sample to stand for 2 hours without disruption
in order that the precipitated asphaltenes can collect at the
bottom of the tube.
[0050] e) After this time has lapsed, the volume of the sediment is
estimated using the graduations, the appearance of the overall
sample is recorded and then 1 ml is carefully taken up using a
pipette from the supernatant phase.
[0051] f) The amount pipetted off is dissolved in 5 ml of a 99:1
toluene/triethanolamine mixture and measured photometrically at 600
nm.
[0052] Evaluation of the Dispersion Test
[0053] The dispersion A) is calculated using the following
equation:
A=100 (D-D.sub.0)/D.sub.0,
[0054] Where D and D.sub.0 are the optical density of the
measurement solution and blank. The maximum achievable value of A,
A.sub.max, corresponds to complete dispersion of the asphaltenes.
It can be estimated by carrying out an experiment without
dispersant, with toluene instead of heptane--as a reuslt the
asphaltenes remain completely dispersed. The volume of the sediment
gives further information regarding the effectiveness of the
dispersant. The smaller the amount of sediment, the better
dispersed is the substance.
[0055] Dispersion Effect of the Example compounds
[0056] Using an asphaltene-rich oil from Venezuela, substances
according to the invention were tested using the dispersion test.
The dispersion concentration was 2000 ppm.
1 Dispersion effect A [%] Product from example 1 99.5 Product from
example 2 98.6 Product from example 3 97.4 Product from example 4
98.5 Product from example 5 98.7 Product from example 6 99.8
Commercial product 81.4 Without dispersant 0
[0057] In this experimental series, the maximum dispersion effect
A.sub.max was about 99.5%.
* * * * *