U.S. patent application number 13/608825 was filed with the patent office on 2014-06-12 for methods and apparatus for converting organic material.
This patent application is currently assigned to Altaca Insaat Ve Dis Ticaret AS. The applicant listed for this patent is Steen BRUMMERSTEDT IVERSEN, Karsten FELSVANG, Tommy LARSEN, Viggo LUTHJE. Invention is credited to Steen BRUMMERSTEDT IVERSEN, Karsten FELSVANG, Tommy LARSEN, Viggo LUTHJE.
Application Number | 20140161682 13/608825 |
Document ID | / |
Family ID | 36646063 |
Filed Date | 2014-06-12 |
United States Patent
Application |
20140161682 |
Kind Code |
A2 |
BRUMMERSTEDT IVERSEN; Steen ;
et al. |
June 12, 2014 |
METHODS AND APPARATUS FOR CONVERTING ORGANIC MATERIAL
Abstract
The present invention relates to a method and apparatus for
intensifying the energy content of an organic material by
converting the material into hydrocarbons and the resulting product
thereof. A method for converting an organic material into
hydrocarbon fuels is disclosed. The method comprising the steps of
pressurising said organic material being in a fluid to a pressure
above 225 bar, heating said organic material in said fluid to a
temperature above 200 C in the presence of a homogeneous catalyst
comprising a compound of at least one element of group IA of the
periodic table of elements. The disclosed method further comprises
the steps of contacting said organic material in said fluid with a
heterogeneous catalyst comprising a compound of at least one
element of group IVB of the periodic table and/or alpha-alumina
assuring that said fluid has initially a pH value of above 7.
Inventors: |
BRUMMERSTEDT IVERSEN; Steen;
(DK) ; FELSVANG; Karsten; (DK) ; LARSEN;
Tommy; (Slagelse, DK) ; LUTHJE; Viggo;
(DK) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
BRUMMERSTEDT IVERSEN; Steen
FELSVANG; Karsten
LARSEN; Tommy
LUTHJE; Viggo |
Vedbaek
Allerod
Slagelse
Bagsvaerd |
|
DK
DK
DK
DK |
|
|
Assignee: |
Altaca Insaat Ve Dis Ticaret
AS
Atasehir, Istanbul
TR
|
Prior
Publication: |
|
Document Identifier |
Publication Date |
|
US 20130195732 A1 |
August 1, 2013 |
|
|
Family ID: |
36646063 |
Appl. No.: |
13/608825 |
Filed: |
September 10, 2012 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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11912824 |
Nov 14, 2008 |
|
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|
PCT/DK2006/000232 |
Apr 28, 2006 |
|
|
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13608825 |
|
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60675876 |
Apr 29, 2005 |
|
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Current U.S.
Class: |
422/187 |
Current CPC
Class: |
C10G 2300/1014 20130101;
C02F 11/10 20130101; C02F 11/121 20130101; C10G 2300/805 20130101;
Y02W 10/40 20150501; B01J 21/04 20130101; C10G 2300/1003 20130101;
C10L 9/086 20130101; Y02E 50/30 20130101; B01J 8/00 20130101; Y02E
50/10 20130101; C10G 1/086 20130101; B01J 21/066 20130101; C10G
2300/80 20130101; C10L 5/44 20130101; Y02W 10/30 20150501; B01J
21/06 20130101; Y02P 30/20 20151101 |
Class at
Publication: |
422/187 |
International
Class: |
B01J 8/00 20060101
B01J008/00 |
Foreign Application Data
Date |
Code |
Application Number |
Apr 29, 2005 |
DK |
PA 2005 00634 |
Claims
1-102. (canceled)
103. An apparatus for converting an organic material into
hydrocarbons, comprising: a pre-conversion system and a product
recovery system (11), said pre-conversion system comprises a first
heating unit (4) for heating a feed of fluid comprising organic
material a catalyst reactor (7) for contacting the feed of fluid
comprising organic material, and an adjusting unit for adjusting
the fluid to have a pH value of above 7, and said product recovery
system (11) comprises membrane-filter (13) for separating a first
stream (L; H, O, P, E) of oils and water soluble salts in from a
second stream (K; F, Q, G; R) of water and water soluble
organics.
104. An apparatus according to claim 103, wherein the
pre-conversion system further comprises a storage for feeding
organic material to the fluid in a feeding direction.
105. An apparatus according to claim 103, wherein the
pre-conversion system further comprises a pre-treating unit (1)
situated after the feedstock and before the first heating unit (4)
in the feeding direction.
106. An apparatus according to claim 103, wherein the
pre-conversion system further comprises a first particle separating
unit (5) situated after the first heating unit (4) in the feeding
direction.
107. An apparatus according to claim 103, wherein the
pre-conversion system further comprises a second heating unit (6)
situated after the first particle separating unit (5) and before
the catalyst reactor (7) in the feeding direction.
108. An apparatus according to claim 103, wherein the
pre-conversion system further comprises a second particle
separation unit (9) after the catalyst reactor (7) in the feeding
direction.
109. An apparatus according to claim 103, wherein the
pre-conversion system further comprises means for re-circulating
(8) part of the feed of fluid after the catalyst reactor (7) into
the feed of fluid before the second heating unit (6) in the feeding
direction.
110. An apparatus according to claim 103, wherein the first heating
unit (4) is a first heat exchanger, which besides heating cools the
fluid from pre-conversion system before entering the product
recovery system.
111. An apparatus according to claim 103, wherein the pre-treating
unit further comprises a heat exchange, which besides heating the
fluid in the pre-treating system cools the fluid from
pre-conversion system before entering the product recovery
system.
112. An apparatus according to claim 103, wherein the pre-treating
unit further comprises a first expansion unit (10), which is
situated between the first heat exchanger (4) and the second heat
exchanger (1).
113. An apparatus according to claim 103, wherein the product
recovery system further comprises a gas separating unit (12) for
separation of gas (I), such as fuel gas, the gas separating unit
(12) is situated after the second heat exchanger (4) and before the
first membrane-filter (13) in the feeding direction.
114. An apparatus according to claim 111, wherein the product
recovery system further comprises means for re-circulating said gas
(I), such as fuel gas for heating the fluid in the second heating
unit.
115. An apparatus according to claim 103, wherein the product
recovery system further comprises a second expansion unit situated
after the first membrane-filter (13) in the feeding direction.
116. An apparatus according to claim 103, wherein the product
recovery system further comprises a phase separator unit (14) for
separation of oil (H) from the first stream (L), said phase
separator unit (14) is situated after the membrane-filter (13) in
the feeding direction.
117. An apparatus according to claim 103, wherein the product
recovery system further comprises means for re-circulating part (E)
of the first stream into the pre-treating unit (1) of the
pre-conversion system.
118. An apparatus according to claim 103, wherein the product
recovery system further comprises direct methanol fuel cell (18)
for generating electricity from the second stream.
119. An apparatus according to claim 103, wherein the product
recovery system further comprises one or more membrane-filters (15,
16, 17) is/are selected from the group consisting of membrane
processes comprising ultra-filtration, nano-filtration, reverse
osmosis or pervaporation or a combination thereof.
120. An apparatus according to claim 119, wherein the product
recovery system further comprises the second membrane-filter for
separating a purified methanol compound (F) from the second stream
(K).
121. An apparatus according to claim 120, wherein the product
recovery system further comprises means for re-circulating the
purified methanol compound (F) from the second stream to the
pre-treating unit (1) of the pre-conversion system.
122-136. (canceled)
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This is a divisional patent application of U.S. patent
application Ser. No. 11/912,824, filed Nov. 14, 2008, now U.S. Pat.
No. 8,299,315, which is a national stage application of
International Patent Application PCT/DK2006/000232, filed Apr. 28,
2006, which claims priority to PA 2005 00634, filed Apr. 29, 2005
and U.S. Provisional Patent Application No. 60/675,876, filed Apr.
29, 2005, the disclosures of each of which are hereby incorporated
by reference.
DESCRIPTION
[0002] The present invention relates to a method and apparatus for
intensifying the energy content of an organic material by
converting the material into hydrocarbons and the resulting product
thereof.
BACKGROUND
[0003] The world's energy demand is increasing, and the fossil fuel
sources are depleted, leading to increasing competition for the
available energy sources, and thereby hampering economical growth
by high energy prices. To overcome this situation renewable energy
sources must be brought into exploitation. The only renewable
energy source with sufficient capacity to cover significant parts
of the energy demand is biomass conversion. Biomass is efficiently
converted into heating and electricity by existing technologies,
but transportation fuels, which accounts for one third of the total
energy consumption, must be available as high energy density
fluids, preferably compatible with fossil fuels like diesel oil and
gasoline. Therefore technologies for transforming and intensifying
the energy content of biomass are required.
[0004] At the same time all kinds of waste are produced all over
the world from factories, households etc., and as a result waste
disposal has increased to an insuperable amount of waste over the
last decades. Dumping of waste has become an increasingly problem
and therefore a cheap effective dispose of waste has become
increasingly more important.
[0005] A known method of waste disposal is refuse incineration. But
numerous wastes are due to the high water content not suitable for
incineration, e.g. sewage sludge and industrial waste water
treatment residues. Incineration of such wastes require additional
energy input, i.e. the overall process energy is negative.
[0006] In view of this new methods have been developed for
treatment of such wastes. However these known methods are still
very limited in regards to the kind of waste, which may be treated
in the same apparatus and in regards to how much of the converted
waste which is turned into recyclable products. Additionally, the
energy of the organic material, which is converted into recyclable
products are still very low compared to the amount of energy added
to the method. Therefore in order to make conversion of organic
material commercial interesting there is still a need of a more
energy effective process.
[0007] Furthermore, known methods have shown that char and soot
deposit inside the apparatus in such an amount that regular
cleaning of the apparatus is needed. Such cleaning operations are
time consuming and therefore expensive.
[0008] Corrosion of the materials used for making apparatus for the
converting of organic material has in known methods been such a
problem that the materials for these components had to be chosen in
a more expensive group of materials. This problem of corrosion has
increased the cost of the apparatus for the converting and
therefore decreased the incentive for using converting of waste
instead of refuse incineration.
SUMMARY OF THE INVENTION
[0009] An objective of the present invention is to provide an
improved method and an improved apparatus for converting organic
material, such as waste, sludge, biomass etc., into recyclable
products, such as hydrocarbon fuel, which method at least partly
overcome or at least mitigate the aforementioned problems and
disadvantages.
[0010] Another objective of the present invention is to provide an
improved recyclable product from the conversion of organic
material, which improved product is reusable as some kind of
energy. These objectives and several others objectives, which will
become evident below are obtained by a first aspect of the present
invention by providing a method for converting an organic material
into hydrocarbon fuels, comprising the steps of:
[0011] pressurising said organic material in a fluid to a pressure
above 225 bar, and
[0012] heating said organic material in said fluid to a temperature
above 200 C in the presence of a homogeneous catalyst comprising a
compound of at least one element of group IA of the periodic table
of elements,
wherein the method further comprises the steps of:
[0013] contacting said organic material in said fluid with a
heterogeneous catalyst comprising a compound of at least one
element of group IVB of the periodic table and/or alpha-alumina,
and
[0014] adjusting said fluid to a pH value of above 7.
[0015] An improved method for converting organic material into
recyclable products is hereby obtained. By contacting the organic
material with a heterogeneous catalyst comprising a compound of at
least one element of group WE of the periodic table and/or
alpha-alumina, the catalyst may be reused and a continuously
converting of organic material is possible. Thereby the amount of
catalyst spent for converting one amount of organic material is
decreased whereby the cost for converting the material is
considerable decreased.
[0016] Additionally, the process time has been decreased
considerably due to the fact that dividing the catalyst process
into two separate processes increases the velocity of
conversion.
[0017] Furthermore, by adjusting the fluid to above 7 the corrosion
of the materials used for the involved components in the apparatus
is considerably decreased. The corrosion of these materials has
decreased to such an amount that cheap standard materials may be
used for the construction of the apparatus.
[0018] According to another aspect of the present invention the
method may comprise the step of maintaining the pH value of said
fluid containing said organic material in the range 7-14, such as
7-12 and preferably in the range 7-10 such as in the range 7-9.5.
It is hereby obtained that when converting the organic material
into hydrocarbon fuel the corrosion of the materials used for the
involved components of the apparatus is substantial decreased to at
least an insignificant amount of corrosion.
[0019] Furthermore, according to an aspect of the present invention
the method may comprise the step of pre-treating the organic
material at a pressure of 4-15 bar at the temperature of 100-170 C
for a period of 0.5-2 hours. By pre-treating the organic material
at this pressure, the organic material is pre-converted whereby the
subsequent conversion may be performed more quickly than without
the pre-treatment.
[0020] Subsequently, the pre-treating step may according to another
aspect of the invention comprise a step of size reducing of the
material such as a cutting, grinding, milling, or sieving step or a
combination thereof. By such a size reduction the conversion
process of the organic material is performed even more quickly than
without the size reduction.
[0021] Additionally, the pre-treating step may comprise the step of
adding additives to the fluid according to the present invention,
whereby the conversion process is improved even further in regards
to speed of the conversion time and in regards to the resulting
product from the conversion of the organic material into
hydrocarbon fuels. The product resulting from the conversion of the
organic material may by adding these additives be regulated, so
that the resulting product may have variable composition of oil,
methanol, water, water soluble organics, water soluble salts, etc.
It is then possible to adjust the recyclable product in regards to
the wishes of the subsequent use of the products.
[0022] In one aspect of the present invention the step of
pre-treating may comprise the step of adjusting the pH of said
fluid comprising said organic material to above 7. It hereby
obtained to adjustment of the pH value in the fluid comprising the
organic material at an early stage of the conversion process,
whereby the process time for the conversion is reduced.
[0023] By the step of pretreating the fluid comprising the organic
material it is possible to increase the amount of solid-state
material in the fluid, which again leads to a higher rate of
conversion and thereby a higher production capacity. This results
in a more efficient and cost saving converting of organic
material.
[0024] In another aspect of the present invention the method may
further comprise a step of separating particles from the fluid
comprising the organic material. By separating particles before
contacting the fluid comprising the organic material with the
heterogeneous catalyst the product resulting from the conversion
process, such as oil, is then substantially free of being bound to
these particles and therefore much more reusable straight after
this conversion process. A second process, such as an refinery is
thereby dispensable.
[0025] In yet another aspect of the present invention the method
may further comprise a second step of heating the fluid. The
temperature of fluid comprising the organic material is hereby
adjustable just before contacting the heterogeneous catalyst,
whereby the process is optimised, which leads to a reduced process
time. Furthermore, by separating the particles away from the fluid
at such an early stage a substantially amount of energy for
transporting the separated particles is saved, which again
decreases the amount of energy spend in the conversion process as a
total.
[0026] Additionally, the method may according to the invention
comprise a second separating of particles, which step is merely for
safety reason in regards to the first step of separating particles.
This step reduces for the same reasons as the first step of
separating particles the total amount of energy spend for the
conversion process.
[0027] Furthermore, the method may according to the invention
comprise a step of cooling the fluid. By cooling the fluid the
resulting product from converting of the organic material may be
optimized in relations to the composition of product.
[0028] Advantageously, the step of cooling may according to the
present invention be performed by heat exchanging with the first
step of heating and/or a step of pre-heating the fluid in the
pre-treating step. It is hereby obtained to reuse the heat from the
fluid, which needs to cool down before the second part of
conversion into the recyclable products, in the fluid in the first
part of conversion process before contacting the fluid with the
heterogeneous catalyst. The total amount of energy for the
converting of organic material is thereby kept to a minimum.
[0029] Said method may according to one aspect the present
invention further comprise a step of separation gas from the fluid,
such as fuel gas. By separating this gas one kind of recyclable
product is obtained, which was an objective of the invention.
[0030] The method may according to one aspect the present invention
further comprise the step that the fuel gas is used for heating the
fluid in the second heating step. By using the separated gas it is
reused in converting the organic material and therefore
resuable.
[0031] Furthermore, the method may according to the invention
further comprise a step of filtrating water and water soluble
organics from oil and water soluble salts in a first
membrane-filter. By this separating a recyclable products is
obtained and a further converting into recyclable products is
possible.
[0032] In an aspect of the present invention the water and water
soluble organics are transformed into electricity in a direct
methanol fuel cell. This is one way of using one of the recyclable
products of the present invention. It may also be regarded as a
subsequent step of converting the recycle products into a usable
product in form of electricity.
[0033] The method may also according to another aspect of the
present invention comprise a second step of filtering water soluble
organics from the water, such as an purification of methanol in a
second membrane-filter. By this conversion step one recycle product
is obtained.
[0034] Subsequently, said one or more membrane-filters may be
selected from the group of membrane processes comprising
ultra-filtration, nano-filtration, reverse osmosis or pervaporation
or a combination thereof. By this selection different kinds of
recycle products are obtainable.
[0035] According to one aspect of the present invention, the water
and water soluble organics after the second filtering step may be
transformed into drinkable water in a process of reverse osmosis.
By the method comprising the process of reverse osmosis one very
usable recyclable product is obtained.
[0036] According to one aspect of the present invention, the water
soluble organic may comprising up-concentrated methanol may be
re-circulated to the pre-treating step. A further optimization of
the converting method is hereby obtained, and the converted product
of up-concentrated methanol is reused.
[0037] Additionally, the method may according to one aspect of the
invention comprise a phase separator, whereby separation of oil as
product is obtained.
[0038] According to one aspect of the present invention, the step
of contacting the organic material in the fluid with a
heterogeneous catalyst may be performed while the temperature is
kept substantially constant. By keeping the temperature constant in
the contacting step the contacting of the fluid with the
heterogeneous catalyst is kept in the same condition and the
conversion is therefore constant throughout the contacting step. A
further advantage is that the equilibriums and reaction rates of
the chemical reactions involved in the conversion are kept constant
throughout the contacting step, thereby ensuring uniformity in the
products formed by the conversion.
[0039] In another aspect of the present invention, the temperature
in the step of contacting may be in the range 200-650.degree. C.,
such as in the range 200-450.degree. C., and preferably in the
range 200-374.degree. C., and even more preferably in the range
250-374.degree. C., such as in the range 275-350.degree. C. By
keeping these low temperatures the conversion process is using less
energy in converting the same amount of organic material than at
higher temperatures. A low temperature together with a pH value
above 7 decreases the corrosion of the materials used for the
apparatus in which the present method is performed.
[0040] A low temperature in the contacting step increases the
fraction of the organic material being converted into hydrocarbon
fuels, and thereby the oil production capacity of the contacting
step. At such low temperatures the solubility of salts is high
compared to higher temperature whereby the conversion process is
further advantageous due to almost no salts depositing occurs
inside the apparatus. Furthermore, at such low temperatures the
organic material is less converted into soot and tar, which
products are not very recyclable. Finally such low temperature
allows construction of the apparatus from less corrosion resistant
materials, further improving the competitive.
[0041] According to another aspect of the present invention, the
pressure for said conversion may be in the range 225-600 bars, such
as in the range 225-400 bars and preferably in the range 225-350
bars, such as in the range 240-300 bars. By using pressures inside
these ranges it is obtained that standard components and equipment
may be used for the present method whereby the cost of the
conversion process and apparatus is substantially decreased
compared to the same at higher pressures.
[0042] Furthermore, the method may according to the invention
further comprise the step of contacting is done in less than 30
minutes, such as less than 20 minutes, preferably less 10 minutes,
such as less than 7.5 minutes, and even more preferably in the
range 0.5-6 minutes, such as in the range 1-5 minutes. By
contacting the fluid at in a short period the conversion process
time is decreased without decreasing the conversion processing of
organic material substantially.
[0043] Additionally, the compound of at least one element of group
IVB of the periodic table may comprise zirconium and/or titanium
according to another aspect of the present invention. By using
zirconium and/or titanium as a heterogeneous catalyst the
conversion process time is decreased without decreasing the
conversion processing of organic material.
[0044] In another aspect of the present invention the compound of
at least one element of group NB of the periodic table may be on an
oxide and/or hydroxide form or a combination of the two. By using
the heterogeneous catalyst on an oxide and/or hydroxide form the
conversion process time is decreased without decreasing the
conversion processing of organic material.
[0045] Advantageously, the compound of at least one element of
group NB of the periodic table is at least partly on a sulphate or
sulphide form according to another aspect of the present invention.
By using the heterogeneous catalyst on a sulphate or sulphide form
the conversion process time is decreased without decreasing the
conversion processing of organic material.
[0046] According to one aspect of the present invention, the
heterogeneous catalyst may further comprise at least one element
selected from the group consisting of Fe, Ni, Co, Cu, Cr, W, Mn,
Mo, V, Sn, Zn, Si in an amount up to 20% by weight, such as an
amount up to 10% by weight, preferably in an amount up to 5% by
weight, such as up to 2.5% by weight. By using the aforementioned
heterogeneous catalyst together with one or more elements of this
group the conversion process time is substantially decreased
without decreasing the conversion processing of organic
material.
[0047] Furthermore, these elements may be on an oxide and/or
hydroxide form according to another aspect of the present
invention, whereby the conversion process time is further decreased
without decreasing the conversion processing of organic
material.
[0048] In yet another aspect of the present invention said
heterogeneous catalyst may be in the form of a suspended particles,
tablets, pellets, rings, cylinders, a honey comb structure, a
fibrous structure and/or a combination of these. The advantage of
said heterogeneous catalyst structures is to control the flow
distribution of the organic material stream being contacted with
the catalyst, while ensuring reasonable pressure drop and contact
to all of the catalyst surface.
[0049] Additionally, said heterogeneous catalyst is at least partly
contained in a reactor according to another aspect of the present
invention. It is hereby possible to reuse that part of the
catalyst, which is inside the reactor.
[0050] Advantageously, said reactor is a fixed bed reactor
according to another aspect of the present invention. By using a
fixed bed reactor, it is hereby possible to even more easily reuse
that part of the catalyst, which is inside the reactor.
[0051] According to one aspect of the present invention, said
heterogeneous catalyst may have a BET surface area of at least 10
m2/g, such as 25 m2/g, and preferably at least 50 m2/g, such as 100
m2/g, and even more preferably at least 150 m2/g, such as at least
200 m2/g. By having this BET surface area, the conversion process
time is further decreased without decreasing the quality of the
conversion process, as sufficient catalytic active surface area is
ensured.
[0052] According to another aspect of the present invention, said
heterogeneous catalyst may comprise at least one surface area
stabilizer selected from the group consisting of Si, La, Y or Ce or
a combination thereof. By having this surface stabilizer, the
catalyst service lifetime time is further expanded without
decreasing the quality of the conversion process.
[0053] Advantageously, said heterogeneous catalyst may according to
one aspect of the present invention comprise said at least one
surface area stabilizer in an effective amount up to 20% by weight,
such as an effective amount up to 10% by weight, preferably said
surface area stabilizers in an effective amount up to 7.5% by
weight, such as surface stabilizers in an effective amount up to 5%
by weight, and more preferably said surface stabilizers are present
in an effective amount from 0.5-5% by weight, such as 1-3% by
weight. By having this surface stabilizer in up to 20% by weight,
the catalyst service lifetime is further expanded without
decreasing the quality of the conversion process.
[0054] In yet another aspect of the present invention said
heterogeneous catalyst may have a BET surface area of at least 10
m2/g after 1000 hours of use, such as BET surface area of at least
25 m2/g after 1000 hours of use, and preferably a BET surface area
of at least 50 m2/g after 1000 hours of use, such as a BET surface
area of at 100 m2/g after 1000 hours of use, and even more
preferably a BET surface area of at least 150 m2/g after 1000 hours
in use, such as at a BET surface area of least 200 m2/g after 1000
hours in use. By having this BET surface area of at least 10 m2/g
after 1000 hours of use, the conversion process time is further
decreased without decreasing the quality of the conversion process,
as sufficient catalytic active surface area is ensured.
[0055] Furthermore, said heterogeneous catalyst is produced from
red mud according to another aspect of the present invention. It is
hereby obtained to use waste product in the converting of the
organic material, which also is a waste product.
[0056] Additionally, the method may according to the invention
further comprise the step of re-circulating carbonates and/or
hydrogen carbonates. By re-circulating carbonates and/or hydrogen
carbonates the method is reusing products resulting from the
conversion method and an optimizing of the method is hereby
obtained.
[0057] The concentration of said carbonates and/or hydrogen
carbonates may according to an aspect of the invention be at least
0.5% by weight, such as at least 1% by weight, and preferably at
least 2% by weight, such as at least 3% by weight, and more
preferably at least 4% by weight, such as at least 5% by weight.
The carbonates and bi-carbonates are important activators in the
catalytic conversion performed by the homogenous catalyst.
[0058] Furthermore, the method may according to the invention
further comprise the step of re-circulating at least one alcohol.
By re-circulating at least one alcohol the method is reusing
products resulting from the conversion method and an optimizing of
the method is hereby obtained.
[0059] According to one aspect of the present invention, said at
least one alcohol may comprise methanol, whereby a very usable
recyclable product is reused in optimizing the method.
[0060] According to another aspect of the present invention, the
methanol content in said fluid may be at least 0.05% by weight,
such as at least 0.1% by weight, and preferably at least 0.2% by
weight, such as at least 0.3% by weight, and even more preferably
at least 0.5% methanol by weight, such as at least 1% by weight.
Methanol is involved in the chemical reactions responsible for
producing the oil product, and in the chemical reactions destroying
the radicals otherwise responsible for formation of soot and tar
during the decomposition of the organic material.
[0061] Advantageously, the method may according to another aspect
of the present invention comprise the step of re-circulating a
fluid containing hydrogen. By re-circulating a fluid containing
hydrogen the method is reusing products resulting from the
conversion method and an optimizing of the method is hereby
obtained.
[0062] In yet another aspect of the present invention the hydrogen
content of said fluid corresponds to at least 0.001% by weight of
the amount of said organic material to be treated, such as at least
0.01% by weight of the amount of said organic material to be
treated, and preferably 0.1% by weight of the amount of said
organic material to be treated, such as 0.2% by weight of the
amount of said organic material to be treated, and even more
preferably the hydrogen content of the fluid is at least 0.5% by
weight of the amount of said organic material to be treated, such
as at least 1% by weight of the amount of said organic material to
be treated. Hydrogen is involved in the chemical reactions
producing saturated oil compounds, and in the reactions destroying
free radicals, otherwise leading to formation of soot and tar
during the thermal decomposition of the organic material during the
conversion.
[0063] Furthermore, the method may according to the invention
further comprise the step of re-circulating at least one carboxylic
acid. By re-circulating at least one carboxylic acid the method is
reusing products resulting from the conversion method and an
optimizing of the method is hereby obtained.
[0064] Additionally, said at least one carboxylic acid may comprise
at least one carboxylic acid having a chain length corresponding to
1-4 carbon atoms according to another aspect of the present
invention. The said at least one carboxylic acid corresponding to
1-4 carbon atoms is involved in the chemical chain formation
reactions producing the oil product,
[0065] Furthermore, said at least one carboxylic acid may comprise
formic acid and/or acetic acid according to another aspect of the
present invention. The said at least one carboxylic acid
corresponding to 1-4 carbon atoms is involved in the chemical chain
formation reactions producing the oil product.
[0066] Advantageously, the concentration of said carboxylic acid(s)
in said fluid may according to the present invention be at least
100 part per million by weight, such as at least 250 part per
million by weight, and preferably at least 400 parts per million by
weight, such as at least 500 parts per million by weight. At this
concentration level the oil product producing chemical reactions
rates are sufficient to ensure conversion of the organic material
to said oil product.
[0067] In one aspect of the present invention the method may
comprise the step of re-circulating at least one aldehyde and/or at
least one ketone. By re-circulating at least one aldehyde and/or at
least one ketone the method is reusing products resulting from the
conversion method and an optimizing of the method is hereby
obtained.
[0068] In another aspect of the present invention said at least one
aldehyde and/or at least one ketone comprises at least one aldehyde
and/or at least one ketone having a chain length corresponding to
1-4 carbon atoms. The said at least one aldehyde or ketone
corresponding to 1-4 carbon atoms is involved in the chemical chain
formation reactions producing the oil product.
[0069] In yet another aspect of the present invention said at least
one aldehyde and/or at least one ketone comprises formaldehyde
and/or acetaldehyde. The said at least one aldehyde or ketone
corresponding to 1-4 carbon atoms is involved in the chemical chain
formation reactions producing the oil product.
[0070] According to the present invention, the concentration of
said at least one aldehyde and/or at least one ketone in said fluid
may be at least 100 part per million by weight, such as at least
250 part per million by weight, and preferably at least 400 parts
per million by weight, such as at least 500 parts per million by
weight. At this concentration level the oil product producing
chemical reactions rates are sufficient to ensure conversion of the
organic material to said oil product.
[0071] Advantageously, the homogeneous catalyst comprises potassium
and/or sodium according to one aspect of the present invention. By
using potassium and/or sodium as a homogeneous catalyst the
conversion process time is decreased without decreasing the
conversion processing of organic material, and the rates chemical
reactions involved in the oil product formation are enhanced to
facilitate production of said oil product.
[0072] Furthermore, according to another aspect of the present
invention the homogeneous catalyst may comprise one or more water
soluble salts selected from the group consisting of KOH,
K.sub.2CO.sub.3, KHCO.sub.3, NaOH, Na.sub.2CO.sub.3 or NaHCO.sub.3
or a combination thereof. In combination with the carbon dioxide
formed as part of the conversion of the organic material said salts
are converted into the carbonate involved in the chemical reactions
as activator.
[0073] In another aspect of the present invention the concentration
of the homogeneous catalyst may be at least 0.5% by weight, such as
at least 1% by weight, and preferably at least 1.5% by weight, such
as at least 2.0% by weight, and even more preferably above 2.5% by
weight, such as at least 4% by weight. At this concentration level
the oil product producing chemical reactions rates are sufficient
to ensure conversion of the organic material to said oil
product.
[0074] Additionally, said fluid comprises water according to
another aspect of the present invention. Water is a cheap an very
frequent fluid and therefore by using water the cost to method of
converting organic material is kept to a minimum and the method may
be used in all areas of the world.
[0075] According to one aspect of the present invention, said water
may have a concentration of at least 5% by weight, such as at least
10% by weight, and preferably at least 20% by weight, such as at
least 30% by weight, and even more preferably at least 40% by
weight. The organic material to be converted must be pumpable.
[0076] The concentration of said water in said fluid may according
to another aspect of the present invention be up to 99.5% by
weight, such as up to 98% by weight, and preferably up to 95% by
weight, such as up to 90% by weight, and even more preferably up to
85% by weight, such as up to 80% by weight. By decreasing the water
content the heat value of the feedstock is increased, leading to
increased oil production capacity at constant processing cost,
without sacrificing the pumpability of the organic material to be
converted.
[0077] In one aspect of the present invention said at least one
carbonate and/or at least one hydrogen carbonate and/or at least
one alcohol and/or at least one carboxylic acid and/or at least one
aldehyde and/or at least one ketone may at least partly be produced
by the conversion of said organic material. By reusing a product
resulting from the conversion process, the conversion process time
is decreased without decreasing the conversion processing of
organic material. Furthermore expenses for treating an effluent
stream are saved.
[0078] In another aspect of the present invention said at least one
carbonate and/or at least one hydrogen carbonate and/or at least
one alcohol and/or at least one carboxylic acid and/or at least one
aldehyde and/or at least one ketone may be re-circulated after the
step of contacting. It is hereby obtained that some of the
resulting products from the conversion process is reused and that
the conversion process time is decreased without decreasing the
conversion processing of organic material.
[0079] Furthermore, at least part of a stream of said recirculation
may according to another aspect of the present invention be mixed
in a ratio with a feed stream of said fluid comprising said
homogeneous catalyst and organic material to be converted before
entering the catalytic reactor. It is hereby obtained that some of
the resulting products from the conversion process is reused and
that the conversion process time is decreased without decreasing
the conversion processing of organic material.
[0080] Additionally, the ratio of the re-circulating stream to the
feed stream of said fluid may according to another aspect of the
present invention be in the range 1-20, such as 1-10, and
preferably within the range 1.5-7.5, such as in the range 2-6, and
more preferably in the range 2.5-5. It is hereby obtained that some
of the resulting products from the conversion process is reused and
that the conversion process time is decreased without decreasing
the conversion processing of organic material.
[0081] Advantageously, the conversion of said organic material may
according to another aspect of the present invention be at least
90%, such as at least 95%, and preferably above 97.5% %, such as
above 99%, and even more preferably above 99.5%, such as above
99.9%. The high conversion leads to maximization of the oil
production capacity, and minimizes or eliminates the content of
unconverted organic material in oil product and mineral product,
thereby eliminating the need for a purification step.
[0082] According to one aspect of the present invention said
reactor with heterogeneous catalyst may be subjected to a treatment
with hot pressurised water at pre-selected intervals.
[0083] According to another aspect of the present invention, said
treatment with hot pressurised water may have a duration of less
than 12 hours, such as a duration of less than 6 hours, preferably
a duration of less than 3 hours, such as a duration of less than 1
hour.
[0084] In another aspect of the present invention the interval
between such treatment with hot pressurised water may be at least 6
hours, such as at least 12 hours, preferably said interval between
such treatment with hot pressurised water is at least 24 hours,
such as at least one week.
[0085] By treating or flushing the reactor with hot pressurised
water, the life time of the reactor is increased and the cost of
the method is thereby substantially decreased.
[0086] In yet another aspect of the present invention said organic
material may be selected from the group consisting of sludge, such
as sewage sludge, liquid manure, corn silage, clarifier sludge,
black liquor, residues from fermentation, residues from juice
production, residues from edible oil production, residues from
fruit and vegetable processing, residues from food and drink
production, leachate or seepage water or a combination thereof.
[0087] According to one aspect of the present invention, said
organic material may comprise a lignocelulotic materials, selected
from the group consisting of biomass, straw, grasses, stems, wood,
bagasse, wine trash, sawdust, wood chips or energy crops or a
combination thereof.
[0088] According to another aspect of the present invention, said
organic material may comprise a waste, such as house hold waste,
municipal solid waste, paper waste, auto shredder waste, plastics,
polymers, rubbers, scrap tires, cable wastes, CCA treated wood,
halogenated organic compounds, PCB bearing transformer oils,
electrolytic capacitors, halones, medical waste, risk material from
meat processing, meat and bone meal, liquid streams, such as
process or waste water streams containing dissolved and/or
suspended organic material.
[0089] Advantageously, said sludge may according to another aspect
of the present invention be sludge from a biological treatment
process.
[0090] According to one aspect of the present invention said
organic material may be sludge from a waste water treatment
process.
[0091] In another aspect of the present invention said biological
treatment process may be part of a waste water treatment
process.
[0092] Furthermore, said biological water treatment process may
according to another aspect of the present invention be an aerobic
process.
[0093] Additionally, said biological water treatment process may be
an anaerobic process according to another aspect of the present
invention.
[0094] The method is capable of converting many kinds of organic
material as mentioned above. Even though the method is performed at
a relatively low temperature and a relatively low pressure the
temperature and pressure is still sufficient to disinfect the
resulting product. Which means regardless what organic material the
resulting products is usable without infecting risk, e.g. residues
from residues from food production, such as meat from a cow or a
veal will not result in the spreading of the disease BSE. Likewise
will virus, bacteria etc. from the organic material not be spread
in a subsequent use of the resulting products.
[0095] Advantageously, said organic material may have been
subjected to a mechanical dewatering according to another aspect of
the present invention. By dewatering the organic material the heat
value of the feedstock is increased, leading to increased oil
production capacity at constant processing cost, without
sacrificing the pumpability of the organic material to be
converted.
[0096] Furthermore, said mechanically dewatered organic material
may according to another aspect of the present invention have a dry
solid content of at least 10% by weight, preferably at least 15% by
weight, more preferably at least 20% by weight, most preferred 25%
by weight.
[0097] By the pre-treatment step of the method it is obtained to
increase the dry solid content, which again decreases the
conversion process time.
[0098] Additionally, said organic material may according to another
aspect of the present invention comprise a mixture of sludge,
lignocelulotic materials or waste.
[0099] In another aspect of the present invention the concentration
of said organic material in said fluid may be at least 5% by
weight, such as at least 10% by weight, preferably the
concentration of said organic material is at least 15% by weight,
such as at least 200% by weight, and more preferably the
concentration of said organic material is at least 30% by weight,
such as at least 50% by weight.
[0100] Advantageously, the elements of group IA of the periodic
table may be ash obtained from combustion of biomass or ash from
coal firing according to another aspect of the present
invention.
[0101] By mixing the different organic materials it is obtained
that less catalyst has to used in the further processing and/or
that the rate of the processing time is increased.
[0102] The present invention further relates to the product
obtained by the aforementioned method. Said product may according
to the present invention comprise hydrocarbon in the form of oil. A
resulting product which is very usable is hereby obtained in that
oil is presently a very demanded product all over the world. A
product such as oil is possible to obtain in that the method is
performed at very low temperatures.
[0103] In another aspect of the present invention said fluid may
have a feed carbon content and a feed hydrocarbon content, where
the hydrocarbon oil product comprises at least 20% of the feed
carbon content, such as at least 35% of the feed hydrocarbon
content, preferably comprises said hydrocarbon oil product at least
50% of the feed carbon content, such as at least 65% of the feed
carbon content and more preferably said hydrocarbon oil product
comprises at least 80% of the feed carbon content.
[0104] In another aspect of the present invention at least 20% of
an energy content in the feed stream may be recovered in said
hydrocarbon oil product, such as at least 35% of the energy
content, preferably is at least 50% of the energy content in the
feed recovered in said hydrocarbon oil product, such as at least
65% of the feed energy content and even more preferable at least
80% of said feed energy content is recovered in said hydrocarbon
oil product.
[0105] Furthermore, said hydrocarbon oil product comprises
hydrocarbons with 12 to 16 carbon atoms according to another aspect
of the present invention.
[0106] Advantageously, said hydrocarbon oil product may be
substantially free of sulphur according to another aspect of the
present invention.
[0107] Additionally, said hydrocarbon oil product may be
substantially free of halogens according to another aspect of the
present invention.
[0108] By the method according to the present invention a
hydrocarbon oil product free of sulphur and/or halogens is hereby
obtained. Such oils free of sulphur and/or halogens is very
recyclable into new forms of energy without polluting the
surroundings with reactions caused by sulphur and/or halogens.
[0109] Said hydrocarbon oil product may according to one aspect of
the present invention comprise fatty acid esters and/or fatty acid
methyl esters. The oxygen content of the fatty acid esters and
methyl esters is known to improve the properties of the hydrocarbon
oil as transportation fuel, due to the reduced particle emission
from the combustion of the fuel.
[0110] The hydrocarbon oil product may have diesel-like properties
according to another aspect of the present invention. The
diesel-like hydrocarbon fuel might be mixed directly into
conventional diesel oil, thereby saving the cost of refining the
oil product.
[0111] Furthermore, the hydrocarbon oil product may have a oxygen
content in the range 0.1-30% according to another aspect of the
present invention. The oxygen content of the hydrocarbon fuel is
known to improve the properties as transportation fuel, due to the
reduced particle emission from the combustion of the fuel.
[0112] Additionally, the hydrocarbon oil product may be adsorbed on
the surface of a mineral product according to another aspect of the
present invention. This oil containing mineral product is an
improved starting material for molten mineral processing
processes.
[0113] The hydrocarbon product may also comprise methanol according
to another aspect of the present invention. By further purification
a purified methanol product might be obtained, which is preferred
fuel for fuel cells or additive to gasoline for production of
sustainable transportation fuels.
[0114] In another aspect of the present invention said hydrocarbon
product comprising methanol may comprise at least 20% of the feed
carbon content, such as at least 35% of the feed carbon content,
preferably comprises said methanol product at least 50% of the feed
carbon content, such as at least 65% of the feed carbon content and
more preferably comprises said methanol product at least 80% of the
feed carbon content. By further purification a purified methanol
product might be obtained, which is preferred fuel for fuel cells
or additive to gasoline for production of sustainable
transportation fuels.
[0115] In yet another aspect of the present invention at least 20%
of the energy content in the feed may be recovered in said
hydrocarbon product comprising methanol, such as at least 35% of
the energy content in the feed is recovered in said hydrocarbon
product comprising methanol, preferably is at least 50% of the
energy content in the feed recovered in said hydrocarbon product
comprising methanol, such as at least 65% of the feed energy
content is recovered in said hydrocarbon product comprising
methanol and more preferably is at least 80% of said feed energy
content recovered in said hydrocarbon product comprising methanol.
By further purification a purified methanol product might be
obtained, which is preferred fuel for fuel cells or additive to
gasoline for production of sustainable transportation fuels.
[0116] The present invention further relates to the use of the
aforementioned product for driving an engine or generator, for
power production in an oil fired power plant, for process heating
or domestic heating. These are all means of producing energy from a
sustainable source, yet without having to replace or renew the
hardware installations or infrastructure established for energy
production from fossil fuels.
[0117] Furthermore, the present invention relates to the use of the
aforementioned product as a blending component in petrodiesel or
gasoline or in a suspension fired system or in a process for molten
mineral processing. These are all means of producing energy from a
sustainable source, yet without having to replace or renew the
hardware installations or infrastructure established for energy
production from fossil fuels.
[0118] Additionally, the present invention relates to the use of
the aforementioned for producing a fertilizer product or for
producing clean water stream. Said clean water stream may
furthermore have drinking water quality.
[0119] The present invention additionally relates to an apparatus
for converting an organic material into hydrocarbons, comprising: a
pre-conversion system and a product recovery system, said
pre-conversion system comprises
[0120] a first heating unit for heating a feed of fluid comprising
organic material
[0121] a catalyst reactor for contacting the feed of fluid
comprising organic material, and
[0122] an adjusting unit for adjusting the fluid to have a pH value
of above 7, and said product recovery system comprises
[0123] membrane-filter for separating a first stream of oils and
water soluble salts in from a second stream of water and water
soluble organics.
[0124] According to one aspect of the present invention, the
pre-conversion system may further comprise a storage for feeding
organic material to the fluid in a feeding direction.
[0125] Furthermore, the pre-conversion system may further comprise
a pre-treating unit situated after the feedstock and before the
first heating unit in the feeding direction, according to another
aspect of the present invention. By pre-treating the fluid
comprising the organic material it is possible to increase the
amount of solid-state material in the fluid, which again leads to a
higher rate of conversion and thereby a higher production capacity.
This results in a more efficient and cost saving converting of
organic material.
[0126] Additionally, the pre-conversion system may according to the
present invention further comprise a first particle separating unit
situated after the first heating unit in the feeding direction. By
separating particles before contacting the fluid comprising the
organic material with the heterogeneous catalyst the product
resulting from the conversion process, such as oil, is then
substantially free of being bound to these particles and therefore
much more reusable straight after this conversion process. A second
process, such as an refinery is thereby dispensable.
[0127] Said pre-conversion system may according to the invention
further comprise a second heating unit situated after the first
particle separating unit and before the catalyst reactor in the
feeding direction. It is hereby possible to optimize the
temperature before entering the fluid into the reactor and thereby
an optimization of the conversion process.
[0128] In another aspect of the present invention the
pre-conversion system may further comprise a second particle
separation unit after the catalyst reactor in the feeding
direction. This particle separating unit is for the same reason as
above advantageous.
[0129] In yet another aspect of the present invention the
pre-conversion system may further comprise means for re-circulating
part of the feed of fluid after the catalyst reactor into the feed
of fluid before the second heating unit in the feeding direction.
It is hereby obtained that some of the resulting products from the
conversion process is reused and that the conversion process time
is decreased without decreasing the conversion processing of
organic material.
[0130] Furthermore, the first heating unit may according to the
present invention comprise a first heat exchanger, which besides
heating cools the fluid from pre-conversion system before entering
the product recovery system. It is hereby obtained to reuse energy
inside the apparatus and thereby same energy in the total amount of
energy used in converting the organic material.
[0131] Additionally, the pre-treating unit may according to the
invention further comprise a heat exchange, which besides heating
the fluid in the pre-treating system cools the fluid from
pre-conversion system before entering the product recovery system.
This heat exchanger is for the same reason as above
advantageous
[0132] The pre-treating unit may further comprise a first expansion
unit, which is situated between the first heat exchanger and the
second heat exchanger, according to an aspect of the present
invention. It is hereby obtained to produce gas, such as fuel
gas.
[0133] In one aspect of the present invention the product recovery
system may further comprise a gas separating unit for separation of
gas, such as fuel gas, the gas separating unit is situated after
the second heat exchanger and before the first membrane-filter in
the feeding direction. It is hereby obtained to separate the
aforementioned gas, such as fuel gas from the rest of the
fluid.
[0134] In another aspect of the present invention the product
recovery system may further comprise means for re-circulating said
gas, such as fuel gas for heating the fluid in the second heating
unit. It is hereby obtained that some of the resulting products
from the conversion process is reused and that the conversion
process time is decreased without decreasing the conversion
processing of organic material.
[0135] In yet another aspect of the present invention the product
recovery system may further comprise a second expansion unit
situated after the first membrane-filter in the feeding direction.
It is hereby obtained to produce oil out from the fluid, and
thereby a very
[0136] Furthermore, the product recovery system may according to
one aspect of the present invention further comprise a phase
separator unit for separation of oil from the first stream, said
phase separator unit is situated after the membrane-filter in the
feeding direction. It is hereby obtained to separate oil from the
fluid.
[0137] Additionally, the product recovery system may according to
another aspect of the present invention further comprises means for
re-circulating part of the first stream into the pre-treating unit
of the pre-conversion system. It is hereby obtained that some of
the resulting products from the conversion process is reused and
that the conversion process time is decreased without decreasing
the conversion processing of organic material.
[0138] Advantageously, the product recovery system may according to
another aspect of the present invention further comprise direct
methanol fuel cell for generating electricity from the second
stream.
[0139] According to yet another aspect of the present invention the
product recovery system further comprises one or more
membrane-filters may be selected from the group of membrane
processes comprising ultra-filtration, nano-filtration, reverse
osmosis or pervaporation or a combination thereof.
[0140] Furthermore, the product recovery system may according to an
aspect of the invention further comprise the second membrane-filter
for separating a purified methanol compound from the second
stream.
[0141] In another aspect of the present invention the product
recovery system may further comprise means for re-circulating the
purified methanol compound from the second stream to the
pre-treating unit of the pre-conversion system. It is hereby
obtained that some of the resulting products from the conversion
process is reused and that the conversion process time is decreased
without decreasing the conversion processing of organic
material.
[0142] The present invention further relates to a plant comprising
the aforementioned apparatus, for producing the aforementioned
product by using the aforementioned method.
[0143] In one aspect of the present invention the plant may
comprise means for supplying organic material to the apparatus and
means for removal of the products from the apparatus.
[0144] In another aspect of the present invention the plant may
further comprise a refinery
[0145] The present invention further relates to a heterogeneous
catalyst for use in a method for converting an organic material
into hydrocarbons, comprising a compound of at least one element of
group IVB of the periodic table and/or alpha-alumina.
[0146] Additionally, the compound of at least one element of group
IVB of the periodic table may comprise zirconium and/or titanium
according to an aspect of the present invention.
[0147] Furthermore, the compound of at least one element of group
IVB of the periodic table may be on an oxide and/or hydroxide form
or a combination of the two according to an aspect of the present
invention.
[0148] Advantageously, the compound of at least one element of
group IVB of the periodic table may be at least partly on a
sulphate or sulphide form according to an aspect of the present
invention.
[0149] In another aspect of the present invention the heterogeneous
catalyst may further comprise at least one of element selected from
group of Fe, Ni, Co, Cu, Cr, W, Mn, Mo, V, Sn, Zn, Si in an amount
up to 20% by weight, such as an amount up to 10% by weight,
preferably in an amount up to 5% by weight, such as up to 2.5% by
weight.
[0150] Furthermore, these elements are on an oxide and/or hydroxide
form according to another aspect of the present invention.
[0151] Additionally, the heterogeneous catalyst is in the form of
suspended particles, tablets, pellets, rings, cylinders, a
honeycomb structure and/or a combination of these according to yet
another aspect of the present invention.
[0152] In yet another aspect of the present invention the
heterogeneous catalyst may have a BET surface area of at least 10
m2/g, such as 25 m2/g, and preferably at least 50 m2/g, such as 100
m2/g, and even more preferably at least 150 m2/g, such as at least
200 m2/g.
[0153] Advantageously, the heterogeneous catalyst further comprises
at least one surface area stabilizer selected from the group of Si,
La, Y and/or Ce according to an aspect of the present
invention.
[0154] Subsequently, the heterogeneous catalyst may according to an
aspect of the present invention comprise said at least one surface
area stabilizer in an effective amount up to 20% by weight, such as
an effective amount up to 10% by weight, preferably said surface
area stabilizers in an effective amount up to 7.5% by weight, such
as surface stabilizers in an effective amount up to 5% by weight,
and more preferably said surface stabilizers are present in an
effective amount from 0.5-5% by weight, such as 1-3% by weight.
[0155] In another aspect of the present invention the heterogeneous
catalyst may have a BET surface area of at least 10 m2/g after 1000
hours of use, such as BET surface area of at least 25 m2/g after
1000 hours of use, and preferably a BET surface area of at least 50
m2/g after 1000 hours of use, such as a BET surface area of at 100
m2/g after 1000 hours of use, and even more preferably a BET
surface area of at least 150 m2/g after 1000 hours in use, such as
at a BET surface area of least 200 m2/g after 1000 hours in
use.
[0156] Finally, the heterogeneous catalyst may be produced from red
mud according to an aspect of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0157] The present invention will in the following be described
with reference to the accompanying drawings, in which:
[0158] FIG. 1 show schematic drawing of laboratory scale
set-up,
[0159] FIG. 2 shows a general process flow sheet,
[0160] FIG. 3 shows one aspect of product recovery according to the
present invention,
[0161] FIG. 4 shows another aspect of product recovery according to
the present invention,
[0162] FIG. 5 shows yet another aspect of product recovery
according to the present invention, and
[0163] FIG. 6 shows yet another aspect of product recovery
according to the present invention.
[0164] The drawings are schematically and shown for the purpose of
illustration.
[0165] FIG. 1 is a schematic drawing of the laboratory set-up used
for the tests given in the examples. The pre-treated fluid
containing the homogeneous catalysts and organic material to be
converted is supplied to the system at the position A. The fluid is
pressurized by means of the pump 1 and is heated to approximately
230 C in the heater 2 comprising a heat exchanger and a temperature
controller TIC. A second fluid is supplied to the system at
position B. This stream is pressurized by means of the pump 3 and
heated in the heater 4 to the temperature necessary to obtain the
desired conversion temperature of the mixed fluid streams at
position 4, comprising a heat exchanger and a temperature
controller TIC. The heterogeneous catalyst is located in the
tubular catalytic reactor 5. After contact with the heterogeneous
catalyst, the fluid containing the converted organic material is
cooled to ambient temperature in the cooler 6, and filtered in the
filter 7 for separation and collection of suspended particles.
Subsequently the fluid is expanded to ambient pressure over the
valve 8. The system pressure is maintained by controlling the flow
through 8, utilizing the pressure controller PIC. The expanded
fluid temperature is measured with the thermocouple 9. The liquid
fraction of the stream is collected in a liquid trap 10, and the
gas is vented off from the trap at position G. The flow rate of the
produced gas is continuously measured by a gas meter placed in H
(not shown). The composition of the gas is analysed by gas
chromatography (not shown) of a small sample taken through I, at
controlled pressure established by the flow control valve and the
pressure controller (PIC) 11.
[0166] FIG. 2 shows a schematic drawing of a preferred aspect of a
method according to the present invention. Organic material for
conversion is received in a feed storage (not shown on the figure).
Said organic material may comprise a wide range of biomass and
wastes, and may also comprise fossil fuels such coal, shale,
orimulsion, heavy fractions of crude oil etc. Many aspects
according to the present invention involve treatment of organic
material from a mixture of different sources of material as just
mentioned.
[0167] The feed storage will typically have a capacity
corresponding to three days of plant operation. The feed storage is
preferably a concealed and agitated silo, such as an agitated
concrete silo. A fluid containing the organic material is pumped to
the pre-treatment step 1 at position A.
[0168] The first part of the pre-treatment comprises in this aspect
a size reduction of the feed e.g. by cutting, grinding, milling
and/or sieving the material. This size reduction may be an integral
part of feeding pump (not shown). During the feeding operation to
the pre-treatment the pressure of the fluid containing the organic
material to be treated is increased to a pressure in the range 4-15
bars. In the second part of the pre-treatment the fluid containing
said organic material is typically maintained in a pre-treatment
vessel for a period of 0.5-2 hours. The pre-treatment vessel is
preferably an agitated vessel, which is maintained at a temperature
of 100-170 C, and preferably in the range 110 to 140 C. The energy
for this pre-heating of said fluid comprising said organic material
to be converted is preferably supplied, by recovering heat from one
of the process streams to be cooled. In the figure this is
illustrated by integrating the heat exchanger 2 in vessel for
recovery of heat from the process stream D.
[0169] The pH in the pre-treatment vessel is adjusted to a value
above 7, and preferable in the range 8-10. This pH adjustment is in
many aspects according to the present invention performed by adding
additives to the vessel either directly into the pre-treatment
vessel and/or through its inlet, e.g. by adding a base, which may
also comprise an element of group IA of the periodic table.
Non-limiting examples of such additives are KOH, NaOH,
K.sub.2CO.sub.3, Na.sub.2CO.sub.3, ash from biomass or coal
combustion. Such additives may be added to the vessel through a
stream S either streaming into stream A or streaming directly into
the vessel 1. Feed of the stream S may be provided by a feeding
pump (not shown).
[0170] During the residence in the pre-treatment vessel larger
molecules such as cellulose, hemicellulose and lignin are
hydrolyzed, and cells from biomass addition is opened facilitating
the release of cell contents, such as salts. For a number of
potential feedstock this cell opening involve release of catalysts
such as potassium from the feedstock itself, thereby allowing for a
very efficient process. A number of other additives may also
enhance the pre-conversion of the organic material and are further
advantageous for the subsequent processing. Such other additives
include alcohols, such as methanol, carboxylic acids, aldehydes,
and/or ketones. In a preferred aspect of the invention a number of
such additives being utilized in the pre-treatment, are produced
in-situ in the process and re-circulated to the pre-treatment step
as shown by the streams E and F. Typical compositions of these
recirculation streams is further described in relation to the FIGS.
3-5.
[0171] A fluid stream containing pre-converted organic material is
withdrawn from pre-treatment vessel by the feed pump 3, and
pressurized to the operating pressure e.g. 250 bars. The feed pump
may comprise a plunger pump.
[0172] After pressurization the fluid containing the pre-converted
organic material, the homogeneous catalyst and other additives is
heated in the first heating step 4 by heat exchange with the hot
converted product stream from the catalytic reactor. The
temperature of the fluid containing the pre-converted organic
material will in many applications according to the present
invention be in the order of 20-30.degree. C. below the operating
temperature of the catalytic reactor. During this first heating
step the organic material in the feed is further thermally
decomposed. A number of undesirable side reactions may proceed
during this thermal decomposition, such soot and char formation.
Besides reducing the overall efficiency of the process, this may
lead to operational problems such as plugging or reduced efficiency
of heat exchanger, and deposition on downstream equipment. The
aforementioned additives reduce these undesirable side reactions
and enhance further the conversion of the organic material into
desirable products.
[0173] From the heat exchanger 4, the fluid containing said
pre-converted organic material may pass a first particle separation
device 5 for collection of suspended particles, which may be formed
during said pre-conversion during heat-up. This particles
separation device 5 may comprise any conventional means for
particle separation, e.g. a cyclone, a filter, a gravimetric
settling chamber etc. Particles collected are withdrawn from the
process shown by the stream B.
[0174] After the first particle separation device 5 the fluid
containing said pre-converted organic material is mixed with a
re-circulating stream from the catalytic reactor. This mixing will
typically increase the temperature of the mixed fluid with 10-20 C,
and the recirculation will further introduce desirable compounds
for the further conversion into the feed. After mixing with the
re-circulation stream the mixed fluid passes to a trimheater
(second heating unit) 6, wherein the temperature is raised to the
operating temperature of the catalytic reactor 7. The trimheater 6
may in many aspects according to the present invention be a gas or
oil fired heater, and is preferably at least partly fuelled by
re-circulating gas and/or other fuel products produced in the
process. In a preferred aspect, this trimheater is fuelled by
re-circulating the produced gas denoted I in FIG. 3. The
recirculation of said produced gas I may include a purification
step.
[0175] In the catalytic reactor 7, the fluid containing homogeneous
catalyst, additives, and pre-converted organic material is
contacted with the heterogeneous catalyst. The heterogeneous
catalyst will typically be contained in a tubular fixed bed, and
the catalytic reactor may comprise multiple tubular fixed beds.
During the conversion a dissolved fuel gas, a water soluble
organics and an oil is generally produced. The product distribution
is adjustable within a wide range of concentration of resulting
products as shown in the examples below, and may be controlled by
selecting a suitable combination of residence time, re-circulation
flow rate, reaction temperature, and concentration of homogeneous
catalyst and additives.
[0176] Part of the product stream from the catalytic reactor is
re-circulated by the pump 8, and mixed with the fluid containing
the pre-converted organic material as described above.
[0177] The remaining part corresponding to the mass flow of the
fluid containing the pre-converted organic material before mixing
with the re-circulating stream is withdrawn to the second particle
separation device 9. As for the first particle separation device
this second particles separation device may comprise any
conventional means for particle separation e.g. a cyclone, a
filter, a gravimetric settling chamber etc. The main feature is to
provide a hot separation of potential suspended particles produced
oil prior to cooling and expansion to avoid adsorption of the oil
to the suspended particles. However, in a number of applications of
the present invention e.g. for feedstock with a low ash content
this particle separation device may be optional. Particles
collected in the second particle separation device are withdrawn
from the process shown by the stream C.
[0178] Subsequent to the passage of the second particle separation
device the fluid stream is cooled in by heat exchange with the feed
stream in the heat exchanger 4, and in the heat exchanger 2 and
expanded to a pressure in the range 75-225 bars over the expansion
valve 10, and separated in the product recovery system 11. Some of
the separated fluid stream from the product recovery system 11,
such as the streams F and/or E may be re-circulated to the
pre-treatment step as described above. The product recovery system
11 is further illustrated and described below in the FIGS. 3-6.
[0179] The separation system, illustrated in FIG. 3, comprises a
gas-liquid separator 12, separating the gas products in stream I
and the liquid products in stream J. In an aspect the gas product
is used internally for fuelling the trimheater 6. The liquid
products are further separated in a first membrane filter 13. The
membrane filtration separation is pressure driven, and in many
applications applying a nano- or ultrafiltration membrane. The
filtration retentate in stream L includes parts of the feed water,
the oil product and the dissolved inorganic compounds, e.g. salts
from the feedstock and the homogenous catalyst. The oil product is
separated from stream L in an oil separator (phase separator unit)
14 operating at atmospheric conditions, and forming the oil product
stream H. The remaining water and dissolved inorganic compounds
forms stream O. The main part of stream O is recycled to the
pre-conversion 1, 2 in stream E, thereby recycling the homogenous
catalyst, while a purge stream P is discharged to balance the
inorganic compound input from the feedstock.
[0180] The further processing of the membrane filtration permeate,
denoted stream K, is illustrated in FIGS. 4-6. Stream K contains
smaller water soluble organics like C 1-4 alcohols and carboxylic
acids.
[0181] In one aspect illustrated in FIG. 4 stream K is fed to a
separation unit (membrane filter) 15, producing pure water of
drinking water quality in stream G and a stream of water soluble
organics in stream F. The separation unit 15 is in an aspect of the
invention a reverse osmosis membrane unit, comprising a multitude
of membrane modules. The retained water soluble organics in stream
F are recycled to the pre-conversion step 1, 2.
[0182] In a further aspect, illustrated in FIG. 5, stream K is
split into a concentrated water soluble organics stream F and an
organics depleted water stream Q. The separation unit 16 involved
is in many applications a membrane separation driven by temperature
or concentration gradients, like membrane distillation or
pervaporation. The water stream Q is further purified in a
polishing step 17, producing the pure water stream G. The polishing
step 17 is preferably an activated carbon filter or like means for
absorption of very low concentrations of impurities from a water
stream.
[0183] In an aspect illustrated in FIG. 6 the water soluble organic
stream K is fed to a direct methanol fuel cell 18, producing
electricity and a process water stream R. The direct methanol fuel
cell 18 might include feed stream and effluent conditioning
steps.
Examples
Illustrative Example 1
Conversion of Sewage Sludge
[0184] Anaerobic digested sewage sludge below was converted
according to the method of the present invention in the laboratory
scale plant shown in FIG. 1.
[0185] The dry matter content of the sewage sludge was 5%. The main
components of the dry matter in weight % were:
[0186] C=28.3%
[0187] H=4.33%
[0188] N=3.55%
[0189] O=28.4%
[0190] P=4.49%
[0191] Al=7.77%
[0192] Si=7.44%
[0193] Ca=6.95%
[0194] Fe=3.17%
[0195] K=1.62%
[0196] An elemental analysis of sewage sludge dry matter was
further analyzed by induced coupled plasma (ICP) revealing the
following composition:
TABLE-US-00001 O Al H Ca Si C [%] [%] [%] [%] [%] [%] N [%] P [%] K
[%] 30.9 30.5 6.15 5.2 5.03 4.98 4.66 4.62 2.36 Fe Na Mg Zn Cl [%]
S [%] [%] [%] [%] [%] Ti [%] Ba [%] Mn [%] 1.13 1.09 1.04 0.938
0.875 0.226 0.195 0.0652 0.0375
[0197] The combustible fraction amounts to 58% of the dry matter
content, with a heat value of 22.2 MJ/kg, which translates into a
calorific value of 476 KJ/kg in the sewage sludge as received.
[0198] Prior to the test the sewage sludge was pre-treated by
sizing to less than 1 mm by cutting longer particles by a Seepex
macerator (type 25/15-I-I-F12-2) and milling by a colloid mill
(Probst and Class, type N100/E), and filtered by a screen basket
filter (mesh width Imm).
[0199] Subsequently 1.5% by weight of potassium in the form of
potassium carbonate was added to the resulting slurry. The pH value
of the slurry was 9.0.
[0200] 125 ml of ZrO.sub.2 heterogeneous catalyst stabilized with
2.2 atomic mole % of Si. The catalyst in the form of cylindrical
pellets of 3 mm length and a diameter of 3 mm was added to the
tubular reactor.
[0201] 63 g/h of the pre-treated sewage sludge was pressurized to
250 bars and heated to 230 C in the pre-heating step. This stream
was mixed with 393 g/h of pressurized water heated to a temperature
so as to obtain a substantially constant temperature of 360.+-.5 C
after mixing.
[0202] The mixed flow was subsequently contacted with the
heterogeneous catalyst in the reactor. The feed to water ratio
translates into a water to feed ratio of 6:1, and the total flow of
456 g/h translates into a contact time of approximately 4
minutes.
[0203] After to the contact with the heterogeneous catalyst, the
fluid containing the converted organic material is cooled to
ambient temperature, filtered through a particle filter for
collection of suspended particles, and expanded to ambient
pressure. The liquid fraction on the stream was collected in a
liquid trap, and the gas is vented off.
[0204] The experiment resulted in three product streams, a gas, an
aqueous product and a solid precipitate. Samples for analysis was
collected for a period of 15.5 hours.
Gas Analysis
[0205] The flow rate and composition of the produced gas was
measured continuously by a gas meter with sampling. The composition
was measured by gas chromatography.
[0206] The analysis of the gas phase revealed the following
results:
TABLE-US-00002 Gas analysis Hydrogen [vol. %] 55.13 Carbon dioxide
[vol. %] 31.92 Carbon monoxide [vol. %] 0.00 Methane [vol. %] 12.87
Ethene [vol. %] 0.00 Ethane [vol. %] 0.00 Propene [vol. %] 0.00
Propane [vol. %] 0.00 C4-compounds [vol. %] 0.00 Total [vol. %]:
99.92 Total amount of carbon, g 0.91
Liquid Analysis
[0207] The liquid product was contained suspended particles. The
filtered liquid was analyzed by ion chromatography, Induced Plasma
Emission (ICP) and high temperature total carbon analyzers and mass
spectrometry.
[0208] The analysis of the liquid phase revealed the following
results:
TABLE-US-00003 Liquid analysis pH 8.32 Total Organic Carbon (TOC),
[ppm by weight] 726.8 Total Inorganic Carbon (TIC), [ppm by weight]
361.5 Total Carbon, [ppm by weight] 1088.3 Methanol [ppm by weight]
600 Ethanol [ppm by weight] 300 Acetic acid [ppm by weight] 332.7
Formic acid [ppm by weight] 10.3 Acetaldehyde [ppm by weight] 104.9
Total amount of carbon in liquid 9.30 g
[0209] The inorganic carbon content in the liquid was found
primarily to be due to the presence of carbonate.
Solid Analysis
[0210] The solid fractions was analyzed by means of a total carbon
analyzer and by elemental analysis by an induced coupled plasma
analyzer (ICP). An organic phase was found to be adsorbed to the
inorganic particles under the experimental conditions used.
[0211] This organic phase was extracted prior to the solid analysis
using CH.sub.2Cl.sub.2. The extractable fraction of the organic
carbon was found to be an oil phase, primarily consisting of
saturated hydrocarbons with a chain length of 12 to 16 carbon
atoms, and there for comparable to fuel or diesel oil. The oil
contained 2-hexadecanone, heptadecane, 6,10-dimethyl-2-undecanone,
hexadecane, 3-methyl-indole, 2-tridecanone and other compounds. A
sulphur and halogen analysis performed at the extracted oil, showed
that the oil was essentially free of sulphur and halogen compounds.
The total amount of oil extracted from the solids was 3.86 g and
the total amount of carbon found in the oil phase was equivalent to
3.28 g.
[0212] No carbon was detected in the solid product after extraction
of adsorbed oil, indicating 100% conversion of the organic material
in the feed. The same result can be concluded from the carbon
balance below:
Carbon Balance
TABLE-US-00004 [0213] Input C: Output C: Sewage sludge: 13.81 g
0.91 g gas C .fwdarw. 4.97% K.sub.2CO.sub.3: 4.51 g 4.34 g TIC
liquid .fwdarw. 23.68% 9.3 g TOC liquid .fwdarw. 50.74% 0.0 TOC
solid .fwdarw. 0.00% 3.28 g C in oil .fwdarw. 17.9% .SIGMA. 18.33 g
.SIGMA. 17.83 g conversion .fwdarw. 97.3%
Energy Balance:
TABLE-US-00005 [0214] Heat Value Amount Energy Fraction Component
[kJ/kg] [g] [% of energy input with feed] Feed sludge 476 976.5
Methane 50,400 0.25 2.71 Hydrogen 240,103 0.21 10.8 Methanol 19,918
13.67 58.6 Oil 41,900 3.86 34.8 Sum 107.0
Illustrative Example 2
Conversion of Sewage Sludge
[0215] Anaerobic digested sewage sludge with characteristics as
given above in example was preheated and converted using the same
catalyst and experimental set-up.
[0216] 140 g/h of the pretreated sewage sludge was pressurized to
250 bar and heated to 230 C in the pre-heating step. This stream
was mixed with 414 g/h of pressurized water heated to a temperature
so as to obtain a substantially constant temperature of 300.+-.5 C
after mixing.
[0217] The mixed flow was subsequently contacted with the
heterogeneous catalyst in the reactor. The feed to water ratio
translates into a water to feed ratio of 3:1, and the total flow of
545 g/h translates into a contact time of 3.3 minutes.
[0218] After to the contact with the heterogeneous catalyst, the
fluid containing the converted organic material is cooled to
ambient temperature, filtered through a particle filter for
collection of suspended particles, and expanded to ambient
pressure. The liquid fraction on the stream is collected in a
liquid trap, and the gas is vented off.
[0219] The experiment resulted in three product streams, a gas, an
aqueous product and a solid precipitate. Samples for analysis was
collected for a period of 10.5 hours.
Gas Analysis
[0220] The analysis of the gas phase revealed the following
results:
TABLE-US-00006 Gas analysis Hydrogen [vol. %] 31.36 Carbon dioxide
[vol. %] 41.17 Carbon monoxide [vol. %] 2.25 Methane [vol. %] 24.22
Ethene [vol. %] 0.00 Ethane [vol. %] 0.00 Propene [vol. %] 0.00
Propane [vol. %] 0.00 C4-compounds [vol. %] 0.00 Total [vol. %]:
99.00 Total amount of carbon, g 0.54
Liquid Analysis
[0221] The analysis of the liquid phase revealed the following
results:
TABLE-US-00007 Liquid analysis pH 7.42 Total Organic Carbon (TOC),
[ppm by weight] 985.1 Total Inorganic Carbon (TIC), [ppm by 439.3
weight] Total Carbon, [ppm by weight] 1424.4 Methanol [ppm by
weight] 800 Ethanol [ppm by weight] 0 Acetic acid [ppm by weight]
347.2 Formic acid [ppm by weight] 43.2 Acetaldehyde [ppm by weight]
156.5 Total amount of carbon in liquid 13.33 g
[0222] The inorganic carbon content in the liquid was found
primarily to be due to the presence of carbonate.
Solid Analysis
[0223] The solid fractions was analyzed by means of a total carbon
analyzer. An organic phase was found to be adsorbed to the
inorganic particles under the experimental conditions used.
[0224] This organic phase was extracted prior to the solid analysis
using CH.sub.2Cl.sub.2. The extractable fraction of the organic
carbon was found to be an oil phase, primarily consisting of
saturated hydrocarbons with a chain length of 12 to 16 carbon
atoms, and there for comparable to fuel or diesel oil. The oil
contained 2-hexadecanone, heptadecane, 6,10-dimethyl-2-undecanone,
hexadecane, 3-methyl-indole, 2-tridecanone and other compounds. The
total amount of oil extracted from the solids was 12.73 g and the
total amount of carbon found in the oil phase was equivalent to
10.83 g.
[0225] No carbon was detected in the solid product after extraction
of adsorbed oil, indicating 100% conversion of the organic material
in the feed.
Carbon Balance:
TABLE-US-00008 [0226] Input C: Output C: Sewage sludge: 20.58 g
0.54 g gas C .fwdarw. 1.97% K.sub.2CO.sub.3: 6.78 g 6.43 g TIC
liquid .fwdarw. 23.5% 6.3 g TOC liquid .fwdarw. 23.02% 0.0 TOC
solid .fwdarw. 0.00% 10.83 g C in oil .fwdarw. 39.58% .SIGMA. 27.36
g .SIGMA. 24.1 g conversion .fwdarw. 88.1%
Energy Balance:
TABLE-US-00009 [0227] Energy Fraction Heat Value Amount [% of
Component [kJ/kg] [g] energy input with feed] Feed sludge 476 1470
Methane 50,400 0.28 2.01 Hydrogen 240,103 0.07 2.40 Methanol
equivalents 19,918 9.30 26.37 Oil 41,900 12.73 76.2 Sum 107.0
Illustrative Example 3
Conversion of Corn Silage
[0228] Corn silage was pretreated and converted using the same
catalyst and experimental set-up as described above in example 1
and 2.
[0229] Prior to the test the sewage sludge was pretreated by sizing
to less than 1 mm by cutting longer particles by a Seepex macerator
(type 25/15-I-I-F12-2) and milling by a colloid mill (Probst und
Class, type N100/E), and filtered by a screen basket filter (mesh
width 1 mm).
[0230] Subsequently 1.5% by weight of potassium in the form of
potassium carbonate was added to the resulting slurry. The pH value
of the slurry was 9.6.
[0231] The characteristics of the corn silage after the
pretreatment was the following:
TABLE-US-00010 Corn silage feedstock Dry matter content [% weight]
11.29 Inorganic fraction of dry matter [% Weight] 29.4 Density
[kg/m.sup.3] 1.0099 pH 9.6 Heat of combustion.sup.1 [kJ/kg] 1435
.sup.1Based on 18 MJ/kg heat of combustion for the organic fraction
of the dry matter.
[0232] The inorganic content of the dry matter was mainly the added
potassium carbonate, accounting for approximately 3/4 of the dry
matter inorganic compounds. GC-MS analysis of the corn silage
feedstock revealed numerous compounds, but all were present in
concentrations too low for identification. Particularly aromatics
like phenols were not found in any significant amount.
[0233] The dry matter content of the corn silage feedstock was
analyzed, revealing the following composition:
TABLE-US-00011 Corn silage dry matter TC [mg/kg] 325000 Mo [mg/kg]
7.82 TOC [mg/kg] 315000 N [mg/kg] 6960 Al [mg/kg] 233 Na [mg/kg]
825 Ca [mg/kg] 2023 Ni [mg/kg] 11.1 Cl [mg/kg] 1682 S [mg/kg]
<0.1 Cr [mg/kg] 28 Si [mg/kg] 2090 Fe [mg/kg] 4571 Zr [mg/kg]
2.24 K [mg/kg] 112350
[0234] 140 g/h of the pretreated sewage sludge was pressurized to
250 bar and heated to 230 C in the pre-heating step. This stream
was mixed with 377 g/h of pressurized water heated to a temperature
so as to obtain a substantially constant temperature of 350.+-.5 C
after mixing.
[0235] The mixed flow was subsequently contacted with the
heterogeneous catalyst in the reactor. The feed to water ratio
translates into a water to feed ratio of 3.75:1, and the total flow
of 517 g/h translates into a contact time of 3.3 minutes.
[0236] After the contact with the heterogeneous catalyst, the fluid
containing the converted organic material was cooled to ambient
temperature, filtered through a particle filter for collection of
suspended particles, and expanded to ambient pressure. The liquid
fraction on the stream is collected in a liquid trap, and the gas
is vented off.
[0237] The experiment resulted in four product streams, a gas, an
aqueous product, a free oil phase and a solid precipitate. Samples
for analysis was collected for a period of 16 hours.
Gas Analysis
[0238] The analysis of the gas phase revealed the following
results:
TABLE-US-00012 Gas analysis Hydrogen [vol. %] 7.5 Carbon dioxide
[vol. %] 88.74 Carbon monoxide [vol. %] 0.00 Methane [vol. %] 0.33
Ethene [vol. %] 0.06 Ethane [vol. %] 0.06 Propene [vol. %] 0.25
Propane [vol. %] 0.05 C4-compounds [vol. %] 0.00 Total [vol. %]:
Total amount of carbon, g 15.2
Liquid Analysis
[0239] The analysis of the liquid phase revealed the following
results:
TABLE-US-00013 Liquid analysis pH 8.30 Total Organic Carbon (TOC),
[ppm by weight] 2105 Total Inorganic Carbon (TIC), [ppm by weight]
201 Total Carbon, [ppm by weight] 2305 Methanol [vol %] 1.64
Ethanol [vol %] 0.27 Acetic acid [ppm by weight] 5185 Formic acid
[ppm by weight] 2206 Glycol acid 10470 Acetaldehyde [ppm by weight]
115.0 Total amount of carbon in liquid 40.1 g
[0240] The inorganic carbon content in the liquid was found
primarily to be due to the presence of carbonate.
Solid Analysis
[0241] The solid fractions was analyzed by means of a total carbon
analyzer. An organic phase was found to be adsorbed to the
inorganic particles under the experimental conditions used.
[0242] This organic phase was extracted prior to the solid analysis
using CH.sub.2Cl.sub.2. The extractable fraction of the organic
carbon was found to be an oil phase, primarily consisting of
saturated hydrocarbons with a chain length of 12 to 16 carbon
atoms, and there for comparable to fuel or diesel oil. The oil
contained phenol, toluene, 4-ethyl-phenol, 4-ethyl-3-methylphenol,
cyclopent-2-ene-1-one 2,3,4 trimethyl, 2-methyl-1-penten-3-yne and
other compounds. A sulphur analysis of the oil showed that the oil
phase was essentially free of sulphur. A similar analysis for
halogen compounds showed that the oil phase was essentially free of
halogen. The total amount of oil extracted from the solids was
14.76 g and the total amount of carbon found in the oil phase was
equivalent to 12.55 g.
[0243] No carbon was detected in the solid product after extraction
of adsorbed oil, indicating 100% conversion of the organic material
in the feed. The same result can be concluded from the carbon
balance below:
Carbon Balance:
TABLE-US-00014 [0244] Input C: Output C: Corn silage feed: 82.19 g
15.2 g gas C .fwdarw. 18.5% 40.1 g TOC liquid .fwdarw. 48.8% 0.0
TOC solid .fwdarw. 0.0% 28.35 g C in oil .fwdarw. 34.5% .SIGMA.
82.19 g .SIGMA. 83.62 g conversion .fwdarw. 101.8%
Energy Balance:
TABLE-US-00015 [0245] Heat Value Amount Energy Fraction Component
[kJ/kg] [g] [% of feed energy content] Feed sludge 476 2240
Hydrogen 240,103 0.07 1.6 Methanol 19,918 28.9 17.9 Ethanol 28,200
4.20 4.2 Glycol acid 14,400 0.41 10.4 Acetic acid 18,200 1.23 6.5
Oil 41,900 14.76 45.1 Sum 85.7
[0246] Additionally the following are definitions used in the
description of the present invention.
[0247] The term hydrocarbon fuel is in the present invention
intended to define all hydrocarbon based fuels, which may or may
not comprise other elements than carbon and hydrogen, e.g. some of
said hydrocarbons may comprise oxygen and other elements e.g. in
the form of groups of alcohols, aldehydes, ketones, carboxylic
acid, ester, esthers etc. and reaction products thereof.
[0248] The membrane processes of the present invention is well
known in the prior art (e.g. W. S. HO et al, "Membrane Handbook",
Van Nordstrand Reinhold, p. 103-132, p. 263-446, 1992, ISBN
0442-23747-2, K. Scott, "Handbook of Industrial Membranes" Elsevier
Science Publishers, 1995, p. 3-163, p. 331-355, p. 575-630, ISBN 1
85617 233 3)
[0249] The surface areas referred to throughout this specification
and claims are the nitrogen BET surface areas determined by the
method described in the article by Brunauer, P. Emmett and E.
Teller, J. Am. Chem. Soc, Vol. 60, p. 309 (1938). This method
depends on the condensation of nitrogen into the pores, and is
effective for measuring pores with pore diameters in the range of
10 .ANG. to 600 .ANG.. The volume of nitrogen adsorbed is related
to the surface area per unit weight of the support.
[0250] It is well known in the prior art that the activity of a
catalyst is proportional to the surface area (BET), and that
catalysts may show a significant activity drop over time, when
subjected to e.g. hydrothermal conditions as used in relation to
the present invention. In order to minimize such potential activity
loss a surface area stabilizer is incorporated into the
heterogeneous catalyst.
[0251] Red Mud is a waste product of bauxite processing via the
Bayer process. It comprises oxides and hydroxides of mainly
aluminium, iron, titanium, silicon, and sodium.
* * * * *