CA1213233A - Process for producing isopropyl alcohol from cellulosic substrates - Google Patents
Process for producing isopropyl alcohol from cellulosic substratesInfo
- Publication number
- CA1213233A CA1213233A CA000457164A CA457164A CA1213233A CA 1213233 A CA1213233 A CA 1213233A CA 000457164 A CA000457164 A CA 000457164A CA 457164 A CA457164 A CA 457164A CA 1213233 A CA1213233 A CA 1213233A
- Authority
- CA
- Canada
- Prior art keywords
- carried out
- effluents
- minutes
- fermentation
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000000034 method Methods 0.000 title claims abstract description 38
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 title claims description 34
- 239000000758 substrate Substances 0.000 title 1
- 238000000855 fermentation Methods 0.000 claims abstract description 36
- 230000004151 fermentation Effects 0.000 claims abstract description 36
- 239000000203 mixture Substances 0.000 claims abstract description 25
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 102000004190 Enzymes Human genes 0.000 claims abstract description 12
- 108090000790 Enzymes Proteins 0.000 claims abstract description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 230000000977 initiatory effect Effects 0.000 claims abstract description 10
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims abstract description 8
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000007062 hydrolysis Effects 0.000 claims abstract description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 238000004821 distillation Methods 0.000 claims abstract description 4
- 235000019260 propionic acid Nutrition 0.000 claims abstract description 4
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims abstract description 4
- 150000002989 phenols Chemical class 0.000 claims abstract description 3
- 229940107700 pyruvic acid Drugs 0.000 claims abstract description 3
- 229940061610 sulfonated phenol Drugs 0.000 claims abstract description 3
- -1 aluminate acetate Chemical class 0.000 claims abstract 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 36
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 24
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 239000006227 byproduct Substances 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 2
- 239000005862 Whey Substances 0.000 abstract description 11
- 102000007544 Whey Proteins Human genes 0.000 abstract description 11
- 108010046377 Whey Proteins Proteins 0.000 abstract description 11
- 239000008267 milk Substances 0.000 abstract description 11
- 210000004080 milk Anatomy 0.000 abstract description 11
- 235000013336 milk Nutrition 0.000 abstract description 11
- 239000010902 straw Substances 0.000 abstract description 10
- 210000003608 fece Anatomy 0.000 abstract description 5
- 239000010871 livestock manure Substances 0.000 abstract description 5
- 239000003415 peat Substances 0.000 abstract description 3
- 239000002028 Biomass Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000007789 gas Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000010411 cooking Methods 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 239000011368 organic material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 3
- 239000008246 gaseous mixture Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000029087 digestion Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229940095574 propionic acid Drugs 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
Landscapes
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE:
A process for producing lower alcanols from organic residues and effluents such as milk whey, manure, must, wort, straw, peat moss and biomass. This process comprises the steps of: subjecting the residues if any, to hydrolysis; subjecting the effluents and/or hydrolyzed residues to fermentation in the presence of a fermentation initiating agent consisting of amylytic enzymes; adding basic aluminate acetate and a compound selected from the group consisting pyruvic acid, propionic acid and mixtures of formaldehyde with phenol or sulfonated phenol to the fermented effluents of the first step; heating the mixture obtained in the second step at a temperature ranging between 120°C and 160°C under a pressurization of at least 1.5 kg/cm2 until the requested alcanols are produced; and recovering the produced alcanols by distillation.
A process for producing lower alcanols from organic residues and effluents such as milk whey, manure, must, wort, straw, peat moss and biomass. This process comprises the steps of: subjecting the residues if any, to hydrolysis; subjecting the effluents and/or hydrolyzed residues to fermentation in the presence of a fermentation initiating agent consisting of amylytic enzymes; adding basic aluminate acetate and a compound selected from the group consisting pyruvic acid, propionic acid and mixtures of formaldehyde with phenol or sulfonated phenol to the fermented effluents of the first step; heating the mixture obtained in the second step at a temperature ranging between 120°C and 160°C under a pressurization of at least 1.5 kg/cm2 until the requested alcanols are produced; and recovering the produced alcanols by distillation.
Description
L3~33 r The present invention relates in general to the production of lower alcanols, especially methanol and isopropyl alcohol, and/or of gaseous mixtures useful as combustibles, from organic effluents or residues such as milk whey, manure, must, wont, straw, peat moss, Bahamas and the like.
j More particularly, the invention relates to a pro-cuss that requires less than two hours to carry out such alcohol or gas production.
It is a well known fact that the world's supply of oil as a source of energy, especially gasoline for use in internal combustion engines or in industrial furlers, has become limited and that exhaustion of the supply is inevi-table. To present restriction, it is therefore necessary to develop alternative sources of energy. More specifically, it is necessary to find new kinds of liquid fuels capable of being used either alone or as a proportionate part with gasoline for driving internal combustion engines. The raw materials to be used in the production of such alternative sources of energy must be readily available and the cost of the process for producing the new fuel in terms of energy, material and processing expenses must be such that the process is commercially feasible and the cost of the resulting product within reason.
It is also a well known fact that very large qua-lilies of organic materials are not only available but often present problems of disposal. Organic materials of all kinds, including manure, milk whey must wont, straw, peat moss, Bahamas and other agricultural residues are available in very large quantity. Some of them, such as manure, have even already been employed as starting materials fox the production of combustible gases.
The present invention proposes an industrial pro-cuss for producing a liquid fuel, mainly composes of lower alcanols, which process makes use of organic materials such L3~3;3 ., ..
/
as manure, milk whey, must, wont and the like as starting material. The invention also proposes a process that can be used for producing a combustible gaseous mixture as main or by-product.
As aforesaid, the process according to the present invention makes use of organic waste or surplus, that is of readily available raw materials, for producing lower alcanols such as methanol or isopropyl alcohol that can be used, , preferably in the ratio of one part of alcohol per two parts of gasoline, as a fuel for normal gasoline-fueled internal combustion engines, without special adjustment of the engines.
With some engine alteration, the alcohol can be used in larger proportion and in some instances even without inter-' mixing with gasoline.
The process according to the invention can be carried out in a very fast and easy manner, usually in less than two hours, and only requires an acceptable amount of energy and quantities of reagent and catalytic materials.
Contributing to the favorable economics of the process is the production of some useful by-products such as the above mentioned combustible gaseous mixtures.
The process according to the invention basically consists in subjecting to fermentation the raw organic material under specific conditions of temperature and pros-sure, using specific chemical reagents and enzymes as catalysts.
More particularly, the process according to the invention for producing lower alcanols from organic effluents ` and residues, comprises the steps of:
(a) subjecting the residues, if any, to hydrolysis;
by subjecting the effluents and/or hydxolysed residues to fermentation in the presence of a fermentation initiating agent consisting of amylytic enzymes (c) adding basic acuminate acetate and a compound selected from the group consisting of pyruvic acid, prop ionic acid and mixtures of formaldehyde with phenol or sulfonated J, phenol to the fermented effluents of step (a);
(d) heating the mixture obtained in step (c3 at a I; temperature of at least 100C under a pressurization of at least 1.5 kg/cm2 until the requested alcanols are produced;
and (e) recovering the produced alcanols by distillation.
The hydrolysis of stop (a) to which must be subjected the organic residues if such are used as starting material can be carried out with a heated solution of sodium carbonate.
The hydrolysis can be carried out in an autoclave pressurized Z to at least 1.5 kg/cm2 for about 55 minutes. If necessary, l the hydrolyzed cellulose that is extracted can be subjected to a further digestion in a heated solution containing $ aluminum isopropyl ate or isopropyl alcohol together with sodium acetate and, if desired, acetic acid. This further digestion can be carried out in an autoclave pressurized to at least 1.5 kg/cm2 for about 55 minutes.
It should be noted that such a hydrolysis is not I compulsory when the starting material is an effluent.
Fermentation step (b) can be carried out at a fermentation temperature ranging from 30 to 45C (preferably 38C), for a period ranging from 25 to 50 minutes (preferably ¦ 35 minutes). During this step, use is preferably made of 30 to 100 grams of fermentation initiating agent per 10 liters of effluents or hydrolyzed residues (preferably 40 grams).
If step (b) is carried out for a period of time longer than 50 minutes such as r for example, 110 minutes, a Jo gas useful as combustible material, is produced.
Step (c) can be carried out at a temperature ranging from 30 to 45C (preferably 40C) within a few minutes.
During this step, use is preferably made of 10 to 50 grams (preferably 17 g) of basic acetate and of 100 to 300 grams (preferably 130 grams of a mixture of formaldehyde with phenol I- or sulfonated phenol or of pyrrhic acid or of prop ionic acid per 10 liters of effluents or hydrolyzed residues. The 1' .
lo _ 3 _ `~`
.
, ~2~3;~33 /
mixture may comprise, for example, 65~ by weight of formal-Dodd and 35% by weight of phenol.
Step (d) can be carried out in an autoclave for a period of time ranging from 35 to 110 minutes (preferably ; 5 55 minutes depending on the selected temperature and pros-sure. Step (d) is also preferably carried out under vitro-gun or similar pressurization.
In accordance with a further preferred embodiment of the invention, the process according to the invention may comprises the additional steps of:
(f) preheating the effluents if any in the presence of sodium carbonate and acetic acid before subjecting them to fermentation step (b); and (g) carrying out fermentation step (a) for a longer period of time to produce and recover a gas useful as come bustible before carrying out step (c).
Step [f) may be carried out at a temperature ranging from 30 to 45C (preferably 40C) for US to 50 minutes preferably 35 minutes. In this step, use can be made of 50 to 200 grams (preferably 80 g) of sodium carbonate and of 10 to 50 grams (preferably 14 g) of acetic acid per 10 liters of effluents or hydrolyzed residues.
As aforesaid, the invention also proposes a pro-cuss for producing a CJaSeOUS mixture useful as combustible organic effluents or hydrolyzed residues, which process comprises the steps of:
(a) preheating the effluents or hydrolyzed of residues preferably in the presence of sodium carbonate and acetic acid;
IBM subjecting the preheated effluents to ferment station in the presence of a fermentation initiating agent consisting of amylytic enzymes; and (c) continuing fermentation step (by to produce and recover the requested gas.
, ..;
I;; Step (a) of this particular process can be carried out at a temperature of 43C for about 35 minutes with about 80 g of sodium carbonate and about 14 g of acetic acid per I, 10 liters of effluents or hydrolyzed residues. Step (by is i 5 preferably carried out at a temperature of about 40~C for about 35 minutes in the presence of 40 g of fermentation initiating agent per 10 liters of effluents or hydrolyzed residues, while step (c) is carried out at a temperature of ' 40~C.
It is highly preferably that all of these steps be carried out under anaerobic pressurization (nitrogen).
, The process according to the invention and its 3- advantages will be better understood upon reading of the ; following nonrestrictive description of two specific examples given with reference to the accompanying drawings in which:
Fig. 1 is a flow-chart detailing the process ` described in example l; and Fig. 2 is a flow-chart detailing the process described in example 2.
¦ 20 EXAMPLE 1 10 liters of milk whey were fed into an autoclave and preheated therein at a temperature ranging between 37 and 40C. 40 grams of amylytic enzymes then were added to the autoclave to initiate fermentation.
the milk whey was allowed to ferment ate at a temperature of about 36C for about 35 minutes at normal pressure.
Then, 17 grams of basic acuminate acetate and 130 g of a mixture of 65~ of formaldehyde and 35~ by weight of phenol were added to the fermentation mixture. This chemical addition was carried out for about 5 minutes under normal atmosphere. After completion of the chemical addition, the autoclave was pressurized with nitrogen at a pressure of about 0.6 kg/cm2 and heated up to 120C.
, :
~3~33 .' The autoclave was hold at 120C for 55 minutes to cook the effluent mixture and achieve its fermentation into isopropyl alcohol. Of course, heating to 120C of the mixture inside the autoclave resulted in a substantially increase of the pressure. This pressure was of 1.5 kg/cm2 at the end of the cooking. In this connection, it should be noted that top temperature and pressure inside of the auto-crave are of course interdependent. Accordingly, one may compensate a decrease of temperature with an increase in I 10 pressure. Similarly, one may operate under a lower pressure i provided at the temperature be increased accordingly.
Last of all, the autoclave was opened and the is-propel alcohol produced by fermentation was distilled off.
The entire process, excluding the distillation, was conducted within 95 minutes, that is within less than ' 2 hours and gave a very good yield namely 600 g of isopro-panel per 10 liters of milk whey. In a variant of this process which variant is shown in figure 1, the ferment-lion of the step was carried out for approximatively 12Q
minutes under nitrogen pressurization, instead of being carried out for approximatively 35 minutes after the addition of enzymes. This increase in the duration of the ferment-lion step resulted in the production of a gas useful as combustible. After extraction of the gas, the fermentation mixture was subjected to chemicals addition and cooking as disclosed hereinabove, and gave substantially the same result, namely the production of a substantial quantity of isopropanol.
The process disclosed in EXAMPLE 1 was tested again, except that the milk whey effluent used as starting material fed into the autoclave, was previously preheated at 40C and mixed with 120 grams of sodium carbonate and with about 14 grams of acetic acid for about 35 to 40 minutes. During this mixing step, the milk whey effluent was kept at 40C.
3;~33 Jo Thereafter, the same amount of enzymes was added to the mixture initiate fermentation The fermentation was carried out as disclosed in EXAMPLE 1 for about 35 minutes.
After this period of time, the gas generated during the fermentation was extracted for about 35 additional minutes while keeping the effluent mixture at about 40C.
A substantial amount of a highly inflammable gas was so produced. The resulting effluent mixture was then treated as disclosed hereinabove, with chemicals addition and cooking. In spite of the fact that a substantial amount of combustible gas was already extracted in a really short period of time, a substantial amount of isopropanol was also obtained.
1 Kg. of crushed straw was washed with water at 37C for about 10 minutes and placed in a mixer/autoclave.
3 liters of water containing 40 grams of sodium carbonate was added. The autoclave was closed and heat applied.
Nitrogen gas was connected to the autoclave and sl1pplied at a pressurization of 0.5 kg/cm2 and the mixture was heated to a temperature of 120C for 55 minutes up to a pressurization of 1~5 kg/cm2. Heat was then discontinued and the autoclave opened. A first black liquid was poured off and the straw washed with water.
The treated straw was replaced in the autoclave and 40 grams of sodium acetate, 27 grams of isopropyl alcohol and 7 grams of acetic acid mixed in 3 liters of water preheated at 37C was added thereto. Heat was applied and nitrogen gas under pressure supplied to the autoclave. The temperature of the mixture was raised to about 120nC with a nitrogen pressurization over 1.5 kg/cm~ for about 55 minutes.
The autoclave was opened and a second black liquid was poured into a container to cool for reuse. The digested straw then was washed with cold water.
r ':~
~3~33 ., ..
After cooling at 40C, 40 grams of amylytic enzymes ;, were added to the autoclave to initiate fermentation and the straw was allowed to ferment ate at about 38C for about 35 minutes. 17 grams of basic acuminate acetate was added to , 5 the second black liquid previously obtained at about 40C and 'J 130 grams of a mixture of 65~ by weight of formaldehyde and 35~ by weight of phenol were added to the resulting mixture.
' The so obtained reactive was added to the straw and the autoclave was pressurized with nitrogen at a pressure 10 of about 0.5 kg/cm2 and heated up to 120C.
j The autoclave was hold at 120C for 55 minutes to Cook the effluent mixture and complete its fermentation into isopropyl alcohol. Of course, heating to 120C of the mixture inside the autoclave resulted in a substantially 15 increase of the pressure. This pressure was of about 1.5 I, kg/cm2 at the end of the cooking.
it Last of all the autoclave was opened and the is-, propel alcohol produced by fermentation was distilled off.
350 grams of isopropyl alcohol were so produced from 1 kg of straw.
. . .
10 liters of milk whey were fed into an autoclave and preheated therein at a temperature of 40C.
80 grams of amylytic enzymes then were added to 25 the autoclave to initiate fermentation. The milk whey was allowed to ferment ate at a temperature ranging from 38C
to 40~.
After this period of time, the autoclave residue was extracted and distilled off. 600 ml of methanol were thus 30 obtained.
This example proves that selection of the lower alcanol desired a final product can be obtained by appear-private selection of the amount of enzymes added to the start-in compound in the fermentation step.
,
j More particularly, the invention relates to a pro-cuss that requires less than two hours to carry out such alcohol or gas production.
It is a well known fact that the world's supply of oil as a source of energy, especially gasoline for use in internal combustion engines or in industrial furlers, has become limited and that exhaustion of the supply is inevi-table. To present restriction, it is therefore necessary to develop alternative sources of energy. More specifically, it is necessary to find new kinds of liquid fuels capable of being used either alone or as a proportionate part with gasoline for driving internal combustion engines. The raw materials to be used in the production of such alternative sources of energy must be readily available and the cost of the process for producing the new fuel in terms of energy, material and processing expenses must be such that the process is commercially feasible and the cost of the resulting product within reason.
It is also a well known fact that very large qua-lilies of organic materials are not only available but often present problems of disposal. Organic materials of all kinds, including manure, milk whey must wont, straw, peat moss, Bahamas and other agricultural residues are available in very large quantity. Some of them, such as manure, have even already been employed as starting materials fox the production of combustible gases.
The present invention proposes an industrial pro-cuss for producing a liquid fuel, mainly composes of lower alcanols, which process makes use of organic materials such L3~3;3 ., ..
/
as manure, milk whey, must, wont and the like as starting material. The invention also proposes a process that can be used for producing a combustible gaseous mixture as main or by-product.
As aforesaid, the process according to the present invention makes use of organic waste or surplus, that is of readily available raw materials, for producing lower alcanols such as methanol or isopropyl alcohol that can be used, , preferably in the ratio of one part of alcohol per two parts of gasoline, as a fuel for normal gasoline-fueled internal combustion engines, without special adjustment of the engines.
With some engine alteration, the alcohol can be used in larger proportion and in some instances even without inter-' mixing with gasoline.
The process according to the invention can be carried out in a very fast and easy manner, usually in less than two hours, and only requires an acceptable amount of energy and quantities of reagent and catalytic materials.
Contributing to the favorable economics of the process is the production of some useful by-products such as the above mentioned combustible gaseous mixtures.
The process according to the invention basically consists in subjecting to fermentation the raw organic material under specific conditions of temperature and pros-sure, using specific chemical reagents and enzymes as catalysts.
More particularly, the process according to the invention for producing lower alcanols from organic effluents ` and residues, comprises the steps of:
(a) subjecting the residues, if any, to hydrolysis;
by subjecting the effluents and/or hydxolysed residues to fermentation in the presence of a fermentation initiating agent consisting of amylytic enzymes (c) adding basic acuminate acetate and a compound selected from the group consisting of pyruvic acid, prop ionic acid and mixtures of formaldehyde with phenol or sulfonated J, phenol to the fermented effluents of step (a);
(d) heating the mixture obtained in step (c3 at a I; temperature of at least 100C under a pressurization of at least 1.5 kg/cm2 until the requested alcanols are produced;
and (e) recovering the produced alcanols by distillation.
The hydrolysis of stop (a) to which must be subjected the organic residues if such are used as starting material can be carried out with a heated solution of sodium carbonate.
The hydrolysis can be carried out in an autoclave pressurized Z to at least 1.5 kg/cm2 for about 55 minutes. If necessary, l the hydrolyzed cellulose that is extracted can be subjected to a further digestion in a heated solution containing $ aluminum isopropyl ate or isopropyl alcohol together with sodium acetate and, if desired, acetic acid. This further digestion can be carried out in an autoclave pressurized to at least 1.5 kg/cm2 for about 55 minutes.
It should be noted that such a hydrolysis is not I compulsory when the starting material is an effluent.
Fermentation step (b) can be carried out at a fermentation temperature ranging from 30 to 45C (preferably 38C), for a period ranging from 25 to 50 minutes (preferably ¦ 35 minutes). During this step, use is preferably made of 30 to 100 grams of fermentation initiating agent per 10 liters of effluents or hydrolyzed residues (preferably 40 grams).
If step (b) is carried out for a period of time longer than 50 minutes such as r for example, 110 minutes, a Jo gas useful as combustible material, is produced.
Step (c) can be carried out at a temperature ranging from 30 to 45C (preferably 40C) within a few minutes.
During this step, use is preferably made of 10 to 50 grams (preferably 17 g) of basic acetate and of 100 to 300 grams (preferably 130 grams of a mixture of formaldehyde with phenol I- or sulfonated phenol or of pyrrhic acid or of prop ionic acid per 10 liters of effluents or hydrolyzed residues. The 1' .
lo _ 3 _ `~`
.
, ~2~3;~33 /
mixture may comprise, for example, 65~ by weight of formal-Dodd and 35% by weight of phenol.
Step (d) can be carried out in an autoclave for a period of time ranging from 35 to 110 minutes (preferably ; 5 55 minutes depending on the selected temperature and pros-sure. Step (d) is also preferably carried out under vitro-gun or similar pressurization.
In accordance with a further preferred embodiment of the invention, the process according to the invention may comprises the additional steps of:
(f) preheating the effluents if any in the presence of sodium carbonate and acetic acid before subjecting them to fermentation step (b); and (g) carrying out fermentation step (a) for a longer period of time to produce and recover a gas useful as come bustible before carrying out step (c).
Step [f) may be carried out at a temperature ranging from 30 to 45C (preferably 40C) for US to 50 minutes preferably 35 minutes. In this step, use can be made of 50 to 200 grams (preferably 80 g) of sodium carbonate and of 10 to 50 grams (preferably 14 g) of acetic acid per 10 liters of effluents or hydrolyzed residues.
As aforesaid, the invention also proposes a pro-cuss for producing a CJaSeOUS mixture useful as combustible organic effluents or hydrolyzed residues, which process comprises the steps of:
(a) preheating the effluents or hydrolyzed of residues preferably in the presence of sodium carbonate and acetic acid;
IBM subjecting the preheated effluents to ferment station in the presence of a fermentation initiating agent consisting of amylytic enzymes; and (c) continuing fermentation step (by to produce and recover the requested gas.
, ..;
I;; Step (a) of this particular process can be carried out at a temperature of 43C for about 35 minutes with about 80 g of sodium carbonate and about 14 g of acetic acid per I, 10 liters of effluents or hydrolyzed residues. Step (by is i 5 preferably carried out at a temperature of about 40~C for about 35 minutes in the presence of 40 g of fermentation initiating agent per 10 liters of effluents or hydrolyzed residues, while step (c) is carried out at a temperature of ' 40~C.
It is highly preferably that all of these steps be carried out under anaerobic pressurization (nitrogen).
, The process according to the invention and its 3- advantages will be better understood upon reading of the ; following nonrestrictive description of two specific examples given with reference to the accompanying drawings in which:
Fig. 1 is a flow-chart detailing the process ` described in example l; and Fig. 2 is a flow-chart detailing the process described in example 2.
¦ 20 EXAMPLE 1 10 liters of milk whey were fed into an autoclave and preheated therein at a temperature ranging between 37 and 40C. 40 grams of amylytic enzymes then were added to the autoclave to initiate fermentation.
the milk whey was allowed to ferment ate at a temperature of about 36C for about 35 minutes at normal pressure.
Then, 17 grams of basic acuminate acetate and 130 g of a mixture of 65~ of formaldehyde and 35~ by weight of phenol were added to the fermentation mixture. This chemical addition was carried out for about 5 minutes under normal atmosphere. After completion of the chemical addition, the autoclave was pressurized with nitrogen at a pressure of about 0.6 kg/cm2 and heated up to 120C.
, :
~3~33 .' The autoclave was hold at 120C for 55 minutes to cook the effluent mixture and achieve its fermentation into isopropyl alcohol. Of course, heating to 120C of the mixture inside the autoclave resulted in a substantially increase of the pressure. This pressure was of 1.5 kg/cm2 at the end of the cooking. In this connection, it should be noted that top temperature and pressure inside of the auto-crave are of course interdependent. Accordingly, one may compensate a decrease of temperature with an increase in I 10 pressure. Similarly, one may operate under a lower pressure i provided at the temperature be increased accordingly.
Last of all, the autoclave was opened and the is-propel alcohol produced by fermentation was distilled off.
The entire process, excluding the distillation, was conducted within 95 minutes, that is within less than ' 2 hours and gave a very good yield namely 600 g of isopro-panel per 10 liters of milk whey. In a variant of this process which variant is shown in figure 1, the ferment-lion of the step was carried out for approximatively 12Q
minutes under nitrogen pressurization, instead of being carried out for approximatively 35 minutes after the addition of enzymes. This increase in the duration of the ferment-lion step resulted in the production of a gas useful as combustible. After extraction of the gas, the fermentation mixture was subjected to chemicals addition and cooking as disclosed hereinabove, and gave substantially the same result, namely the production of a substantial quantity of isopropanol.
The process disclosed in EXAMPLE 1 was tested again, except that the milk whey effluent used as starting material fed into the autoclave, was previously preheated at 40C and mixed with 120 grams of sodium carbonate and with about 14 grams of acetic acid for about 35 to 40 minutes. During this mixing step, the milk whey effluent was kept at 40C.
3;~33 Jo Thereafter, the same amount of enzymes was added to the mixture initiate fermentation The fermentation was carried out as disclosed in EXAMPLE 1 for about 35 minutes.
After this period of time, the gas generated during the fermentation was extracted for about 35 additional minutes while keeping the effluent mixture at about 40C.
A substantial amount of a highly inflammable gas was so produced. The resulting effluent mixture was then treated as disclosed hereinabove, with chemicals addition and cooking. In spite of the fact that a substantial amount of combustible gas was already extracted in a really short period of time, a substantial amount of isopropanol was also obtained.
1 Kg. of crushed straw was washed with water at 37C for about 10 minutes and placed in a mixer/autoclave.
3 liters of water containing 40 grams of sodium carbonate was added. The autoclave was closed and heat applied.
Nitrogen gas was connected to the autoclave and sl1pplied at a pressurization of 0.5 kg/cm2 and the mixture was heated to a temperature of 120C for 55 minutes up to a pressurization of 1~5 kg/cm2. Heat was then discontinued and the autoclave opened. A first black liquid was poured off and the straw washed with water.
The treated straw was replaced in the autoclave and 40 grams of sodium acetate, 27 grams of isopropyl alcohol and 7 grams of acetic acid mixed in 3 liters of water preheated at 37C was added thereto. Heat was applied and nitrogen gas under pressure supplied to the autoclave. The temperature of the mixture was raised to about 120nC with a nitrogen pressurization over 1.5 kg/cm~ for about 55 minutes.
The autoclave was opened and a second black liquid was poured into a container to cool for reuse. The digested straw then was washed with cold water.
r ':~
~3~33 ., ..
After cooling at 40C, 40 grams of amylytic enzymes ;, were added to the autoclave to initiate fermentation and the straw was allowed to ferment ate at about 38C for about 35 minutes. 17 grams of basic acuminate acetate was added to , 5 the second black liquid previously obtained at about 40C and 'J 130 grams of a mixture of 65~ by weight of formaldehyde and 35~ by weight of phenol were added to the resulting mixture.
' The so obtained reactive was added to the straw and the autoclave was pressurized with nitrogen at a pressure 10 of about 0.5 kg/cm2 and heated up to 120C.
j The autoclave was hold at 120C for 55 minutes to Cook the effluent mixture and complete its fermentation into isopropyl alcohol. Of course, heating to 120C of the mixture inside the autoclave resulted in a substantially 15 increase of the pressure. This pressure was of about 1.5 I, kg/cm2 at the end of the cooking.
it Last of all the autoclave was opened and the is-, propel alcohol produced by fermentation was distilled off.
350 grams of isopropyl alcohol were so produced from 1 kg of straw.
. . .
10 liters of milk whey were fed into an autoclave and preheated therein at a temperature of 40C.
80 grams of amylytic enzymes then were added to 25 the autoclave to initiate fermentation. The milk whey was allowed to ferment ate at a temperature ranging from 38C
to 40~.
After this period of time, the autoclave residue was extracted and distilled off. 600 ml of methanol were thus 30 obtained.
This example proves that selection of the lower alcanol desired a final product can be obtained by appear-private selection of the amount of enzymes added to the start-in compound in the fermentation step.
,
Claims (17)
1. A process for producing lower alcanols from organic residues and effluents, comprising the steps of:
(a) subjecting the residues if any, to hydrolysis;
(b) subjecting the effluents and/or hydrolyzed residues to fermentation in the presence of a fermentation initiating agent consisting of amylytic enzymes;
(c) adding basic aluminate acetate and a compound selected from the group consisting pyruvic acid, propionic acid and mixtures of formaldehyde with phenol or sulfonated phenol to the fermented effluents of step (a);
(d) heating the mixture obtained in step (b) at a temperature ranging between 120°C and 160°C under a pressuriza-tion of at least 1.5 kg/cm2 until the requested alcanols are produced; and (e) recovering the produced alcanols by distillation.
(a) subjecting the residues if any, to hydrolysis;
(b) subjecting the effluents and/or hydrolyzed residues to fermentation in the presence of a fermentation initiating agent consisting of amylytic enzymes;
(c) adding basic aluminate acetate and a compound selected from the group consisting pyruvic acid, propionic acid and mixtures of formaldehyde with phenol or sulfonated phenol to the fermented effluents of step (a);
(d) heating the mixture obtained in step (b) at a temperature ranging between 120°C and 160°C under a pressuriza-tion of at least 1.5 kg/cm2 until the requested alcanols are produced; and (e) recovering the produced alcanols by distillation.
2. The process of claim 1, wherein step (a) is carried out in an autoclave with a heated solution of sodium carbonate and subsequently with a solution of aluminum isopropylate or isopropyl alcohol with sodium acetate and acetic acid.
3. The process of claim 1, wherein step (b) is carried out at a temperature of about 40°C for about 35 minutes.
4. The process of claim 2, wherein step (b) is carried out in the presence of about 40 g of fermentation initiating agent per 10 liters of effluents.
5. The process of claim 1, wherein step (c) is carried out at a temperature of about 40°C for about 5 minutes.
6. The process of claim 5, wherein step (c) is carried out with about 17 g of basic acetate and about 130 g of a mixture of 65% by weight formaldehyde with 35% by weight phenol per 10 liters of effluents.
7. The process of claim 1, wherein step (d) is carried out for about 55 minutes.
8. The process of claim 7, wherein step (d) is carried out under anaerobic pressurization.
9. The process of claim 2, wherein:
- step (b) is carried out at a temperature of about 40°C for about 35 minutes in the presence of 40 g of fermentation initiating agent per 10 liters of effluents;
- step (c) is carried out at a temperature of about 40°C for about 5 minutes with 17 g of a basic acetate and 130 g of a mixture of 65% by weight formaldehyde with 35% by weight phenol per 10 liters of effluent; and - step (d) is carried out for about 55 minutes under anaerobic pressurization if isopropyl alcohol is used in the solution of step (a).
- step (b) is carried out at a temperature of about 40°C for about 35 minutes in the presence of 40 g of fermentation initiating agent per 10 liters of effluents;
- step (c) is carried out at a temperature of about 40°C for about 5 minutes with 17 g of a basic acetate and 130 g of a mixture of 65% by weight formaldehyde with 35% by weight phenol per 10 liters of effluent; and - step (d) is carried out for about 55 minutes under anaerobic pressurization if isopropyl alcohol is used in the solution of step (a).
10. The process of claim 1, wherein step (b) is carried out at a temperature of about 40°C for about 110 minutes to produce a combustible gas as by-product.
11. The process of claim 1, comprising the additional steps of:
(f) preheating the effluents if any in the presence of sodium carbonate and acetic acid before subjecting them to fermentation step (b); and (g) continuing fermentation step (b) to produce and recover a combustible gas before carrying out step (c).
(f) preheating the effluents if any in the presence of sodium carbonate and acetic acid before subjecting them to fermentation step (b); and (g) continuing fermentation step (b) to produce and recover a combustible gas before carrying out step (c).
12. The process of claim 11, wherein step (f) is carried out at a temperature of 40°C for about 35 minutes.
13. The process of claim 10, wherein step (f) is carried out with about 80 g of sodium carbonate and about 14 g of acetic acid per 10 liters of effluents.
14. The process of claim 13, wherein all the steps are carried out under anaerobic pressurization.
15. A process for producing a combustible gas from organic effluents or hydrolyzed organic residues, comprising the steps of:
(f) preheating the effluents if any in the presence of sodium carbonate and acetic acid;
(b) subjecting the preheated effluents or hydrolyzed residues to fermentation in the presence of a fermentation initiating agent consisting of amylytic enzymes; and (h) continuing fermentation step (b) to produce and recover the requested gas.
(f) preheating the effluents if any in the presence of sodium carbonate and acetic acid;
(b) subjecting the preheated effluents or hydrolyzed residues to fermentation in the presence of a fermentation initiating agent consisting of amylytic enzymes; and (h) continuing fermentation step (b) to produce and recover the requested gas.
16. The process of claim 15, wherein:
- step (f) is carried out at a temperature of 40°C for about 35 minutes with about 80 g of sodium carbonate and about 14 g of acetic acid per 10 liters of effluents;
- step (b) is carried out at a temperature of about 40°C for about 35 minutes in the presence of 40 g of fermentation initiating agent per 10 liters of effluents;
- step (h) is carried out at a temperature of 40°C.
- step (f) is carried out at a temperature of 40°C for about 35 minutes with about 80 g of sodium carbonate and about 14 g of acetic acid per 10 liters of effluents;
- step (b) is carried out at a temperature of about 40°C for about 35 minutes in the presence of 40 g of fermentation initiating agent per 10 liters of effluents;
- step (h) is carried out at a temperature of 40°C.
17. The process of claim 16, wherein steps (f), (g) and (h) are carried out under anaerobic pressurization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000457164A CA1213233A (en) | 1984-06-21 | 1984-06-21 | Process for producing isopropyl alcohol from cellulosic substrates |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000457164A CA1213233A (en) | 1984-06-21 | 1984-06-21 | Process for producing isopropyl alcohol from cellulosic substrates |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1213233A true CA1213233A (en) | 1986-10-28 |
Family
ID=4128146
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000457164A Expired CA1213233A (en) | 1984-06-21 | 1984-06-21 | Process for producing isopropyl alcohol from cellulosic substrates |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1213233A (en) |
-
1984
- 1984-06-21 CA CA000457164A patent/CA1213233A/en not_active Expired
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