CN100567475C - From waste gas, prepare acetate with biological method - Google Patents

Abstract

Disclosed and be used in the future the method and apparatus that industrial processes waste gas such as refining of petroleum, carbon black, coke, system ammonia and methanol production freely change into useful product.This method comprises introduces a biological reactor with waste gas, and here they are fermented into various product by the anaerobic bacterium in the bio-reactor, as organic acids, alcohols, H ₂, SCP and organic acid salt.These organic final products are recovered, separation and purifying.

Description

From waste gas, prepare acetate with biological method

Patent application of the present invention is that international application no is PCT/US96/11146, international filing date is that the PCT international application on July 1st, 1996 enters the application of China national after the stage, application number is 96180363.0, and denomination of invention is divided an application for the application for a patent for invention of " preparing acetate with biological method from waste gas ".

The present invention relates to be used for to prepare product, raw material, intermediate etc. from the exhaust flow of some industrial processes (as biological method, technology, microorganism and the device of organic acid, single cell protein (SCP), hydrogen, alcohols and organic acid salt, relates more specifically to utilize under oxygen free condition successive gas phase fermenting substrate to reach the method for this transformation.

The conventional program that is used to prepare organic acid, alcohols, hydrogen and organic acid salt is the raw material of chemosynthesis petroleum derivation.The rapid raising of oil cost makes people to utilizing callable or the depleted material prepares these valuable products as raw material by fermentation process and produced great interest.Single cell protein is to produce as the by product that ferments, as animal-feed.

A large amount of atmospheric polluting materials that produce in the traditional industry and greenhouse gases have also caused people's attention gradually.Environmental protection institution predicts that recently discharge above six hundred ten thousand ton carbon monoxide with near four hundred ten thousand ton hydrogen by industrial mixture every year.The major portion of these carbon monoxide and hydrogen is that carbon black factory and coke production factory produce, and guestimate is about 2,600,000 tons of CO and 500,000 tons and H ₂The sulfate pulping (286 pounds of paper pulp per ton) of ammonia industry (1991 is 125144 tons of CO), refining of petroleum (per 1000 barrels 8 tons), steel mill's (152 pounds of one ton of steel of every production) and timber is made in the source that produces a large amount of carbon monoxide or hydrogen in addition.In 1991, hexanodioic acid industry produced 40773 tons of carbon monoxide, and these carbon monoxide are burned to be utilized fuel value or burnt in vain.Under many situations, these gases are discharged in the atmosphere, and environment is caused heavy pollution load.

Usually the process industry product is to discharge waste gas under low pressure and temperature.Modern technologies can not be utilized the gas of these dilutions under this condition.Utilize prior art from these exhaust flows, to separate and reclaim hydrogen and carbon monoxide is arm and a leg and unpractiaca.

In view of the front said, need a kind of practical methods again with low cost, microorganism and device in order to producing product, raw material, intermediate etc. with above-mentioned waste gas, for example organic acid, alcohols, hydrogen and organic acid salt, and without the raw material of chemosynthesis petroleum derivation.

The summary of invention

According to the present invention, with the useless carbon monoxide in the industrial processes, hydrogen and/or carbon dioxide production product, raw material, intermediate etc., for example organic acid, alcohols, hydrogen, single cell protein and/or organic acid salt, thus reduce environmental pollution, and save simultaneously can and chemical feedstocks.

According to the cited technology of the present invention, the component of required diluted gas mixture is introduced in the bio-reactor that contains a strain or the many strains anaerobic bacterium strain through cultivating, the compound that these bacterial strains can utilize waste gas component production to need by direct way.The recovery method of the compound that utilization is suitable for producing, the liquid phase from one or more containers reclaims this compound.The example of recovery method comprises extracting, distillation or it is used in combination, or other effective recovery method.Reclaim bacterium and recirculation from liquid phase, avoiding its toxicity and to keep high cell concentration, thereby make speed of response reach maximum.If desired, the separation of cell can be finished with centrifugal, membrane ultrafiltration or other technology.

Main purpose of the present invention provides from carbon monoxide, hydrogen and/or carbon dioxide production product, intermediate, raw material etc., for example method of organic acid, hydrogen, single cell protein, alcohols and/or organic acid salt and/or microorganism.

Another object of the present invention provides exhaust flow production such as organic acid from the industrial processes such as refining of petroleum, carbon black, coke, system ammonia and methanol production, alcohols, hydrogen, single cell protein and or method, microorganism and the device of the product of salt.

A further object of the invention provides the exhaust flow of the same composition of finding and produces acetate and/or alcoholic acid method from make with carbon black.

Of the present invention another more specifically purpose provide and comprise that continuous gas fermenting substrate under anaerobic changes into method, microorganism and the device of useful product as the organic acid that comprises acetate, alcohols, hydrogen, single cell protein bletilla organic acid salt with the exhaust flow of finishing some industrial processes.

Other purpose of the present invention and further range of application will become obvious in conjunction with the accompanying drawings by following detailed, represent identical part with identical label in the accompanying drawing.

Fig. 1 is the synoptic diagram by waste gas production acetic acid process.

Fig. 2 is a synoptic diagram of being produced CMA technology by waste gas.

Fig. 3 is a synoptic diagram of being produced ethanol by waste gas.

Fig. 4 is according to one embodiment of the present of invention graphic representation one system of continuously fermenting.

Fig. 5 is the diagram of cell concn (OD) and timing relationship.

Fig. 6 is the diagram of acetate (HAC) and timing relationship.

Term used herein " waste gas " or " waste gas streams " refer to carbon monoxide and hydrogen, other element and compound have wherein been mixed, comprise carbon dioxide, nitrogen and methane, they exist with gaseous form, usually directly or by burning are released or are emptied in the atmosphere. Common release is to occur under the stack temperature of standard and pressure. Therefore, method of the present invention is applicable to these atmosphere pollutions are transformed into useful product, such as organic acids, alcohols and organic acid salt. These products include, but is not limited to acetic acid, propionic acid and butyric acid; Methyl alcohol, ethanol, propyl alcohol and n-butanol; And salt, such as calcium-magnesium acetic (CMA) and potassium acetate (KA).

Known can be the Acetobacterium kivui that the anaerobic bacteria of alcohols, acids and acid salt comprises acetobacter with carbon monoxide and water or hydrogen and carbon dioxide conversion, C.ljungdahlii PETC and the Peptostreptococcus productus of the acetic acid butyric acid kind of the Butyribacterium methylotrophicum of A.woodii, acetic acid clostridium, Butyribacterium, Clostridium, arboxylic acid kind, C.kluyveri, thermophilic acetic acid kind, thermophilic fiber kind, C.thermohydrosulfuricum, thermophilic solution sugar kind, Eubacterium limosum, Clostridium. Knownly can comprise from the anaerobic bacteria of carbon monoxide and aquatic product hydrogen rhodospirillum rubrum and the red utmost point hair of colloid bacillus.

More precisely, produce acetate such as Acetogenium kivui, Peptostreptococcus productus, Acetobacterium woodii, Clostridium thermoaceticum and this bacterioid of Eubacterium limosus by following reaction:

4CO+2H ₂O→CH ₃COOH+2CO ₂DG=-39 kilocalorie/reaction (1)

Known many anaerobic bacterias also can be by H₂And CO₂Produce acetic acid. These bacterial isolates comprise A. Kivui, P.productus and Acetobacterium kind, and they pass through anaerobism ground hydrogen oxide and CO according to following reaction equation₂Utilize the homotype acetic fermentation:

4H ₂+2CO ₂→CH ₃COOH+2H ₂DG=-25 kilojoule that/reaction (2)

Acetobacterium woodii and Acetoanaerobium noterae according to top reaction by H₂And CO₂Produce acetate, but except acetate, A.noterae also produces some propionate and butyrate. Another kind of chemolithotrophic bacteria, Clostridium aceticum can utilize the glycine decarboxylase approach from CO₂Produce acetate.

Some bacterium is such as A.kivui, P.productus and A.Woodii, from CO and H₂O or H₂And CO₂Produce acetate. P.productus provides express conversion rate and demonstrates height endurability to CO; Yet this bacterium shows follows reaction equation (1) and is better than reaction equation (2).

Except the bacterium that these are enumerated, also have the two strain bacterium of Clostridium to be split into, they can be from CO and H ₂O or H ₂And CO ₂Produce acetate or ethanol.Wherein a strain is Clostridium ljungdahlii ERI2, and it is shaft-like, and Gram-positive is non-thermophilic anerobe, and it provides high acetate productive rate and reacts under low pH condition, and this can improve the rate of recovery of product greatly.C.ljungdahlii ERI2 can carry out vigorous glucose and produce acetic acid fermentation.It also forms gemma once in a while and mainly carries out hexose or H ₂: CO ₂The product acetic acid fermentation.It is by the periphery flagellar movement.This new C.ljungdahlii bacterial strain is named and is ERI2, is separated to from open water supply, and send the American Type Culture Collection that is stored in Maryland State Rockwell (ATCC), catalog number: 55380 on December 8th, 1992.

Can use above-named when preparing product of the present invention " hybrid bacterial strain ".So-called hybrid bacterial strain is meant the mixed culture of two strains or many strains anaerobic bacterium.This hybrid bacterial strain can produce organic acid (as acetate and so on) or their salt, alcohols, hydrogen, SCP etc. when being used for described technology.

In research process of the present invention, isolate some new anaerobism bacterial strains, they can carry out high efficiency conversion.In addition, changing fermentation condition can make some bacterial strain produce ethanol rather than acetate.According to used concrete bacterial strain, when forming product by waste gas, must consider the following changing factor, comprise that nutritive ingredient and concentration, substratum, pressure, temperature, gas flow rate, flow rate of liquid, pH value in reaction, stirring velocity (if using the agitator tank reactor that continuously ferments), inoculation level, maximum substrate (gas of input) concentration are to avoid restraining effect and maximum production concentration to avoid restraining effect.

According to one embodiment of the present of invention and shown in Figure 1, the first step of conversion process is to prepare to supply with the substratum (10) of anerobe.The composition of nutritional medium will change according to type and the desirable product of used anerobe.Nutrient constantly is transfused to bio-reactor or fermentor tank (12), it is made up of the tower of one or more containers and/or a type, comprises continuously stirring jar reactor (CSTR), immobilized cell reactor (ICR), trickle bed (TBR), bubble cap column, airlift fermentor or other suitable fermentation reactor.The culture that is used for the single of gas conversion process or blended anaerobic species is placed in the bio-reactor (12).In CSTR, TBR, bubble cap column and air lift type fermentation container, these bacteriums are scattered in the liquid phase of reactor and live, but when using ICR, bacterial adhesion is in the medium of inner filling.This filling medium must provide maximum surface area, high mass transfer velocity, low pressure drop, uniformly gas and liquid distribute and must make obstruction, to send out dirty smelly, do nest and the tube wall channel is reduced to minimum level.The example of such dielectric material has ceramic arc saddle packing, Raschig tubes or other high performance filled thing.

Waste gas (14) is introduced bio-reactor (12) continuously.The retention time of gas in bio-reactor (12) will make the efficient of this technology reach maximum value.Discharge then and contain the unreacted substrate gas of inert (16).Effusive liquid (18) is by whizzer, hollow film or other filtration unit (20), to isolate the microorganism that is contained in wherein.These microorganisms (22) are returned bio-reactor (12) and produce the required high cell concn (cell recycling) of faster reaction speed to keep.

Next step of this technology is the product of producing from the biological process of filtrate or centrifugate (24) separation needs.Among the embodiment shown in Figure 1, filtrate or centrifugate (24) make it to contact with solvent (28) by extraction cell (26) therein.Solvent (28) should have required final product high partition ratio, high recovery factor, to people's hypotoxicity, to the hypotoxicity of bacterium, with water unmixability, suitable high boiling point and do not form emulsion with the component of bio-reactor.Distribution between solvent and the water will determine thermodynamics feasibility and the amount of taking out the required solvent of final product.Typical solvent comprises secondary amine and tertiary amines, tributyl phosphate, ethyl acetate, the trioctyl-phosphine oxide that is dissolved in the appropriate solvent and is dissolved in related compound, long-chain alcohols, hexane, hexanaphthene, chloroform and zellon in the suitable cosolvent.

Nutrient in the water (30) and raw material return bio-reactor (12) and solvent/acid/aqueous solution (32) by distillation column (34), and being heated to therein is enough to temperature that solvent (28) is separated from water and acid (36).Solvent (28) comes out to be cooled to the temperature that is suitable for extracting most by cooling room (38) from distillation column (34), turns back to extraction cell (26) then for utilizing again.The acid and the aqueous solution (36) are by last distillation column (40), and required here final product (42) and water sepn also are removed.Water (44) is recycled to support to divide and prepares.

Fig. 2 represents to produce from waste gas (48) technology of road deicing agent calcium-magnesium acetic (CMA) (46).This technology and Fig. 1 to pass through solvent-extracted acetic acid process identical.Promptly use identical bacterium, nutrient and processing condition to continuously ferment, comprise reaction vessel.Equally, in this technology, adopt hollow cortina, centrifugal or other filtration units with cell recirculation identically.Adopt at last and in extraction cell, extract acetate, subsequently with the technology of anacidity substratum recirculation.

After the extraction, the technology of producing CMA is different from the acetic acid production technology of Fig. 1 greatly.The solvent (50) and the less water that contain acetate in CMA technology are admitted to reaction vessel (52) production CMA.The water content of solvent streams depends on the used solvent of extraction acetate.Moreover, can use secondary amine and tertiary amines, tributyl phosphate, ethyl acetate, the trioctyl-phosphine oxide in being dissolved in suitable cosolvent and be dissolved in solvent related compound, long-chain alcohols, hexane, hexanaphthene, chloroform and the zellon in the suitable cosolvent, the effect difference.Producing the most suitable reaction vessel (52) of CMA is continuously stirring jar reactor (CSTR), though also can use other reactor.Dolomitic lime soluble in water and magnesian mixture are added in the solvent that contains acetate and water.The reaction of CMA has taken place to produce, and reaches capacity in the aqueous solution or is lower than saturated level.

Then CMA, water and solvent (56) are sent into sedimentation device (58) to divide dried up and solvent phase.Solvent phase (60) returns extraction cell for recirculation.CMA/ water (62) is sent to drying/sedimentation (64) to produce settled CMA product.

Replace dolomitic lime can produce another kind of product potassium acetate (KA) with Ke Xingjia (or potassium oxide).Because KA produces with the form of 50% aqueous solution, therefore do not need drying and sedimentation.

Fig. 3 represents to produce alcoholic acid technology from waste gas.As Fig. 1, waste gas (66) and nutrient (68) are transfused to the reactor (70) that contains microorganisms cultures.Reactor can be any type of top Fig. 1 narration.The bacterium that alcohol production technology is used must can produce ethanol rather than acetate/acetate.Generally need low fermentation pH4.0-5.5, limit nutrition simultaneously.Above-namedly can be used to this alcohol production technology on the bacterium of low pH level reaction.

Waste gas is fed into to contain can produce alcoholic acid bacterial cultures and essential nutraceutical reactor.Produce product ethanol in the mode among similar Fig. 1.Can utilize the recirculation (72) of cell to improve cell concn in the reactor, but not need this operation for this technology is moved.The filtrate that contains Diluted Alcohol in the substratum (74) from the cell recirculation unit is sent to distillation (76), at this branch dried up (78) and ethanol (80).95% ethanol ejects from distillation column, and water (exhausted substratum) comes out at the bottom of post.The exhausted substratum turns back to reactor as the recirculation of water.95% ethanol is sent to molecular sieve system (82) and produces dehydrated alcohol (84).

Can pass through the valuable organic acid of gaseous substrate fermentative production, alcohols or organic acid salt now according to the present invention like this, not only reduce valuable chemical feedstocks consumption, and remove deleterious atmospheric polluting material from many industrial gaseous waste streams.In the past make the technology of these chemical based on sugar-fermenting with biological method.

It is desirable in the above-mentioned technology carry out this technology being higher than under the normal atmosphere.Be preferably under height to 30 an atmospheric pressure, be more preferably under height to 20 normal atmosphere, preferably under height to 15 normal atmosphere, carry out.

The specific embodiment that provides below just is used for explanation rather than limitation of the present invention.Except as otherwise noted, used umber and percentage ratio is all by volume in this specification sheets and claims.

Embodiment 1 produces acetate by carbon black waste gas

Present embodiment relates to the method that is used for the waste gas composite that carbon black is produced the waste gas that process furnace discharges is changed into acetate.Described waste gas consist of about 13% carbon monoxide, 14% hydrogen and 5% carbonic acid gas, major part is a nitrogen in remaining 68%, also has a small amount of oxygen and sulphur compound.To be coal gas or oil formed the result of decolorizing carbon by air partial oxidation in shortage in the generation of waste gas, and every pound of elemental carbon produces about 1.2 pounds of carbon monoxide.These waste gas cause serious atmosphere polluting problem, also are the valuable chemical feedstocks resources that is not recovered at present.

When this technology of research, studied two approach of producing acetate from carbon black waste gas.Direct way is respectively with CO and H according to equation (1) and (2) ₂O or H ₂And CO ₂Directly change into acetate.Approach is with CO and H by the water gas shift reaction indirectly ₂O changes into H ₂And CO ₂, subsequently from H ₂And CO ₂Produce acetate.Find that this indirect approach is that the lower technology of efficient is used.

Proof acetate produces bacterium and is summarized in the table 1.Directly produce this bacterioid of acetate from CO, A.kivui and new isolated bacterial strain C.ljungdahlii ERI2 are for CO and H ₂Utilization all show much higher speed.Further experiment is carried out with this two strains anaerobic bacterium.

Utilize carbon monoxide and hydrogen that bacterium is had tangible advantage simultaneously.The atmospheric polluting material that this can utilize waste gas most effectively and remove maximum.

Laboratory scale is operated above-mentioned production acetic acid process

As shown in Figure 4,, a laboratory scale continuous conversion system has been described, has comprised BioFlo IIC fermentor tank (150) (available from the New BrunswickScientific Co. of New Jersey Edison, Inc.) according to one embodiment of the present of invention.Stirring motor, pH controller, foam controller, thermostatted, dissolved oxygen probe, nutriment pump and 2.5 liters of culture vessels are housed in the fermentor tank (150).Reaction volume can change (1.5-2.0 liter).Other variable operating parameters comprises the substratum speed (dilution rate) of feeding, and gas flow rate (gas retention time) stirs (rpm).Emit or expellant gas is discharged through aqueous vapor valve and thief hole by the condenser that is fixed on the vapor hood by fermentor tank (150).

Fermented liquid (152) is by hollow fibre unit (154) recirculation of peristaltic pump (available from Cole Parmer company) by cross-stream.Recirculation rate is about the 80-100 ml/min.Hollow fibre unit (154) has following properties: surface-area is 0.35 square feet, and the aperture is 0.2 micron, and the diameter in chamber is 1 millimeter.Filtrate (156) is pumped to storage vessel (158) (raw material storage).Culturing cell returns fermentor tank along pipeline (155).

The adverse current acetic acid extraction system that comprises two segmentation mixing tanks and subsider comprises: first and second mixing tank (160) and (162) and first and second subsider (164) and (166).Filtrate (168) from storage vessel (158) is pumped to mixing tank (160) by flow speed controller (170).Solvent (172) passes through flow speed controller (176) pump to mixing tank (162) from solvent storage containers (174).Stirring mechanism is housed for two mixing tanks (160) and (162) so that water and solvent phase reach good mixing.Two-phase mixture from mixing tank (160) and (162) enters subsider (164) and (166) respectively.In subsider, finish and be separated.Water (178) from subsider (164) is pumped to mixing tank (162), solvent phase (180) from subsider (166) is pumped to separator (182), water (184) from subsider (166) is pumped to raffinate storage tank (186), is pumped to mixing tank (160) from the solvent phase (188) of subsider (166).Raffinate is recycled to CSTR (50) along pipeline (190).This recirculation conduit (190) is located partly to be discharged to remove the factor of disinthibiting in (192).

The solvent (180) that contains acetate is pumped to matrass (194) by preheater (196).Matrass (194) is equipped with two thermopairs (196) and (198) with the temperature in monitoring and the control liquid and gas.Determine that heating distillatory temperature is so that acetate reaches maximum evaporation.Acetic acid steam in condenser (100) condensation and be collected in the bottle (102) in.The solvent (104) of having removed acetate is pumped to solvent feed tank (174) by cooling spiral (106).

The laboratory scale operating gear of the described technology shown in Fig. 4 under lab assembles, and purpose is the productive rate of determining under the optimum condition.Raise to the nutritional blend of bacterium as follows:

1.80.0 milliliter salt, it consists of

KH ₂PO ₄3.00 grams per liter

K ₂HPO ₄3.00 grams per liter

(NH ₄) ₂SO ₄6.00 grams per liter

NaCl 6.00 grams per liters

MgSO ₄.2H ₂O 1.25 grams per liters

2.1.0 gram yeast extract

3.1.0 gram trypticase

4.3.0 milliliter PFN (Pfenning) trace-metal solution

FeCl ₂.4H ₂1500 milligrams of O

ZnSO ₄.7H ₂100 milligrams of O

MnCl ₂.4H ₂30 milligrams of O

H ₃BO ₃300 milligrams

CoCl ₂.6H ₂200 milligrams of O

CuCl ₂.H ₂10 milligrams of O

NiCl ₂.6H ₂20 milligrams of O

NaMoO ₄.2H ₂30 milligrams of O

Na ₂SeO ₃10 milligrams

1000 milliliters of distilled water

5.10.0 milliliter vitamins B

10 milligrams of pyridoxal .HCl

50 milligrams in riboflavin

50 milligrams of VitB1 .HCl

50 milligrams in nicotinic acid

50 milligrams of Ca-D-pantothenates

60 milligrams of Thioctic Acids

50 milligrams of Para-Aminobenzoics

20 milligrams in folic acid

20 milligrams of vitamin Hs

50 milligrams of cyanocobalamins

1000 milliliters of distilled water

6.0.5 gram halfcystine .HCl

7.0.06 gram CaCl ₂.2H ₂O

8.2.0 gram NaHCO ₃

9.1.0 milliliter resazurin (0.01%)

10.920.0 ml distilled water

When using A.Kivui, the pH regulator to 6.6 of nutrient solution, and when using new bacterial strain C.ljungdahlii ERI2, pH regulator to 4.9.It is very favourable can operating in the acetate recovery under low pH condition.Use 20%CO then ₂And 80%N ₂Mixed gas sprayed solution 20 minutes shifts under the anaerobic situation and autoclaving 15 minutes then.

A large amount of experiments have all been carried out with continuous-stirring reactor (CSTR) and immobilized cell reactor (ICR).The gained result is illustrated in the data of back.

Carry out the CSTR experiment with bacterial isolates A.kivui and C.ljungdahlii ERI2

Laboratory scale system with CSTR and anaerobic bacterium, C.ljungdahlii ERI2 and A.kivui operation comprises hollow fibre film unit and extraction and and the distillation column that New Brunswick Scientific Bioflo IIc fermentation container, a recirculation cell are used.Nutritional blend is fed into bio-reactor with the speed of 3.2 cubic centimetres of per minutes.The volume of reactor is 2.5 liters, wherein keeps 1.5 liters constant fluid level.With various friction-motion speed stirred liq, speed can reach per minute 1000 changes, and gas is with the about 500 cubic centimetres speed input of per minute.Best gas retention time is in three minutes scopes.Being fed into the picked-up of bacterium to it of gas changes, and picked-up then is the function of cell density.

Liquid from bio-reactor passes through hollow cortina with the speed of 55 to 70 milliliters of per minutes.Speed with 1.5 milliliters of per minutes is collected the filtrate of passing through hollow cortina.Analyze this filtrate and show, the acetate/acetate concentration in this stage surpasses every liter 20 gram.Use C.ljungdahlii ERI2 to operate under the pH4.9 condition, 42% product is the form of acid.The acid productive rate only is 1.4% during with A.kivui.The result of the different experiments of making of these two kinds of bacteriums comprises that transformation efficiency and productive rate all are summarized in table 2 and 3.

The ICR that makes of bacterial strain C.ljungdahlii ERI2 tests

Immobilized cell reactor (ICR) comprises 2 inches external diameters and 24 inches high Glass tubings, wraps with sustenticular cell with as the Enkamat7020 of mounting medium with fabric, also is used to test acetic acid production technology.When producing the anerobe of acetate, is that 100% carbon monoxide and 79% hydrogen have been transformed under 20 minutes the condition with C.ljungdahlii ERI2 in the gas retention time.Acetic acid concentration is about every liter 6.0 gram in the liquid that takes out.The ICR result of study is summarized in the table 4.

ICR has certain magnetism on technical scale, because the energy consumption cost of operant response device has significantly reduced.Suitably select lapping, solution phase and pressure, may make the productive rate of productive rate near CSTR.

The recovery of acetate

Tested with various solvent and reclaimed acetate from filtrate, the result is summarized in the table 5.Identify the existing high partition ratio of tributyl phosphate, high boiling point is arranged again.Solvent and filtrate from cell separator are mixed in two-section extraction technology.Not so can use a kind of column extractor.Filtrate is introduced in one 3 litre flask, here and the solvent that enters mixed.Carry out finely with a solvent to the ratio extraction of a filtrate, obtained high-recovery.Make liquid from the merging of mixing tank by 4 liters of settling pockets, here solvent/acetate mixture is separated from water and nutritive ingredient as low density.The retention time of using in subsider is approximately 15 minutes.Low density is extracted out and is sent to matrass mutually.Here it contacts with solvent again by second mixing tank from the raffinate of first subsider, moves on to second settling pocket then.Can extract acetate more completely like this; When using tributyl phosphate, the rate of recovery is elevated to more than 96% from 82%.Come since then that the solvent/acetate mixture of settling pocket turns back to first mixing tank, and water and organic raffinate are sent back to bio-reactor.

The distillation unit is 5 litre flasks of a band boiling cover.Can use the common distillation column of taking back stream with complete recovered acid.Because the boiling point height of tributyl phosphate, a step can reach recovery almost completely.Heated solvent/acetate mixture to 120 ℃, and in the overhead product of the top of condensation spiral tube, collect acetate.In this system, distillation efficiency reaches 70% in step.

Also tried out solvent mixture, the partition ratio of mixed solvent is summarized in the table 6.

Embodiment 2

Reclaim acetate from carbon black waste gas

Under high pressure

This system of operation can further improve the mass transfer in the cell response under the rising pressure condition.Carried out simple batch of experiment to test the kinetics of this system.Find that speed of response increases the pressure ratio that is in line, and correspondingly reduced effective retention time.High pressure down another advantage of operation is that reaction volume also can linear fashion reduce, promptly reactor volume required under 10 normal atmosphere be under 1 normal atmosphere reactor volume 1/10th.Fig. 5 and 6 expression cell densities and acetic acid concentration increase with pressurize respectively.This acetic acid concentration far surpasses typical case's batch concentration of following batch of reactor of normal pressure.

Embodiment 3

Use tensio-active agent to produce acetate by carbon black waste gas

Use tensio-active agent also to improve mass transfer.The result of C.Ljungdahlii ERI2 picked-up carbon monoxide under the situation of the various different commercial surfactant of table 7 expression interpolation.In each example, the CO picked-up in 100 (%) control value representative batch fermentation, and sample value represents to add the percentage ratio of the contrast of following batch of fermentation of tensio-active agent situation.

Table 1 is used to test CO, H ₂And CO ₂The product acetic acid bacteria that transforms

Bacterial pathway	CO and H 2In time, consume
		Direct way
P.productus	Not
		E.limosum	Not
A.noterae	Not
		C.aceticum	Not
C.thermoaceticum	Not
		S.sphaeroides	Not
A.woodii	Be
		A.kivui	Be
C.ljungdahlii ERI2	Be
		Indirect approach
R.gelatinosa	Not
		R.rubrum	Not

Table 2 has that the ER12 experimental result gathers in the CSTR system of cell recirculation

Table 3 has that the A.kivui experimental result gathers in the CSTR system of cell recirculation

Table 4 utilizes the fabric ICR performance of ERI2

The research of table 5 acetate partition ratio

Solvent	The aqueous acetic acid equilibrium concentration, g/l	The acetate partition ratio
			Hexane	6.559	0.0
Decane	5.968	0.08
			Chloroform	5.128	0.09
Kerosene	4.648	0.11
			N-Hexadecane	5.866	0.13
Dodecane	4.654	0.13
			Acetate	5.787	0.15
Dibutyl phosphate	4.615	0.18
			Oleyl alcohol	5.114	0.28
Trioctylamine	3.785	0.31
			Undecyl alcohol	4.528	0.40
Ethyl acetate	4.550	0.41
			Ethyl butyrate	4.665	0.42
Dexyl alcohol	3.890	0.42
			Octanol	4.358	0.45
Nonyl alcohol	3.470	0.55
			2-ethyl-1-hexanol	3.308	0.77
3 methyl cyclohexanol	2.110	1.26
			Pimelinketone	2.702	1.66
Tributyl phosphate	1.657	2.38

The partition ratio of table 6 mixed solvent

Solvent mixture	Partition ratio	Percentage increase
			Oleyl alcohol (10cc)	0.17
Oleyl alcohol (10cc)+Cyc (1cc)	0.31	72
			Oleyl alcohol (10cc)+TBP (1cc)	0.29	61
Oleyl alcohol (10cc)+Cyc (2cc)	0.45	150
			Oleyl alcohol (10cc)+TBP (2cc)	0.42	133
Oleyl alcohol (10cc)+Cyc (3cc)	0.36	100
			Oleyl alcohol (10cc)+TBP (3cc)	0.42	133
Oleyl alcohol (10cc)+Cyc (4cc)	0.35	94
			Oleyl alcohol (10cc)+TBP (4cc)	0.40	122
Oleyl alcohol (10cc)+Cyc (6cc)	0.52	188
			Oleyl alcohol (10cc)+TBP (6cc)	0.65	261
Oleyl alcohol (10cc)+Cyc (7cc)	0.69	283
			Oleyl alcohol (10cc)+TBP (7cc)	0.74	311

Table 7 in the presence of tensio-active agent ERI2 to the consumption of CO

Embodiment 4

From carbon black waste gas, prepare CMA

Will be at N ₂In contain about 14%CO, 17%H ₂And 4%CO ₂As the carbon black exhaust blast of main component to remaining on 6 normal atmosphere, 37 ℃ and containing in 160 liters of continuously stirring jar reactors (tank reactor) of Clostridium Ijungdahlii isolate ER12 (through the ATCC preservation, preserving number is 55380).Result as hydro carbons and insufficient air partial oxidation formation decolorizing carbon produces waste gas, and every pound of elemental carbon produces about 1.2 pounds of carbon monoxide.These waste gas form serious atmosphere polluting problem, but also mean that valuable chemical principle material source also is not utilized at present.Gas residence time (being defined as the ratio of reactor volume and flow rate of gas under the standard conditions) remained on 0.52 minute.With 1.05hr ^-1Liquid diluting speed (being defined as the ratio of liquid flow rate and the reactor volume) water-based liquid medium that will contain water, alkaline salt, B-VITAMIN, source nitrogen and source of sulphide add in the reactor.Stir speed (S.S.) is 322rpm in this reactor, and temperature is 37 ℃, and the pH value is 5.03.Under these conditions, the transformation efficiency of CO is 83%, H ₂Transformation efficiency be 54%.Use hollow fibre theca cell recirculation unit (hollow fiber membrane cell recycle unit) to make the cell concn of inside reactor remain on 10.5 grams per liters.The acetic acid,diluted that the contains 13.2 grams per liter acetate/acetates/acetate product stream of autoreactor is sent in three sections reverse extraction plants, is extracted with solvent in the future.Solvent is 1: 4 to the ratio of charging.Acetic acid content is 3.7 grams per liters in acetate/acetate product stream.Leave that acetic acid concentration is 16.7 grams per liters in the solvent of extractor.To send recirculation in the fermentor tank back to from the water (substratum) of extraction plant.

Rhombspar matter lime/MgO directly is added in the acetate in the solvent phase forms CMA.With saturated CMA solution drying and sedimentation, every pound of acetate forms 1.15 pounds and contains Ca after the reaction ²⁺/ Mg ²⁺The CMA of (mol ratio is 3/7).

Embodiment 5

From carbon black waste gas, prepare acetate

Will be at N ₂In contain about 14%CO, 17%H ₂And 4%CO ₂Carbon black exhaust blast to 1.58 normal atmosphere, 37 ℃ and contain in 144 liters of trickle bed reactors of Clostridium Ijungdahlii isolate ER12 (through the ATCC preservation, preserving number is 55380).Trickle bed reactor is the packed column with commercially available weighting material (as ring type filling or Berl saddle packing), and they are in contact with one another therein on liquids and gases are flowed through this post.In the present embodiment, liquids and gases all enter cylinder from the top in mode in the same way, though countercurrent flow (gas enters from the bottom, and liquid enters from the top) also is possible.Gas residence time remained on 0.46 minute, and the liquid medium dilution rate is 0.57hr ^-1Described liquid medium contains the composition identical with embodiment 1.By liquid circulation, use the cycle rate of 60gpm that stirring is provided in reactor.PH value during operation in the reactor is 5.05.Under these conditions, the transformation efficiency of CO is 57%, H ₂Transformation efficiency be 58%.Use hollow fibre device (hollow fiberunit) to make the cell concn of inside reactor remain on 13.6 grams per liters.

Acetic acid,diluted/acetate product the stream that will contain 6.4 grams per liter blended acetate/acetates and 2 grams per liter acetate is sent in three sections reverse column extractors.Solvent is 1: 4 to the ratio of charging.Leave that acetic acid content is 10 grams per liters in the solvent of extractor.To send recirculation in the reactor back to from the water (medium) of extraction plant.

The solvent that will contain acetate is delivered in the water distilling apparatus with recovered acid and solvent.In separation, use vacuum solvent distillation column and acetate distillation column.The final product that produces is a Glacial acetic acid.

Embodiment 6

From carbon black waste gas, prepare potassium acetate

Carbon black waste gas with embodiment 4 prepares potassium acetate rather than CMA.All fermentations keep identical with the solvent extraction condition.With Ke Xingjia (potassium oxide) and acetic acidreaction, directly in solvent phase, generate 50% potassium acetate solution.

Embodiment 7

From coke-fired furnace waste gas, prepare SCP

To contain about 6%CO, 2%CO ₂, 57%H ₂, 5%N ₂Add in the jar reactor with the cell recirculation described in top embodiment 4 of continuously stirring with the coke-fired furnace waste gas of 27% hydrocarbon gas.Adopt this reactor made such as products such as acetic acid,diluted or ethanol.In addition, cell concn is 13.6 grams per liters in the reactor.These cells (microorganism) can collect the bacterial single cell protein that is used for as animal-feed.To deliver to the moisture eliminator to be processed into the exsiccant single cell protein from the celliferous purge flow that reactor is discharged.

Embodiment 8

From refinery's waste gas, prepare H ₂

To contain about 45%CO, 50%H ₂And 5%CH ₄Refinery's exhaust blast to 50 ℃ and several inches hydraulic pressure under, and (it has carried out preservation in the American Type Culture Collection of on March 18th, 1993 at Maryland, USA Rockville (American Type Culture Collection), and has obtained preservation and prove among 1 liter of CSTR of (being numbered 55404) to contain Bacillus smithii isolate ERIH2.Substratum in the reactor is 1.0 grams per liter corn impregnation liquids.CO in the waste gas changes into CO with water ₂And H ₂Contain 3.2%CO, 64.4%H in the air-flow of discharging ₂, 28.8%CO ₂And 3.6%CH ₄From air-flow, remove CO, CO by solvent extraction ₂And CH ₄

Embodiment 9

The compound that from carbon black waste gas, prepares other

About 14%CO, 17%H will be contained in the nitrogen ₂And 4%CH ₄Carbon black exhaust blast to 37 ℃ and 1 liter of CSTR under several inches hydraulic pressure in.Substratum in the reactor is the basic saline admixture of moisture, B-VITAMIN, salt and mineral substance.In the reactor separately or mixed culture produce the liquid product of methyl alcohol, propyl alcohol, butanols, propionic acid, butyric acid or other required product.System be provided with embodiment 6 in used basic identical. after the product dilution, reclaim product in suitable product recovery system, described recovery system comprises extraction, distills or other product recovery technology of knowing.If produce multiple product, then adopt segmentation product recovery system.

Therefore, the invention provides and improvedly highly effectively be used for that waste gas is converted into acids and (comprise organic acid, as acetate; Alcohols; Hydrogen; SCP or organic acid salt) method, reached major objective fully with this method.For a person skilled in the art, by top narration and accompanying drawing, for described example do not exceed the improvement of the scope of the invention and/or variation be can expect and also be conspicuous.Therefore, top narration and accompanying drawing are illustrative example preferably, rather than limitation of the present invention, and this point is obvious.Definite spirit and scope of the present invention are determined by claims.

Claims (2)

1. the preserving number in the American type culture collection preservation is Shi Shi genus bacillus (bacillus smithii) ERI-H2 of ATCC No.55404.

2. method of making hydrogen said method comprising the steps of:

Comprising the water-based nutrient media and be the waste gas that fermentation comprises carbon monoxide in the bio-reactor of Shi Shi genus bacillus ERI-H2 of ATCCNo.55404 at the preserving number of American type culture collection preservation, described Shi Shi genus bacillus ERI-H2 can produce described hydrogen by the described carbon monoxide of anaerobically fermenting; And recover hydrogen therefrom.

Images