CN111349661A - Method and device for efficiently and biologically fixing butanol fermentation tail gas and industrial ethylene oxide tail gas - Google Patents
Method and device for efficiently and biologically fixing butanol fermentation tail gas and industrial ethylene oxide tail gas Download PDFInfo
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Abstract
The invention relates to production of succinic acid by butanol fermentation and bioconversion of ethylene oxide industrial tail gasA method. The invention discloses a butanol fermentation tail gas and industrial tail gas combined fermentation device, which fixes CO during succinic acid production according to escherichia coli anaerobic fermentation2The characteristic of causing the content change of the succinic acid is that a gas regulation strategy is introduced into a fermentation system, the tail gas proportion and CO in the succinic acid fermentation process are adjusted2Regulating and controlling the supply concentration and maintaining CO in the fermentation process2The content is 95-90%, compared with the common succinic acid fermentation process, the yield, the output and the yield of the succinic acid are respectively improved by 14.2%, 14.7%, 8.2%, and CO2The fixation efficiency is improved by 16%, the invention combines butanol fermentation and ethylene oxide industrial tail gas, strengthens the succinic acid fermentation process, has simple and convenient operation, and provides a new way for enterprise technical innovation, energy conservation and emission reduction.
Description
Technical Field
The invention relates to a production method for biotransformation of succinic acid by using butanol fermentation and ethylene oxide industrial tail gas, in particular to a method for preparing succinic acid by fermenting escherichia coli through tail gas proportion regulation, belonging to the technical field of biological fermentation.
Background
With the global population and industrialization growing, the energy demand is growing sharply. In recent years, butanol has received much attention from researchers at home and abroad as an excellent fuel substitute. However, during the fermentation process for preparing fuel butanol by biological method, the decarboxylation reaction of pyruvic acid and acetoacetic acid and the action of anaerobic respiration release a large amount of CO2Gas, while intracellular reducing power NAD (P) H will be in the form of H2Is lost, resulting in a large waste of carbon and energy, which greatly reduces the atom economy of the anaerobic fermentation process. In the process of biological butanol fermentation, 8-10 cubes of tail gas can be generated by each cube of fermentation liquor, wherein the tail gas contains 60-80% of CO2And 20 to 40 percent H2. The part of CO is converted by a biotransformation process2And H2The recycling can not only reduce the emission of greenhouse gases, but also further improve the carbon atom economy in the biotransformation process and show the characteristic of circular biological economy.
The anaerobic succinic acid fermentation process can fix CO in large quantity2But is considered as a green and environmentally friendly biological process. One molecule of CO can be fixed every time one molecule of succinic acid is formed2. CO in succinic acid fermentation process2Gas is firstly dissolved in solution through a gas-liquid interface and then ionized into HCO3 -, CO3 2-And CO2Three forms (the sum of which is collectively referred to as dissolved CO)2，dCO2) Finally, it is dissociated into HCO through the cell membrane entering the cell3 －Is utilized by the bacterial cells. Thus, CO2The supply method of (2) is also determined by the CO fixation with succinic acid2One of the keys to efficiency. Insufficient supply of intracellular reducing power NADH in the anaerobic succinic acid fermentation is an important factor limiting further improvement of the yield thereof. H2As a substance with high reducing power, the substance not only can effectively maintain the anaerobic environment of a fermentation system, but also can be converted into intracellular reducing power NADH by a part of microorganisms for cell growth and product synthesis.
The industrial ethylene oxide gas is mainly prepared by oxidizing ethylene under the action of a catalyst silver, and the main reaction is as follows:
the side reactions produce large amounts of carbon dioxide and water, and therefore the resulting reaction products are primarily ethylene oxide, carbon dioxide and water, with about 85% ethylene oxide, less than 0.1% acetaldehyde being produced, and less formaldehyde being produced. Thus, dehydrated CO is produced in the tail gas from the ethylene oxide production process2The content can reach 99 percent. Although the ethylene oxide tail gas can be collected by a high-price treatment device, the treatment modes used by international colleagues are few so far, and the finding of the treatment modes is difficultTo a thorough, economical and reasonable method.
Disclosure of Invention
The invention provides a production method for biologically converting succinic acid by using butanol fermentation and ethylene oxide industrial tail gas, which obviously improves the fermentation efficiency of succinic acid, and has high yield of the fermented succinic acid, high sugar conversion rate, CO2The fixing efficiency is high.
The technical scheme adopted by the invention is as follows:
a method for efficiently and biologically fixing butanol fermentation tail gas and industrial ethylene oxide tail gas comprises the following steps:
step 3, obtaining a culture medium for biologically fixing butanol fermentation tail gas and industrial ethylene oxide tail gas;
and 4, feeding the butanol fermentation tail gas and the industrial ethylene oxide tail gas obtained in the step 1 and the seed liquid obtained in the step 2 into a culture medium for fermentation to obtain fermentation liquid containing succinic acid.
In one embodiment, the seed medium comprises: LB culture medium, including peptone 10 g/L, yeast powder 5g/L, and NaCl 5 g/L.
In one embodiment, the fermentation medium comprises, per liter: 3.0 g citric acid, 3.0 g Na2HPO4·7H2O, 8.0 g KH2PO4, 8.0 g (NH4)2HPO4, 0.2 g NH4Cl, 0.8 g (NH4)2SO4, 1.0g MgSO4·7H2O, 10.0 mg CaCl2·2H2O, 0.5 mg ZnSO4·7H2O, 0.3 mg CuCl2·2H2O,2.5mg MnSO4·H2O, 1.8 mg CoCl2·6H2O, 0.1 mg H3BO3, 1.8 mg Al2(SO4)3·5H2O, 0.5mg Na2MoO4·2H2O, 16.1 mg of ferric citrate, 20.0 mg of VB1, and 2.0 mg of biotin, 0.12 g of betaine, 100g/L of glucose.
In one embodiment, when the fermentation is performed in the 4 th step, the method further comprises: CO in mixed gas formed by butanol fermentation tail gas and industrial ethylene oxide tail gas2Regulating and controlling the content.
In one embodiment, the regulation and control refers to regulating and controlling the volume ratio of the butanol fermentation tail gas and the industrial ethylene oxide tail gas.
In one embodiment, the regulation refers to the regulation of CO in the mixed gas2The content is adjusted to 95 to 90 percent.
In one embodiment, the butanol fermentation tail gas contains CO2The content is 60-80 percent, and the rest is H2。
In one embodiment, the dehydrated tail gas CO produced by the ethylene oxide byproduct2The content is about 99%.
In one embodiment, the fermentation temperature in the 4 th step is 35-38 ℃, and the fermentation time is controlled to be 50-100 h.
In one embodiment, the succinic acid fermenting strain in the 4 th step isE. coliBSM 209 or succinic acid high-yielding industrial Escherichia coli.
In one embodiment, further comprising: a step of extracting succinic acid from the succinic acid-containing fermentation broth obtained in the step 4, comprising the steps of:
s1, filtering the fermentation liquor by using a microfiltration membrane;
s2, concentrating the microfiltration permeate by using an ultrafiltration membrane;
s3, concentrating the permeate of the ultrafiltration membrane by using a first nanofiltration membrane;
and S4, crystallizing and centrifuging the concentrated solution of the nanofiltration membrane to obtain succinic acid.
In one embodiment, the average pore size of the microfiltration membrane is in the range of 50 to 200 nm.
In one embodiment, the ultrafiltration membrane has a molecular weight cut-off of 5000-.
In one embodiment, the molecular weight cut-off of the first nanofiltration membrane is 200-400 Da.
In one embodiment, a flocculating agent is added into the concentrated solution of the ultrafiltration membrane for flocculation treatment, divalent metal salt ions are added into the clear solution after flocculation treatment, then the clear solution is sent into a second nanofiltration membrane for filtration treatment, so that succinic acid permeates through the second nanofiltration membrane, and after the reverse osmosis membrane is used for concentrating the permeated solution of the second nanofiltration membrane, crystallization and centrifugation treatment are carried out to obtain succinic acid.
In one embodiment, the molecular weight cut-off of the second nanofiltration membrane is 400-.
In one embodiment, the divalent metal salt ion is magnesium chloride or calcium chloride and is added in an amount of 1 to 5 g/L.
An efficient biological fixation butanol fermentation tail gas and industrial ethylene oxide tail gas's device includes:
the fermentation tank is used for fermenting the succinic acid by adopting an anaerobic method;
the ethylene oxide tail gas inlet is connected to the fermentation tank and is used for supplying ethylene oxide production tail gas to the fermentation tank;
the butanol fermentation tail gas inlet is connected to the fermentation tank and used for supplying butanol fermentation tail gas to the fermentation tank;
the microfiltration membrane is connected with the fermentation tank and is used for carrying out microfiltration treatment on the fermented liquid after fermentation to remove thalli and solid impurities;
the ultrafiltration membrane is connected to the permeation side of the microfiltration membrane and is used for performing ultrafiltration treatment on the permeation liquid of the microfiltration membrane and separating protein and succinic acid;
the first nanofiltration membrane is connected to the permeation side of the ultrafiltration membrane and is used for concentrating succinic acid in a permeation liquid of the ultrafiltration membrane;
the crystallizer is connected to the interception side of the first nanofiltration membrane and is used for crystallizing the concentrated solution of the first nanofiltration membrane;
and the centrifuge is connected with the crystallizer and is used for centrifuging mother liquor generated by crystallization to obtain succinic acid.
In one embodiment, the concentrated side of the ultrafiltration membrane is connected to a flocculation tank, and the flocculation tank is used for performing flocculation treatment on the concentrated solution obtained from the ultrafiltration membrane to remove macromolecular proteins and colloids; a flocculating agent adding tank is arranged on the flocculation tank and is used for adding a flocculating agent into the flocculation tank;
further comprising:
the second nanofiltration membrane is connected to the clear liquid side of the flocculation tank and is used for performing nanofiltration treatment on the clear liquid obtained in the flocculation tank to separate the micromolecular protein from the succinic acid; a divalent salt adding port is connected to the feed port of the second nanofiltration membrane and is used for adding divalent salt into the feed port;
the reverse osmosis membrane is connected to the permeation side of the second nanofiltration membrane and is used for concentrating the penetrating fluid of the second nanofiltration membrane; the concentrate side of the reverse osmosis membrane is connected to the crystallizer.
In one embodiment, the molecular weight cut-off of the first nanofiltration membrane is 200-.
In one embodiment, the molecular weight cut-off of the second nanofiltration membrane is 400-.
In one embodiment, further comprising: CO 22Sensor instrument, H2The sensor, the pH electrode and the temperature probe are respectively connected to the fermentation tank and are respectively used for CO in the fermentation tank2、H2pH and temperature.
Advantageous effects
The invention provides a method for utilizing butanol fermentation tail gas and industrial ethylene oxide tail gas, which is successfully applied to a fermentation preparation process of succinic acid.
Meanwhile, the invention regulates and controls the volume ratio of the two tail gases to ensure that CO is generated2The content is 95-90%, and the yield, the yield and the yield of the succinic acid are improved compared with the common succinic acid fermentation process.
The invention adopts a membrane separation method to extract the succinic acid from the fermentation liquor, realizes the reutilization of the concentrated solution in the microfiltration membrane and further improves the yield of the succinic acid.
Drawings
FIG. 1 is a diagram of a fermentation apparatus according to the present invention.
Fig. 2 is a diagram of an extraction device of the present invention.
Wherein 1, CO2A sensor; 2. h2A sensor; 3. a pH electrode; 4. a temperature probe; 5. a sampling port; 6. an ethylene oxide tail gas inlet; 7. introducing butanol fermentation tail gas into the inlet; 8. a fermentation tank; 9. a microfiltration membrane; 10. ultrafiltration membranes; 11. a first nanofiltration membrane; 12. a crystallizer; 13. a centrifuge; 14. a flocculation tank; 15. a flocculant adding tank; 16. a divalent salt addition port; 17. a second nanofiltration membrane; 18. a reverse osmosis membrane.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments. It will be understood by those skilled in the art that the following examples are illustrative of the present invention only and should not be taken as limiting the scope of the invention. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Approximating language, as used herein throughout the specification and claims, may be applied to modify any quantitative representation that could permissibly vary without resulting in a change in the basic function to which it is related. Accordingly, a value modified by a term or terms, such as "about," is not to be limited to the precise value specified. In at least some instances, the approximating language may correspond to the precision of an instrument for measuring the value. Unless context or language indicates otherwise, range limitations may be combined and/or interchanged, and such ranges are identified and include all the sub-ranges included herein. Other than in the operating examples, or where otherwise indicated, all numbers or expressions referring to quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as modified in all instances by the word "about".
The recitation of values by ranges is to be understood in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a concentration range of "about 0.1% to about 5%" should be interpreted to include not only the explicitly recited concentration of about 0.1% to about 5%, but also include individual concentrations (e.g., 1%, 2%, 3%, and 4%) and sub-ranges (e.g., 0.1% to 0.5%, 1% to 2.2%, 3.3% to 4.4%) within the indicated range.
The term "removal" in the present specification includes not only a case where a target substance is completely removed but also a case where the target substance is partially removed (the amount of the substance is reduced). "purification" in this specification includes the removal of any or specific impurities.
The words "include," "have," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to those elements, but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The method of the invention is detailed as follows:
in the method, butanol fermentation tail gas and industrial ethylene oxide tail gas are utilized;
removing oil and water from butanol tail gas in the collecting process, filtering for sterilization before blowing into the fermentation tank, and removing CO in butanol fermentation tail gas2The content is 60-80 percent, and the rest is H2。
Dehydrated tail gas CO generated by ethylene oxide byproduct2The content is about 99%.
The two are mixed and used in the fermentation process of the succinic acid. The succinic acid fermentation strain isE. coliBSM 209 or succinic acid high-yielding industrial Escherichia coli.
In the invention, the content of the mixed gas is regulated and controlled in the fermentation process, so that better fermentation yield can be obtained. Mixing CO in the gas2The content is adjusted to 95 to 90 percent.
In the above fermentation process, the main control parameters are: the fermentation temperature is 35-38 deg.C, and the fermentation time is controlled at 50-100 h.
After the fermentation liquor is obtained, the invention firstly carries out microfiltration treatment on the fermentation liquor, and aims to remove bacteria, large-particle impurities, debris and the like in the fermentation liquor, and the average pore diameter of the microfiltration membrane is 50-200 nm.
Then the fermentation liquor is filtered by an ultrafiltration membrane, which is mainly used for separating the protein and the succinic acid in the fermentation liquor, therefore, the cut-off molecular weight of the ultrafiltration membrane is properly smaller and can be controlled at 5000-20000 Da. In this range, the majority of the protein can be retained and the succinic acid can permeate the nanofiltration membrane.
And concentrating the ultrafiltered penetrating fluid with a nanofiltration membrane, wherein the molecular weight cut-off of the nanofiltration membrane used in the concentrating process can be smaller, preferably 200 Da, so that succinic acid is cut off, and inorganic salts in the concentrated solution can penetrate through the nanofiltration membrane to enter the penetrating side. And the succinic acid in the nanofiltration membrane concentrated solution can be recovered through crystallization and centrifugation.
The concentrated solution of the ultrafiltration membrane still has more volume and contains more protein and also contains succinic acid. In order to separate and purify the part of components again, the invention adopts a method that firstly the concentrated solution of the ultrafiltration membrane is flocculated, for example, 100-200mg/L polyaluminium chloride flocculant is added to flocculate macromolecular proteins so that the macromolecular proteins can be settled. In addition, a part of small-molecular proteins are remained in the concentrated solution, the small-molecular proteins can be denatured by adding a certain amount of divalent salt (such as 1-5g/L of magnesium chloride or calcium chloride) into the flocculated supernatant liquid, the molecular weight is increased, the increased small-molecular proteins can be intercepted by a nanofiltration membrane with higher molecular weight interception, and the succinic acid penetrates through the nanofiltration membrane, and the small-molecular proteins are intercepted in the nanofiltration membrane, so that the small-molecular proteins and the succinic acid are further separated. Succinic acid is mainly left in the permeate of the nanofiltration membrane, and the succinic acid can be recovered through crystallization and centrifugation after the concentrate of the nanofiltration membrane is concentrated through a reverse osmosis membrane.
Based on the above method, the apparatus provided by the present invention, as shown in fig. 1 and 2, comprises:
a fermentation tank 8 for fermenting succinic acid by an anaerobic method;
an ethylene oxide tail gas inlet 6 connected to the fermentation tank 8 for supplying ethylene oxide production tail gas to the fermentation tank 8;
a butanol fermentation tail gas inlet 7 connected to the fermentation tank 8 for supplying butanol fermentation tail gas to the fermentation tank 8;
the microfiltration membrane 9 is connected with the fermentation tank 8 and is used for carrying out microfiltration treatment on the fermented liquid after fermentation to remove thalli and solid impurities;
an ultrafiltration membrane 10 connected to the permeation side of the microfiltration membrane 9 for performing ultrafiltration treatment on the permeate of the microfiltration membrane 9 to separate protein and succinic acid;
a first nanofiltration membrane 11 connected to the permeate side of the ultrafiltration membrane 10, for concentrating succinic acid in the permeate of the ultrafiltration membrane 10;
the crystallizer 12 is connected to the interception side of the first nanofiltration membrane 11 and is used for crystallizing the concentrated solution of the first nanofiltration membrane 11;
and a centrifuge 13 connected to the crystallizer 12 for centrifuging the mother liquor generated by crystallization to obtain succinic acid.
In one embodiment, the concentrated side of the ultrafiltration membrane 10 is connected to a flocculation tank 14, and the flocculation tank 14 is used for performing flocculation treatment on the concentrated solution obtained in the ultrafiltration membrane 10 to remove macromolecular proteins and colloids; a flocculating agent adding tank 15 is arranged on the flocculation tank 14 and is used for adding a flocculating agent into the flocculation tank 14;
further comprising:
a second nanofiltration membrane 17 connected to the clear liquid side of the flocculation tank 14, for performing nanofiltration treatment on the clear liquid obtained in the flocculation tank 14 to separate small molecular proteins from succinic acid; a divalent salt adding port 16 is connected to the feed port of the second nanofiltration membrane 17 and is used for adding divalent salt into the feed port;
a reverse osmosis membrane 18 connected to the permeate side of the second nanofiltration membrane 17 for concentrating the permeate of the second nanofiltration membrane 17; the concentrate side of reverse osmosis membrane 18 is connected to crystallizer 12.
In one embodiment, the molecular weight cut-off of the first nanofiltration membrane 11 is 200-.
In one embodiment, the molecular weight cut-off of the second nanofiltration membrane 17 is 400-800 Da.
In one embodiment, further comprising: CO 22 Sensor 1, H2The sensor 2, the pH electrode 3 and the temperature probe 4 are respectively connected to the fermentation tank 8 and are respectively used for measuring CO in the fermentation tank2、H2pH and temperature.
Example 1 Regulation of exhaust gas composition
In this example, the fermentation strain with succinic acid wasE. coliBSM 209 was subjected to anaerobic fermentation. First, the strain is inoculated into a seed culture medium, which includes: LB culture medium, including peptone 10 g/L, yeast powder 5g/L, and andNaCl 5 g/L. Then inoculating the seed culture medium into a fermentation culture medium, wherein the adopted fermentation culture medium comprises the following components in percentage by liter: 3.0 g citric acid, 3.0 g Na2HPO4·7H2O, 8.0 g KH2PO4, 8.0 g (NH4)2HPO4, 0.2 gNH4Cl, 0.8 g (NH4)2SO4, 1.0 g MgSO4·7H2O, 10.0 mg CaCl2·2H2O, 0.5 mg ZnSO4·7H2O, 0.3 mg CuCl2·2H2O, 2.5mg MnSO4·H2O, 1.8 mg CoCl2·6H2O, 0.1 mg H3BO3,1.8 mg Al2(SO4)3·5H2O, 0.5 mg Na2MoO4·2H2O, 16.1 mg of ferric citrate, 20.0 mg of VB1, and 2.0 mg of biotin, 0.12 g of betaine, 100g/L of glucose.
In this example, butanol fermentation tail gas CO was used2The content is 70 percent, and the rest is H2(ii) a CO in industrial ethylene oxide tail gas adopted2The content is about 99%. By regulating and controlling the volume ratio of the two tail gases, different CO can be realized2And H2The concentration ratio of (A) to (B) can be controlled mainly by controlling the volume ratio of the two components to CO2Is about 92%, and H2Approximately close to 8%.
The fermentation temperature is regulated to 35-38 ℃, and the fermentation time is controlled to 72 h. The fermentation yields obtained under different conditions are shown in the following table:
as can be seen from the above table, it has been unexpectedly found in the present invention that when the volume ratio of butanol fermentation tail gas to industrial ethylene oxide tail gas is controlled, CO is generated2Is about 92%, and H2At approximately 8%, excellent production yields were obtained and the succinic acid concentration reached the highest 66.02g/L, indicating a higher CO2Partial pressure and slight H2The introduction and the stirring change the microbial fermentation process in the fermentation system, and the fermentation effect can be improved.
Example 2 extraction of succinic acid
The fermentation broth obtained in example 1 was subjected to the following extraction of succinic acid.
Filtering the fermentation liquor by adopting a ceramic microfiltration membrane with the average pore diameter of 50 nm; concentrating the microfiltration permeate by using an ultrafiltration membrane with the molecular weight cutoff of 5000 so that the succinic acid permeates the ultrafiltration membrane and the protein is remained in the cutoff side of the ultrafiltration membrane; concentrating the permeate of the ultrafiltration membrane by using a nanofiltration membrane with the molecular weight cutoff of 200, so that the inorganic salt permeates the nanofiltration membrane, and the succinic acid is remained in the nanofiltration concentrate; and (4) cooling and crystallizing the nanofiltration concentrated solution, centrifuging, and drying to obtain purified succinic acid (named as succinic acid I).
Adding 100mg/L polyaluminium chloride into the concentrated solution of the ultrafiltration membrane for flocculation, so that macromolecular protein is flocculated and settled, adding 4g/L magnesium chloride into the flocculated clear solution, so that the micromolecular protein is denatured, improving the molecular weight of the micromolecular protein, separating the micromolecular protein from succinic acid by using a nanofiltration membrane with the molecular weight cutoff of 600, enabling the succinic acid to permeate the nanofiltration membrane, concentrating the succinic acid by using a reverse osmosis membrane, centrifuging, and drying to obtain the purified succinic acid (named as succinic acid II).
Example 3
This example differs from example 2 in that: the protein is denatured by adding divalent salt ions to the clear liquid without flocculation.
Filtering the fermentation liquor by adopting a ceramic microfiltration membrane with the average pore diameter of 50 nm; concentrating the microfiltration permeate by using an ultrafiltration membrane with the molecular weight cutoff of 5000 so that the succinic acid permeates the ultrafiltration membrane and the protein is remained in the cutoff side of the ultrafiltration membrane; concentrating the permeate of the ultrafiltration membrane by using a nanofiltration membrane with the molecular weight cutoff of 200, so that the inorganic salt permeates the nanofiltration membrane, and the succinic acid is remained in the nanofiltration concentrate; and (4) cooling and crystallizing the nanofiltration concentrated solution, centrifuging, and drying to obtain purified succinic acid (named as succinic acid I).
Adding 100mg/L polyaluminium chloride into the concentrated solution of the ultrafiltration membrane for flocculation, so that macromolecular protein is flocculated and settled, separating the micromolecular protein and succinic acid from the flocculated clear solution through a nanofiltration membrane with the molecular weight cutoff of 600, enabling succinic acid to permeate the nanofiltration membrane, concentrating the succinic acid through a reverse osmosis membrane, centrifuging, and drying to obtain purified succinic acid (named as succinic acid II).
The separation of the purified succinic acid and the nanofiltration membrane in the above examples is as follows:
as can be seen from the above table, the succinic acid product with better purity can be obtained by the above method, the part is mainly obtained by directly purifying from the fermentation liquor, the purity can reach more than 99.5%, and the succinic acid II obtained from the concentrated solution passing through the ultrafiltration membrane is separated from other impurities, so the purity is reduced compared with the succinic acid I; in addition, in the embodiment 2, because the protein denaturation treatment of adding the divalent salt is carried out on the flocculated clear liquid, the molecular weight of the small molecular protein can be increased, the separation performance of the nanofiltration membrane on succinic acid and protein is better, the protein penetrating through the nanofiltration membrane is reduced, the rejection rate is improved, and the purity of succinic acid II is also improved.
Claims (10)
1. A method for efficiently and biologically fixing butanol fermentation tail gas and industrial ethylene oxide tail gas is characterized by comprising the following steps:
step 1, obtaining butanol fermentation tail gas and industrial ethylene oxide tail gas;
step 2, obtaining a seed liquid for succinic acid fermentation;
step 3, obtaining a culture medium for biologically fixing butanol fermentation tail gas and industrial ethylene oxide tail gas;
and 4, feeding the butanol fermentation tail gas and the industrial ethylene oxide tail gas obtained in the step 1 and the seed liquid obtained in the step 2 into a culture medium for fermentation to obtain fermentation liquid containing succinic acid.
2. The method for efficient bio-fixation of butanol fermentation tail gas and industrial ethylene oxide tail gas according to claim 1, wherein in one embodiment, the seed culture medium comprises: LB culture medium, including peptone 10 g/L, yeast powder 5g/L, and NaCl 5 g/L; in one embodiment, the fermentation medium comprises, per liter: 3.0 g citric acid, 3.0 g Na2HPO4·7H2O, 8.0 g KH2PO4, 8.0 g (NH4)2HPO4, 0.2 g NH4Cl, 0.8 g(NH4)2SO4, 1.0 g MgSO4·7H2O, 10.0 mg CaCl2·2H2O, 0.5 mg ZnSO4·7H2O, 0.3 mgCuCl2·2H2O, 2.5mg MnSO4·H2O, 1.8 mg CoCl2·6H2O, 0.1 mg H3BO3, 1.8 mg Al2(SO4)3·5H2O, 0.5 mg Na2MoO4·2H2O, 16.1 mg of ferric citrate, 20.0 mg of VB1, and 2.0 mg of biotin, 0.12 g of betaine, 100g/L of glucose.
3. The method for efficient biological fixation of butanol fermentation tail gas and industrial ethylene oxide tail gas according to claim 1, wherein the fermentation in step 4 further comprises: CO in mixed gas formed by butanol fermentation tail gas and industrial ethylene oxide tail gas2Regulating and controlling the content; in one embodiment, the regulation and control refers to regulating and controlling the volume ratio of butanol fermentation tail gas to industrial ethylene oxide tail gas; in one embodiment, the regulation refers to the regulation of CO in the mixed gas2Adjusting the content to 95-90%; in one embodiment, the butanol fermentation tail gas contains CO2The content is 60-80 percent, and the rest is H2(ii) a In one embodiment, the dehydrated tail gas CO produced by the ethylene oxide byproduct2The content is about 99%.
4. The method for high efficiency biological fixation of butanol fermentation tail gas and industrial ethylene oxide tail gas according to claim 1, wherein in one embodiment, the fermentation temperature in the 4 th step is 35-38 ℃, and the fermentation time is controlled at 50-100 h; in one embodiment, the succinic acid fermenting strain in the 4 th step isE. coliBSM 209 or succinic acid high-yielding industrial Escherichia coli.
5. The method for efficient bio-fixation of butanol fermentation tail gas and industrial ethylene oxide tail gas according to claim 1, further comprising, in one embodiment: a step of extracting succinic acid from the succinic acid-containing fermentation broth obtained in the step 4, comprising the steps of: s1, filtering the fermentation liquor by using a microfiltration membrane; s2, concentrating the microfiltration permeate by using an ultrafiltration membrane; s3, concentrating the permeate of the ultrafiltration membrane by using a first nanofiltration membrane; and S4, crystallizing and centrifuging the concentrated solution of the nanofiltration membrane to obtain succinic acid.
6. The method for efficient bio-fixation of butanol fermentation tail gas and industrial ethylene oxide tail gas according to claim 5, wherein in one embodiment, the average pore size of the microfiltration membrane is in the range of 50 to 200 nm; in one embodiment, the ultrafiltration membrane has a molecular weight cut-off of 5000-; in one embodiment, the molecular weight cut-off of the first nanofiltration membrane is 200-400 Da; in one embodiment, a flocculating agent is added into a concentrated solution of an ultrafiltration membrane for flocculation treatment, divalent metal salt ions are added into a clear solution after flocculation treatment, then the clear solution is sent into a second nanofiltration membrane for filtration treatment, so that succinic acid permeates the second nanofiltration membrane, and after a reverse osmosis membrane is used for concentrating a permeate of the second nanofiltration membrane, crystallization and centrifugation treatment are carried out to obtain succinic acid; in one embodiment, the molecular weight cut-off of the second nanofiltration membrane is 400-; in one embodiment, the divalent metal salt ion is magnesium chloride or calcium chloride and is added in an amount of 1 to 5 g/L.
7. The utility model provides a device of high-efficient biological fixed butanol fermentation tail gas and industry ethylene oxide tail gas which characterized in that includes:
a fermenter (8) for carrying out the fermentation of succinic acid by an anaerobic method;
an ethylene oxide tail gas inlet (6) connected to the fermentation tank (8) for feeding ethylene oxide production tail gas into the fermentation tank (8);
a butanol fermentation tail gas inlet (7) connected to the fermentation tank (8) for supplying butanol fermentation tail gas to the fermentation tank (8);
the microfiltration membrane (9) is connected with the fermentation tank (8) and is used for carrying out microfiltration treatment on the fermented liquid after fermentation to remove thalli and solid impurities;
an ultrafiltration membrane (10) connected to the permeation side of the microfiltration membrane (9) for performing ultrafiltration treatment on the permeate of the microfiltration membrane (9) to separate protein and succinic acid;
a first nanofiltration membrane (11) which is connected to the permeation side of the ultrafiltration membrane (10) and is used for concentrating succinic acid in the permeation liquid of the ultrafiltration membrane (10);
the crystallizer (12) is connected to the interception side of the first nanofiltration membrane (11) and is used for crystallizing the concentrated solution of the first nanofiltration membrane (11);
and the centrifuge (13) is connected with the crystallizer (12) and is used for centrifuging mother liquor generated by crystallization to obtain succinic acid.
8. The device for high-efficiency biological fixation of butanol fermentation tail gas and industrial ethylene oxide tail gas according to claim 7, characterized in that, in one embodiment, the concentration side of the ultrafiltration membrane (10) is connected to a flocculation tank (14), and the flocculation tank (14) is used for carrying out flocculation treatment on the concentrated solution obtained in the ultrafiltration membrane (10) to remove macromolecular proteins and colloids; a flocculating agent adding tank (15) is arranged on the flocculation tank (14) and is used for adding a flocculating agent into the flocculation tank (14);
further comprising:
the second nanofiltration membrane (17) is connected to the clear liquid side of the flocculation tank (14) and is used for performing nanofiltration treatment on the clear liquid obtained in the flocculation tank (14) so as to separate the micromolecular protein from the succinic acid; a divalent salt adding port (16) is connected to the feed port of the second nanofiltration membrane (17) and is used for adding divalent salt into the feed port;
a reverse osmosis membrane (18) connected to the permeate side of the second nanofiltration membrane (17) and used for concentrating the permeate of the second nanofiltration membrane (17); the concentrate side of the reverse osmosis membrane (18) is connected to the crystallizer (12).
9. The device for high-efficiency biological fixation of butanol fermentation tail gas and industrial ethylene oxide tail gas according to claim 7, wherein in one embodiment, the molecular weight cut-off of the first nanofiltration membrane (11) is 200-400 Da; in one embodiment, the molecular weight cut-off of the second nanofiltration membrane (17) is 400-800 Da.
10. The apparatus for efficient bio-fixation of butanol fermentation tail gas and industrial ethylene oxide tail gas according to claim 7, further comprising in one embodiment: CO 22Sensor (1), H2The sensor (2), the pH electrode (3) and the temperature probe (4) are respectively connected with the fermentation tank (8) and are respectively usedTo CO in the fermenter2、H2pH and temperature.
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