CN212270107U - Device for biologically fixing butanol fermentation tail gas and industrial ethylene oxide tail gas - Google Patents

Device for biologically fixing butanol fermentation tail gas and industrial ethylene oxide tail gas Download PDF

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CN212270107U
CN212270107U CN201922439049.8U CN201922439049U CN212270107U CN 212270107 U CN212270107 U CN 212270107U CN 201922439049 U CN201922439049 U CN 201922439049U CN 212270107 U CN212270107 U CN 212270107U
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tail gas
fermentation
membrane
succinic acid
ethylene oxide
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贺爱永
许家兴
张哲玮
胡磊
夏军
刘晓燕
徐继明
邱忠洋
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Huaiyin Normal University
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Huaiyin Normal University
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Abstract

The utility model relates to a device for biologically fixing butanol fermentation tail gas and industrial ethylene oxide tail gas. The method comprises the following steps: 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; a butanol fermentation tail gas inlet connected to the fermentation tank; the microfiltration membrane is connected with the fermentation tank; an ultrafiltration membrane connected to the permeate side of the microfiltration membrane; the first nanofiltration membrane is connected to the permeation side of the ultrafiltration membrane; the crystallizer is connected to the interception side of the first nanofiltration membrane; and the centrifugal machine is connected with the crystallizer to obtain the succinic acid. The utility model discloses allied oneself with butanol fermentation and ethylene oxide industry tail gas, strengthened succinic acid fermentation process, it is easy and simple to handle, provide a new way for enterprise's technical innovation, energy saving and emission reduction.

Description

Device for biologically fixing butanol fermentation tail gas and industrial ethylene oxide tail gas
Technical Field
The utility model relates to an utilize butanol fermentation and ethylene oxide industry tail gas bioconversion succinic apparatus for producing, concretely relates to method of fermentation escherichia coli preparation succinic acid is regulated and control through tail gas proportion belongs to biological fermentation technical field.
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 20-40% of 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:
Figure DEST_PATH_DEST_PATH_IMAGE001
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 a thorough, economic and reasonable method is difficult to find.
SUMMERY OF THE UTILITY MODEL
The utility model provides a production method for biologically converting succinic acid by utilizing butanol fermentation and ethylene oxide industrial tail gas, which obviously improves the fermentation efficiency of succinic acid and realizes fermentationHigh yield of succinic acid, high conversion rate of sugar, and high content of CO2The fixing efficiency is high.
The utility model adopts the technical scheme as follows:
a method for efficiently and biologically fixing butanol fermentation tail gas and industrial ethylene oxide tail gas comprises 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.
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, 1.0 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 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 gas2Adjusting the contentAnd (5) controlling.
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 utility model discloses in, provide a method for utilizing butanol fermentation tail gas and industry ethylene oxide tail gas, successfully be applied to succinic fermentation preparation process with it.
And simultaneously, the utility model discloses a volume ratio to two kinds of tail gases is regulated and control, makes CO2The 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 utility model discloses adopted membrane separation's method to carry out the extraction of succinic acid to the zymotic fluid, realized the reuse to the concentrate in the microfiltration membrane simultaneously, further improved succinic acid yield.
Drawings
FIG. 1 is a view of a fermentation apparatus of the present invention.
Fig. 2 is a drawing of the 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 utility model is detailed as follows:
in the method of the utility model, 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 utility model discloses in use for succinic acid's fermentation process after mixing both. The succinic acid fermentation strain isE. coliBSM 209 or succinic acid high-yielding industrial Escherichia coli.
The utility model discloses in, discover to regulate and control the content of mist in fermentation process, can obtain better fermentation yield. 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 utility model firstly carries out microfiltration treatment on the fermentation liquor, and aims to remove bacteria, large-particle impurities, fragments and the like in the fermentation liquor, and the average aperture range 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. The utility model discloses in order to separate purification this part of composition once more, the method of adoption is at first to the concentrated solution of milipore filter flocculate, for example add 100 and supplementarily 200 mg/L's polyaluminium chloride flocculating agent, can be with the protein flocculation of macromolecule, make it can subside. In addition, a part of micromolecule protein is remained in the concentrated solution, the utility model discloses in through add a certain amount of divalent salt (for example 1-5g/L magnesium chloride or calcium chloride) in the supernatant fluid of flocculation, can make the micromolecule protein take place the denaturation, make molecular weight increase, just can be through the great some nanofiltration membrane of trapped molecular weight with these increase micromolecule protein interception to make succinic acid permeate the nanofiltration membrane, and the micromolecule protein is held back in the nanofiltration membrane, has just realized the further separation of micromolecule protein and succinic acid. 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 present invention provides a device as shown in fig. 1 and fig. 2, including:
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, H2Sensor 2, pH electrode3. Temperature probes 4 respectively connected to the fermentation tank 8 and respectively used for detecting 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 NaCl 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 g NH4Cl, 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:
Figure DEST_PATH_RE-DEST_PATH_IMAGE002
as can be seen from the above table, the present invention unexpectedly found 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:
Figure DEST_PATH_DEST_PATH_IMAGE003
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 (5)

1. The utility model provides a device of biological stationary 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.
2. The apparatus for bio-immobilizing butanol fermentation tail gas and industrial ethylene oxide tail gas according to claim 1, wherein the concentration 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 from 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).
3. The apparatus for bio-immobilizing butanol fermentation tail gas and industrial ethylene oxide tail gas according to claim 2, wherein the molecular weight cut-off of the first nanofiltration membrane (11) is 200-400 Da.
4. The apparatus for bio-immobilizing butanol fermentation tail gas and industrial ethylene oxide tail gas according to claim 3, wherein the molecular weight cut-off of the second nanofiltration membrane (17) is 400-800 Da.
5. The apparatus for bio-immobilizing butanol fermentation tail gas and industrial ethylene oxide tail gas according to claim 4, further comprising: CO 22Sensor (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 the CO in the fermentation tank2、H2pH and temperature.
CN201922439049.8U 2019-12-30 2019-12-30 Device for biologically fixing butanol fermentation tail gas and industrial ethylene oxide tail gas Expired - Fee Related CN212270107U (en)

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