CN100343187C - Treatment process for industrial wastewater of VB12 production and dedicated wastewater treatment machine therefor - Google Patents
Treatment process for industrial wastewater of VB12 production and dedicated wastewater treatment machine therefor Download PDFInfo
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- CN100343187C CN100343187C CNB2005100125296A CN200510012529A CN100343187C CN 100343187 C CN100343187 C CN 100343187C CN B2005100125296 A CNB2005100125296 A CN B2005100125296A CN 200510012529 A CN200510012529 A CN 200510012529A CN 100343187 C CN100343187 C CN 100343187C
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- 239000010842 industrial wastewater Substances 0.000 title claims abstract description 30
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- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 19
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- 102000004169 proteins and genes Human genes 0.000 claims description 28
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- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The present invention relates to resource treatment technology for treating industrial wastewater of VB12 production and a special wastewater treatment machine thereof. The technology comprises the steps: albumen is extracted by a chemical flocculation method, and propionic acid is extracted and reversely extracted; calcium dipropionate is prepared, and acetic acid is extracted and reversely extracted; glacial acetic acid is prepared, and the AOPs ultra-oxidation of extracted residual wastewater and the composite microwave treatment of O3/H2O2 are carried out. The present invention also provides a special wastewater treatment machine for extracting albumen by a chemical flocculation method and a special wastewater treatment machine for the ultra-oxidation of wastewater which is obtained by extracting the albumen, the propionic acid and the acetic acid from the industrial wastewater of VB12 production. The special wastewater treatment machine is used for the resource treatment of the industrial wastewater of VB12 production through the technology. The albumen, the propionic acid, the acetic acid, etc. in the wastewater are extracted so as to further prepare an additional product. The zero discharge the industrial wastewater are realized without secondary pollution, the extracted residual wastewater is further treated so as to become reclaimed water for recycling, and sludge becomes superior organic fertilizer.
Description
Technical Field
The invention belongs to the field of industrial wastewater treatment, and particularly relates to a resource treatment process of industrial wastewater for producing VB12 and a special wastewater treatment machine.
Background
COD in wastewater discharged in VB12 production processCrHas a concentration of about (6 to 7) × 104mg/l, sulfate concentration is about 3000mg/l, water contains 1.9% propionic acid, about 1% acetic acid and a large amount of amino acid protein, the treatment of the formed high-concentration and high-chroma organic wastewater becomes an old, big and difficult problem in the industry, and the discharge is difficult to reach the standard by the existing technical means. The traditional treatment technology is to mix the water with other slightly polluted waste water in proportion to ensure that COD is generatedCrIs diluted to about 1000mg/l, SO4 2-Until the concentration is about 700mg/l, a UASB anaerobic reactor is adopted, and a large amount of methane and H are generated in the treatment process of the process2S, the odor causes secondary pollution to the atmosphere, the process running time is about 20 hours, the structure is huge, about 1500 ten thousand yuan of investment is needed, but CODCrRemoval rate ofThe amount of the waste water is only about 80 percent, and if the waste water is calculated by 500 tons of daily treatment amount, the operation cost is over 300 ten thousand yuan per year.
Disclosure of Invention
The invention aims to solve the technical problem of providing a recycling treatment process for realizing zero discharge and no secondary pollution of industrial wastewater for producing VB12, carrying out recycling extraction on protein, propionic acid, acetic acid and the like in the wastewater and further preparing additional products, finally treating the rest wastewater into reclaimed water for recycling, and changing sludge into high-quality organic fertilizer.
The invention also aims to provide a special wastewater treatment machine for extracting protein by using a chemical flocculation method, which is used for extracting the protein from the industrial wastewater for producing VB 12.
The invention further aims to provide a special wastewater treatment machine for carrying out super oxidation treatment on wastewater after protein, propionic acid and acetic acid are extracted from industrial wastewater for producing VB12, wherein a terminal is connected with a microwave processor, and the wastewater after microwave treatment is reclaimed water for reuse.
The invention is realized by the following technical scheme to solve the technical problems: a resource treatment process for industrial wastewater from VB12 production comprises the following steps:
a. extracting protein from VB12 production wastewater by a chemical flocculation method, and reserving the rest wastewater A for later use;
b. extracting propionic acid from the wastewater A by an extraction and back extraction method to prepare calcium propionate, and reserving the residual wastewater B for later use;
c. extracting acetic acid from the wastewater B by an extraction and back extraction method to prepare glacial acetic acid and obtain the residual wastewater E;
d. waste water E is super-oxidized by AOPs, O3/H2O2And performing solid-liquid separation after microwave composite treatment to obtain a liquid part which is reclaimed water and a solid part which is sludge D.
Wherein,
the chemical flocculation method is used for extracting protein by the following method steps:
e. adding 2-4 per mill chitosan aqueous solution into VB12 production wastewater, wherein the adding amount is 80-100 mg/L; then the
f. Adding 4-6% basic aluminum chloride aqueous solution with the addition amount of 60-80 mg/L; then the
g. Adding 0.5-1.5 per mill of sodium polyacrylate water solution at a dosage of 4-6mg/L to flocculate protein in the wastewater sufficiently to form floc and clear liquid; then the
h. And (3) adding the supernatant into the flocs, filtering, concentrating and drying to obtain the finished product protein.
The extraction and back extraction method is used for extracting the propionic acid, and the preparation of the calcium propionate is carried out by the following method steps:
i. adding an extractant into the wastewater A in an extraction tower to extract propionic acid, then adding a back extractant into a back extractant to prepare a calcium propionate alkali liquor, and performing neutralization filtration, concentration cooling, crystallization filtration to obtain a calcium propionate crude product;
j. the crude product of calcium propionate is heated, dissolved, decolored, filtered, concentrated, cooled, crystallized, filtered and dried to obtain the refined product of calcium propionate, namely the edible calcium propionate.
The extraction and back extraction method is used for extracting acetic acid, and the preparation of glacial acetic acid is carried out by the following method steps:
k. extracting, back-extracting and distilling the wastewater B to obtain an acetic acid aqueous solution;
rectifying acetic acid to obtain glacial acetic acid.
The step d is carried out according to the following steps in sequence:
wastewater E through O2+O3Air stripping ammonia nitrogen, flocculating to remove residual protein, settling in intermediate settling tank, decoloring and internal electrolysis, and O3/H2O2Reaction, microwave treatment and solid-liquid separation to obtainThe liquid part is reclaimed water, and the solid part is sludge D;
and the sludge D is subjected to physical treatment such as concentration, centrifugal compression and the like to finally obtain the sterile organic fertilizer.
The extractant is trioctylamine, tributylphosphine oxide, n-octanol and tributyl phosphate; the stripping agent is Ca (OH)2And aqueous NaOH solution.
A special wastewater treatment machine for extracting protein by chemical flocculation comprises dosing tanks 1, 2 and 3 controlled by a flow meter, a flocculation reaction tank 8 for mixing by a pipeline and a pump, a centrifuge 5 for solid-liquid separation, and a dryer 6 for forming a production line; the front end, namely a water inlet, is connected with a storage tank 7 for storing industrial wastewater produced by VB12, and the terminal is a liquid outlet; a chitosan dosing tank 1, a PAC dosing tank 2 and a sodium polyacrylate dosing tank 3 are communicated with a pipeline between the water inlet and the pump body before filtration in sequence;
a chitosan medicine adding tank 1 which contains 2-4 per mill of chitosan water solution with weight percentage concentration;
the PAC dosing tank 2 is filled with aluminum salt PAC, namely 4-6% basic aluminum chloride aqueous solution;
a sodium polyacrylate medicine adding tank 3, and an auxiliary agent sodium polyacrylate, namely 0.5-1.5 per mill of sodium polyacrylate solution, is filled in the medicine adding tank.
The invention also provides a special wastewater treatment machine for wastewater super-oxidation treatment, which comprises a medicine adding tank 11, 121, 122, 131, 132, 14 and 15, an ozone generator 171 and 171, an intermediate sedimentation tank 191 and 192, a reactor 18 and 20, an inner electrolytic tank 21, a static mixer 221, 222, 223 and 224, a pump body 241, 242, 243, 244 and 245 and a corresponding anti-corrosive liquid pipeline, wherein the medicine adding tank is controlled by a flow meter, the main body of the special wastewater treatment machine is formed by sequentially connecting the reactor 18, the pump body 241, the intermediate sedimentation tank 191, the pump body 242, the inner electrolytic tank 21, the reactor 20, the pump body 243, the intermediate sedimentation tank 192 and the pump body 245 in series through pipelines, the front end, namely a water inlet, of the special wastewater treatment machine is connected with a VB12 industrial wastewater pipeline which is subjected to protein extraction, calcium propionate and glacial acetic acid production, and the terminal of the; at the water inlet and reactThe upper part of the pipeline between the devices 18 is communicated with a medicine feeding tank 11; the pipelines between the reactor 18 and the pump body 241 and between the pump body 242 and the intermediate sedimentation tank 191 are respectively communicated with the dosing tanks 121 and 131 and the static mixers 221 and 222 in turn; a pipeline between the intermediate sedimentation tank 191 and the inner electrolytic tank 21 is provided with H2SO4The medicine adding tank 14 is communicated with the medicine adding tank; on the pipe between the reactor 20 and the pump body 243 there is H2O2The medicine feeding tank 15 is communicated with the medicine feeding tank; the liquid outlet pipe of the reactor 20 reaches the intermediate sedimentation tank 192 through the dosing tank 122, the static mixer 223, the pump body 244, the dosing tank 132 and the static mixer 224, and is connected with the terminal water outlet through the pump body 245; at the bottom of the two reactors 18, 20, there are vent pipes of ozone generators 171, 172 respectively communicated with their inner cavities;
the medicine adding tanks 11, 121, 131, 14, 15, 122 and 132 are filled with the following medicines from the water inlet in sequence:
20-25% Ca (OH)2+ 1-2% MgCl2+ 1-2% Ca (ClO)2Mixing water;
a mixed aqueous solution of basic aluminum chloride PAC + 3-5% of fly ash;
1-2 per mill sodium polyacrylate (anion) solution;
20～25％H2SO4an aqueous solution;
h with a concentration of 5-10%2O2An aqueous solution;
a mixed aqueous solution of basic aluminum chloride PAC + 3-5% of fly ash;
1-2 per mill sodium polyacrylate (anion) solution;
a medium Fe + C + TiO is arranged in the inner electrolytic tank2。
The invention sequentially extracts a large amount of amino acid protein, propionic acid and acetic acid contained in the waste water discharged in the VB12 production process by the treatment process, and further can be used for preparing food additivesThe agent, the sterile organic fertilizer and the like are sold as commodities, so that the waste is changed into valuable, and the income is increased; the process treats the sludge into the organic fertilizer, not only thoroughly solves the problems of environmental pollution, garbage storage and treatment and the like in the prior art, but also realizes the increase of the income of agricultural products; final waste water treatment into CODCrThe recycled water less than 60 is recycled, so that the pollution of the waste water discharged in the original VB12 production process to the environment is thoroughly solved, and the win-win effect of social benefit and economic benefit is realized. The process is suitable for treating industrial wastewater generated in VB12 production, and can be extended and popularized to the pharmaceutical industry of fermentation processes.
The wastewater treatment machine for flocculating and extracting protein is used for extracting protein in industrial wastewater for producing VB 12.
The microwave processor for wastewater super-oxidation provided by the invention is used for processing industrial wastewater from VB12 production by protein extraction, propionic acid and acetic acid, and terminal drainage is reclaimed water which can be recycled.
The invention will be described in further detail below with reference to the figures and specific embodiments.
Drawings
FIG. 1 is a block diagram of a chemical flocculation process for protein extraction according to the present invention;
FIG. 2 is a schematic diagram of a wastewater treatment machine for extracting protein by chemical flocculation;
FIG. 3 is a block diagram of the process for preparing calcium propionate by the extraction and stripping method of the present invention;
FIG. 4 is a block diagram of a process for preparing glacial acetic acid by an extraction and stripping method according to the invention;
FIG. 5 is a block diagram of a process for treating wastewater E in the process of the present invention;
FIG. 6 is a schematic process diagram of a wastewater super-oxidation microwave processor of the process shown in FIG. 5;
FIG. 7 is a block diagram of the overall process flow of the present invention.
1-chitosan medicine adding tank, wherein a chitosan water solution with the concentration of 2-4 per mill is filled in the medicine adding tank;
a 2-PAC dosing tank filled with aluminum salt PAC (polyaluminium chloride), namely 4-6% basic aluminum chloride aqueous solution;
3-sodium polyacrylate medicine adding tank, wherein the medicine adding tank is filled with auxiliary agent sodium polyacrylate, namely sodium polyacrylate water solution with 0.5-1.5 per mill concentration;
41-static mixer; 42-a filter; 5-a centrifuge; 6-drying machine; 7-a storage tank; 8-a flocculation tank;
11-medicine adding pot containing 20-25% Ca (OH)2+ 1-2% MgCl2+ 1-2% Ca (ClO)2Mixing the aqueous solution;
121. 122-a medicine adding tank, wherein a fly ash aqueous solution of a basic aluminum chloride PAC + 3-5% solution is filled in the medicine adding tank;
131. 132-a medicine adding tank, wherein sodium polyacrylate, namely 1-2 per mill sodium polyacrylate (anion) aqueous solution, is contained in the medicine adding tank;
14-medicine adding tank filled with 20-25% concentration H2SO4An aqueous solution;
15-medicine adding tank filled with 5-10% concentration H2O2An aqueous solution;
16-a flow meter; 171. 172-an ozone generator; 18-a reactor;
191. 192-an intermediate settling tank; 20-a reactor; 21-internal electrolysis tank;
221. 222, 223, 224-static mixers; 23-a pipeline;
241. 242, 243, 244, 245-pump body.
Detailed Description
Resource for producing VB12 industrial wastewaterThe treatment process is carried out according to the process flow shown in fig. 7, namely: industrial waste water from VB12 production → chemical flocculation to extract protein → extraction and reverse extraction to extract propionic acid, calcium propionate → extraction and reverse extraction to extract acetic acid, glacial acetic acid → AOPs of raffinate water3/H2O2And (5) performing composite microwave treatment.
Specifically, the process is realized according to the following method steps:
the chemical flocculation method is used for extracting protein from VB12 producing waste water, and the waste water processor for extracting protein by the chemical flocculation method shown in figure 2 is carried out according to the process steps shown in figure 1.
FIG. 2 is a wastewater treatment machine for chemical flocculation protein extraction, which is a production line. The device comprises a dosing tank 1-3 controlled by a flow meter, a centrifugal sewage pump, a connecting valve, a static mixer 41, a filter 42, a flocculation tank 8, a centrifuge 5, a dryer 6 and a corresponding anti-corrosive liquid pipeline, wherein a pump body before mixing, the static mixer 41, the flocculation tank 8, a pump body before filtering, the filter 42, the centrifuge 5 and the dryer 6 are sequentially connected in series into a whole through the pipeline, a water inlet at the front end of the device is connected with a storage tank 7 for storing industrial wastewater produced by VB12, and a liquid outlet is at the terminal; a chitosan dosing tank 1 and a PAC dosing tank 2 are communicated with a pipeline between the water inlet and the pre-mixing pump body in sequence; a sodium polyacrylate dosing tank 3 is communicated with a pipeline between the pump body and the static mixer 41 before mixing; wherein
A chitosan medicine adding tank 1 which contains 2-4 per mill chitosan water solution;
a PAC dosing tank 2 filled with aluminum salt PAC, namely 4-6% basic aluminum chloride solution;
the sodium polyacrylate medicine adding tank 3 is internally filled with an auxiliary agent sodium polyacrylate, namely 0.5-1.5 per mill sodium polyacrylate water solution.
FIG. 1 is a process for extracting protein by chemical flocculation, which is realized by the following steps:
(1) in the storage tank 7, in order to produce VB12 industrial wastewater, 2-4 per mill chitosan aqueous solution is put into the dosing tank 1 before pumping; then the
(2) PAC (polyaluminium chloride), namely 4-6% basic aluminum chloride solution, is added into a medicine adding tank 2; then the
(3) Adding sodium polyacrylate as adjuvant, i.e. 0.5-1.5 ‰ sodium polyacrylate solution, into the dosing tank 3 after pumping, introducing into the flocculation tank 8 via the static mixer 41 to flocculate protein in wastewater to form flocculate and clear solution;
(4) filtering the floc with a clear solution through a filter 42, performing solid-liquid separation and concentration through a centrifuge 5, and drying through a dryer 6 to obtain a finished product protein which can be further used as a feed additive; the residual wastewater A is reserved;
② the calcium propionate is further prepared by extracting propionic acid by using the waste water A and a back extraction method, and the method is realized by the steps shown in figure 3:
(1) adding extractant into waste water A in a reciprocating vibration type extraction tower to extract propionic acid, and then adding alkali-lime, namely NaOH + Ca (OH) into a back extraction tower2(pure lime with Mg content less than or equal to 0.5%) is used to prepare calcium propionate alkali solution, which is neutralized by about 20% industrial sulfuric acid, concentrated and cooled by membrane filtration and multiple-effect evaporator, and the alkali solution is refluxed and 20M by conical liquid separator2Crystallizing and filtering by a plate-and-frame filter press to obtain a crude product of calcium propionate;
(2) dissolving calcium propionate crude product in deionized water at below 100 deg.C, decolorizing with activated carbon, filtering and concentrating in vacuum suction filter, cooling, crystallizing, filtering at 20M2Filtering in a plate-and-frame filter press, and drying in a drying oven at 100Kg and 100 ℃ to obtain a fine calcium propionate product, namely food-grade calcium propionate;
and the rest wastewater B is reserved.
Thirdly, acetic acid is extracted by using the wastewater B and a back extraction method to further prepare glacial acetic acid, and the steps of the method shown in the figure 4 are as follows:
adding an extracting agent prepared from n-octanol and tributyl phosphate into the wastewater B in a reciprocating vibration type extraction tower for extraction, performing back extraction in a back extraction tower by using soda lime as the back extracting agent, neutralizing by using about 20% industrial sulfuric acid after filtering, adding deionized water for filtering, preparing an acetic acid crude product in a crude distillation tower, and obtaining glacial acetic acid through a rectification tower.
And (4) residual wastewater E.
Treatment of wastewater E
The wastewater treating machine special for wastewater super-oxidation treatment shown in FIG. 6 is used for super-oxidation treatment, and then microwave treatment and solid-liquid separation are carried out. The processor comprises dosing tanks 11, 121, 122, 131, 132, 14 and 15, ozone generators 171 and 171, intermediate sedimentation tanks 191 and 192, reactors 18 and 20, an inner electrolytic tank 21, static mixers 221, 222, 223 and 224, pump bodies 241, 242, 243, 244 and 245 and corresponding anti-corrosive liquid pipelines controlled by flow meters, wherein the main body of the processor is formed by sequentially connecting the reactors 18, the pump body 241, the intermediate sedimentation tank 191, the pump body 242, the inner electrolytic tank 21, the reactor 20, the pump body 243, the intermediate sedimentation tank 192 and the pump body 245 in series through pipelines, the front end, namely a water inlet, of the processor is connected with a VB12 industrial wastewater pipeline after protein extraction, calcium propionate and glacial acetic acid are extracted, and the terminal of the pipeline is connected with a microwave processor; a medicine adding tank 11 is arranged above the pipeline between the water inlet and the reactor 18 and communicated with the pipeline; the pipelines between the reactor 18 and the pump body 241 and between the pump body 242 and the intermediate sedimentation tank 191 are respectively communicated with the dosing tanks 121 and 131 and the static mixers 221 and 222 in turn; a pipeline between the intermediate sedimentation tank 191 and the inner electrolytic tank 21 is provided with H2SO4The medicine adding tank 14 is communicated with the medicine adding tank; on the pipe between the reactor 20 and the pump body 243 there is H2O2The medicine feeding tank 15 is communicated with the medicine feeding tank; the liquid outlet pipe of the reactor 20 reaches the intermediate sedimentation tank 192 through the dosing tank 122, the static mixer 223, the pump body 244, the dosing tank 132 and the static mixer 224, and is connected with the terminal water outlet through the pump body 245; at the bottom of the two reactors 18, 20, there are vent pipes of ozone generators 171, 172 respectively communicated with their inner cavities;
the medicine adding tanks 11, 121, 131, 14, 15, 122 and 132 are filled with the following medicines from the water inlet in sequence:
20-25% Ca (OH)2+ 1-2% MgCl2+ 1-2% Ca (ClO))2, mixing water;
a mixed aqueous solution of basic aluminum chloride PAC + 3-5% of fly ash;
1-2 per mill sodium polyacrylate (anion) solution;
20～25％H2SO4an aqueous solution;
h with a concentration of 5-10%2O2An aqueous solution;
a mixed aqueous solution of basic aluminum chloride PAC + 3-5% of fly ash;
1-2 per mill sodium polyacrylate (anion) solution;
a medium Fe + C + TiO is arranged in the inner electrolytic tank2Fe and C in a weight ratio of 1: 1, TiO2Is 1-2% aqueous solution.
The process of the treatment is carried out by the following method steps, see fig. 5:
(1) the wastewater E is input from a water inlet pipe, and is added with the No. 1 drug from a drug adding tank 11 through a flowmeter 16, and the mixture enters a reactor 18; at the same time, the ozone generator 171 sends O2、O3To reactor 18. The residual protein in the wastewater E is oxidized and decomposed with derivatives such as acetic acid, propionic acid and the like through reaction to generate NO and CO2、H2O；
(2) Pumping water in the reactor 18 into a pipe by a pump, adding the No. 2 medicine into a medicine adding tank 121, staying in a mixer 221 and fully reacting;
(3) the liquid is stirred and mixed by the pump, then the No. 3 medicine is added from the medicine adding tank 131 after the pump, the liquid is fully mixed in the mixer 222 and then enters the intermediate sedimentation tank 191, and then the liquid is pumped into the pipe, and the No. 4 medicine is added from the medicine adding tank 14 before the pump, so that the PH value of the liquid is adjusted to about 4;
(4) the liquid enters a decoloring internal electrolytic tank 21 after being pumped, stays for 30 seconds, is put into No. 5 medicine from a medicine adding tank 15 in a pipe after being discharged from the internal electrolytic tank 21, enters a reactor 20 and stays for 60 minutes;
(5) in the reactor 20, the No. 1 drug was put so that the pH was more than 9, and O was blown in from the ozone generator 1722、O3The oxidation reaction is carried out for 30 seconds again, the reaction gas is blown into the water tank through the pipe 23 for absorption, the water in the reactor 20 is pumped out through the pump, the steps of adding the No. 2 medicine and the No. 3 medicine are repeated, two phases of floc and water are formed, the floc and the water enter a post-treatment microwave system, and the COD is obtained through solid-liquid separationCrAnd (5) qualified reclaimed water of less than 60.
Fifthly, the sludge D is condensed and centrifugally compressed to become the sterile organic fertilizer.
Claims (9)
1. A resource treatment process for industrial wastewater from VB12 production is characterized in that: the treatment process comprises the following method steps:
a. extracting protein from VB12 production wastewater by a chemical flocculation method, and reserving the rest wastewater A for later use;
b. extracting propionic acid from the wastewater A by an extraction and back extraction method to prepare calcium propionate, and reserving the residual wastewater B for later use;
b. extracting acetic acid from the wastewater B by an extraction and back extraction method to prepare glacial acetic acid and obtain the residual wastewater E;
d. treating wastewater E with super-oxidized microwaves: by passingSuper oxidation of AOPs, O3/H2O2And performing solid-liquid separation after microwave composite treatment to obtain a liquid part which is reclaimed water and a solid part which is sludge D.
2. The resource treatment process of industrial wastewater for producing VB12, according to claim 1, characterized in that: the chemical flocculation method is used for extracting protein by the following method steps:
e. adding 2-4 per mill chitosan aqueous solution into VB12 production wastewater, wherein the adding amount is 80-100 mg/L; then the
f. Adding 4-6% basic aluminum chloride aqueous solution with the addition amount of 60-80 mg/L; then the
g. Adding 0.5-1.5 per mill of sodium polyacrylate water solution at a dosage of 4-6mg/L to flocculate protein in the wastewater sufficiently to form floc and clear liquid; then the
h. And (3) adding the supernatant into the flocs, filtering, concentrating and drying to obtain the finished product protein.
3. The resource treatment process of industrial wastewater for producing VB12, according to claim 1, characterized in that: the extraction and back extraction method is used for extracting the propionic acid, and the preparation of the calcium propionate is carried out by the following method steps:
i. adding an extractant into the wastewater A in an extraction tower to extract propionic acid, then adding a back extractant into a back extractant to prepare a calcium propionate alkali liquor, and performing neutralization filtration, concentration cooling, crystallization filtration to obtain a calcium propionate crude product;
j. the crude product of calcium propionate is heated, dissolved, decolored, filtered, concentrated, cooled, crystallized, filtered and dried to obtain the refined product of calcium propionate, namely the edible calcium propionate.
4. The resource treatment process of industrial wastewater for producing VB12, according to claim 1, characterized in that: the extraction and back extraction method is used for extracting acetic acid, and the preparation of glacial acetic acid is carried out by the following method steps:
k. extracting, back-extracting and distilling the wastewater B to obtain an acetic acid aqueous solution;
rectifying acetic acid to obtain glacial acetic acid.
5. The resource treatment process of industrial wastewater for producing VB12, according to claim 1, characterized in that: the superoxide microwave treatment is carried out according to the following steps in sequence:
wastewater E through O2+O3Air stripping ammonia nitrogen, flocculating to remove residual protein, settling in intermediate settling tank, decoloring and internal electrolysis, and O3/H2O2Reacting, microwave treating and solid-liquid separating to obtain a liquid part which is reclaimed water and a solid part which is sludge D.
6. The resource treatment process of industrial wastewater for producing VB12, according to claim 1 or 5, characterized in that: and the sludge D is subjected to concentration, centrifugal compression and physical treatment to finally obtain the sterile organic fertilizer.
7. The process for recycling industrial wastewater containing VB12 according to any one of claims 1, 3 and 4, wherein the process comprises the following steps: the extractant is trioctylamine, tributylphosphine oxide, n-octanol and tributyl phosphate; the stripping agent is Ca (OH)2And aqueous NaOH solution.
8. A special wastewater treatment machine for extracting protein by a chemical flocculation method is characterized in that: the treatment machine comprises dosing tanks (1, 2 and 3) controlled by a flow meter, the dosing tanks are mixed by a pipeline and a pump, enter a flocculation reaction tank (8), are subjected to solid-liquid separation by a centrifugal machine (5) and then form a production line by a dryer (6); the front end, namely a water inlet, is connected with a storage tank (7) for storing industrial wastewater of VB12, and the terminal is a liquid outlet; a chitosan dosing tank (1), a PAC dosing tank (2) and a sodium polyacrylate dosing tank (3) are communicated with the pipeline between the water inlet and the pump body before filtration in sequence;
a chitosan medicine adding tank (1) filled with 2-4 per mill chitosan water solution by weight percentage;
a PAC dosing tank (2) filled with aluminum salt PAC, namely 4-6% basic aluminum chloride aqueous solution;
a sodium polyacrylate medicine adding tank (3) which is internally filled with an auxiliary agent sodium polyacrylate, namely 0.5-1.5 per mill of sodium polyacrylate solution.
9. A special waste water processor for waste water super-oxidation treatment is characterized in that: the device comprises a dosing tank (11, 121, 122, 131, 132, 14, 15), an ozone generator (17), an intermediate sedimentation tank (191, 192), a reactor (18, 20), an inner electrolytic tank (21), a static mixer (221, 222, 223, 224), a pump body (241, 242, 243, 244, 245) and corresponding anti-corrosive liquid pipelines, wherein the dosing tank is controlled by a flow meter, the main body of the device is formed by sequentially connecting the reactor (18), the pump body (241), the intermediate sedimentation tank (191), the pump body (242), the inner electrolytic tank (21), the reactor (20), the pump body (243), the intermediate sedimentation tank (192) and the pump body (245) in series through pipelines, the front end, namely a water inlet, of the device is connected with a VB12 industrial wastewater pipeline after protein extraction, calcium propionate extraction and glacial acetic acid extraction, and the terminal of the device is connected with a microwave processor; a medicine adding tank (11) is arranged above the pipeline between the water inlet and the reactor (18) and communicated with the pipeline; the pipelines between the reactor (18) and the pump body (241) and between the pump body (242) and the intermediate sedimentation tank (191) are respectively communicated with the medicine adding tanks (121, 131) and the static mixers (221, 222) in sequence; h is arranged on a pipeline between the intermediate sedimentation tank (191) and the inner electrolytic tank (21)2SO4The medicine feeding tank (14) is communicated with the medicine feeding tank; the pipeline between the reactor (20) and the pump body (243) is provided with H2O2The medicine feeding pot (15) is communicated with the medicine feeding pot; a liquid outlet pipe of the reactor (20) reaches the intermediate sedimentation tank (192) through the dosing tank (122), the static mixer (223), the pump body (244), the dosing tank (132) and the static mixer (224), and is connected with a terminal water outlet through the pump body (245); at the bottom of the two reactors (18, 20), an air pipe of an ozone generator (17) is respectively communicated with the inner cavities of the reactors;
the medicine adding tanks (11, 121, 131, 14, 15, 122 and 132) are filled with the following medicines from the water inlet in sequence:
20-25% Ca (OH)2+ 1-2% MgCl2+1 to 2% Ca (ClO)2Mixing water;
a mixed aqueous solution of basic aluminum chloride PAC + 3-5% of fly ash;
1-2 per mill sodium polyacrylate (anion) solution;
20～25％H2SO4an aqueous solution;
h with a concentration of 5-10%2O2An aqueous solution;
a mixed aqueous solution of basic aluminum chloride PAC + 3-5% of fly ash;
1-2 per mill sodium polyacrylate (anion) solution;
a medium Fe + C + TiO is arranged in the inner electrolytic tank2。
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| CN102212336B (en) * | 2011-05-30 | 2014-05-28 | 广东慧信环保有限公司 | Method for preparing calcium magnesium carboxylate snow-melting agent by utilizing municipal sludge |
| CN102303987B (en) * | 2011-08-01 | 2013-04-24 | 郭占富 | Production method of organic nutrient fertilizer |
| CN103130353B (en) * | 2011-11-25 | 2014-01-15 | 中国石油天然气股份有限公司 | Treatment method of high-calcium organic wastewater |
| CN107417024B (en) * | 2017-07-26 | 2019-01-25 | 中广核环保产业有限公司 | A kind of medication chemistry sewage treatment process |
| CN108178431A (en) * | 2017-12-27 | 2018-06-19 | 杭州司迈特水处理工程有限公司 | A kind of processing system and processing method for preparing ultrafiltration membrane filature wastewater |
| CN112642183A (en) * | 2020-12-09 | 2021-04-13 | 瑞安市合盛环保科技有限公司 | Recycling treatment process for treating industrial wastewater from VB12 production and special wastewater treatment device thereof |
| CN114380443A (en) * | 2021-12-30 | 2022-04-22 | 呼伦贝尔东北阜丰生物科技有限公司 | Deep extraction method of glutamic acid fermentation tail liquid |
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| SU842053A1 (en) * | 1979-07-30 | 1981-06-30 | Ленинградский Ордена Октябрьскойреволюции И Ордена Трудового Kpac-Ного Знамени Технологический Институтим. Ленсовета | Method of waste purification in production of protein-vitamin concentrate |
| JPH06126295A (en) * | 1992-10-20 | 1994-05-10 | Ishikawajima Harima Heavy Ind Co Ltd | Method for recovering raw material for vitamin b12 |
| RU2151183C1 (en) * | 1999-02-01 | 2000-06-20 | Тумченок Виктор Игнатьевич | Fermenter |
| WO2004108609A1 (en) * | 2003-06-06 | 2004-12-16 | Forskningscenter Risø | Fermentation media comprising wastewater and use hereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU842053A1 (en) * | 1979-07-30 | 1981-06-30 | Ленинградский Ордена Октябрьскойреволюции И Ордена Трудового Kpac-Ного Знамени Технологический Институтим. Ленсовета | Method of waste purification in production of protein-vitamin concentrate |
| JPH06126295A (en) * | 1992-10-20 | 1994-05-10 | Ishikawajima Harima Heavy Ind Co Ltd | Method for recovering raw material for vitamin b12 |
| RU2151183C1 (en) * | 1999-02-01 | 2000-06-20 | Тумченок Виктор Игнатьевич | Fermenter |
| WO2004108609A1 (en) * | 2003-06-06 | 2004-12-16 | Forskningscenter Risø | Fermentation media comprising wastewater and use hereof |
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Assignee: Hebei Huarong Pharmaceutical Co., Ltd. Assignor: Li Gengcheng|Wang Dongzhi Contract fulfillment period: 2009.7.24 to 2014.7.23 contract change Contract record no.: 2009130000101 Denomination of invention: Treatment process for industrial wastewater of VB12 production and dedicated wastewater treatment machine therefor Granted publication date: 20071017 License type: Exclusive license Record date: 2009.8.10 |
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