CN109851057B - Method for deodorizing nifuratel wastewater by using zymophyte - Google Patents
Method for deodorizing nifuratel wastewater by using zymophyte Download PDFInfo
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- CN109851057B CN109851057B CN201910042883.5A CN201910042883A CN109851057B CN 109851057 B CN109851057 B CN 109851057B CN 201910042883 A CN201910042883 A CN 201910042883A CN 109851057 B CN109851057 B CN 109851057B
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Abstract
The invention belongs to the technical field of wastewater treatment, and particularly relates to a method for deodorizing nifuratel wastewater by using zymophyte. Mixing zymophyte with the pretreated nifuratel intermediate wastewater for fermentation treatment, and performing post-treatment to obtain a solution almost without odor. The zymophyte is SUKAAgri-C3009G zymophyte. The process disclosed by the invention is simple to operate, high in efficiency and good in deodorization effect, solves the problem of stink in a production field, improves the working environment, reduces the emission of waste gas, belongs to a green process, and the treated solution can be directly discharged; no toxic and harmful gas is emitted in the process of treating the wastewater; the safety and sanitation of the production field are ensured, and no odor is generated. The SUKAAgri-C3009G zymocyte has low cost and short fermentation time, and can be used as fertilizer to be thrown into farmland.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a method for deodorizing nifuratel wastewater by using zymophyte.
Background
One intermediate of nifuratel is methylthioepoxypropane, CAS number 45378-62-9[1 ]]Molecular formula C4H8OS, molecular weight: 104.1707, is mainly used as a pharmaceutical intermediate.
Currently, epichlorohydrin and sodium methyl mercaptide solution are generally used as raw materials in industrial production, and are directly reacted in dichloromethane solvent at low temperature to prepare dichloromethane solution containing the methyl mercaptide, and then the dichloromethane solution is washed by water and subjected to dichloromethane phase reduced pressure rectification to prepare the methyl mercaptide.
The methylthio propylene oxide produced by the method contains waste water and organic waste liquid generated in the processes of liquid separation and reduced pressure distillation, contains sodium methyl mercaptide, methyl mercaptan, volatile by-product methyl sulfide and the like, has foul smell, is a toxic pollutant, and causes the odor and the taste of a production site and even the whole plant area.
In order to reduce the emission of odor and pollution, the waste water and organic waste liquid must be deodorized.
Most of the wastewater containing the thioether is treated by an oxidation method, but the treatment effect is not obvious, and a large amount of organic wastewater is generated. Therefore, the search for an efficient and environment-friendly deodorization method has better social significance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for deodorizing nifuratel wastewater by using zymophyte, the method has the advantages of simple process operation, high efficiency and better deodorizing effect, solves the problem of stink in a production field, improves the working environment, reduces the emission of waste gas, belongs to a green process, and the treated solution can be directly discharged; no toxic and harmful gas is emitted in the process of treating the wastewater; the safety and sanitation of the production field are ensured, and no odor is generated.
The method for deodorizing nifuratel wastewater by using zymophyte disclosed by the invention is characterized in that zymophyte and pretreated nifuratel intermediate wastewater are mixed for fermentation treatment, and then the mixture is subjected to post-treatment to obtain a nearly odorless solution.
Wherein:
all the raw materials are wastewater generated in the production process of the nifuratel intermediate. The nifuratel intermediate wastewater is as follows: adding a catalyst into a dichloromethane solution of epoxy chloropropane, dropwise adding a sodium methyl mercaptide solution at the low temperature of 0-15 ℃, then preserving the temperature for 3-3.2 hours within the temperature range, and then carrying out liquid separation, wherein the separated water phase is the nifuratel intermediate wastewater. The pH value of the nifuratel intermediate wastewater is 10-12, and most organic matters in the wastewater are thioether compounds. The main components of the nifuratel intermediate wastewater are methyl mercaptan, sodium methyl mercaptide and epoxy methyl sulfide, and preferably, the nifuratel intermediate wastewater comprises the following components in concentration: 0.1 to 1 percent of methyl mercaptan, 2 to 3 percent of sodium methyl mercaptide and 0.5 to 1 percent of epoxy methyl sulfide.
The pretreatment is to adjust the pH value of the nifuratel intermediate wastewater to 6-8, and the material used for adjusting the pH value in the pretreatment is acetic acid or 36% concentrated hydrochloric acid. The nifuratel intermediate wastewater is pretreated, and the pH value is adjusted to 6-8, so that the zymocyte has a good fermentation environment.
The fermentation bacteria are SUKAAgri-C3009G fermentation bacteria, the nifuratel intermediate wastewater is alkaline, the pH value is 6-8 after pretreatment, and the salt content is increased. The inventor finds that only the SUKAAgri-C3009G zymocyte is suitable for the high-salt and pressurized fermentation environment of the invention, and other zymocytes are easy to lose activity and can not achieve ideal fermentation effect. Most of organic matters in the wastewater are thioether compounds, the SUKAAgri-C3009G zymocyte contains high-concentration nonpathogenic beneficial microorganisms, and is added with a plurality of enzymes capable of decomposing various macromolecular substances, and the sulfur-containing compounds in the wastewater can be catalyzed by the enzymes to become sulfur-containing amino acid; the microorganisms in the SUKAAgri-C3009G zymocyte can generate a series of digestive enzymes in the composting process to decompose the sulfur-containing amino acids and other organic matters, thereby providing energy for the metabolism of the microorganisms and achieving the aim of deodorizing waste water.
The mass ratio of the pretreated nifuratel intermediate wastewater to the SUKAAgri-C3009G zymocyte is 1000:3-1000:6, and within the mass ratio range, the wastewater can be effectively deodorized, and the cost for treating the wastewater can be controlled.
The method for deodorizing nifuratel wastewater by using zymophyte comprises the following steps:
(1) adjusting the pH value of the nifuratel intermediate wastewater to 6-8;
(2) adding the solution obtained in the step (1) into an aerobic bioreactor, adding SUKAAgri-C3009G zymocyte, introducing air, and sealing to raise the temperature;
(3) supplementing air to the solution obtained in the step (2) at intervals, and reacting for 72 hours;
(4) and (4) carrying out filter pressing on the solution obtained in the step (3) to obtain a solution with almost no odor.
Wherein:
in the step (2), the temperature is raised to 35-55 ℃ in a closed manner.
And (3) introducing air to 0.2MPa in the step (2).
The step (3) is as follows: and (3) supplementing air to the solution obtained in the step (2) at an interval of 8 hours until the pressure is 0.2MPa for 72 hours, and detecting by an LT-CG-103-A2800-12 type wireless sensor to obtain qualified odor with the concentration of less than or equal to 1 ppm. The treatment of the nifuratel intermediate wastewater mainly comprises the steps of pressurizing during fermentation, intermittently supplementing air, and pressurizing to improve the activity of the SUKAAgri-C3009G zymocyte.
And (4) performing filter pressing in a plate-frame filter pressing mode in the step (4), wherein the filter cake can be used as a fertilizer to be thrown into a farmland. The working pressure of the filter pressing is 15-18 MPa. The insoluble substances in the fermented wastewater are subjected to sedimentation treatment by a viscous common method, and the treatment time is long; the invention adopts a filter pressing mode for treatment, and the working pressure of the filter pressing is 15-18MPa, thereby greatly improving the treatment efficiency.
The pH value of the nifuratel intermediate wastewater is adjusted to 6-8, the nifuratel intermediate wastewater is transferred to an aerobic bioreactor, beneficial microorganisms are added to decompose organic matters in the nifuratel intermediate wastewater, the organic matters are decomposed by aerobic, mesophilic and thermophilic microorganisms in the process, and the odor concentration of the decomposed wastewater is below 1ppm through detection. And then filtering, wherein the filtered solid can be used as fertilizer to be put into farmlands, the COD of the filtrate is 50-100mg/L, the ammonia nitrogen is 10-15mg/L, and the filtrate can be discharged.
SUKAAgri-C3009G is a microbial product containing a high concentration of non-pathogenic beneficial microorganisms with the addition of enzymes capable of breaking down various macromolecular substances. SUKAAgri-C3009G contains aerobic microorganisms with specific decomposition ability, which can grow and decompose organic substances during fermentation; the complex strain in the SUKAAgri-C3009G product can rapidly decompose proteins and organic substances in industrial, municipal and agricultural wastes. The soil conditioner is a good natural covering and soil conditioner, improves the soil structure, texture and ventilation, and enhances the water retention capacity of soil; can be used as a fertilizer for farmland or vegetable fields.
Compared with the prior art, the invention has the following advantages:
(1) the invention has simple process operation, high efficiency and better deodorization effect, solves the problem of stink in the production field, improves the working environment, reduces the emission of waste gas, belongs to a green process, and can directly discharge and treat the treated solution.
(2) The invention can not emit poisonous and harmful gas in the process of treating the waste water; the safety and sanitation of the production field are ensured, and no odor is generated.
(3) The fermentation bacteria SUKAAgri-C3009G contains beneficial microorganisms, and can greatly shorten fermentation time, and the fermentation bacteria SUKAAgri-C3009G has low cost, and can be used as fertilizer to be thrown into farmland. The inventor finds that only the SUKAAgri-C3009G zymocyte is suitable for the high-salt and pressurized fermentation environment of the invention, and other zymocytes are easy to lose activity and can not achieve ideal fermentation effect. Most of organic matters in the wastewater are thioether compounds, the SUKAAgri-C3009G zymocyte contains high-concentration nonpathogenic beneficial microorganisms, and is added with a plurality of enzymes capable of decomposing various macromolecular substances, and the sulfur-containing compounds in the wastewater can be catalyzed by the enzymes to become sulfur-containing amino acid; the microorganisms in the SUKAAgri-C3009G zymocyte can generate a series of digestive enzymes in the composting process to decompose the sulfur-containing amino acids and other organic matters, thereby providing energy for the metabolism of the microorganisms and achieving the aim of deodorizing waste water.
(4) The treatment of the nifuratel intermediate wastewater mainly comprises the steps of pressurizing during fermentation, intermittently supplementing air, and pressurizing to improve the activity of the SUKAAgri-C3009G zymocyte.
(5) The insoluble substances in the fermented wastewater are viscous and are treated in a filter pressing mode, and the working pressure of the filter pressing is 15-18MPa, so that the treatment efficiency is greatly improved; and the common method is sedimentation treatment, so that the treatment time is longer.
Detailed Description
The present invention will be further described with reference to the following examples.
All the raw materials are wastewater generated in the production process of the nifuratel intermediate; the nifuratel intermediate wastewater is as follows: adding a catalyst into a dichloromethane solution of epoxy chloropropane, dropwise adding a sodium methyl mercaptide solution at the low temperature of 0-15 ℃, then preserving the temperature for 3-3.2 hours within the temperature range, and then carrying out liquid separation, wherein the separated water phase is the nifuratel intermediate wastewater.
Odor detection was detected with a LT-CG-103-A2800-12 wireless sensor. Specifically, the wireless sensor probe is placed at the liquid level, and the display displays that the numerical value is below 1ppm, namely the product is qualified.
Example 1
The main components in the nifuratel intermediate wastewater adopted in example 1 are methyl mercaptan, sodium methyl mercaptide and epoxy methyl sulfide. The nifuratel intermediate wastewater comprises the following components in concentration: 0.6 percent of methyl mercaptan, 2.1 percent of sodium methyl mercaptide, 0.6 percent of epoxy methyl sulfide, 4365mg/L of COD, 653mg/L of ammonia nitrogen and 10-12 of pH.
A method for deodorizing nifuratel wastewater by using zymophyte comprises the following steps:
(1) 1000kg of the nifuratel intermediate wastewater was transferred to a wastewater treatment reaction kettle, and 6.67kg of acetic acid was used to adjust the pH to 7.1.
(2) Transferring the wastewater with the adjusted pH value into an aerobic bioreactor, adding 3kg of SUKAAgri-C3009G zymocyte, introducing 0.2MPa of air, sealing the reactor, heating to 35 ℃, starting to rotate, and keeping the temperature of the system at 40 +/-5 ℃.
(3) And (3) introducing air to 0.2MPa at intervals of 8 hours in the step (2) for three days. When the odor concentration was detected to be 0.5ppm, the process was stopped.
(4) And (4) performing filter pressing on the solution in the step (3), specifically performing filter pressing in a plate-frame filter pressing mode, keeping the working pressure at 15.7MPa, and collecting filter cakes after the filter pressing is finished, wherein the filtrate is a solution almost without odor.
Through detection, COD in the filtrate is 68mg/L, ammonia nitrogen is 11mg/L, and the concentration of the main components in the filtrate is as follows: 0.002% of methyl mercaptan, 0.001% of epoxy methyl sulfide, and no sodium methyl mercaptide; an exhaust treatment may be performed.
Example 2
The main components in the nifuratel intermediate wastewater adopted in the example 2 are methyl mercaptan, sodium methyl mercaptide and epoxy methyl sulfide. The nifuratel intermediate wastewater comprises the following components in concentration: 0.6 percent of methyl mercaptan, 2.2 percent of sodium methyl mercaptide, 0.8 percent of epoxy methyl sulfide, 4432mg/L of COD, 675mg/L of ammonia nitrogen and 10-12 of pH.
A method for deodorizing nifuratel wastewater by using zymophyte comprises the following steps:
(1) 500kg of the nifuratel intermediate wastewater was transferred to a wastewater treatment reaction vessel, and 3.33kg of acetic acid was used to adjust the pH to 7.0.
(2) Transferring the wastewater with the adjusted pH value into an aerobic bioreactor, adding 1.5kg of SUKAAgri-C3009G zymocyte, introducing air of 0.2MPa, sealing the reactor, heating to 35 ℃, starting to rotate, and keeping the temperature of the system at 45 +/-5 ℃.
(3) And (3) introducing air to 0.2MPa at intervals of 8 hours in the step (2) for three days. When the odor concentration was detected to be 0.8ppm, the process was stopped.
(4) And (4) performing filter pressing on the solution in the step (3), specifically performing filter pressing in a plate-frame filter pressing mode, keeping the working pressure at 16.1MPa, and collecting filter cakes after the filter pressing is finished, wherein the filtrate is a solution almost without odor.
Through detection, COD in the filtrate is 71mg/L, ammonia nitrogen is 12mg/L, and the concentration of the main components in the filtrate is as follows: 0.002% of methyl mercaptan, undetected sodium methyl mercaptide and undetected epoxy methyl sulfide, and can be discharged.
Example 3
The main components in the nifuratel intermediate wastewater adopted in example 3 are methyl mercaptan, sodium methyl mercaptide and epoxy methyl sulfide. The nifuratel intermediate wastewater comprises the following components in concentration: 0.4 percent of methyl mercaptan, 2.1 percent of sodium methyl mercaptide, 0.5 percent of epoxy methyl sulfide, 4283mg/L of COD, 629mg/L of ammonia nitrogen and 10-12 of pH.
A method for deodorizing nifuratel wastewater by using zymophyte comprises the following steps:
(1) 1000kg of nifuratel intermediate wastewater is transferred into a wastewater treatment reaction kettle, 11.3kg of 36% concentrated hydrochloric acid is used, and the pH value is adjusted to 6.8.
(2) Transferring the wastewater with the adjusted pH value into an aerobic bioreactor, adding 3kg of SUKAAgri-C3009G zymocyte, introducing 0.2MPa of air, sealing the reactor, heating to 35 ℃, starting to rotate, and keeping the temperature of the system at 40 +/-5 ℃.
(3) And (3) introducing air to 0.2MPa at intervals of 8 hours in the step (2) for three days. When the odor concentration was detected to be 0.7ppm, the process was stopped.
(4) And (4) performing filter pressing on the solution in the step (3), specifically performing filter pressing in a plate-frame filter pressing mode, keeping the working pressure at 16.3MPa, and collecting filter cakes after the filter pressing is finished, wherein the filtrate is a solution almost without odor.
Through detection, COD of the filtrate is 71mg/L, ammonia nitrogen is 11mg/L, and the concentration of the main components in the filtrate is as follows: 0.001% of methyl mercaptan, no sodium methyl mercaptide and 0.001% of epoxy methyl sulfide, and can be discharged.
Comparative example 1
Comparative example 1 the nifuratel intermediate wastewater and deodorization method used was the same as in example 1, the only difference being that instead of the SUKAAgri-C3009G fermenters, EM probiotics were used.
Through detection, COD is 3983mg/L in the filtrate, ammonia nitrogen is 562mg/L, and the concentration of the main components in the filtrate is as follows: 1.3 percent of methyl mercaptan, 0.2 percent of sodium methyl mercaptide and 0.2 percent of epoxy methyl sulfide. The EM probiotics have no effect in the fermentation process in the reactor and do not achieve the expected effect.
Comparative example 2
Comparative example 2 the nifuratel intermediate wastewater and deodorization method used was the same as in example 2, except that compost ferments were used instead of SUKAAgri-C3009G ferments.
Through detection, COD 3620mg/L and ammonia nitrogen 512mg/L are contained in the filtrate, and the concentration of the main components in the filtrate is as follows: 1.1 percent of methyl mercaptan, 0.08 percent of sodium methyl mercaptide and 0.03 percent of epoxy methyl sulfide. The compost zymophyte does not play a role in the fermentation process in the reactor and does not achieve the expected effect.
Claims (6)
1. A method for deodorizing nifuratel wastewater by using zymophyte is characterized in that: mixing zymophyte with the pretreated nifuratel intermediate wastewater for fermentation treatment, and performing post-treatment to obtain a solution almost without odor;
the method comprises the following steps:
(1) adjusting the pH value of the nifuratel intermediate wastewater to 6-8;
(2) adding the solution obtained in the step (1) into an aerobic bioreactor, adding SUKAAgri-C3009G zymocyte, introducing air, and sealing to raise the temperature;
(3) supplementing air to the solution obtained in the step (2) at intervals, and reacting until the odor concentration is below 1ppm to obtain qualified product;
(4) carrying out filter pressing on the solution obtained in the step (3) to obtain a solution almost without odor;
wherein: in the step (2), the temperature is raised to 35-55 ℃ in a closed manner; introducing air to 0.2MPa in the step (2);
the step (3) is as follows: and (3) supplementing air to the solution obtained in the step (2) at an interval of 8 hours until the pressure is 0.2MPa for 72 hours, and detecting by an LT-CG-103-A2800-12 type wireless sensor to obtain qualified odor with the concentration of below 1 ppm.
2. The method for deodorizing nifuratel wastewater by using fermentation tubes according to claim 1, characterized in that: the mass ratio of the pretreated nifuratel intermediate wastewater to the SUKAAgri-C3009G zymocyte is 1000:3-1000: 6.
3. The method for deodorizing nifuratel wastewater by using fermentation tubes according to claim 1, characterized in that: the nifuratel intermediate wastewater is as follows: adding a catalyst into a dichloromethane solution of epoxy chloropropane, dropwise adding a sodium methyl mercaptide solution at the low temperature of 0-15 ℃, then preserving the temperature for 3-3.2 hours within the temperature range, and then carrying out liquid separation, wherein the separated water phase is the nifuratel intermediate wastewater.
4. The method for deodorizing nifuratel wastewater by using fermentation tubes according to claim 3, wherein: the pH value of the nifuratel intermediate wastewater is 10-12, and the nifuratel intermediate wastewater comprises the following components in concentration: 0.1 to 1 percent of methyl mercaptan, 2 to 3 percent of sodium methyl mercaptide and 0.5 to 1 percent of epoxy methyl sulfide.
5. The method for deodorizing nifuratel wastewater by using fermentation tubes according to claim 1, characterized in that: the pretreatment is to adjust the pH value of the nifuratel intermediate wastewater to 6-8; the material used for adjusting the pH value by pretreatment is acetic acid or 36 percent concentrated hydrochloric acid.
6. The method for deodorizing nifuratel wastewater by using fermentation tubes according to claim 1, characterized in that: and (4) performing filter pressing in a plate-frame filter pressing mode in the step (4), wherein the working pressure of the filter pressing is 15-18 MPa.
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| CN1636603A (en) * | 2004-01-09 | 2005-07-13 | 味之素株式会社 | Deodorizing agent containing dry cell of microorganism as active ingredient and deodorizing method |
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| CN104324607A (en) * | 2014-10-15 | 2015-02-04 | 宁夏宝塔石化科技实业发展有限公司 | Biological deodorization method for sodium methyl mercaptide tail gas treatment |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1636603A (en) * | 2004-01-09 | 2005-07-13 | 味之素株式会社 | Deodorizing agent containing dry cell of microorganism as active ingredient and deodorizing method |
| CN104232551A (en) * | 2014-09-29 | 2014-12-24 | 山东苏柯汉生物工程股份有限公司 | Pig-chicken excrement fermenting compound bacteria, preparation method and method of utilizing compound bacteria to ferment and prepare organic fertilizer |
| CN104324607A (en) * | 2014-10-15 | 2015-02-04 | 宁夏宝塔石化科技实业发展有限公司 | Biological deodorization method for sodium methyl mercaptide tail gas treatment |
Non-Patent Citations (1)
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