CN107311254A - A kind of resource utilization method of thiram waste water - Google Patents
A kind of resource utilization method of thiram waste water Download PDFInfo
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- CN107311254A CN107311254A CN201710754366.1A CN201710754366A CN107311254A CN 107311254 A CN107311254 A CN 107311254A CN 201710754366 A CN201710754366 A CN 201710754366A CN 107311254 A CN107311254 A CN 107311254A
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- Prior art keywords
- waste water
- thiram
- evaporation
- resource utilization
- activated carbon
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Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention discloses a kind of resource utilization method of thiram waste water, using the method for highly efficient distilling, light component in waste water（Dimethylamine and carbon disulfide）And heavy constituent（Organic salt）Separate and as reaction raw materials recycling, the low concentration wastewater isolated reaches emission request after charcoal absorption is handled.Organic substance in thiram waste water is carried out recycling by this method so that raw material availability height, small waste discharge amount, process stabilizing, simple to operate.
Description
Technical field
The invention belongs to technical field of waste water processing, more particularly to a kind of resource utilization method of thiram waste water.
Background technology
Thiram, is also tetramethylthiuram disulfide, is widely used in industry and agricultural, is used as vulcanization accelerator, sterilization
Agent and seed drenching agent are used.In industrial production using more thiram preparation method be usually two steps synthesis, the first step by
Secondary amine, carbon disulfide and alkali reaction generation dithiocar-bamate, second step is oxidized, dimerization obtains thiuram-disulfide.
The preparation method of traditional thiram is chlorine-air method, can produce substantial amounts of waste gas, waste water and abraum salt, big for environment pollution, ring
Protecting input, to account for manufacturing cost too high, and process safety is relatively low.Although CN104592074A is synthesized with hydrogen peroxide oxidation Sodium Dimethyldithiocarbamate
Thiram, but sodium sulfate salt is generated, dangerous waste processing cost is added, and expend a large amount of liquid caustic soda and sulfuric acid.CN1299814 is reported
Road uses hydrogen peroxide as oxidant, but has used ammoniacal liquor, subsequent oxidation is generated ammonium salt.Application number CN01104137.4
It is that oxidant carries out synthesis thiram to be disclosed with CN200910064565.5 using air, oxygen or hydrogen peroxide, but is needed
Organic solvent is used, operating condition is harsh, it is dangerous high, and difficult solvent recovery.
From the viewpoint of chemically reacting, alternative chemical oxidizing agent has air, natrium nitrosum, hydrogen peroxide, secondary chlorine
Sour sodium, bromine, iodine, persulfate, perbromate, potassium permanganate and oxygen etc..In addition, electroxidation method is also a kind of way of oxidation
Footpath.At present, China mainly makees oxidant using air and natrium nitrosum, is either aoxidized with air or with natrium nitrosum
Agent, after oxidation is completed, they enter waste water all in the form of compound with the alkali needed for first step reaction and waste gas is discharged into ring
Border, produces a large amount of intractable salt-containing organic wastewaters during the course of the reaction.
Thiram waste water is handled for non-biochemical process, publication number CN104016447 is disclosed to be located in advance using a kind of electrochemistry
The method for managing thiram agricultural chemicals waste water, high concentration thiram waste water is passed through using titanium-based tin ash antimony ruthenium cobalt cerium electrode as anode
Electrolytic cell, persistently handle waste water for a period of time under certain current density.This method is to destroy it by chemically reacting
In sulfur-bearing, containing ammonia nitrogen substances, COD clearances reach that more than 60%, BOD/COD is increased to more than 0.3 from less than 0.1, raising
Its biodegradability.Publication number CN106882867A disclose in a kind of modified graphene catalytic oxidation treatment thiram sulfur-bearing and
The method of ammonia nitrogen waste water, by adding nano level modified graphene, dripping hydrogen peroxide medicament, catalytic oxidation in waste water
The structure of sulphur-containing substance therein and ammonia nitrogen substances is destroyed, the purpose of degraded is reached, not extracts active ingredients therein
Utilize, and saline solution therein is not also handled.
High big with solvent consumption for the inorganic salt content in waste water, Chinese patent CN106699622 discloses a kind of nothing
The efficient green synthetic method of the thiram of organic solvent is needed, it does reaction dissolvent with water, add dimethylamine solution and curing
Carbon carries out synthetic intermediate;Then add hydrogen peroxide and carry out oxidative synthesis, separation of solid and liquid, drying, you can obtain described Fu Mei
It is double.The reaction of the method is carried out in water, the thiram through 2 step one pot process, it is not necessary to organic solvent, it is not necessary to inorganic base
Or organic base, sewage is easy to be recycled, with technique is simple, maneuverable feature, and the purity of thiram can reach 98%
More than.Mother liquor recovery after reverse-osmosis treated in the method, aquifer yield is small, does not produce abraum salt, extremely environmental protection and economy.But
The waste water contains higher organic salt, and reverse osmosis membrane operating cost is high.Sulphur and ammonia-nitrogen content are high in the waste water simultaneously, COD contents
Also very high, biodegradability is poor, and due to variation water quality, often due to thiram and the content overproof of other reaction products in waste water
Cause strain not adapt to and dead, cause wastewater biochemical treatment facility not run and influence production, so biochemical process is not yet
Suitable for the processing of the waste water.
The content of the invention
In order to overcome the above-mentioned deficiencies of the prior art, the invention provides a kind of recycling side of thiram waste water
Method.For thiram synthetic wastewater, inorganic salts are free of in waste water, N, N- DDD dimethylammonium dimethyl dithiocarbamates is mainly contained
Salt and unreacted dimethylamine and carbon disulfide, using highly efficient distilling technology, isolate carbon disulfide in thiram waste water and
Dimethylamine and its corresponding salting liquid, return to recycling in production respectively.
The invention provides a kind of resource utilization method of thiram waste water, comprise the steps of：
（1）The thiram production waste water of 100 parts of volumes is taken, mechanical admixture is filtered to remove and gelatinous solid obtains clear filtrate；
（2）Filtrate carries out highly efficient distilling, and tower top obtains the light component solution of 5 ~ 20 parts of volumes, and direct reuse is into production, tower reactor
Obtain the heavy constituent devaporation of 80 ~ 95 parts of volumes；Highly efficient distilling pressure tower is -0.1 ~ 0.1MPa, and bottom temperature control exists（50℃
~100℃）± 10 DEG C, tower top temperature control exists（30℃~90℃）±10℃；Preferential highly efficient distilling pressure tower is 0.1MPa, tower reactor
Temperature control is at 100 DEG C ± 1 DEG C, and tower top temperature is controlled at 90 DEG C ± 2 DEG C.
（3）Deviate from the solution of light component by concentration, the pressure of concentration is -0.1 ~ 1MPa, can use multiple-effect evaporation, subtract
Press one or two kinds of evaporation mode combinations of evaporation, atmospheric evaporation, mechanical compress evaporation, rectifying.Obtain 35 ~ 50 parts of volume left sides
Right organic slat solution, is back to use in production；The evaporation lime set for obtaining the low COD of 30 ~ 60 parts of volumes goes water process；
（4）Evaporation lime set obtains COD≤150mg/L, ammonia nitrogen≤25mg/L through charcoal absorption processing.Evaporate lime set processing
Activated carbon can select carbo lignius, coconut husk charcoal, coal mass active carbon, bamboo charcoal, petroleum-type activated carbon, regenerated carbon, and specific surface area reaches 100-
2000m2/ g, micro pore volume 30 ~ 90% or so, its micropore size are 10A ° -100A ° of activated carbon；It is preferential to be reached from specific surface area
1000-1600m2/ g, micro pore volume 50 ~ 70% or so, its micropore size are 20A ° -40A ° of activated carbon.
Compared with prior art, the invention has the advantages that：
A. the present invention uses highly efficient distilling to thiram waste water first, and isolated dimethylamine and carbon disulfide, which return to production, to be continued
Use, effectively increase the utilization rate of raw material, while substantially reducing the content of sulphur and ammonia nitrogen substances in waste water.
B. the present invention continues to thiram waste water using concentration, and obtained organic slat solution can also be used as in the middle of reaction and produce
Thing returns to production and is continuing with, and further increases the utilization rate of reaction raw materials.
C. the waste water that thiram waste water is obtained after highly efficient distilling, concentration in the present invention, COD is low, ammonia nitrogen is low, through making a living
After property charcoal adsorption treatment, you can qualified discharge.
D. the useful component in the present invention in thiram waste water is back to production, not only effectively reduces environmentally friendly load, simultaneously
Also save production cost.
Embodiment
With reference to instantiation, the present invention will be further described.
Example 1
Take 500mL mother liquors, be added to after filtering in cucurbit, using electric heating cover, control in cucurbit temperature be 100 ±
0.5 DEG C, 90 ± 2 DEG C of tower top temperature；Infinite reflux starts extraction after 1 hour, control reflux ratio 4:1, when tower top temperature is begun to ramp up
To stopping extraction at 95 DEG C.Overhead extraction about 60mL solution, its content is：Carbon disulfide 2.6%；Dimethylamine 3.1%；Tower reactor is remained
440mL solution.Tower top light component passes through reuse verification experimental verification, can meet production requirement.
Tower reactor 440mL solution, rotated evaporimeter, under the conditions of -0.06MPA, temperature 60 C, vacuum evaporation 1 is small
When, obtain concentrating salting liquid 240mL, obtain evaporation condensate 200mL, its COD is 900 mg/L.Obtained salting liquid component table
Levying content is：Carbon disulfide 1.9%, dimethylamine 0.5%；By reuse verification experimental verification, production and application requirement can be met.
The activated carbon that obtained evaporation lime set 200mL is passed through with 10ml/min flow velocity（Bamboo charcoal, specific surface area reaches
1500m2/g）After pillar filtering, obtained waste water COD=75mg/L, ammonia nitrogen≤12mg/L meets garden emission request.
Example 2
Mother liquors of the 1000mL after filtering is taken, is added in cucurbit, using electric heating cover, controls the temperature in cucurbit to be
101 ± 0.5 DEG C, 90 ± 2 DEG C of tower top temperature；Infinite reflux starts extraction after 1 hour, control reflux ratio 3:1, when tower top temperature starts
Stop extraction when rising to 95 DEG C.Overhead extraction about 150mL solution, its content is：Carbon disulfide 2.1%；Dimethylamine 3.5%；Tower
Kettle remains 850mL solution.Tower top light component passes through reuse verification experimental verification, can meet production requirement.
Tower reactor 850mL solution, rotated evaporimeter, under the conditions of -0.08MPA, temperature 50 C, vacuum evaporation 1 is small
When, obtain concentrating salting liquid 500mL, obtain evaporation condensate 350mL, its COD is 450 mg/L.Obtained salting liquid component table
Levying content is：Carbon disulfide 1.8%；Dimethylamine 0.6%；By reuse verification experimental verification, production and application requirement can be met.
The activated carbon that obtained evaporation lime set 350mL is passed through with 10ml/min flow velocity（Coal mass active carbon, specific surface area reaches
1200m2/g）After pillar filtering, obtained waste water COD 90mg/L, ammonia nitrogen≤13mg/L meets garden emission request.
Example 3
Mother liquors of the 100mL/h after filtering is added to the middle part of rectifying column, and it is 20KPa, infinite reflux 1 hour to control tower top pressure
After start extraction, control reflux ratio 4:1, overhead extraction light component liquid inventory about 14mL/h, its content is：Carbon disulfide
2.8%；Dimethylamine 4.6%；Tower bottom produces lime set, and flow is about 35mL/h, the activated carbon that lime set is passed through with 10ml/min flow velocity
（Coal mass active carbon, specific surface area reaches 1200m2/g）After pillar filtering, obtained waste water COD 90mg/L, ammonia nitrogen≤13mg/L is full
Sufficient garden emission request.Tower reactor discharge concentration salting liquid, flow is about 50mL/h, and light component and heavy constituent are returned to be made in production
With by reuse verification experimental verification, production and application requirement can be met.
Claims (4)
1. a kind of resource utilization method of thiram waste water, it is characterised in that：Two in waste water are isolated by highly efficient distilling
The light component such as methylamine and carbon disulfide is simultaneously back to production as raw material, reduces sulphur and ammonia-nitrogen content in solution；Rectifying kettle liquid is again
It is concentrated, certain density salting liquid reuse is reached, obtained evaporation lime set can meet emission request by activated carbon processing,
Comprise the steps of：
（1）The thiram production waste water of 100 parts of volumes is taken, the filter that mechanical admixture and gelatinous solid are clarified is filtered to remove
Liquid；
（2）Filtrate, which is put into rectifying column, carries out highly efficient distilling, and tower top obtains 5 ~ 20 parts of volume light component solution, is returned directly to production
Use, tower reactor obtains the heavy constituent devaporation of 80 ~ 95 parts of volumes；
（3）Tower reactor heavy constituent obtains 35 ~ 50 parts of volumes or so organic slat solution, returns to production and application by concentration；Obtain 30 ~
The low COD of 60 parts of volumes evaporation lime set goes water process；
（4）Evaporation lime set is handled through charcoal absorption, obtains COD≤150mg/L in waste water, ammonia nitrogen≤25mg/L.
2. a kind of resource utilization method of thiram waste water according to required by right 1, it is characterised in that：High-efficient spiral-screen column pressure
Power is -0.1 ~ 0.1MPa, and bottom temperature control exists（50℃~100℃）± 10 DEG C, tower top temperature control exists（30℃~90℃）±
10℃；Preferential highly efficient distilling pressure tower is 0.1MPa, bottom temperature control at 100 DEG C ± 1 DEG C, tower top temperature control 90 DEG C ±
2℃。
3. a kind of resource utilization method of thiram waste water according to required by right 1, it is characterised in that：Deviate from light component
Solution is by concentration, and the pressure of concentration is -0.1 ~ 1MPa, can use multiple-effect evaporation, reduction vaporization, atmospheric evaporation, machinery pressure
Contracting evaporation, one or two kinds of evaporation mode combinations of rectifying.
4. a kind of resource utilization method of thiram waste water according to required by right 1, it is characterised in that：Evaporate lime set processing
Activated carbon can select carbo lignius, coconut husk charcoal, coal mass active carbon, bamboo charcoal, petroleum-type activated carbon, regenerated carbon, and specific surface area reaches
100-2000m2/ g, micro pore volume 30 ~ 90% or so, its micropore size are 10A ° -100A ° of activated carbon；It is preferential to select than surface
Product reaches 1000-1600m2/ g, micro pore volume 50 ~ 70% or so, its micropore size are 20A ° -40A ° of activated carbon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201710754366.1A CN107311254A (en) | 2017-08-29 | 2017-08-29 | A kind of resource utilization method of thiram waste water |
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| CN201710754366.1A CN107311254A (en) | 2017-08-29 | 2017-08-29 | A kind of resource utilization method of thiram waste water |
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| CN107311254A true CN107311254A (en) | 2017-11-03 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108101297A (en) * | 2017-11-27 | 2018-06-01 | 杭州师范大学钱江学院 | A kind of processing method of the agricultural chemicals waste water containing dithio formate |
| CN108128971A (en) * | 2017-12-22 | 2018-06-08 | 杭州师范大学钱江学院 | Wastewater treatment equipment containing dithio formate |
| CN108178411A (en) * | 2017-12-22 | 2018-06-19 | 杭州师范大学钱江学院 | A kind of device for recycling carbon disulfide in waste water containing dithio formate |
| CN110256318A (en) * | 2019-07-19 | 2019-09-20 | 山东阳谷华泰化工股份有限公司 | A kind of clean method for producing of tetra-benzyl thiram disulfide |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103145577A (en) * | 2013-02-25 | 2013-06-12 | 天津天中福大科技发展有限公司 | Method and equipment for recycling dimethylacetamide from waste pharmaceutical liquor and thermal coupling method |
| CN106699622A (en) * | 2017-03-07 | 2017-05-24 | 河北冠龙农化有限公司 | High-efficiency green synthesis method for thiram |
-
2017
- 2017-08-29 CN CN201710754366.1A patent/CN107311254A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103145577A (en) * | 2013-02-25 | 2013-06-12 | 天津天中福大科技发展有限公司 | Method and equipment for recycling dimethylacetamide from waste pharmaceutical liquor and thermal coupling method |
| CN106699622A (en) * | 2017-03-07 | 2017-05-24 | 河北冠龙农化有限公司 | High-efficiency green synthesis method for thiram |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108101297A (en) * | 2017-11-27 | 2018-06-01 | 杭州师范大学钱江学院 | A kind of processing method of the agricultural chemicals waste water containing dithio formate |
| CN108101297B (en) * | 2017-11-27 | 2020-05-05 | 杭州师范大学钱江学院 | Method for treating pesticide wastewater containing dithioformate |
| CN108128971A (en) * | 2017-12-22 | 2018-06-08 | 杭州师范大学钱江学院 | Wastewater treatment equipment containing dithio formate |
| CN108178411A (en) * | 2017-12-22 | 2018-06-19 | 杭州师范大学钱江学院 | A kind of device for recycling carbon disulfide in waste water containing dithio formate |
| CN108178411B (en) * | 2017-12-22 | 2020-06-16 | 杭州师范大学钱江学院 | Device for recovering carbon disulfide in dithioformate-containing wastewater |
| CN108128971B (en) * | 2017-12-22 | 2023-05-23 | 杭州师范大学钱江学院 | Dithioformate-containing wastewater treatment device |
| CN110256318A (en) * | 2019-07-19 | 2019-09-20 | 山东阳谷华泰化工股份有限公司 | A kind of clean method for producing of tetra-benzyl thiram disulfide |
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Application publication date: 20171103 |