CN105668889A - Process for recycling sulfuric acid and methylamine in sulfuric acid and methylamine salt wastewater through bipolar membrane electrodialysis method - Google Patents
Process for recycling sulfuric acid and methylamine in sulfuric acid and methylamine salt wastewater through bipolar membrane electrodialysis method Download PDFInfo
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- CN105668889A CN105668889A CN201610008636.XA CN201610008636A CN105668889A CN 105668889 A CN105668889 A CN 105668889A CN 201610008636 A CN201610008636 A CN 201610008636A CN 105668889 A CN105668889 A CN 105668889A
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- Prior art keywords
- methylamine
- liquid
- sulphuric acid
- bipolar membrane
- concentration
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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
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/86—Separation
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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
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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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/101—Sulfur compounds
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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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
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
Abstract
The invention relates to a process for recycling sulfuric acid and methylamine in sulfuric acid and methylamine salt wastewater through a bipolar membrane electrodialysis method. The process comprises the steps: firstly, diluting a raw liquid by tap water supplement A, then carrying out first step diffusion dialysis in a diffusion dialysis device A, and directly reusing a received liquid A in a production line; diluting the residual liquid A through tap water supplement B, carrying out second step diffusion dialysis in a diffusion device B, carrying out evaporation and concentration A of a received liquid B to obtain a liquid, mixing the obtained liquid into the raw liquid, carrying out first step diffusion dialysis, allowing the residual liquid B to enter a bipolar membrane device, separating methylamine and sulfuric acid, and respectively concentrating and recycling. The process has the beneficial effects that the diffusion dialysis treatment process does not consume electric energy, the operation cost is low, high-economic-benefit sulfuric acid and methylamine in the wastewater are recycled, and the method has the advantages of economy and environmental protection.
Description
Technical field
The invention belongs to field of waste water treatment, particularly relate to a kind of bipolar membrane electrodialysis method and reclaim the technique of sulphuric acid and methylamine in sulphuric acid and methylamine salt waste water.
Background technology
Methylamine, is a kind of organic compound, chemical formula CH3NH2, it being important Organic Chemicals, belong to lower toxicity, form explosive mixture with air mixing energy, its aqueous solution is a kind of highly basic. It is the derivant that a hydrogen in ammonia is formed after methyl substituted. Methylamine is simplest primary amine. Commercially available product is usually its methanol, ethanol, oxolane or aqueous solution, or as anhydrous gas pressurized storage in canister. Industrial goods pass through trailer transportation after often being pressurizeed by anhydrous gas. It has very strong fishlike smell. Methylamine is used as synthesizing the raw material of a lot of other compound, about can produce more than one hundred million kilograms every year.
Methylamine can be used for the production of pesticide industry; Pharmaceutical industry can be used for the production of the multi-medicaments such as anesthetis, analgesic, antibiotics; Can also be used for producing the products such as surfactant, aqueous gels, feed additive, developer solution. Recycle and be worth height.
Sulphuric acid is widely used in each industrial department, mainly has chemical fertilizer technique, metallurgical industry, petroleum industry, mechanical industry, medical industry, the production of detergent, war industry, atomic energy industry and aerospace industry etc. It is additionally operable to produce fuel, pesticide, chemical fibre, plastics, coating. And various substantially organic and inorganic chemical product. Use extensively, recycle high financial profit.
But for high concentrated acid brine waste, processing recovery technology Shanghai existing defects at present. The way of conventionally employed neutralization, need to consume substantial amounts of alkaline matter, generally generates salt and does offal treatment, not environmentally in process; Or reclaim but high expensive, economic benefit is inconspicuous.
Summary of the invention
It is an object of the invention to the deficiency overcoming prior art to exist, and provide a kind of bipolar membrane electrodialysis method to reclaim the technique of sulphuric acid and methylamine in sulphuric acid and methylamine salt waste water, while processing waste water, reclaim sulphuric acid and methylamine resource, the cycling and reutilization of solid line resource.
It is an object of the invention to complete by following technical solution.This bipolar membrane electrodialysis method reclaims the technique of sulphuric acid and methylamine in sulphuric acid and methylamine salt waste water, and first stock solution carries out first step diffusion dialysis after supplementing A dilution by tap water in diffusion dialysis device A, receives liquid A direct reuse in production line; Residual liquid A carries out second step diffusion dialysis after supplementing B dilution by tap water in diffusion facilities B, receives liquid B after evaporation and concentration A, is mixed into stock solution and carries out first step diffusion dialysis, and residual liquid B enters bipolar membrane device separation methylamine and sulphuric acid, respectively concentration and recovery.
Described reception liquid B is after evaporation and concentration A, and reception liquid C is mixed into stock solution and carries out the tap water mixing that first step diffusion dialysis, fresh water and tap water supplement in A.
Described residual liquid B processes at bipolar membrane device after supplementing C dilution by tap water, generate residual liquid C, separating methylamine and sulphuric acid, wherein methylamine recovered liquid passes through after evaporation and concentration B concentration and recovery, retrieval of sulfuric acid liquid and reception liquid A mix by evaporation and concentration C concentration and recovery.
The invention have the benefit that diffusion dialysis processes technique and do not consume electric energy, operating cost is low, has reclaimed sulphuric acid and the methylamine of high financial profit in waste liquid, economic and environment-friendly.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of the present invention.
Accompanying drawing illustrates: stock solution 1, diffusion facilities A2, and tap water supplements A3, receiving liquid A4, residual liquid A5, tap water supplements B6, diffusion facilities B7, residual liquid B8, receive liquid B9, evaporation and concentration A10, tap water supplements C11, bipolar membrane device 12, evaporation and concentration B13, methylamine 14, sulphuric acid 15, residual liquid C16, receives liquid C17, evaporation and concentration C18.
Detailed description of the invention
Below in conjunction with accompanying drawing, the present invention done detailed introduction:
As it can be seen, this bipolar membrane electrodialysis method reclaims the technique of sulphuric acid and methylamine in sulphuric acid and methylamine salt waste water, first stock solution 1 carries out first step diffusion dialysis after supplementing A3 dilution by tap water in diffusion dialysis device A 2; Residual liquid A5 carries out second step diffusion dialysis after supplementing B6 dilution by tap water in diffusion facilities B7, receive liquid B9 after evaporation and concentration A10, it is mixed into stock solution 1 and carries out first step diffusion dialysis, described residual liquid B8 processes at bipolar membrane device 12 after supplementing C11 dilution by tap water, generate residual liquid C16, separating methylamine 14 and sulphuric acid 15, wherein the recovered liquid of methylamine 14 passes through after evaporation and concentration B13 concentration and recovery, the recovered liquid of sulphuric acid 15 and reception liquid A4 mix by evaporation and concentration C18 concentration and recovery. Described reception liquid B9 is after evaporation and concentration A10, and reception liquid C17 (dense water) is mixed into stock solution 1 and carries out the tap water mixing that first step diffusion dialysis, fresh water and tap water supplement in A3.
Bipolar membrane device waste liquid does biochemical treatment. Being back in stock solution after concentrating because of the reception liquid of second step diffusion dialysis and process together, total water yield increases, and when reaching to balance, the water yield of each several part reaches the numerical value of mark on process route.
Example 1: in Fine Chemical, has strand waste water to contain mass fraction 50% sulphuric acid and mass fraction 20% methylamine salt, and inlet amount is 2t/h. Due to both mixture, it is impossible to use as product or raw material, process only as waste water, and to spend a large amount of manpower and materials to process, waste again much useful sulphuric acid and methylamine resource.
Recycle by a kind of bipolar membrane electrodialysis method, receive liquid A4 sulfuric acid content about 35%, methylamine salt content less than 2.5%, can direct reuse in production line. Residual liquid A5 sulfur acid about 22%, methylamine salt about 19%, then carry out second diffusion dialysis.Receiving liquid B9 sulfur acid about 15%, methylamine salt about 6%, this part, after evaporation and concentration 3 times, is mixed into stock solution and carries out first step diffusion dialysis. Residual liquid B8 is containing about 7% sulphuric acid and about 14% methylamine salt, and this part enters Bipolar Membrane separation methylamine and sulphuric acid, is separately recovered. Being back in stock solution after concentrating because of the reception liquid of second step diffusion dialysis and process together, total water yield increases, and when reaching to balance, the water yield of each several part reaches the numerical value of mark on process route.
The present invention is not limited to above-mentioned embodiment, no matter making any change, every employing structural design provided by the present invention on its shape or material are constituted, being all a kind of deformation of the present invention, being all considered as within scope.
Claims (3)
1. a bipolar membrane electrodialysis method reclaims the technique of sulphuric acid and methylamine in sulphuric acid and methylamine salt waste water, it is characterized in that: first stock solution (1) carries out first step diffusion dialysis after supplementing A (3) dilution by tap water in diffusion dialysis device A (2), receive liquid A (4) direct reuse in production line; Residual liquid A (5) carries out second step diffusion dialysis after supplementing B (6) dilution by tap water in diffusion facilities B (7), receive liquid B (9) after evaporation and concentration A (10), it is mixed into stock solution (1) and carries out first step diffusion dialysis, residual liquid B (8) enters bipolar membrane device (12) and separates methylamine (14) and sulphuric acid (15), respectively concentration and recovery.
2. bipolar membrane electrodialysis method according to claim 1 reclaims the technique of sulphuric acid and methylamine in sulphuric acid and methylamine salt waste water, it is characterized in that: described reception liquid B (9) is after evaporation and concentration A (10), reception liquid C (17) is mixed into stock solution (1) and carries out the tap water mixing that first step diffusion dialysis, fresh water and tap water supplement in A (3).
3. bipolar membrane electrodialysis method according to claim 1 reclaims the technique of sulphuric acid and methylamine in sulphuric acid and methylamine salt waste water, it is characterized in that: described residual liquid B (8) processes at bipolar membrane device (12) after supplementing C (11) dilution by tap water, generate residual liquid C (16), separate methylamine (14) and sulphuric acid (15), wherein the recovered liquid of methylamine (14) passes through after evaporation and concentration B (13) concentration and recovery, the recovered liquid of sulphuric acid (15) and reception liquid A (4) mix by evaporation and concentration C (18) concentration and recovery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610008636.XA CN105668889A (en) | 2016-01-07 | 2016-01-07 | Process for recycling sulfuric acid and methylamine in sulfuric acid and methylamine salt wastewater through bipolar membrane electrodialysis method |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610008636.XA CN105668889A (en) | 2016-01-07 | 2016-01-07 | Process for recycling sulfuric acid and methylamine in sulfuric acid and methylamine salt wastewater through bipolar membrane electrodialysis method |
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| CN105668889A true CN105668889A (en) | 2016-06-15 |
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| CN201610008636.XA Pending CN105668889A (en) | 2016-01-07 | 2016-01-07 | Process for recycling sulfuric acid and methylamine in sulfuric acid and methylamine salt wastewater through bipolar membrane electrodialysis method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110997577A (en) * | 2017-07-18 | 2020-04-10 | 埃科莱布美国股份有限公司 | Recycled automotive phosphate rinse water stream |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07232038A (en) * | 1994-02-25 | 1995-09-05 | Asahi Glass Co Ltd | Method for recovering alkali from liquid containing alkali |
| CN1334376A (en) * | 2001-08-30 | 2002-02-06 | 上海交通大学 | Alkali recovery process for black liquor of straw pulp |
| CN101343039A (en) * | 2008-08-20 | 2009-01-14 | 北京科技大学 | Method for recycling pure acid from metallic ion containing waste acid and regenerating alkali |
| CN101838288A (en) * | 2009-03-18 | 2010-09-22 | 湖州四方格林自动化技术有限公司 | Processing method of glyphosate mother liquor |
| CN105084600A (en) * | 2015-08-28 | 2015-11-25 | 浙江奇彩环境科技有限公司 | Method for efficiently treating salt-containing organic wastewater and application of method |
-
2016
- 2016-01-07 CN CN201610008636.XA patent/CN105668889A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07232038A (en) * | 1994-02-25 | 1995-09-05 | Asahi Glass Co Ltd | Method for recovering alkali from liquid containing alkali |
| CN1334376A (en) * | 2001-08-30 | 2002-02-06 | 上海交通大学 | Alkali recovery process for black liquor of straw pulp |
| CN101343039A (en) * | 2008-08-20 | 2009-01-14 | 北京科技大学 | Method for recycling pure acid from metallic ion containing waste acid and regenerating alkali |
| CN101838288A (en) * | 2009-03-18 | 2010-09-22 | 湖州四方格林自动化技术有限公司 | Processing method of glyphosate mother liquor |
| CN105084600A (en) * | 2015-08-28 | 2015-11-25 | 浙江奇彩环境科技有限公司 | Method for efficiently treating salt-containing organic wastewater and application of method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110997577A (en) * | 2017-07-18 | 2020-04-10 | 埃科莱布美国股份有限公司 | Recycled automotive phosphate rinse water stream |
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Application publication date: 20160615 |
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