CN105084627A - Acrylonitrile ammonium sulphate waste water processing method - Google Patents
Acrylonitrile ammonium sulphate waste water processing method Download PDFInfo
- Publication number
- CN105084627A CN105084627A CN201410202287.6A CN201410202287A CN105084627A CN 105084627 A CN105084627 A CN 105084627A CN 201410202287 A CN201410202287 A CN 201410202287A CN 105084627 A CN105084627 A CN 105084627A
- Authority
- CN
- China
- Prior art keywords
- sulphuric acid
- ammonia
- amine wastewater
- vinyl cyanide
- acrylonitrile
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Fertilizers (AREA)
Abstract
The present invention relates to a method for recycling ammonia in acrylonitrile ammonium sulfate wastewater processing process, and mainly solves the problems of high COD and high total cyanide of processed ammonium sulfate wastewater, not high ammonia utilization rate, and environmentally unfriendliness in the prior art. According to the process, ammonium sulfate wastewater I produced by acrylonitrile production process is mixed with an elemental oxygen-containing gas to enter into a wet oxidation reactor for removal of organic matters to obtain ammonium sulfate wastewater III, the ammonium sulfate wastewater III is concentrated and crystallized for recycling ammonium sulfate VII, a high-purity ammonia gas flow V and a distillation kettle liquid VI can be obtained by ammonia rectification of a condensate IV obtained in the concentration process, the ammonia gas flow V returns to an acrylonitrile reactor for propylene ammonia oxidation reaction, the distillation kettle liquid is used for system water replenishment, by the technical scheme, the problem can be well solved, and the method can be used in acrylonitrile industrial devices.
Description
Technical field
The present invention relates to the treatment process of vinyl cyanide amine wastewater of sulphuric acid.
Background technology
Vinyl cyanide is a kind of important Organic Chemicals, general employing propylene or propane ammoxidation method are produced, propylene or propane, ammonia and oxygen generate vinyl cyanide and by product acetonitrile, prussic acid etc. by the catalyzer in fluidized-bed reactor, then enter recovery and refining system separation and purification vinyl cyanide and by product (USP3936360) from fluidized-bed reactor.There are some unreacted ammonia in this reaction process, vinyl cyanide, acetonitrile etc. in it and reaction product react and generate higher-boiling compound, not only cause the loss of target product vinyl cyanide, and can cause the blocking of rear system, affect the plant running cycle.Therefore, from reactant gases, unreacted ammonia separation must be gone out.
For the removal of unreacted ammonia in Acrylonitrile Production, mostly adopt pickling to generate the method for ammonium salt, disclosed sulfuric acid, hydrochloric acid, phosphoric acid or the nitric acid of adopting of such as US3649179 and US3936360 removes unreacted ammonia.In current actual production process, the method adopting sulfuric acid and ammonia react to generate ammonium sulfate removes unreacted ammonia more, and the amine wastewater of sulphuric acid obtained is buried or reclaimed sulphur ammonium be used as chemical fertilizer mainly through burning disposal, deep-well.Burning method needs to consume a large amount of fuel oil, energy consumption and material consumption higher, economy is bad; And deep-well is buried and not only had requirement to the geologic framework of device location, and be unfavorable for environmental protection; And reclaiming sulphur ammonium method owing to containing the organism such as a small amount of reaction product, superpolymer, high boiling material in solution, the sulphur ammonium adopting the method reclaiming sulphur ammonium to obtain contains environmentally harmful organism.CN1167089A discloses a kind of employing and the volatile organic matter in waste water and ammonia is evaporated, and steam, more at high temperature through a Catalytic Wet Oxidation reactor, generates the method for nitrogen, hydrogen and carbonic acid gas.The method can only process the volatile matter in waste water and cannot process superpolymer and high boiling point organic compound.
Summary of the invention
Technical problem to be solved by this invention is that in prior art, after amine wastewater of sulphuric acid process, COD is high, and total cyanogen is high, and ammonia utilization ratio is low, to the disagreeableness problem of environment, provides a kind of and processes the method reclaiming ammonia in vinyl cyanide amine wastewater of sulphuric acid process.After the method has amine wastewater of sulphuric acid process, COD is low, and total cyanogen is low, and ammonia utilization ratio is high, eco-friendly advantage.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: the treatment process of vinyl cyanide amine wastewater of sulphuric acid, comprise the following steps: propylene or propane ammoxidation are produced in vinyl cyanide process and adopted vitriolated acidic solution to absorb unreacted ammonia in acrylonitrile installation quench tower, produce amine wastewater of sulphuric acid I, this strand of waste water is through sedimentation removing high boiling material and superpolymer, then wet oxidation reaction device is entered after mixing with the gas II containing simple substance oxygen, removing organism obtains amine wastewater of sulphuric acid III, amine wastewater of sulphuric acid III condensing crystal reclaims sulphur ammonium VII, the phlegma IV obtained in concentration process obtains highly purified ammonia flow V and rectifying still liquid VI after ammonia rectifying, ammonia flow V turns back to acrylonitrile reactor and carries out ammoxidation of propylene reaction, rectifying still liquid VI is for system water supplement.
In technique scheme, the COD value of the amine wastewater of sulphuric acid I that acrylonitrile installation quench tower produces is preferably 65000 ~ 180000mg/l, and sulphur ammonium weight percentage is preferably 5 ~ 25%, and total cyanogen content is preferably 300 ~ 1500mg/l.Wet oxidation reaction device can use wet oxidizing catalyst or not use catalyzer.In simple substance oxygen, the consumption containing the gas II of simple substance oxygen is preferably 1 ~ 1.2 times of the COD value meter requisite oxygen tolerance of amine wastewater of sulphuric acid I.The temperature of reaction of wet oxidation reaction device is preferably 230 ~ 320 DEG C; Be more preferably 250 ~ 300 DEG C.Reaction pressure is preferably 5 ~ 12MPa; Be more preferably 6 ~ 9MPa.The residence time is preferably 10 ~ 150 minutes; Be more preferably 20 ~ 120 minutes.The gas containing simple substance oxygen entering wet oxidation reaction device is preferably air, oxygen or the gas mixture of the two.Preferably the pH value of amine wastewater of sulphuric acid I is controlled at 3-5.
By wet oxidation in the inventive method, make organism and oxygen generation free radical reaction, thus organism is constantly degraded, finally generate H
2o, CO
2and N
2etc. nontoxic material, volatile organic matter, high boiling point organic compound and superpolymer can be removed simultaneously, remove thoroughly, thus hazardous and noxious substances in ammonium sulfate products is reduced, environmentally friendly, obtain good technique effect.
Have a certain amount of ammonia of the oxidized generation of nitrogenous compound in wet oxidation process, the present invention adds ammonia rectifier unit makes highly purified ammonia again be utilized, and improves the degree of cleaning for system water supplement simultaneously.
Accompanying drawing explanation
Fig. 1 is the schema of amine wastewater of sulphuric acid wet oxidation process in vinyl cyanide generative process.
In Fig. 1,1 is settling bowl, and 2 is wet oxidation reaction device, and 3 is thiamine recovery crystallizer, and 4 is rectifying tower.
From the amine wastewater of sulphuric acid I of acrylonitrile installation quench tower in Fig. 1, first settling bowl 1 is entered, acid or alkali is added in settling bowl 1, make high boiling material, solids in superpolymer and waste water is out settlement separate, then wet oxidation reaction device 2 is entered with the gas II containing simple substance oxygen, organism in removing waste water, reaction effluent reclaims after reaction heat through heat exchanger, obtain ammonium sulfate solution III, ammonium sulfate solution III enters sulphur ammonium condensing crystal device 3, isolate sulphur ammonium crystal VII after crystallization and be used as chemical fertilizer, the steam that sulphur ammonium condensing crystal device 3 produces enters ammonia rectifying tower 4 rectifying after condensation, obtain high purity ammonia gas V and rectifying still liquid VI, high purity ammonia V returns acrylonitrile reactor and reacts, rectifying still liquid VI is for system water supplement.
Below by embodiment, the invention will be further elaborated, and embodiment is:
Embodiment 1
From in the amine wastewater of sulphuric acid I of acrylonitrile installation quench tower, sulphur ammonium mass percentage is 6%, COD is 180000mg/l, and total cyanogen content is 512mg/l, and pH value is 5.5.First this waste water enter settling bowl 1, in settling bowl, add sulfuric acid adjust ph is 3.0, make the solids in high boiling material, superpolymer and waste water out settlement separate, then wet oxidation reaction device 2 is entered with the ratio of oxygen 1:300 by volume, carry out Characteristic of Homogenous Catalytic Wet Air Oxidation reaction using copper sulfate as catalyzer, copper ion concentration is 300ppm, and temperature of reaction is 320 DEG C, reaction pressure 12MPa, residence time 150min.After reaction, the most of organism in removing waste water.After reaction, the COD of waste water reduces to 16650mg/l, and total cyanogen content reduces to 55mg/l, and pH value becomes 8.2.Reaction effluent reclaims after reaction heat through heat exchanger, obtain ammonium sulfate solution III, ammonium sulfate solution III enters sulphur ammonium condensing crystal device 3, isolate sulphur ammonium crystal VII after crystallization and be used as chemical fertilizer, the steam that sulphur ammonium condensing crystal device 3 produces enters ammonia rectifying tower 4 rectifying after condensation, obtains high purity ammonia gas V and rectifying still liquid VI.In ammonia V, the mass content of ammonia is greater than 99%, and high purity ammonia V returns acrylonitrile reactor and reacts, and rectifying still liquid VI is for system water supplement.
Embodiment 2
From in the amine wastewater of sulphuric acid I of acrylonitrile installation quench tower, sulphur ammonium mass percentage is 23%, COD is 81000mg/l, and total cyanogen content is 466mg/l, and pH value is 5.3.First this waste water enter settling bowl 1, and in settling bowl, add sulfuric acid adjust ph is 4.5, makes the solids in high boiling material, superpolymer and waste water out settlement separate, then enters wet oxidation reaction device 2, with Fe with the ratio of air 1:60 by volume
2o
3-MnO
2complex metal oxides carries out heterogeneous catalyst wet oxidation reaction as catalyzer, and temperature of reaction is 275 DEG C, reaction pressure 10MPa, residence time 120min.After reaction, the most of organism in removing waste water.After reaction, the COD of waste water reduces to 20250mg/l, and total cyanogen content reduces to 102mg/l, and pH value becomes 7.7.Reaction effluent reclaims after reaction heat through heat exchanger, obtain ammonium sulfate solution III, ammonium sulfate solution III enters sulphur ammonium condensing crystal device 3, isolate sulphur ammonium crystal VII after crystallization and be used as chemical fertilizer, the steam that sulphur ammonium condensing crystal device 3 produces enters ammonia rectifying tower 4 rectifying after condensation, and obtain high purity ammonia gas V and rectifying still liquid VI, in ammonia V, the mass content of ammonia is greater than 99%, high purity ammonia V returns acrylonitrile reactor and reacts, and rectifying still liquid VI is for system water supplement.
Embodiment 3
From in the amine wastewater of sulphuric acid I of acrylonitrile installation quench tower, sulphur ammonium mass percentage is 17%, COD is 120000mg/l, and total cyanogen content is 927mg/l, and pH value is 5.6.First this waste water enter settling bowl 1, and in settling bowl, add sulfuric acid adjust ph is 4.0, makes the solids in high boiling material, superpolymer and waste water out settlement separate, then enters wet oxidation reaction device 2, with Pt/TiO with the ratio of air 1:150 by volume
2carry out heterogeneous catalyst wet oxidation reaction as catalyzer, temperature of reaction is 250 DEG C, reaction pressure 6MPa, residence time 10min.After reaction, the most of organism in removing waste water.After reaction, the COD of waste water reduces to 8000mg/l, and total cyanogen content reduces to 18mg/l, and pH value becomes 8.0.Reaction effluent reclaims after reaction heat through heat exchanger, obtain ammonium sulfate solution III, ammonium sulfate solution III enters sulphur ammonium condensing crystal device 3, isolate sulphur ammonium crystal VII after crystallization and be used as chemical fertilizer, the steam that sulphur ammonium condensing crystal device 3 produces enters ammonia rectifying tower 4 rectifying after condensation, and obtain high purity ammonia gas V and rectifying still liquid VI, in ammonia V, the mass content of ammonia is greater than 99%, high purity ammonia V returns acrylonitrile reactor and reacts, and rectifying still liquid VI is for system water supplement.
Embodiment 4
From in the amine wastewater of sulphuric acid I of acrylonitrile installation quench tower, sulphur ammonium mass percentage is 17%, COD is 130000mg/l, and total cyanogen content is 663mg/l, and pH value is 5.6.First this waste water enter settling bowl 1, and in settling bowl, add sulfuric acid adjust ph is 3.5, makes the solids in high boiling material, superpolymer and waste water out settlement separate, then enters wet oxidation reaction device 2, with Ru/ZrO with the ratio of oxygen 1:80 by volume
2carry out heterogeneous catalyst wet oxidation reaction as catalyzer, temperature of reaction is 230 DEG C, reaction pressure 5MPa, residence time 20min.After reaction, the most of organism in removing waste water.After reaction, the COD of waste water reduces to 13800mg/l, and total cyanogen content reduces to 44mg/l, and pH value becomes 8.9.Reaction effluent reclaims after reaction heat through heat exchanger, obtain ammonium sulfate solution III, ammonium sulfate solution III enters sulphur ammonium condensing crystal device 3, isolate sulphur ammonium crystal VII after crystallization and be used as chemical fertilizer, the steam that sulphur ammonium condensing crystal device 3 produces enters ammonia rectifying tower 4 rectifying after condensation, and obtain high purity ammonia gas V and rectifying still liquid VI, in ammonia V, the mass content of ammonia is greater than 99%, high purity ammonia V returns acrylonitrile reactor and reacts, and rectifying still liquid VI is for system water supplement.
Embodiment 5
From in the amine wastewater of sulphuric acid I of acrylonitrile installation quench tower, sulphur ammonium mass percentage is 10%, COD is 65000mg/l, and total cyanogen content is 300mg/l, and pH value is 5.4.First this waste water enter settling bowl 1, in settling bowl, add sulfuric acid adjust ph is 3.5, make the solids in high boiling material, superpolymer and waste water out settlement separate, then wet oxidation reaction device 2 is entered with the ratio of oxygen 1:120 by volume, carry out wet oxidation reaction, temperature of reaction is 260 DEG C, reaction pressure 9MPa, residence time 150min.After reaction, the most of organism in removing waste water.After reaction, the COD of waste water reduces to 19800mg/l, and total cyanogen content reduces to 63mg/l, and pH value becomes 8.5.Reaction effluent reclaims after reaction heat through heat exchanger, obtain ammonium sulfate solution III, ammonium sulfate solution III enters sulphur ammonium condensing crystal device 3, isolate sulphur ammonium crystal VII after crystallization and be used as chemical fertilizer, the steam that sulphur ammonium condensing crystal device 3 produces enters ammonia rectifying tower 4 rectifying after condensation, and obtain high purity ammonia gas V and rectifying still liquid VI, in ammonia V, the mass content of ammonia is greater than 99%, high purity ammonia V returns acrylonitrile reactor and reacts, and rectifying still liquid VI is for system water supplement.
Embodiment 6
From in the amine wastewater of sulphuric acid I of acrylonitrile installation quench tower, sulphur ammonium mass percentage is 25%, COD is 110000mg/l, and total cyanogen content is 1500mg/l, and pH value is 5.6.First this waste water enter settling bowl 1, and in settling bowl, add sulfuric acid adjust ph is 4.0, makes the solids in high boiling material, superpolymer and waste water out settlement separate, then enters wet oxidation reaction device 2, with CuO/Al with the ratio of air 1:230 by volume
2o
3carry out heterogeneous catalyst wet oxidation reaction as catalyzer, temperature of reaction is 300 DEG C, reaction pressure 11MPa, residence time 60min.After reaction, the most of organism in removing waste water.After reaction, the COD of waste water reduces to 15600mg/l, and total cyanogen content reduces to 73mg/l, and pH value becomes 8.9.Reaction effluent reclaims after reaction heat through heat exchanger, obtain ammonium sulfate solution III, ammonium sulfate solution III enters sulphur ammonium condensing crystal device 3, isolate sulphur ammonium crystal VII after crystallization and be used as chemical fertilizer, the steam that sulphur ammonium condensing crystal device 3 produces enters ammonia rectifying tower 4 rectifying after condensation, and obtain high purity ammonia gas V and rectifying still liquid VI, in ammonia V, the mass content of ammonia is greater than 99%, high purity ammonia V returns acrylonitrile reactor and reacts, and rectifying still liquid VI is for system water supplement.
Comparative example
By processing method process vinyl cyanide amine wastewater of sulphuric acid described in patent CN1167089A, extraction process volatile organic matter, cannot process and still remain in superpolymer in waste water and high boiling point organic compound.Owing to can take away large water gaging when extracting volatile organic matter, so processed waste water COD and former amine wastewater of sulphuric acid COD is quite even higher, the process of this part water is not resolved in the prior art yet.
Claims (9)
1. the treatment process of vinyl cyanide amine wastewater of sulphuric acid, comprise the following steps: propylene or propane ammoxidation are produced in vinyl cyanide process and adopted vitriolated acidic solution to absorb unreacted ammonia in acrylonitrile installation quench tower, produce amine wastewater of sulphuric acid I, this strand of waste water is through sedimentation removing high boiling material and superpolymer, then wet oxidation reaction device is entered after mixing with the gas II containing simple substance oxygen, removing organism obtains amine wastewater of sulphuric acid III, amine wastewater of sulphuric acid III condensing crystal reclaims sulphur ammonium VII, the phlegma IV obtained in concentration process obtains highly purified ammonia flow V and rectifying still liquid VI after ammonia rectifying, ammonia flow V turns back to acrylonitrile reactor and carries out ammoxidation of propylene reaction, rectifying still liquid VI is for system water supplement.
2. the treatment process of vinyl cyanide amine wastewater of sulphuric acid according to claim 1, the COD value that it is characterized in that the amine wastewater of sulphuric acid I that acrylonitrile installation quench tower produces is 65000 ~ 180000mg/l, sulphur ammonium weight percentage is 5 ~ 25%, and total cyanogen content is 300 ~ 1500mg/l.
3. the treatment process of vinyl cyanide amine wastewater of sulphuric acid according to claim 1, is characterized in that wet oxidation reaction device uses wet oxidizing catalyst or do not use catalyzer.
4. the treatment process of vinyl cyanide amine wastewater of sulphuric acid according to claim 1, it is characterized in that in simple substance oxygen, the consumption containing the gas II of simple substance oxygen is 1 ~ 1.2 times of the COD value meter requisite oxygen tolerance of amine wastewater of sulphuric acid I.
5. the treatment process of vinyl cyanide amine wastewater of sulphuric acid according to claim 1, is characterized in that the temperature of reaction of wet oxidation reaction device is 230 ~ 320 DEG C.
6. the treatment process of vinyl cyanide amine wastewater of sulphuric acid according to claims 1, is characterized in that the reaction pressure of wet oxidation reaction device is 5 ~ 12MPa.
7. the treatment process of vinyl cyanide amine wastewater of sulphuric acid according to claim 1, is characterized in that the residence time of wet oxidation reaction device is 10 ~ 150 minutes.
8. the treatment process of vinyl cyanide amine wastewater of sulphuric acid according to claim 1, is characterized in that the gas containing simple substance oxygen entering wet oxidation reaction device is air, oxygen or the gas mixture of the two.
9. the treatment process of vinyl cyanide amine wastewater of sulphuric acid according to claim 1, is characterized in that the pH value of amine wastewater of sulphuric acid I to control at 3-5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410202287.6A CN105084627A (en) | 2014-05-14 | 2014-05-14 | Acrylonitrile ammonium sulphate waste water processing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410202287.6A CN105084627A (en) | 2014-05-14 | 2014-05-14 | Acrylonitrile ammonium sulphate waste water processing method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105084627A true CN105084627A (en) | 2015-11-25 |
Family
ID=54566078
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410202287.6A Pending CN105084627A (en) | 2014-05-14 | 2014-05-14 | Acrylonitrile ammonium sulphate waste water processing method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105084627A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106904718A (en) * | 2017-04-25 | 2017-06-30 | 重庆紫光化工股份有限公司 | A kind of processing method of waste acid water |
| CN111423433A (en) * | 2019-01-10 | 2020-07-17 | 中国石油天然气股份有限公司 | Extracting agent, preparation method and application thereof |
| CN112694164A (en) * | 2019-10-23 | 2021-04-23 | 中国石油化工股份有限公司 | Method for treating acrylonitrile device wastewater |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102452737A (en) * | 2010-10-21 | 2012-05-16 | 中国石油化工股份有限公司 | Ammonium sulfate wastewater treatment method during acrylonitrile production process |
| CN103523978A (en) * | 2012-07-03 | 2014-01-22 | 中国石油化工股份有限公司 | Method or treating ammonium sulfate wastewater in acrylonitrile process |
-
2014
- 2014-05-14 CN CN201410202287.6A patent/CN105084627A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102452737A (en) * | 2010-10-21 | 2012-05-16 | 中国石油化工股份有限公司 | Ammonium sulfate wastewater treatment method during acrylonitrile production process |
| CN103523978A (en) * | 2012-07-03 | 2014-01-22 | 中国石油化工股份有限公司 | Method or treating ammonium sulfate wastewater in acrylonitrile process |
Non-Patent Citations (1)
| Title |
|---|
| 宋学周等: "《废水 废气 固体废物专项治理与综合利用实务全书（上、中、下卷）》", 30 November 2000 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106904718A (en) * | 2017-04-25 | 2017-06-30 | 重庆紫光化工股份有限公司 | A kind of processing method of waste acid water |
| CN106904718B (en) * | 2017-04-25 | 2020-09-15 | 重庆紫光化工股份有限公司 | Method for treating waste acid water |
| CN111423433A (en) * | 2019-01-10 | 2020-07-17 | 中国石油天然气股份有限公司 | Extracting agent, preparation method and application thereof |
| CN111423433B (en) * | 2019-01-10 | 2022-02-01 | 中国石油天然气股份有限公司 | Extracting agent, preparation method and application thereof |
| CN112694164A (en) * | 2019-10-23 | 2021-04-23 | 中国石油化工股份有限公司 | Method for treating acrylonitrile device wastewater |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102503016B (en) | Device and method for treating ammonia nitrogen wastewater, recycling ammonia and preparing ammonium sulfate | |
| CN106495404B (en) | A kind of processing method of the high salinity cupric organic wastewater of highly acidity | |
| CN101502746B (en) | Method for processing nitrous oxides in chlorinated exhaust of nitroaromatic compounds | |
| CN102452711B (en) | Wet oxidation treatment method of ammonium sulfate waste water in acrylonitrile production process | |
| CN103408460B (en) | Recovery method of secondary products of iminodiacetonitrile and mother liquid treatment method | |
| CN106830487A (en) | A kind of comprehensive processing technique of the high-concentration ammonia nitrogenous wastewater containing organic matter thiocarbamide | |
| CN102452737B (en) | Ammonium sulfate wastewater treatment method during acrylonitrile production process | |
| CN105084627A (en) | Acrylonitrile ammonium sulphate waste water processing method | |
| CN106277480A (en) | A kind of process technique of high-concentration ammonia nitrogenous wastewater | |
| CN105923877A (en) | Wastewater treatment process for wet-process chromium metallurgy | |
| CN108947012B (en) | Method for separating and recovering ammonia from ammonia nitrogen wastewater | |
| CN103145206B (en) | Composite nitrogen-removal medicament | |
| CN107381892A (en) | A kind of handling process of high-concentration ammonia nitrogenous wastewater | |
| CN104860465B (en) | Double-tower catalysis thermal-coupling reflux deamination method and deamination device thereof | |
| CN104108779B (en) | The method of sulfur-bearing ammonium Catalytic Wet Air Oxidation for Wastewater | |
| CN101549898A (en) | Resource recycling technique of low-concentration formaldehyde wastewater and formaldehyde tail gas | |
| CN104108780B (en) | Method of wastewater treatment in acrylonitrile process subtractive process | |
| CN101311107A (en) | Method for gas stripping and separating hydrazine from hydrazine-containing solution using acetone and use thereof | |
| CN105314610A (en) | Preparation method for hydroxylammonium chloride | |
| CN103523978A (en) | Method or treating ammonium sulfate wastewater in acrylonitrile process | |
| CN106379875A (en) | Production method and application of nitroso-sulfuric acid | |
| CN103435214B (en) | Comprehensive treatment method for formaldehyde-containing acid wastewater | |
| CN113479985B (en) | Method for transformation deamination of ammonia nitrogen wastewater | |
| CN109607915A (en) | A kind of processing method of Benzotriazole Ultraviolet Stabilizer production waste water | |
| CN104276685A (en) | Process for recovering ammonia from wastewater containing ammonia nitrogen |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20151125 |
|
| RJ01 | Rejection of invention patent application after publication |