CN102115095B - Production method of anhydrous ammonium hydrogen fluoride - Google Patents
Production method of anhydrous ammonium hydrogen fluoride Download PDFInfo
- Publication number
- CN102115095B CN102115095B CN201010624793.6A CN201010624793A CN102115095B CN 102115095 B CN102115095 B CN 102115095B CN 201010624793 A CN201010624793 A CN 201010624793A CN 102115095 B CN102115095 B CN 102115095B
- Authority
- CN
- China
- Prior art keywords
- ammonium
- fluoride
- hydrogen fluoride
- anhydrous
- ammonium hydrogen
- 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.)
- Expired - Fee Related
Links
Landscapes
- Removal Of Specific Substances (AREA)
- Cleaning Or Drying Semiconductors (AREA)
Abstract
The invention discloses a production method of anhydrous ammonium hydrogen fluoride. The production method comprises the following steps: 1, a neutralization reaction occurs between hydrous hydrofluoric acid or anhydrous hydrofluoric acid and liquid ammonia in a reaction kettle to produce a mixed solution of ammonium fluoride and ammonium hydrogen fluoride; 2, the mixed solution of ammonium fluoride and ammonium hydrogen fluoride is pumped into a concentration tower for vacuum low-temperature concentration so that the concentration of the mixed solution of ammonium fluoride and ammonium hydrogen fluoride reaches more than 70%; 3, the mixed solution of ammonium fluoride and ammonium hydrogen fluoride with the concentration more than 70% is pumped to a high-temperature transformation kettle, and ammonia gas that is decomposed during the transformation process is guided into the reaction kettle for recovery; and 4, a discharge valve of the high-temperature transformation kettle is opened so that the material flow passes through a scraping machine to produce sheet-like anhydrous ammonium hydrogen fluoride. The production method is reasonable in design, has lower requirements for equipment conditions, is easy to promote, and plays a positive role in environmental protection as well as comprehensive resource utilization.
Description
Technical field
The production method that the present invention relates to a kind of anhydrous ammonium hydrogen fluoride, belongs to chemical production field.
Background technology
The external anhydrous ammonium hydrogen fluoride of producing all adopts anhydrous hydrogen fluoride, liquefied ammonia as raw material at present, first by these two kinds of material gasifications, under gaseous state condition, react, under melting condition, remove unnecessary hydrogen fluoride and ammonia, again through cooling, moulding, make product, its chemical principle is: 2AHF (gas phase)+NH
3(gas phase)-NH
4hF
2.The problem that uses the method to exist has: 1, must use anhydrous hydrogen fluoride, limited raw material sources, and cost be higher; 2, material is through gasification, reaction, defluorination except ammonia, cooling, recovery, moulding, and technical process is longer, and equipment requirements is high, and production capacity is low, the corresponding cost that increased.
Liquid phase method is produced ammonium bifluoride, and be to pass into liquefied ammonia having in water hydrofluoric acid, or anhydrous hydrogen fluoride is passed into and in water, first made water hydrofluoric acid and pass into liquefied ammonia again, through crystallisation by cooling, centrifuge dehydration, finished product packing.In product, contain the moisture of 3%-5%, cannot use in the occasion of having relatively high expectations, and very easily caking, domestic many manufacturers, for preventing caking, add anti-caking additive, but can affect use in product, if increase baking operation, temperature control is improper, can cause product to decompose, contaminate environment and increase cost; Because the ammonium bifluoride reaction end of liquid phase method production shows with pH value, product is the mixture of Neutral ammonium fluoride and ammonium bifluoride, and its chemical principle is: HF+H
2o+NH
3-NH
4f
2+ NH
4f+H
2o.
Summary of the invention
Object of the present invention aims to provide a kind of production method of anhydrous ammonium hydrogen fluoride, the anhydrous ammonium hydrogen fluoride of production, and quality is good, and cost is low, does not lump.
For achieving the above object, the production method of anhydrous ammonium hydrogen fluoride of the present invention comprises the following steps:
1, with having water hydrofluoric acid or anhydrous hydrogen fluoride and liquefied ammonia to carry out neutralization reaction in reactor, control pH value between 3.5-6, control temperature at 40 ℃--between 80 ℃, in reaction process, by water quench, generate the mixing solutions of Neutral ammonium fluoride and ammonium bifluoride;
2, the mixing solutions of Neutral ammonium fluoride and ammonium bifluoride being pumped into concentrated tower reactor, to enter vacuum and low temperature concentrated, and temperature is controlled at 65 ℃--and between 90 ℃, vacuum degree control, between 0.5-0.95pa, reaches more than 70% the mixing solutions concentration of Neutral ammonium fluoride and ammonium bifluoride;
3, concentration is reached to more than 70% Neutral ammonium fluoride and the mixing solutions of ammonium bifluoride and pump into pyrolytic conversion still, temperature is controlled at 130 ℃--between 200 ℃, in still, negative pressure control, between 0.4-0.9pa, maintains 10-20 minute, and the ammonia decompositing in conversion imports reactor and recycles;
4, open the discharging lock of pyrolytic conversion still, streams, through scraping machine, forms sheet anhydrous ammonium hydrogen fluoride.
The main chemical reactions principle of production method of the present invention is:
1、nHF+H
2O+nNH
3→nNH
4HF
2+nNH
4F+H
2O
2、NH
4HF
2+NH
4F+H
2O→NH
4F+NH
4F
2+H
2O↑
3、2NH
4F→NH
4HF
2+NH
3↑
The production method of anhydrous ammonium hydrogen fluoride of the present invention compared with prior art has following excellent effect:
1, adopt byproduct to have water hydrofluoric acid or anhydrous hydrogen fluoride to do raw material, not only cost is low, has also improved quality product;
2, adopt byproduct to have water hydrofluoric acid or anhydrous hydrogen fluoride to do raw material, through cryoconcentration, remove most of moisture, then enter pyrolytic conversion still, under condition of negative pressure, remove unnecessary ammonia element and residual moisture, make product water content at several ppm;
3, the anhydrous ammonium hydrogen fluoride that adopts the inventive method to produce does not lump, and has expanded the scope of application of product;
4, process design of the present invention is reasonable, and appointed condition is less demanding, is easy to promote;
5,, to protection of the environment, utilize resources synthetically all will play active effect.
Embodiment
Embodiment 1
1, with having water hydrofluoric acid or anhydrous hydrogen fluoride and liquefied ammonia to carry out neutralization reaction in reactor, control pH value between 3.5-6, control temperature at 40 ℃--between 80 ℃, in reaction process, by water quench, generate the mixing solutions of Neutral ammonium fluoride and ammonium bifluoride;
2, the mixing solutions of Neutral ammonium fluoride and ammonium bifluoride being pumped into concentrated tower reactor, to enter vacuum and low temperature concentrated, and temperature is controlled at 65 ℃--and between 90 ℃, vacuum degree control, between 0.5-0.95pa, reaches more than 70% the mixing solutions concentration of Neutral ammonium fluoride and ammonium bifluoride;
3, concentration is reached to more than 70% Neutral ammonium fluoride and the mixing solutions of ammonium bifluoride and pump into pyrolytic conversion still, temperature is controlled at 130 ℃--between 200 ℃, in still, negative pressure control, between 0.4-0.9pa, maintains 10-20 minute, and the ammonia decompositing in conversion imports reactor and recycles;
4, open the discharging lock of pyrolytic conversion still, streams, through scraping machine, forms sheet anhydrous ammonium hydrogen fluoride.
Embodiment 2
1, with having water hydrofluoric acid or anhydrous hydrogen fluoride and liquefied ammonia to carry out neutralization reaction in reactor, control pH value between 4.5-5, control temperature at 50 ℃--between 70 ℃, in reaction process, by water quench, generate the mixing solutions of Neutral ammonium fluoride and ammonium bifluoride;
2, the mixing solutions of Neutral ammonium fluoride and ammonium bifluoride being pumped into concentrated tower reactor, to enter vacuum and low temperature concentrated, and temperature is controlled at 70 ℃--and between 85 ℃, vacuum degree control, between 0.6-0.85pa, reaches more than 70% the mixing solutions concentration of Neutral ammonium fluoride and ammonium bifluoride;
3, concentration is reached to more than 70% Neutral ammonium fluoride and the mixing solutions of ammonium bifluoride and pump into pyrolytic conversion still, temperature is controlled at 140 ℃--between 190 ℃, in still, negative pressure control, between 0.5-0.8pa, maintains 10-20 minute, and the ammonia decompositing in conversion imports reactor and recycles;
4, open the discharging lock of pyrolytic conversion still, streams, through scraping machine, forms sheet anhydrous ammonium hydrogen fluoride.
Embodiment 3
1, with having water hydrofluoric acid or anhydrous hydrogen fluoride and liquefied ammonia to carry out neutralization reaction in reactor, control pH value between 4-5.5, control temperature at 55 ℃--between 65 ℃, in reaction process, by water quench, generate the mixing solutions of Neutral ammonium fluoride and ammonium bifluoride;
2, the mixing solutions of Neutral ammonium fluoride and ammonium bifluoride being pumped into concentrated tower reactor, to enter vacuum and low temperature concentrated, and temperature is controlled at 75 ℃--and between 80 ℃, vacuum degree control, between 0.7-0.8pa, reaches more than 70% the mixing solutions concentration of Neutral ammonium fluoride and ammonium bifluoride;
3, concentration is reached to more than 70% Neutral ammonium fluoride and the mixing solutions of ammonium bifluoride and pump into pyrolytic conversion still, temperature is controlled at 150 ℃--between 180 ℃, in still, negative pressure control, between 0.6-0.7pa, maintains 10-20 minute, and the ammonia decompositing in conversion imports reactor and recycles;
4, open the discharging lock of pyrolytic conversion still, streams, through scraping machine, forms sheet anhydrous ammonium hydrogen fluoride.
Embodiment 4
1, with having water hydrofluoric acid or anhydrous hydrogen fluoride and liquefied ammonia to carry out neutralization reaction in reactor, control pH value 3.5, control temperature at 40 ℃, in reaction process, by water quench, generate the mixing solutions of Neutral ammonium fluoride and ammonium bifluoride;
2, the mixing solutions of Neutral ammonium fluoride and ammonium bifluoride being pumped into concentrated tower reactor, to enter vacuum and low temperature concentrated, and temperature is controlled at 65 ℃, and vacuum degree control, at 0.5pa, reaches more than 70% the mixing solutions concentration of Neutral ammonium fluoride and ammonium bifluoride;
3, concentration is reached to more than 70% Neutral ammonium fluoride and the mixing solutions of ammonium bifluoride and pump into pyrolytic conversion still, temperature is controlled at 130 ℃, and in still, negative pressure control, built in 0.4pa, maintains 10-20 minute, and the ammonia decompositing in conversion imports reactor and recycles;
4, open the discharging lock of pyrolytic conversion still, streams, through scraping machine, forms sheet anhydrous ammonium hydrogen fluoride.
Embodiment 5
1, with having water hydrofluoric acid or anhydrous hydrogen fluoride and liquefied ammonia to carry out neutralization reaction in reactor, control pH value 6, control temperature at 80 ℃, in reaction process, by water quench, generate the mixing solutions of Neutral ammonium fluoride and ammonium bifluoride;
2, the mixing solutions of Neutral ammonium fluoride and ammonium bifluoride being pumped into concentrated tower reactor, to enter vacuum and low temperature concentrated, and temperature is controlled at 90 ℃, and vacuum degree control, at 0.95pa, reaches more than 70% the mixing solutions concentration of Neutral ammonium fluoride and ammonium bifluoride;
3, concentration is reached to more than 70% Neutral ammonium fluoride and the mixing solutions of ammonium bifluoride and pump into pyrolytic conversion still, temperature is controlled at 200 ℃, and in still, negative pressure control, built in 0.9pa, maintains 10-20 minute, and the ammonia decompositing in conversion imports reactor and recycles;
4, open the discharging lock of pyrolytic conversion still, streams, through scraping machine, forms sheet anhydrous ammonium hydrogen fluoride.
Claims (1)
1. a production method for anhydrous ammonium hydrogen fluoride, is characterized in that the method comprises the following steps:
(1), with having water hydrofluoric acid and liquefied ammonia to carry out neutralization reaction in reactor, control pH value 6, control temperature at 80 ℃, in reaction process by water quench, the mixing solutions of generation Neutral ammonium fluoride and ammonium bifluoride;
(2), the mixing solutions of Neutral ammonium fluoride and ammonium bifluoride is pumped into concentrated tower reactor, and to enter vacuum and low temperature concentrated, temperature is controlled at 90 ℃, vacuum degree control, at 0.95Pa, reaches more than 70% the mixing solutions concentration of Neutral ammonium fluoride and ammonium bifluoride;
(3), concentration is reached to more than 70% Neutral ammonium fluoride and the mixing solutions of ammonium bifluoride and pump into pyrolytic conversion still, temperature is controlled at 200 ℃, in still, negative pressure control, built in 0.9Pa, maintains 10-20 minute, and the ammonia decompositing in conversion imports reactor and recycles;
(4), open the discharging lock of pyrolytic conversion still, streams, through scraping machine, forms sheet anhydrous ammonium hydrogen fluoride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010624793.6A CN102115095B (en) | 2010-12-31 | 2010-12-31 | Production method of anhydrous ammonium hydrogen fluoride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010624793.6A CN102115095B (en) | 2010-12-31 | 2010-12-31 | Production method of anhydrous ammonium hydrogen fluoride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102115095A CN102115095A (en) | 2011-07-06 |
| CN102115095B true CN102115095B (en) | 2014-05-14 |
Family
ID=44214037
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010624793.6A Expired - Fee Related CN102115095B (en) | 2010-12-31 | 2010-12-31 | Production method of anhydrous ammonium hydrogen fluoride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102115095B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103539156B (en) * | 2013-10-23 | 2016-04-13 | 衢州市鼎盛化工科技有限公司 | The preparation method of anhydrous ammonium hydrogen fluoride and microchannel reaction unit thereof |
| CN104140113B (en) * | 2014-07-15 | 2016-02-24 | 浙江工业大学 | A kind of preparation method of anti-caking ammonium bifluoride |
| CN106044796A (en) * | 2016-06-29 | 2016-10-26 | 福建天福化工有限公司 | Preparation method of high-purity flaky ammonium bifluoride |
| CN108793192B (en) * | 2018-08-20 | 2021-12-10 | 福建永晶科技股份有限公司 | Preparation method and preparation system of ammonium fluoride |
| CN108910916B (en) * | 2018-08-20 | 2022-02-15 | 福建永晶科技股份有限公司 | Preparation method and preparation system of ammonium bifluoride |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1385369A (en) * | 2002-01-15 | 2002-12-18 | 姜仁和 | Proces for direct synthesizing fluoammonium salt |
-
2010
- 2010-12-31 CN CN201010624793.6A patent/CN102115095B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1385369A (en) * | 2002-01-15 | 2002-12-18 | 姜仁和 | Proces for direct synthesizing fluoammonium salt |
Non-Patent Citations (2)
| Title |
|---|
| 曹宏伟等.氟化氢铵生产新工艺研究.《磷肥与复肥》.2010,第25卷(第4期),第30页1.3. |
| 氟化氢铵生产新工艺研究;曹宏伟等;《磷肥与复肥》;20100731;第25卷(第4期);第30页1.3 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102115095A (en) | 2011-07-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102115095B (en) | Production method of anhydrous ammonium hydrogen fluoride | |
| CN109052434B (en) | Method for jointly producing soda ash and composite nitrogen fertilizer by taking mirabilite and ammonium bicarbonate as raw materials | |
| CN102515133A (en) | Preparation method of lithium hexafluorophosphate of lithium ion battery electrolyte | |
| CN105366668A (en) | Method for preparing graphene through supercritical fluid | |
| CN103274403A (en) | Method for recycling strong alkali in preparation process of active carbon having high specific surface area | |
| CN109019638B (en) | Mother liquor treatment method for preparing sodium carbonate by taking mirabilite as raw material | |
| CN101898769B (en) | Method for producing high-purity ammonium bifluoride | |
| CN103601217B (en) | Sodium fluoride production process and sodium fluoride mother liquor recycling process | |
| CN108163812B (en) | Preparation method of hydrogen fluoride and preparation method of hydrofluoric acid | |
| CN110698452A (en) | Preparation method of chlorinated ethylene carbonate by using novel initiator | |
| CN115385352A (en) | Preparation method of lithium tetrafluoroborate | |
| CN104495809B (en) | A kind of micro crystal graphite purifying method | |
| CN102557040B (en) | Comprehensive utilization method of byproduct, namely fluorosilicic acid, of phosphate fertilizer | |
| CN108117074B (en) | Preparation method of super activated carbon and method for recycling produced waste liquid and producing by-product carbonate | |
| CN103224246A (en) | Chemical gypsum-to-ammonium sulfate reaction slurry concentration, waste heat recovery and waste ammonia recovery method | |
| CN103332751A (en) | Ferrous sulfate comprehensive utilization method | |
| CN207404837U (en) | A kind of equipment that hydrogen fluoride is prepared by fluosilicic acid | |
| CN103896761A (en) | Method for composite oxidation and synthesis of glyoxalic acid | |
| CN101077786A (en) | Method for preparing aluminum fluoride | |
| CN103159232A (en) | Method for synthesizing ammonium sulfate by using recovered ammonia water from chemical fertilizer plant | |
| CN113896214A (en) | Method for preparing high-purity lithium carbonate by adsorbing and carbonizing lithium sulfate solution | |
| CN105984887A (en) | Melamine-tail-gas utilization technology | |
| CN100542962C (en) | Produce the method for aluminum fluoride | |
| Yunzhao et al. | Optimization of reactive extraction-crystallization process based on response surface methodology | |
| CN103101934A (en) | Method for preparing high-purity lithium carbonate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent for invention or patent application | ||
| CB02 | Change of applicant information |
Address after: 322100, No. 33, Xihua Road, Dongyang, Zhejiang, Jinhua Applicant after: Ying Lierong Address before: The 334400 Jiangxi County of Yiyang province Guifeng Scenic Area Applicant before: Ying Lierong |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| DD01 | Delivery of document by public notice |
Addressee: Ying Lierong Document name: Notification of Passing Examination on Formalities |
|
| DD01 | Delivery of document by public notice |
Addressee: Ying Lierong Document name: Notification to Pay the Fees |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140514 Termination date: 20151231 |
|
| EXPY | Termination of patent right or utility model |