CN108503532A - A kind of processing method for the by-product tail gas preparing Zassol - Google Patents

A kind of processing method for the by-product tail gas preparing Zassol Download PDF

Info

Publication number
CN108503532A
CN108503532A CN201810457012.5A CN201810457012A CN108503532A CN 108503532 A CN108503532 A CN 108503532A CN 201810457012 A CN201810457012 A CN 201810457012A CN 108503532 A CN108503532 A CN 108503532A
Authority
CN
China
Prior art keywords
tail gas
zassol
formic acid
processing method
intermediate material
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
Application number
CN201810457012.5A
Other languages
Chinese (zh)
Inventor
唐斯萍
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hengyang Normal University
Original Assignee
Hengyang Normal University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hengyang Normal University filed Critical Hengyang Normal University
Priority to CN201810457012.5A priority Critical patent/CN108503532A/en
Publication of CN108503532A publication Critical patent/CN108503532A/en
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41Preparation of salts of carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00Preparation of carboxylic acid amides
    • C07C231/02Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines

Abstract

The present invention provides a kind of processing methods for the by-product tail gas preparing Zassol, include the following steps:The by-product tail gas for preparing Zassol is mixed with formic acid solution, neutralization reaction occurs, obtains intermediate material;Wherein, the by-product tail gas is generated during preparing Zassol by urea and sodium carbonate;The pH value for adjusting the intermediate material obtains ammonium formate or formamide through dehydration.The present invention uses formic acid, and as absorbent, the ammonia reaction in the by-product generated generates ammonium formate or formamide, remarkable in economical benefits are easy to operate with utilizing urea and sodium carbonate to react.

Description

A kind of processing method for the by-product tail gas preparing Zassol
Technical field
The present invention relates to tail gas disposal technique field more particularly to a kind of processing sides for the by-product tail gas preparing Zassol Method.
Background technology
Zassol is widely used in herbicide, bactericidal agent, metal heat treatmet agent and medicine intermediate etc., the production of Zassol Method mainly has solid-state fusion method, absorption process, liquid phase method and liquid-solid reaction method.Liquid-solid reaction method is that industrial use is most wide at present General method is to react to generate Zassol with sodium carbonate or sodium hydroxide using urea.Due to urea with sodium hydroxide the system of reacting The cost of standby Zassol is higher, so being prepared based on Zassol with sodium carbonate and urea reaction at present.But with urea and carbonic acid Sodium reaction generate Zassol during, if the tail gas to generation is not used, will result in a large amount of hydrochloric acid ammonium, The outer row of ammonium hydrogen carbonate and ammonium hydroxide pollutes environment.
Currently, the processing for the tail gas, Chinese patent 200610069084.X is disclosed the tail gas and He Shui The method that composite fertilizer is produced after mixing, but its economic benefit is poor;Chinese patent 201010190456.0 discloses described in utilization The method of End gas production sodium carbonate heptahydrate and ammonium sulfate, but the value of sodium carbonate heptahydrate and sodium sulphate is very low, however it remains warp It helps problem of poor benefits.
Invention content
The purpose of the present invention is to provide a kind of methods that good in economic efficiency processing prepares Zassol by-product tail gas.
In order to achieve the above-mentioned object of the invention, the present invention provides following technical scheme:
The present invention provides a kind of processing methods for the by-product tail gas preparing Zassol, include the following steps:
The by-product tail gas for preparing Zassol is mixed with formic acid solution, neutralization reaction occurs, obtains intermediate material;Wherein, The by-product tail gas is generated during preparing Zassol by urea and sodium carbonate;
The pH value for adjusting the intermediate material obtains ammonium formate or formamide through dehydration.
Preferably, the volume content of ammonia is 35%~45% in the by-product tail gas.
Preferably, the mass concentration of the formic acid solution is 45%~55%.
Preferably, the quality of the formic acid solution and the volume ratio of by-product tail gas are 1Kg:(0.55~0.85) m3
Preferably, the temperature of the neutralization reaction is 40~86 DEG C.
Preferably, the pH value for adjusting the intermediate material is 2.8~3.2.
Preferably, it is formic acid solution to adjust conditioning agent used by the intermediate material pH value;The matter of the formic acid solution Measure a concentration of 50%~85%.
Preferably, the dehydration includes evaporation or distillation.
Preferably, the temperature of the evaporation is 75~105 DEG C.
Preferably, the bottom temperature of the distillation is 145~155 DEG C, and tower top temperature is 95~105 DEG C.
The present invention provides a kind of processing methods for the by-product tail gas preparing Zassol, include the following steps:Cyanogen will be prepared The by-product tail gas of sour sodium is mixed with formic acid solution, and neutralization reaction occurs, obtains intermediate material;Wherein, the by-product tail gas be by Urea and sodium carbonate generate during preparing Zassol;The pH value for adjusting the intermediate material obtains formic acid through dehydration Ammonium or formamide.The present invention, which is reacted using formic acid as absorbent with the ammonia in the by-product tail gas for preparing Zassol, generates formic acid Ammonium or formamide, remarkable in economical benefits are easy to operate.
Description of the drawings
Fig. 1 is the flow chart for the by-product tail gas that processing of the present invention prepares Zassol.
Specific implementation mode
The present invention provides a kind of processing methods for the by-product tail gas preparing Zassol, include the following steps:
The by-product tail gas for preparing Zassol is mixed with formic acid solution, neutralization reaction occurs, obtains intermediate material;Wherein, The by-product tail gas is generated during preparing Zassol by urea and sodium carbonate;
The pH value for adjusting the intermediate material obtains ammonium formate or formamide through dehydration.
The present invention mixes the by-product tail gas for preparing Zassol with formic acid solution, and neutralization reaction occurs, obtains intermediate material. In the present invention, the volume content of ammonia is preferably 35%~45% in the by-product tail gas, and more preferably 38%~42%, most Preferably 39%~40%.
In the present invention, preferably further include carbon dioxide and vapor in the by-product tail gas;The body of the carbon dioxide Product content is preferably 22-28%, more preferably 24-26%;The volume content of the vapor is preferably 20-30%, more preferably For 24.5-25.5%.
In the present invention, the mass concentration of the formic acid solution is preferably 40%~55%, and more preferably 45%~50%, Most preferably 46%~48%.In the present invention, the solvent of the formic acid solution is preferably water.
In the present invention, the quality of the formic acid solution and the volume ratio of by-product tail gas are preferably 1Kg:(0.55~0.85) m3, more preferably 1Kg:(0.65~0.8) m3, most preferably 1Kg:(0.75~0.78) m3
In the present invention, the temperature of the neutralization reaction is preferably 40~86 DEG C, more preferably 50~80 DEG C, most preferably 60~70 DEG C.
In the present invention, the by-product tail gas is the by-product that Zassol is prepared by urea and sodium carbonate reaction.The present invention The condition for preparing Zassol for the urea and sodium carbonate reaction does not have special restriction, using known to those skilled in the art Urea and sodium carbonate reaction prepare the technical solution of Zassol.In the present invention, the substance of the urea and sodium carbonate Amount than be preferably (1.8~2.2):1, more preferably (1.9~2.1):1.In the present invention, the urea and sodium carbonate is anti- It is preferably 165~175 DEG C to answer temperature, more preferably 168~172 DEG C.
In the present invention, the by-product tail gas for preparing Zassol mixes the pair that will preferably prepare Zassol with formic acid solution Production tail gas is passed through in formic acid solution.
In the present invention, when carrying out practical large-scale production, the reaction of the urea and sodium carbonate is preferably anti-in rake It answers in device and carries out, it is specific as shown in Figure 1, the feed inlet on rake reactor top puts into urea and the mixture of sodium carbonate carries out Reaction, the Zassol generated in rake reactor are discharged by the relief hole of reactor bottom;And by-product tail gas then passes through rake Gas outlet above formula reactor enters in absorption tower occurs neutralization reaction with formic acid solution therein.
After obtaining intermediate material, the present invention adjusts the pH value of the intermediate material, through dehydration, obtains ammonium formate or first Amide.The pH value of the intermediate material is preferably adjusted to 2.8~3.2, more preferably 2.9~3.1 by the present invention.In the present invention In, conditioning agent is preferably formic acid solution used by adjusting the intermediate material pH value;The mass concentration of the formic acid solution is excellent It is selected as 50%~85%, more preferably 55%~80%, most preferably 60%~70%.In the present invention, the formic acid solution Solvent be preferably water.
In the present invention, the purpose for the pH value of the intermediate material being adjusted to 2.8~3.2 is can in removal intermediate material Ammonium carbonate existing for energy.
In the present invention, when carrying out practical large-scale production, the process of the intermediate material pH value is adjusted preferably in It is carried out in kettle, it is specific as shown in Figure 1, the by-product tail gas and formic acid solution occur after neutralization reaction above by absorption tower Reflux condenser carries out reflux condensation mode processing, and the tail gas without ammonia is drained into air, and unreacted ammonia passes through with formic acid It is back to absorption tower again after reflux condensation mode processing and participates in neutralization reaction, the intermediate material obtained after the completion of neutralization reaction is from absorption The discharge port of tower bottom is delivered to through circulating pump and neutralizes in kettle, and the pH value of the intermediate material is adjusted to 2.8 using formic acid solution After~3.2, the intermediate material that pH value is 2.8~3.2 is delivered to by dehydrating kettle or steaming according to obtained target product respectively Kettle is evaporated to be carried out dehydrating.
In the present invention, the dehydration is preferably included to evaporate or be distilled.
In the present invention, when being carried out dehydrating using evaporation, obtained target product is ammonium formate;The evaporation Purpose is the hydrone generated during removing neutralization reaction, to obtain ammonium formate.In the present invention, the temperature of the evaporation Preferably 75-105 DEG C, more preferably 85-102 DEG C.
After completing the evaporation, obtained evaporation material is preferably carried out crystallisation by cooling, centrifugation and drying by the present invention successively, Obtain ammonium formate.The present invention is to the crystallisation by cooling, centrifugation and dry no any special restriction, using people in the art Crystallisation by cooling, centrifugation and the technical solution of drying known to member.
The disposing mother liquor that the present invention preferably obtains centrifugation;During the way of recycling preferably participates in mother liquor as preparation With the raw material of the formic acid solution of reaction or be dehydrated again, crystallisation by cooling, centrifugation and drying, prepare ammonium formate.
In the present invention, when carrying out practical large-scale production, the evaporation carries out preferably in dehydrating kettle, specific as schemed Shown in 1, the evaporation material obtained after evaporation is discharged from the discharge port of the dehydrating kettle bottom, carries out follow-up crystallisation by cooling, centrifugation And drying, obtain ammonium formate.
In the present invention, when being carried out dehydrating using distillation, obtained target product is formamide;The distillation Purpose is that intramolecular dehydration occurs for the ammonium formate for making neutralization reaction generate, to generate formamide.In the present invention, the distillation Bottom temperature be preferably 145~155 DEG C, more preferably 148~153 DEG C, most preferably 150~152 DEG C;The tower of the distillation It is 95~105 DEG C to push up temperature, more preferably 98~103 DEG C, most preferably 100~102 DEG C.
After completing the distillation, obtained distilling material is preferably carried out rectification under vacuum by the present invention;In the present invention, described The pressure of rectification under vacuum is preferably≤- 0.093MPa, more preferably≤- 0.095MPa;The bottom temperature of the rectification under vacuum is excellent It is selected as 175~180 DEG C, more preferably 176~178 DEG C;The tower top temperature of the rectification under vacuum is preferably 165~175 DEG C, more excellent It is selected as 168~172 DEG C.
In the present invention, when carrying out practical large-scale production, the distillation carries out preferably in distillation still, the vacuum Rectifying preferably carries out in a distillation column, specific as shown in Figure 1.
Technical scheme of the present invention is further described below in conjunction with actual process production procedure.
Fig. 1 is the flow chart for the by-product tail gas that processing of the present invention prepares Zassol, specifically includes following steps:
Urea and sodium carbonate are put into reactor, the reaction for generating Zassol is carried out, by the Zassol of generation from anti- It answers the relief hole of device to be discharged, while by-product tail gas is inputted into absorption tower, carried out with the formic acid solution being added in absorption tower in advance Neutralization reaction;It is provided with reflux condenser above absorption tower and recycles unreacted formic acid solution, while being obtained after neutralization reaction To the tail gas of removal ammonia be discharged into air by the removal of impurities of demister;
The intermediate material obtained after the neutralization reaction is entered into neutralization kettle by circulating pump, in and passes through addition in kettle Formic acid solution adjusts the pH value of the intermediate material, then inputs the dehydrated material that dehydrating kettle is carried out dehydrating, and will obtain Crystallisation by cooling, centrifugation and drying are carried out, ammonium formate is obtained;Or the intermediate material input distillation still after adjusting pH value is taken off Water process obtains formamide.
The processing method provided by the invention with the by-product tail gas for preparing Zassol is carried out in detail with reference to embodiment Explanation, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
1320kg urea and 1060kg sodium carbonate are uniformly mixed in input rake reactor, 165 DEG C is warming up to, will generate Zassol (mass content 92%) be discharged from relief hole, while obtaining the by-product containing carbon dioxide, ammonia and vapor Tail gas, the volume content of ammonia is 40% in by-product tail gas;
By 699.2M3The aqueous formic acid that it is in advance 50% added with 920kg mass concentrations that the by-product tail gas, which is fed through, In absorption tower, the temperature for controlling absorption tower is 45 DEG C, carries out neutralization reaction, obtains intermediate material;
The intermediate material is sent into and neutralizes kettle, the aqueous formic acid that mass concentration is 50% is added and adjusts intermediate material After pH value is 3, dehydrating kettle is sent to, 85 DEG C of evaporative removal moisture therein obtain ammonium formate through crystallisation by cooling, centrifugation and drying, Purity is 98wt%.
Embodiment 2
1320kg urea and 1060kg sodium carbonate are uniformly mixed in input rake reactor, 175 DEG C is warming up to, will generate Zassol (mass content 94%) be discharged from relief hole, while obtaining the by-product containing carbon dioxide, ammonia and vapor Tail gas, the volume content of ammonia is 42% in by-product tail gas;
By 700M3The aqueous formic acid that it is in advance 50% added with 920kg mass concentrations that by-product tail gas described in volume, which is sent into, In absorption tower, the temperature for controlling absorption tower is 50 DEG C, carries out neutralization reaction, obtains intermediate material;
Intermediate material is sent into and neutralizes kettle, the pH that the aqueous formic acid adjusting intermediate material that weight concentration is 50% is added is After 3, send to dehydrating kettle, 145 DEG C of distillations obtain formamide, purity 90wt%, then by 90% formamide 175 DEG C ,- Rectification under vacuum under the conditions of 0.093MPa obtains formamide, purity 99wt%.
As seen from the above embodiment, the present invention provides a kind of processing methods for the by-product tail gas preparing Zassol, including Following steps:The by-product tail gas for preparing Zassol is mixed with formic acid solution, neutralization reaction occurs, obtains intermediate material;Wherein, The by-product tail gas is generated during preparing Zassol by urea and sodium carbonate;The pH value of the intermediate material is adjusted, is passed through Dehydration obtains ammonium formate or formamide.The present invention using formic acid as absorbent with prepare in the by-product tail gas of Zassol Ammonia reaction generate ammonium formate or formamide, remarkable in economical benefits is easy to operate, and obtained ammonium formate or formamide is pure Degree is in 90wt% or more.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered It is considered as protection scope of the present invention.

Claims (10)

1. a kind of processing method for the by-product tail gas preparing Zassol, includes the following steps:
The by-product tail gas for preparing Zassol is mixed with formic acid solution, neutralization reaction occurs, obtains intermediate material;Wherein, described By-product tail gas is generated during preparing Zassol by urea and sodium carbonate;
The pH value for adjusting the intermediate material obtains ammonium formate or formamide through dehydration.
2. processing method as described in claim 1, which is characterized in that the volume content of ammonia is 35% in the by-product tail gas ~45%.
3. processing method as described in claim 1, which is characterized in that the mass concentration of the formic acid solution be 45%~ 55%.
4. such as claims 1 to 3 any one of them processing method, which is characterized in that the quality and by-product of the formic acid solution The volume ratio of tail gas is 1Kg:(0.55~0.85) m3
5. processing method as described in claim 1, which is characterized in that the temperature of the neutralization reaction is 40~86 DEG C.
6. processing method as described in claim 1, which is characterized in that the pH value for adjusting the intermediate material is 2.8~3.2.
7. processing method as described in claim 1 or 6, which is characterized in that adjust and adjusted used by the intermediate material pH value Section agent is formic acid solution;The mass concentration of the formic acid solution is 50%~85%.
8. processing method as described in claim 1, which is characterized in that the dehydration includes evaporation or distillation.
9. processing method as claimed in claim 8, which is characterized in that the temperature of the evaporation is 75~105 DEG C.
10. processing method as claimed in claim 8, which is characterized in that the bottom temperature of the distillation is 145~155 DEG C, tower It is 95~105 DEG C to push up temperature.
CN201810457012.5A 2018-05-14 2018-05-14 A kind of processing method for the by-product tail gas preparing Zassol Pending CN108503532A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810457012.5A CN108503532A (en) 2018-05-14 2018-05-14 A kind of processing method for the by-product tail gas preparing Zassol

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810457012.5A CN108503532A (en) 2018-05-14 2018-05-14 A kind of processing method for the by-product tail gas preparing Zassol

Publications (1)

Publication Number Publication Date
CN108503532A true CN108503532A (en) 2018-09-07

Family

ID=63400541

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810457012.5A Pending CN108503532A (en) 2018-05-14 2018-05-14 A kind of processing method for the by-product tail gas preparing Zassol

Country Status (1)

Country Link
CN (1) CN108503532A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110950752A (en) * 2019-12-18 2020-04-03 甘肃睿思科新材料有限公司 Preparation method of lithium formate solution

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1656020A (en) * 2002-05-23 2005-08-17 Dsmip财产有限公司 Process for removing ammonia from an ammonia-containing gas stream
CN105084328A (en) * 2014-05-16 2015-11-25 沈阳化工研究院有限公司 Method for producing ammonium sulfamate by utilization of exhaust gas containing ammonia and carbon dioxide

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1656020A (en) * 2002-05-23 2005-08-17 Dsmip财产有限公司 Process for removing ammonia from an ammonia-containing gas stream
CN105084328A (en) * 2014-05-16 2015-11-25 沈阳化工研究院有限公司 Method for producing ammonium sulfamate by utilization of exhaust gas containing ammonia and carbon dioxide

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
申泮文 等: "《化合物词典》", 30 June 2002, 上海辞书出版社 *
程能林: "《溶剂手册(第二版)》", 30 September 1994, 化学工业出版社 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110950752A (en) * 2019-12-18 2020-04-03 甘肃睿思科新材料有限公司 Preparation method of lithium formate solution

Similar Documents

Publication Publication Date Title
CN102145912B (en) Process for preparing calcium chloride solution by utilizing ammonia soda filtration mother liquor
CN105671587B (en) A kind of method and its device for preparing methionine and reclaiming accessory substance carbon dioxide
CN104445276A (en) Method for efficiently preparing monocyanamide solution
US4053507A (en) Method of recovering unreacted materials and heat in urea synthesis
CN108658374A (en) A kind of cleaning method of glycine production waste water
CN108503532A (en) A kind of processing method for the by-product tail gas preparing Zassol
CN108975356B (en) Method for producing sodium bicarbonate and ammonium sulfate from sodium sulfate and/or mirabilite
CN110902696A (en) Preparation method of cyanogen chloride
CN108821944A (en) A kind of comprehensive processing method of amion acetic acid centrifuge mother liquor
EP2488449B1 (en) Process for production of chlorine dioxide
CN105084328B (en) A kind of method that Amcide Ammate is produced using the waste gas containing ammonia and carbon dioxide
CN108440332A (en) The recovery method of D-VB5 mother liquor of calcium
US4003801A (en) Treatment of water vapor generated in concentrating an aqueous urea solution
CN111017931A (en) Method for concentrating fluosilicic acid by high-temperature dilute sulfuric acid
CN108706610B (en) Method for recovering ammonia and high-quality gypsum from ammonium sulfate
CN204588715U (en) A kind of device utilizing melamine tail gas to produce ammonium nitrate solution
CN109928408A (en) The method and system of ammonia is recycled from potassium nitrate process by-product ammonium chloride
CN104496101B (en) A kind of thermo-compression evaporation technique recycling gas cleaning by-product
CN104478514B (en) A kind of utilization gas cleaning accessory substance prepares the thermo-compression evaporation technique of chemical fertilizer
CN105645442A (en) Process for jointly producing melamine, sodium carbonate and ammonium chloride by using urea
CN1161316C (en) Lactic acid refining short range distillation process with drum evaporator
CN107311878A (en) A kind of device for reclaiming glycine waste liquid and the method for reclaiming glycine waste liquid
CN207375977U (en) A kind of device for recycling glycine waste liquid
CN213866026U (en) Energy-saving production increasing device for ammonia extraction urea production process
CN213060531U (en) Ammonium sulfate effluent disposal system

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20180907

RJ01 Rejection of invention patent application after publication