CN107089930A - The method that urea sulfate reaction coupling extract and separate handles Waste Sulfuric Acid - Google Patents
The method that urea sulfate reaction coupling extract and separate handles Waste Sulfuric Acid Download PDFInfo
- Publication number
- CN107089930A CN107089930A CN201710312303.0A CN201710312303A CN107089930A CN 107089930 A CN107089930 A CN 107089930A CN 201710312303 A CN201710312303 A CN 201710312303A CN 107089930 A CN107089930 A CN 107089930A
- Authority
- CN
- China
- Prior art keywords
- sulfuric acid
- waste sulfuric
- reaction
- urea
- extract
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C273/02—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of urea, its salts, complexes or addition compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of method that utilization urea and sulfuric acid reaction coupling solvent extract and separate handle organic Waste Sulfuric Acid.In the technical process of the present invention, ureasulfuric acid is generated as the additive of compound fertilizer using urea and sulfur waste acid reaction, coupling solvent extraction separation process, is subject to extract and separate by organic impurities contained in Waste Sulfuric Acid simultaneously, and extractant is repeated after distillation recovery and utilized.The present invention proposes a kind of organic Waste Sulfuric Acid method of processing of mild condition, can efficiently separate organic impurities in removal Waste Sulfuric Acid, and the sulfuric acid component in Waste Sulfuric Acid is converted into ureasulfuric acid product.It is of the invention compared with existing industrial waste sulfuric acid processing method, have the advantages that energy consumption is relatively low, simple to operate and mild condition.
Description
Technical field
The present invention relates to a kind of urea sulfate reaction coupling extract and separate handle Waste Sulfuric Acid method, belong to industrial waste without
Evilization processing and recycling field.
Background technology
Sulfuric acid is the important source material of Chemical Manufacture, in alkylation, sulfonation, nitrification, esterification, titanium white, acetylene gas purification, gas
The industry such as dry is used widely.But 40%-50% sulfuric acid and product is not converted into industrial production, but produced
The Waste Sulfuric Acid containing impurity is converted into journey, according to statistics, the Waste Sulfuric Acid that China produces every year is up to 100,000,000 tons, wherein inorganic sulfur waste
Acid accounts for 35%, and organic Waste Sulfuric Acid accounts for 65% (content accounts for 46% more than 40%).Organic Waste Sulfuric Acid is containing more organic miscellaneous
The Waste Sulfuric Acid of matter, can produce a large amount of such Waste Sulfuric Acids during alkylate oil and acetylene purification, with viscosity is larger, flowing
Property poor, the problem of processing is difficult.The harmless treatment of the Waste Sulfuric Acid containing organic impurities and recycling, can hold as restriction industry
The major issue of supervention exhibition.
The processing method of current organic Waste Sulfuric Acid mainly has：High-temperature cracking method, absorption method, oxidizing process, neutralisation, extraction
Deng.Industrially frequently with high-temperature cracking method, sulfuric acid and organic matter generation SO at a high temperature of 1000~1200 DEG C2、CO2Deng gas,
SO2Through separating catalysis oxidation generation SO3, and then sulfuric acid is generated, realize reusing for sulfuric acid.This method have treating capacity it is big,
The advantages of product purity is high, but also have the shortcomings that high energy consumption, invest it is big, have impact on this technique promotion and application [Zhang Yu, appoint
Bright space orchids refining waste sulfuric acid from alkylation handling process selection [J] petrochemical industry environmental protection, 2002,25 (2)：60-63；
D.Schwartz,R.Gadiou.A Kinetic Study of the Decomposition of Spent Sulfuric
Acids at High Temperature[J].Industrial&Engineering Chemistry Research,2000,
39(7):2183-2189].The principle of absorption method processing Waste Sulfuric Acid is that activated carbon, biological activated carbon, resin are added in Waste Sulfuric Acid
Deng material, the organic matter in adsorbing separation spent acid, but the problem of adsorbent is expensive, regeneration is difficult can not be avoided
[G.M.Walker,L.R.Weatherley.COD removal from textile industry effluent：pilot
plant studies[J].Chem.Eng.J,2001,84(2)：125-131；G.M.Walker,
L.R.Weatherley.Biological Activated Carbon Treatment of Industrial Wastewater
in Stirred Tank Reactors[J].Chem.Eng.J,1999,75(3)：201-206；The such as Gong Zhansheng, Duan Weidong are big
Hole resin adsorption method processing PNT sulphonation waste acid [J] Tianjin chemical industry, 2013,27 (4):35-38].Oxidizing process adds strong oxidizer,
Attempt at a lower temperature to remove the oxidation operation in Waste Sulfuric Acid, conventional oxidant includes O3, H2O2, KMnO4Deng,
But also generally existing oxidation efficiency is low, the shortcomings of cost is high [grind by Yang Runchang, the catalysis oxidation of week book day Waste Sulfuric Acid In Organic Chemical Industries
Study carefully [J] University Of Xiangtan natural science journal, 1999,21 (4):74-77].Neutralisation can be prepared using the reaction of lime and spent acid
Gypsum, can also generate ammonium sulfate by ammonification, but because the solid impurity in spent acid, organic matter and phosphate impurities influence stone
The quality of cream, so general require that spent acid organic impurity content is less than 2%, and crystallization and evaporation amount is big in ammonium sulfate production, energy consumption
It is high.[such as Zhang Hongxing, Tan Xiaoting utilizes acetylene cleaning Waste Sulfuric Acid Study on Preparation Technology [J] polyvinyl chloride, 2016,44 (4):34-
37；The reason for such as Zhang Hongxing, the Tan Xiaoting influence made gypsum of acetylene cleaning Waste Sulfuric Acid is utilized analysis [J] Shandong chemical industry, 2016,
45(5):22-25；The such as Geng Yang, Qi Wenzhe alkylation spent acid prepares new process [J] Chemical Engineerings of ammonium sulfate, and 2015,
43(11):1-4.].Extraction is studied in the organic impurities during processing nitrifies Waste Sulfuric Acid, uses toluene, heptane and hexamethylene
Alkane solvents extract organic impurities therein.It has the disadvantage single effect of extracting difference, it is necessary to can be only achieved preferably by multitple extraction
Effect of extracting, big [W.S.Chen, C.N.Juan, Recovery of the dinitrotoluenes and of solvent-oil ratio
trinitrotoluene from spent acid of toluene nitration process by solvent
extraction[J].Separation&Purification Technology,2005,43(1):95-101].To being at present
Only, only high-temperature cracking method has industrially been applied, and the processing method of more high-efficiency and economic also needs to constantly be studied hair
Exhibition.
Urea and organic waste sulfuric acid reaction are handled into Waste Sulfuric Acid under conditions of extractant is added the invention provides one kind
Method.This technique adds extractant in reaction system, and urea generates the organic matter in ureasulfuric acid, Waste Sulfuric Acid with sulfuric acid reaction
Extraction enters extraction phase, and the ureasulfuric acid of acquisition can be as additive for compound fertilizer, and extractant is used through being distilled to recover Posterior circle, and is given up
Organic matter in sulfuric acid, which is then separated, to be removed.This method process is simple, and treatment conditions are gentle, can efficiently separate
Except the organic impurities in Waste Sulfuric Acid, ureasulfuric acid product is obtained, while economic benefit is obtained, the potential environment of Waste Sulfuric Acid is eliminated
Risk.
The content of the invention
It is an object of the invention to provide a kind of method for handling the Waste Sulfuric Acid containing organic impurities, in urea and sulfuric acid reaction
During, the extraction and recovery process of extractant is coupled, organic matter is separated, ureasulfuric acid product is obtained, to solve sulfur waste acid treatment
The problem of with using difficulty.This method by react and extraction process is combined, overcome prior art presence high energy consumption, into
This high deficiency.
The method of the organic Waste Sulfuric Acid of utilization Urea treatment of the present invention comprises the following steps：
1) under certain temperature, pressure, raw material Waste Sulfuric Acid is mixed into addition reactor with organic extractant, added afterwards a certain amount of
Two-phase is formed after urea reaction, reaction；
2) upper strata is extraction phase after reacting, and is reused through being distilled to recover extractant, organic impurities is separated and removed；
3) lower floor is sulfuric acid urea solution after reacting.
Described raw material spent acid can come from acetylene washing process and alkylate oil production process containing one kind
Or the higher concentration Waste Sulfuric Acid of a variety of organic impurities, wherein H2SO4Content is 40%~90%.
Described extractant is toluene, carbon tetrachloride, dichloromethane and chloroform etc..
Described process conditions are：Reaction temperature is 0~50 DEG C, and the reaction time is 0.1~3h, extraction phase and Waste Sulfuric Acid volume
Than for 0.2~5, the reaction mol ratio of Waste Sulfuric Acid and urea is 0.5~3.
The advantage of the invention is：Simple to operate, reaction condition is gentle, can also be reacted under normal temperature, economical and efficient is realized
The harmless treatment of Waste Sulfuric Acid and recycling.
Embodiment
Embodiment 1
69.28g toluene is taken, the Waste Sulfuric Acids of 68.71g 36.99% are preheated to 45 DEG C in 250ml three-necked flasks, in molar ratio 2:1
Add 31.1329g urea to be reacted, the reaction time is 2.5h, eventually form two-phase, extraction phase is reclaimed through vacuum distillation and extracted
Agent.It can obtain sulfuric acid urea solution 97.35g, organic impurities clearance 88.85%.
Embodiment 2
Take 79.59g carbon tetrachloride, the Waste Sulfuric Acids of 34.01g 73.55% are preheated to 30 DEG C in 250ml three-necked flasks, by mole
Than 0.5:1 addition 7.7859g urea is reacted, and the reaction time is 0.5h, eventually forms two-phase, and extraction phase is returned through vacuum distillation
Receive extractant.It can obtain sulfuric acid urea solution 41.05g, organic impurities clearance 89.01%.
Embodiment 3
Take 90.12g chloroforms, the Waste Sulfuric Acids of 34.01g 73.55% are preheated to 40 DEG C in 250ml three-necked flasks, by mole
Than 2.5:1 addition 38.9184g urea is reacted, and the reaction time is 1.5h, eventually forms two-phase, extraction phase is through vacuum distillation
Reclaim extractant.It can obtain sulfuric acid urea solution 68.96g, organic impurities clearance 92.47%.
Embodiment 4
Take 106.12g dichloromethane, the Waste Sulfuric Acids of 39.37g 64.56% are preheated to 35 DEG C in 250ml three-necked flasks, by mole
Than 1.5:1 addition 23.3482g urea is reacted, and the reaction time is 1.5h, eventually forms two-phase, extraction phase is through vacuum distillation
Reclaim extractant.It can obtain sulfuric acid urea solution 60.35g, organic impurities clearance 95.21%.
Embodiment 5
Take 79.60g dichloromethane, the Waste Sulfuric Acids of 34.00g 73.55% are preheated to 35 DEG C in 250ml three-necked flasks, by mole
Than 1.5:1 addition 23.3506g urea is reacted, and the reaction time is 2.0h, eventually forms two-phase, extraction phase is through vacuum distillation
Reclaim extractant.It can obtain sulfuric acid urea solution 55.03g, organic impurities clearance 87.01%.
Claims (4)
1. a kind of method that extract and separate coupling urea reaction handles Waste Sulfuric Acid, it is characterised in that mainly walked including following technique
Suddenly：
（1）Under certain temperature, pressure, raw material Waste Sulfuric Acid is mixed into addition reactor with organic extractant, then added certain
Two-phase is formed after the urea reaction of amount, reaction；
（2）Upper strata is organic extraction phase after reaction, and through the separable extractant of distillation and organic impurities, extractant is reused, had
Machine impurity is able to separate and removed；
（3）Lower floor is sulfuric acid urea solution after reaction.
2. the method that a kind of extract and separate coupling urea reaction according to claim 1 handles Waste Sulfuric Acid, it is characterised in that
Described Waste Sulfuric Acid can come from acetylene washing process or the organic impurities containing one or more of alkylate oil production process
Higher concentration Waste Sulfuric Acid, wherein H2SO4Content 40 ~ 90%.
3. the method that a kind of extract and separate coupling urea reaction according to claim 1 handles Waste Sulfuric Acid, it is characterised in that
Described extractant is toluene, carbon tetrachloride, dichloromethane and chloroform.
4. the method that a kind of extract and separate coupling urea reaction according to claim 1 handles Waste Sulfuric Acid, it is characterised in that
Process conditions are：Reaction temperature is 0 ~ 50 DEG C, and the reaction time is 0.1 ~ 3h, the volume ratio of extraction phase and Waste Sulfuric Acid for 0.2 ~
5, the reaction mol ratio of Waste Sulfuric Acid and urea is 0.5 ~ 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710312303.0A CN107089930A (en) | 2017-05-05 | 2017-05-05 | The method that urea sulfate reaction coupling extract and separate handles Waste Sulfuric Acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710312303.0A CN107089930A (en) | 2017-05-05 | 2017-05-05 | The method that urea sulfate reaction coupling extract and separate handles Waste Sulfuric Acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107089930A true CN107089930A (en) | 2017-08-25 |
Family
ID=59638471
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710312303.0A Pending CN107089930A (en) | 2017-05-05 | 2017-05-05 | The method that urea sulfate reaction coupling extract and separate handles Waste Sulfuric Acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107089930A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111807995A (en) * | 2020-07-31 | 2020-10-23 | 山东泓瑞医药科技股份公司 | Method for resource utilization of waste acid in amantadine production |
| WO2022007288A1 (en) * | 2020-07-09 | 2022-01-13 | 定陶三化药业有限公司 | Dl-p-hydroxybenzene hydantoin and urea sulfate/ammonium sulfate production process thereof |
| CN116835535A (en) * | 2023-06-21 | 2023-10-03 | 江苏荣信环保科技有限公司 | System and method for recycling waste sulfuric acid |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4445925A (en) * | 1981-11-05 | 1984-05-01 | Union Oil Company Of California | Methods of producing concentrated urea-sulfuric acid reaction products |
| CN101200439A (en) * | 2006-12-13 | 2008-06-18 | 北京清华紫光英力化工技术有限责任公司 | Novel comprehensive utilization technique of industrial waste sulfuric acid |
| CN102358726A (en) * | 2011-07-11 | 2012-02-22 | 熊建超 | Urea sulfate and preparation method thereof |
| CN103992143A (en) * | 2014-05-29 | 2014-08-20 | 李润祥 | New technology for producing ammonium dihydrogen phosphate and compound fertilizer by utilizing waste sulphuric acid after purification of acetylene |
| EP2774907A2 (en) * | 2013-03-06 | 2014-09-10 | Instytut Nawozów Sztucznych | Method and plant for continuous manufacture of granular USP nitrogen and phosphate type fertilizers and products on their basis |
| CN106316755A (en) * | 2016-11-07 | 2017-01-11 | 四川大学 | Method for treating waste sulfuric acid through extraction separation coupled ammonium chloride reaction |
-
2017
- 2017-05-05 CN CN201710312303.0A patent/CN107089930A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4445925A (en) * | 1981-11-05 | 1984-05-01 | Union Oil Company Of California | Methods of producing concentrated urea-sulfuric acid reaction products |
| CN101200439A (en) * | 2006-12-13 | 2008-06-18 | 北京清华紫光英力化工技术有限责任公司 | Novel comprehensive utilization technique of industrial waste sulfuric acid |
| CN102358726A (en) * | 2011-07-11 | 2012-02-22 | 熊建超 | Urea sulfate and preparation method thereof |
| EP2774907A2 (en) * | 2013-03-06 | 2014-09-10 | Instytut Nawozów Sztucznych | Method and plant for continuous manufacture of granular USP nitrogen and phosphate type fertilizers and products on their basis |
| CN103992143A (en) * | 2014-05-29 | 2014-08-20 | 李润祥 | New technology for producing ammonium dihydrogen phosphate and compound fertilizer by utilizing waste sulphuric acid after purification of acetylene |
| CN106316755A (en) * | 2016-11-07 | 2017-01-11 | 四川大学 | Method for treating waste sulfuric acid through extraction separation coupled ammonium chloride reaction |
Non-Patent Citations (3)
| Title |
|---|
| 杨鼎文: "石化工业废硫酸的净化处理及回收利用", 《化工环保》 * |
| 王光龙等: "固体硫酸脲的研究 ", 《郑州大学学报(工学版)》 * |
| 石兆军: "一种硫酸脲氨化复合肥生产工艺 ", 《磷肥与复肥》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022007288A1 (en) * | 2020-07-09 | 2022-01-13 | 定陶三化药业有限公司 | Dl-p-hydroxybenzene hydantoin and urea sulfate/ammonium sulfate production process thereof |
| CN111807995A (en) * | 2020-07-31 | 2020-10-23 | 山东泓瑞医药科技股份公司 | Method for resource utilization of waste acid in amantadine production |
| CN116835535A (en) * | 2023-06-21 | 2023-10-03 | 江苏荣信环保科技有限公司 | System and method for recycling waste sulfuric acid |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108298581B (en) | System for extracting vanadium from leaching solution containing vanadium, chromium and silicon and preparing vanadium pentoxide and treatment method thereof | |
| WO2015161660A1 (en) | Method for preparing low-silicon vanadium pentoxide from solution containing vanadium, chromium and silicon | |
| CN102531025B (en) | Method for treating rare earth ammonium chloride wastewater | |
| CN101804264B (en) | Treatment method of industrial waste acid | |
| CN101058853A (en) | Method of reclaiming chemical industry products by using industrial slag containing vanadium, chromium, iron and phosphorous | |
| CN107089930A (en) | The method that urea sulfate reaction coupling extract and separate handles Waste Sulfuric Acid | |
| CN103214388A (en) | Nitrated waste acid recycling method | |
| CN103483221A (en) | Preparation method of cyclohexanone oxime | |
| CN109912096A (en) | A kind of pretreated method of o-methyl formate benzene sulfonamide waste water sub-prime | |
| CN109609754B (en) | Waste recovery process generated in precious metal extraction process | |
| CN111675404A (en) | Spent acid recovery system and method | |
| CN108658051B (en) | Method and device for recovering nitration waste acid and sulfuric acid recovered by method and device | |
| CN105348145B (en) | The method of ammonia type flue gas desulfurizing by-product cyclohexanone oxime | |
| CN102390820A (en) | Method for reclaiming nitric acid from nitrified waste acid | |
| CN102628104B (en) | Production process for extracting high-purity rare earth and zirconium compound from solid waste | |
| JP4901883B2 (en) | Method of distillatively removing dinitrotoluene in process wastewater from the process of producing dinitrotoluene by nitrating toluene with nitration acid | |
| CN110790235A (en) | Comprehensive utilization method of fluorine-containing potassium chloride as organic synthesis byproduct | |
| KR102243717B1 (en) | Method for reprocessing wastewater from nitrobenzene production | |
| CN101724758A (en) | Method for recycling molybdenum of molybdenum-contained waste catalyst | |
| CN102199704B (en) | Recycling use method of sodium chloride or sodium sulfate in hydrometallurgy | |
| CN108947012A (en) | A method of separating and recovering ammonia from ammonia nitrogen waste water | |
| CN106316755A (en) | Method for treating waste sulfuric acid through extraction separation coupled ammonium chloride reaction | |
| CN103130296B (en) | Treatment process of industrial organic wastewater containing acetate | |
| RU2701319C1 (en) | Method for complex processing of aluminum-containing salt slag | |
| CN102923877A (en) | Treatment technology for mirabilite tailing wastewater |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20170825 |
|
| WD01 | Invention patent application deemed withdrawn after publication |