CN101475440B - Method for continuous production of n-butyl chloride - Google Patents
Method for continuous production of n-butyl chloride Download PDFInfo
- Publication number
- CN101475440B CN101475440B CN200910028921A CN200910028921A CN101475440B CN 101475440 B CN101475440 B CN 101475440B CN 200910028921 A CN200910028921 A CN 200910028921A CN 200910028921 A CN200910028921 A CN 200910028921A CN 101475440 B CN101475440 B CN 101475440B
- Authority
- CN
- China
- Prior art keywords
- water
- propyl carbinol
- tower
- distillation
- reaction
- 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.)
- Active
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
Abstract
The invention provides a method for continuously producing n-chlorobutane, which belongs to an organic synthesis process. The process consists of reactive distillation stage, an isobutanol recovery stage and a washing distillation stage. The process substitutes hydrogen chloride gas for 30 percent of hydrochloric acid, integrates a reaction stage with a separation stage, adopts an azeotropic water-shift technique, controls the unit consumption needed for producing one ton of 99.5 percent n-chlorobutane to be less than 0.86 ton of isobutanol, 1.8 tons of hydrogen chloride gas, 1.8 tons of steam, 60 kwh or electrical power and less than 0.001 ton of formed COD, reduces 80 percent of sewage discharged during the whole process, and reduces 80 percent of energy consumption. A product obtained by the method contains more than 99.5 percent (weight) of n-chlorobutane, less than 0.02 percent (weight) of isobutanol and less than 0.01 percent (weight) of dibutyl ether.
Description
Technical field
The invention belongs to organic synthesis technology, relating to a kind of is the method for raw material continuous production n-propylcarbinyl chloride with propyl carbinol, hydrogen chloride gas.
Background technology
Chinese invention patent CN91105072.8 discloses " a kind of method of producing n-propylcarbinyl chloride "; It is a continuous production n-propylcarbinyl chloride under raw material, non-extra catalyst, the normal pressure with propyl carbinol and hydrochloric acid; Propyl carbinol and concentration are that technical hydrochloric acid temperature in still of 30-31% is, boiling reaction down in 90-105 ℃ the reaction kettle; The unreacted propyl carbinol of n-propylcarbinyl chloride, water, part and the small amount of hydrochloric acid that generate steam together, get into the azeotropic distillation tower after the condensation, and mixture temperature is 70-80 ℃ in the control azeotropic distillation tower; Tower top temperature is 68 ± 1 ℃, and the azeotrope that steams gets into rectifying tower after separating, washing refining; Be blended at the bottom of the azeotropic distillation Tata be divided in the tower still two-layer; Unreacted propyl carbinol in upper strata and sour water return reaction kettle; Water that lower floor is a large amount of and propyl carbinol and a spot of hydrochloric acid get into the azeotropic device; When azeotropic point, steam the azeotrope that consists of a large amount of propyl carbinols and less water and return reaction kettle, azeotropic device bottom effluent sewerage.
This technology is made up of conversion zone, segregation section, refining section, Butanol Recycling section, and the one way reactivity of conversion zone is low, is merely about 20%; Have repetition heat-processed, raw material consumption, energy consumption are higher, and the ton product consumes 0.95 ton of propyl carbinol; 3 tons of hydrochloric acid; 7.6 tons of steam, electric power 200kwh does not meet environmental protection production requirement energy-conservation, that reduce discharging, lower consumption.In addition; Contain the water about 70% in the raw material hydrochloric acid of this process using, need make it in process of production to be elevated to temperature of reaction, and in other operation, also have consumption such as corresponding steam, electric power from normal temperature; Reaction process will be wasted about 3.5 tons of/ton products of steam; Distillation process will be wasted about 1.5 tons of/ton products of steam, reclaims the propyl carbinol operation and will waste about 0.8 ton of/ton product of steam, and 140kwh/ ton product is wasted in the power consumption of aspects such as cooling water circulation, material circulation approximately; Organism such as propyl carbinol (about 45%) a large amount of in the Qi Fenshui process dissolve wherein, and a certain amount of process loss is arranged when reclaiming propyl carbinol; In actual moving process, the branch water at the bottom of the azeotropic device tower has a large amount of acid (greater than 20%) can't reclaim reaction system, and luxus consumption reaches about 0.72 ton of product per ton waste hydrogen chloride gas, needs with in 2.5 tons of slaked limes and waste water.
Summary of the invention
The present invention is just in order to overcome above-mentioned deficiency, provides that a kind of raw material consumption is low, less energy consumption, sewage be few, contains alcohol, ether in the product, the acid amount is extremely low, product purity is high, not the method for the continuous production n-propylcarbinyl chloride under the extra catalyst normal pressure.Main innovation is to adopt hydrogen chloride gas to substitute 30% hydrochloric acid, can reduce a large amount of steam consumptions; Conversion zone in the background technology and segregation section are united two into one, reduce production link, shortened technical process, reduce the unit consumption of butanols; Adopt azeotropic to move the water technology, utilize propyl carbinol and water azeotropic characteristics, the water azeotropic that reaction is generated goes out reaction system, and through fraction water device water-dividing, yield is less, and the organism loss is low, the hydrogenchloride of especially wasting seldom, the waste water of generation is few.
Specifically be to implement like this: a kind of method of continuous production n-propylcarbinyl chloride is characterized in that technology is made up of reaction distillation section, propyl carbinol recovery zone, water washing and rectification section:
(1) in the reaction distillation section; The synthesis reaction vessel upper outlet is directly installed a distillation tower, and hydrogen chloride gas is fed by synthesis reaction vessel bottom through gas distributor, propyl carbinol drench from the distillation tower bottom into; When azeotropic temperature; Distillation tower top azeotrope is washed the back by rectifying tower rectifying through cooling off the laggard rectifying section of going into to wash through the washing still, drier back packing in drying tower;
(2) water of successive reaction generation, propyl carbinol, dibutyl ether azeotrope get into the water trap in the propyl carbinol recovery zone through the distillation tower middle and lower part outlet of reaction distillation section, get back to synthesis reaction vessel behind the branch water;
(3) water that obtains of water trap bottom reclaims wherein a small amount of organism through the stripping regenerating column and gets back to synthesis reaction vessel and continue reaction, a large amount of water through in still in after the entering treatment tank.
The distillation tower top temperature is controlled at 68 ± 1 ℃ in the reaction distillation section; N-propylcarbinyl chloride content is higher than 92% (weight) in the azeotrope that steams; Propyl carbinol content is lower than 4% (weight); Distillation tower middle and lower part temperature out is controlled at 72 ± 2 ℃, makes water generation reaction migrate out reaction system, and keeps the material balance in the reaction system.Adopt gas distributor to feed hydrogen chloride gas from the synthesis reaction vessel bottom; Can guarantee that reaction continues to carry out; In order to prevent to overflow reaction system on the hydrogen chloride gas; Adopt the distillation tower bottom to drench technology, make propyl carbinol fully contact with the hydrogen chloride gas of overflow, dissolve and Returning reacting system, guarantee the reaction process continous-stable into propyl carbinol.
The present invention utilizes azeotropic water technology, and the water azeotropic that reaction is generated goes out reaction system, and through fraction water device water-dividing, product per ton is told 0.2 ton of water; It is about 12% wherein only to contain propyl carbinol, and hydrogenchloride is about 9%, and yield is less; The organism loss is low, the hydrogenchloride of waste seldom, product per ton is merely 0.02 ton; Amount to 0.06 ton of 30% hydrochloric acid, only need in 0.062 ton of 85% slaked lime and waste water, product per ton reduces 2.3 tons of waste water.
The n-propylcarbinyl chloride content that comes out from the reaction distillation section reaches more than 96%, and propyl carbinol content is less than 4%, and dibutyl ether content is less than 0.1%; Can wash-out propyl carbinol wherein after the distillage washing, it is below 0.2% that propyl carbinol content is lower than, again through after the rectifying tower rectifying; Product purity reaches 99.5%; Butanol content is lower than 0.05%, and dibutyl ether content is lower than 0.01%, meets the n-propylcarbinyl chloride quality product requirement of all kinds of purposes.
Stripping tower in the propyl carbinol recovery zone (theoretical plate number is greater than 5); Feed steam at the bottom of the tower; Cat head drenches the water told into propyl carbinol recovery zone water trap and the washing water of water washing and rectification section, keeps tower top temperature to be not less than 100 ℃, guarantees at the bottom of the tower that organism is lower than 0.08% in the water; During water gets into after cooling off at the bottom of the tower and still, with getting into sewage network with the back sedimentation in the slaked lime of equivalent.
Method of the present invention is made up of reaction distillation section, propyl carbinol recovery zone, water washing and rectification section; In the reaction distillation section, be 0.9-1 in molar ratio: 1 hydrogenchloride and propyl carbinol add in the synthesis reaction vessel continuously, generate n-propylcarbinyl chloride and water; Take the water generation reaction azeotropic out of reaction system with excessive propyl carbinol; The collection cooling from the distillation tower middle and lower part, cooling back divide goes quantitative water, organism such as propyl carbinol to be back to reaction system continuation reaction; The thick product of n-propylcarbinyl chloride that the distillation cat head slips out; Obtain the product more than 99.5% through washing, rectifying, water and the washing water told from the conversion zone water trap reclaim propyl carbinol through stripping stage, and the propyl carbinol that is reclaimed is got back to the reaction distillation section and continued reaction.
The needed unit consumption of n-propylcarbinyl chloride that present method production is 1 ton 99.5% is controlled at propyl carbinol and is lower than 1.8 tons of 0.86 ton of hydrogen chloride gas, 1.8 tons of steam, and electric power 60kwh, formed COD are lower than 0.001 ton; The sewage of discharging in whole worker's process has reduced 80%, and energy consumption has reduced 80%, and the product that obtains contains chloro normal butane high by 99.5% (weight), and propyl carbinol is lower than 0.02% (weight), and dibutyl ether is lower than 0.01% (weight).
Description of drawings
Accompanying drawing is a process flow sheet of the present invention.
Embodiment
A kind of method of continuous production n-propylcarbinyl chloride, technology is made up of reaction distillation section, propyl carbinol recovery zone, water washing and rectification:
(1) in the reaction distillation section; Synthesis reaction vessel 1 upper outlet is directly installed a distillation tower, and hydrogen chloride gas is fed by synthesis reaction vessel bottom through the body sparger, propyl carbinol drench from the distillation tower bottom into; Hydrogenchloride and propyl carbinol are 0.9-1 by mole: 1 adds in the synthesis reaction vessel continuously; The distillation tower top temperature is controlled at 68 ± 1 ℃ in the reaction distillation section, and when boiling temperature, distillation tower top 2 azeotropes are through cooling off the laggard rectifying section of going into to wash; Wash the back by smart tower 6 rectifying through washing still 5, drier back packing in drying tower 7;
(2) water of successive reaction generation, propyl carbinol, dibutyl ether azeotrope are got back to synthesis reaction vessel through exporting the water trap 4 in the 3 entering propyl carbinol recovery zones in the distillation tower of reaction distillation section down behind the branch water, and outlet degree in distillation tower middle and lower part is controlled at 72 ± 2 ℃;
(3) water that obtains of water trap 4 bottoms; Reclaim wherein a small amount of organism through stripping regenerating column 8 and get back to and close reaction kettle and continue reaction, a large amount of water through in still 9 in after entering treatment tank 10, the stripper 8 in the propyl carbinol recovery zone; Feed steam at the bottom of the tower; Cat head drenches the water told into propyl carbinol recovery zone water trap and the water water of water washing and rectification section, keeps tower top temperature to be not less than 100 ℃, at the bottom of the tower in the water organism be lower than 0.08%.
Claims (4)
1. the method for a continuous production n-propylcarbinyl chloride is characterized in that technology is made up of reaction distillation section, propyl carbinol recovery zone, water washing and rectification section:
(1) in the reaction distillation section; The synthesis reaction vessel upper outlet is directly installed a distillation tower, and hydrogen chloride gas is fed by synthesis reaction vessel bottom through gas distributor, propyl carbinol drench from the distillation tower bottom into; When azeotropic temperature; Distillation tower top azeotrope is washed the back by rectifying tower rectifying through cooling off the laggard rectifying section of going into to wash through the washing still, drier back packing in drying tower;
(2) water of successive reaction generation, propyl carbinol, dibutyl ether azeotrope get into the water trap in the propyl carbinol recovery zone through the distillation tower middle and lower part outlet of reaction distillation section, get back to synthesis reaction vessel behind the branch water;
(3) water that obtains of water trap bottom reclaims wherein a small amount of organism through the stripping regenerating column and gets back to synthesis reaction vessel and continue reaction, a large amount of water through in still in after the entering treatment tank.
2. method according to claim 1 is characterized in that the distillation tower top temperature is controlled at 68 ± 1 ℃ in the reaction distillation section, and distillation tower middle and lower part temperature out is controlled at 72 ± 2 ℃.
3. method according to claim 1 and 2; It is characterized in that the stripping tower in the propyl carbinol recovery zone; Feed steam at the bottom of the tower; Cat head drenches the water told into propyl carbinol recovery zone water trap and the washing water of water washing and rectification section, keeps tower top temperature to be not less than 100 ℃, at the bottom of the tower in the water organism be lower than 0.08%.
4. method according to claim 1 is characterized in that the reaction distillation section, and hydrogenchloride and propyl carbinol add in the synthesis reaction vessel for 0.9-1:1 in molar ratio continuously.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910028921A CN101475440B (en) | 2009-01-20 | 2009-01-20 | Method for continuous production of n-butyl chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910028921A CN101475440B (en) | 2009-01-20 | 2009-01-20 | Method for continuous production of n-butyl chloride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101475440A CN101475440A (en) | 2009-07-08 |
| CN101475440B true CN101475440B (en) | 2012-08-29 |
Family
ID=40836231
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910028921A Active CN101475440B (en) | 2009-01-20 | 2009-01-20 | Method for continuous production of n-butyl chloride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101475440B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102963945A (en) * | 2012-11-30 | 2013-03-13 | 宜兴市昌吉利化工有限公司 | Device for recovering low-boiling point organic matters in chloralkane production wastewater by use of stripping tower |
| CN102974130A (en) * | 2012-11-30 | 2013-03-20 | 宜兴市昌吉利化工有限公司 | Device for reducing water content in chloro-alkane by low-temperature cooling method |
| CN105601467A (en) * | 2016-02-26 | 2016-05-25 | 东南大学 | Process and device for preparing bromoethane through reactive distillation |
| CN106242942A (en) * | 2016-09-07 | 2016-12-21 | 山东道可化学有限公司 | The method for continuously synthesizing of a kind of 1 chlorobutane and the equipment of production thereof |
| CN107501040A (en) * | 2017-08-29 | 2017-12-22 | 湖北工程学院 | Chromatographically pure chloro-normal butane and preparation method thereof, production system |
| CN109678647A (en) * | 2018-08-22 | 2019-04-26 | 浙江万盛股份有限公司 | A kind of preparation method of high-purity 1- chlorine normal butane |
| CN109250694B (en) * | 2018-08-24 | 2020-12-11 | 北京化工大学 | Method for preparing hydroxylamine hydrochloride by using hydrogen chloride dry gas |
| CN113480400A (en) * | 2021-06-08 | 2021-10-08 | 山东同成医药股份有限公司 | Chloralkane micro-channel continuous reaction method |
| CN113501744A (en) * | 2021-07-09 | 2021-10-15 | 岳阳隆兴实业有限公司 | Synthesis method of chloro-sec-butyl alkane |
| CN113480401A (en) * | 2021-07-09 | 2021-10-08 | 岳阳隆兴实业有限公司 | Synthesis method of chloro-n-pentane |
| CN113896614B (en) * | 2021-11-08 | 2024-04-02 | 山东绿色海洋化工研究院有限公司 | Method for continuously synthesizing chlorobutane in non-aqueous system |
| CN114478182A (en) * | 2022-01-21 | 2022-05-13 | 安徽伟祥新材料有限公司 | Device and method for producing chloralkane series products |
| CN114656328B (en) * | 2022-04-09 | 2023-05-23 | 江苏昌吉利新能源科技有限公司 | Production process of ultralow-moisture chloro-n-butane |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3981938A (en) * | 1974-07-08 | 1976-09-21 | The Dow Chemical Company | Method for producing dry alkyl halides |
| CN1069018A (en) * | 1991-08-01 | 1993-02-17 | 中国石油化工总公司 | A kind of method of producing n-propylcarbinyl chloride |
-
2009
- 2009-01-20 CN CN200910028921A patent/CN101475440B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3981938A (en) * | 1974-07-08 | 1976-09-21 | The Dow Chemical Company | Method for producing dry alkyl halides |
| CN1069018A (en) * | 1991-08-01 | 1993-02-17 | 中国石油化工总公司 | A kind of method of producing n-propylcarbinyl chloride |
Non-Patent Citations (1)
| Title |
|---|
| 肖桃云.正丁基氯的合成工艺研究.《南京理工大学工程硕士学位论文》.2007,全文. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101475440A (en) | 2009-07-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101475440B (en) | Method for continuous production of n-butyl chloride | |
| CN103102265A (en) | Method and production equipment for variable-pressure distillation and purification of methyl acetate | |
| CN109456190A (en) | A kind of method of the continuous synthesizing propylene glycol monomethyl ether acetate of the highly selective catalytic distillation of low temperature | |
| CN101353289A (en) | Method for extracting trans-dichloroethylene from low-boiling residue of ethinyltrichloride production by gas-phase catalytic process | |
| CN107501042A (en) | A kind of method that isopropanol is prepared by isopropyl acetate ester hydrolysis | |
| CN109748791B (en) | Energy-saving method for producing dimethyl adipate | |
| CN104649862B (en) | With ethyl acetate be raw material production alcohol product method and equipment | |
| CN101434510B (en) | Method and apparatus for recovering methyl chloride in organosilicon monomer synthesis | |
| CN108002995A (en) | A kind of method and its equipment of acetone two-step method synthesizing methyl isobutyl ketone | |
| US9850190B2 (en) | Process for preparing dichloropropanol | |
| CN113896613A (en) | Method and device for synthesizing chloromethane | |
| CN101979365B (en) | Method for continuously preparing dichlorohydrin | |
| CN101289368A (en) | Technological process for continuously producing sec-butyl alcohol by direct hydration of n-butene | |
| CN108774100A (en) | A kind of tert-butyl alcohol and methanol prepare the integrated processes of methyl tertiary butyl ether(MTBE) and isobutene | |
| CN101429099B (en) | Method for producing dichlorohydrin with glycerol | |
| CN105693687B (en) | High-efficiency reactive distillation method and device for glycol acetal/ketone reaction | |
| CN101130495B (en) | Method for separating sec-butyl acetate from mixture after reaction of acetic acid and butylene or mixture of C4 | |
| CN101357880A (en) | Process and system for preparing dichloropropanol through autocatalytic reaction of glycerol and hydrogen chloride | |
| CN205635422U (en) | Device for separating isopropanol from water-containing acetone hydrogenation product | |
| CN111072480A (en) | Method for producing methyl ethyl carbonate by using ionic liquid catalysis ester exchange method | |
| CN217139251U (en) | Dealcoholization tower system in butyl acrylate preparation | |
| CN108658722A (en) | The synthetic method of one kind 1,2,3- trichloropropanes | |
| CN102040479B (en) | System for preparing dichloropropanol through autocatalytic reaction of glycerol and hydrogen chloride | |
| CN103641797B (en) | Preparation method for N-acetyl morpholine | |
| KR20000072037A (en) | Method and apparatus of methyl acetate hydrolysis |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 214253 Wuxi, Jiangsu, Yixing new town, Xinfeng Road, No. 140 Patentee after: Jiangsu Geely Amperex Technology Limited Address before: 214253 Xinfeng Middle Road, new town, Yixing City, Jiangsu Province, No. 140 Patentee before: Yixing Changjili Chemicals Co., Ltd. |