CN1420116A - Process and apparatus for synthesis of thiophene - Google Patents
Process and apparatus for synthesis of thiophene Download PDFInfo
- Publication number
- CN1420116A CN1420116A CN 01135132 CN01135132A CN1420116A CN 1420116 A CN1420116 A CN 1420116A CN 01135132 CN01135132 CN 01135132 CN 01135132 A CN01135132 A CN 01135132A CN 1420116 A CN1420116 A CN 1420116A
- Authority
- CN
- China
- Prior art keywords
- reaction
- thiophene
- gas
- sulfur
- temperature
- 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
Images
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A process for synthesizing thiophene includes the reaction for gas-phase sulfur and 1,3-butadiene, and extracting thiophene from resultant gas. Its apparatus is composed of tubular reactor, reactive settling tank, vertical settling tube, vertical condensing cooler, three-phase separator, tank of semifinished product and rectifying tower. Its advantages are low cost and high purity (more than 99.5%) and quality of product.
Description
Technical Field
The invention relates to a method and a device for producing thiophene.
Background
Thiophene, also known as thiacyldiene, is a colorless, transparent liquid that has an aromatic odor similar to benzene and is flammable. Melting point-383 deg.C, boiling point 84.12 deg.C, relative density 1.0644(20 deg.C), flash point-1.1 deg.C, refractive index 1.5289(20 deg.C), water-insoluble, easily soluble in ethanol, diethyl ether and other organic solvents, and no decomposition when heated to 850 deg.C.
The main uses ofthiophene are: synthetic drugs such as semisynthetic penicillins, cephalosporins, anthelmintics, antihistamines, etc.; synthetic dyes, pesticides, optical brighteners, flavoring agents, and the like; synthesis of several complex reagents; the method is used for extraction and separation of uranium metal and the like. According to recent reports, thiophenes are used in the manufacture of computer chips.
The traditional thiophene production method is to extract naturally occurring substances, and thiophene mainly exists in coal tar and shale oil. The extraction method is roughly as follows: rectifying the mixed fraction of benzene to remove toluene, and then washing with 85% sulfuric acid with 5% of raw material amount to remove unsaturated compounds; then, the mixture was washed with 98% sulfuric acid in an amount of 7% based on the starting material to separate the acid solution from benzene. The method comprises the steps of hydrolyzing waste acid liquor serving as a raw material at 110-150 ℃, enabling gas generated during hydrolysis to enter a tower top condenser through a hydrolysis rectifying tower, and condensing to obtain a product containing 15-25% of thiophene, 50-60% of xylene, benzene, toluene, methylthiophene and some unknown substances. About 10 kg of rectification products can be extracted from each ton of waste acid liquor. And (3) dehydrating the rectification product by using solid sodium hydroxide, and repeatedly rectifying and refining (finally carrying out azeotropic rectification with ethanol) to obtain a thiophene product with the content of 90-95%.
The quality index is as follows: first and second stages
% by weight chromatography 95% 90%
Relative density (20 ℃ C.) 1.0551.044
Refractive index 1.52651.5260
From the above, it is obvious that the method for producing thiophene from naturally occurring substances is very complicated, the cost is high, the product quality is poor, the boiling points of benzene, toluene and thiophene are relatively close, the separation is difficult, and the method is particularly limited by the process for refining coal tar and shale oil (the process is backward, seriously polluted and rarely used).
The organic thiophene synthesis has been reported abroad, and the adopted raw materials mainly comprise carbon disulfide and n-butane or n-butanol.
Disclosure of Invention
The invention aims to solve the technical problem of providing a thiophene synthesis production process and a production device, and industrially producing a high-purity thiophene product at low cost.
The process for synthesizing thiophene of the present invention is characterized in that gas-phase sulfur and 1, 3-butadiene are reacted, and thiophene is extracted from the generated reaction gas product.
The method adopts an organic synthesis process, selects proper raw materials, and obtains products with high concentration of … thiophene which is a target product after the raw materials react, so that the extraction is easy. The gaseous sulfur is obtained from solid sulfur according to known technical methods.
The reaction equation is:
the reaction of the gas-phase sulfur and the 1, 3-butadiene can be carried out in the presence of a catalyst or in the absence of the catalyst, and the reaction conditions without the catalyst provided by the reaction are as follows: the reaction temperature is 250-550 ℃, preferably 380-480 ℃, and the pressure (gauge pressure) is 0.05-0.25 Mpa. In order to achieve sufficient reaction, the linear reaction speed is preferably 1.5 to 3.0m/s, and the reaction time is preferably 1 to 3 seconds. The weight ratio of the gas-phase sulfur to the 1, 3-butadiene is preferably 1.04-1.33: 1.
Meanwhile, in order to control the temperature in the reaction process to be uniform, the reaction depth can be controlled by adopting a mode of external heating and temperature reduction by adding a small amount of water vapor inside (the reaction temperature in the reactor is kept to be uniform). The amount of the steam has no direct influence on the reaction as long as the reaction temperature can be ensured. The addition of steam also reduces the formation of coke by the reaction.
The reaction gas product obtained after the reaction comprises tail gas (rich in hydrogen sulfide), semi-finished product liquid and a small amount of heavy oil, and thiophene is contained in the semi-finished product liquid. Therefore, the reaction gas product is firstly cooled to 250-350 ℃, heavy oil in the reaction by-products is removed, then the reaction gas product is cooled to 40-50 ℃ through condensation, tail gas, sulfur-containing sewage and semi-finished product liquid three-phase substances in the reaction product are separated, semi-finished product liquid substances are rectified, and 83.5-84.5 ℃ fractions are collected, namely thiophene. The tail gas is treated by two-stage alkali washing and desulfurization by a desulfurization catalyst bed layer according to a common method, so that the hydrogen sulfide content in the tail gas finally discharged at high altitude is not more than 2 ppm.
The production device for completing the process comprises a tubular reactor, a reaction settling tank connected with the tubular reactor, a vertical settling tube connected with the reaction settling tank, a vertical condensation cooler connected with the vertical settling tube, wherein the outlet of the condensation cooleris connected with a three-phase separator, the lower part of the three-phase separator is connected with a semi-finished product storage tank, and the storage tank is connected with an intermittent rectifying tower.
The invention has the following effects: by adopting an organic synthesis process, the production cost is greatly reduced, the concentration of a target product after the synthesis reaction is high, the extraction is convenient, the product quality is improved, the purity is more than or equal to 99.5 percent, and the product can reach the enterprise standard of British synthetic chemical company:
thiophene,% by weight 99.5
Density (20 ℃ C.) 1.065
Carbon disulfide,% by weight, 0.1
Colorless liquid in appearance
Aromatic odor with characteristic odor
Water content,% (by weight) 0.03
Drawings
FIG. 1 is a schematic flow chart of a production apparatus of the present invention.
Detailed Description
FIG. 1 does not include preheating of the gas phase 1, 3-butadiene and the conversion of solid sulfur to gas phase sulfur.
The liquid 1, 3-butadiene is pumped into the preheating vaporizer through a metering pump, an electric heater is adopted for heating, and the temperature is controlled to be 180-240 ℃. Steam is injected into the preheating vaporizer according to the mol ratio of 1-3: 1(1, 3-butadiene: steam) to prevent the 1, 3-butadiene from polymerizing at high temperature.
And putting the solid flaky sulfur into a melting tank in batches, heating, controlling the temperature in the melting tank to be 120-150 ℃, and feeding the solid flaky sulfur into a sulfur metering pump. The liquid sulfur is pumped into the vaporizer by a metering pump, an electric heater is adopted for heating, and the temperature of the vaporizer is controlled to be 440-470 ℃.
Mixing gas-phase sulfur and 1, 3-butadiene gas according to the weight ratio of 1.04-1.33: 1, and feeding the mixture into a tubular reactor. The temperature of the reactor is controlled to be 250-550 ℃, preferably 380-480 ℃, the pressure is 0.05-0.25 Mpa (gauge pressure), the reaction linear speed is 1.5-3.0 m/s (meter/second), and the reaction time is 1-3 seconds.
Stainless steel pall ring random packing is filled in the tubular reactor, and a jacket type electric heater is adopted to heat the outside of the tubular reactor. In the reaction process, a small amount of water vapor can be injected into the reactor to keep the reaction temperature in the reactor uniform.
And (3) allowing the reaction product to enter a reaction settling tank from the tubular reactor, cooling the temperature to 250-350 ℃, and intermittently discharging a small amount of heavy tar (reaction by-product) from the reaction settling tank.
The reaction product enters a single-tube-pass vertical condensation cooler from a reaction settling tank through a settling tube, the temperature of a gas phase inlet of the condenser is generally 95-150 ℃, and the gas-liquid two-phase reaction product cooled to 40-50 ℃ enters a three-phase separator.
Natural settling separation is carried out in the three-phase separator, non-condensable gas (tail gas rich in hydrogen sulfide) is separated from the top, and the tail gas is subjected to two-stage alkali washing and desulfurization by adesulfurization catalyst bed layer according to a known technology, so that the content of the hydrogen sulfide in the tail gas finally discharged at high altitude is not more than 2 ppm. Repeatedly absorbing the sodium sulfide by 35-42% sodium hydroxide solution to form sodium sulfide (Na) with the concentration of 40% at the bottom of the absorption tower2S, NaHS) solution, which can be sold as a by-product.
In the middle of the three-phase separator, a small amount of sulfur-containing sewage (a small amount of water vapor injected into the reactor) is separated out, enters a closed storage tank and is periodically transported to an oil refinery for sewage treatment and unified treatment.
The semi-finished product liquid is separated from the lower part of the water dividing hopper of the three-phase separator and flows into a semi-finished product storage tank under self pressure (wherein the content of thiophene is 40-50%).
And feeding the semi-finished product liquid into an intermittent high-efficiency rectifying tower. The temperature of a tower kettle is controlled to be 80-20 ℃, the number of theoretical plates of the rectifying column is about 80, the reflux ratio of the tower top is controlled to be 3-10, and distillate before 83 ℃ is cut into an unqualified tank (accounting for about 8-15% of the feeding material of the rectifying column). Analyzing the purity of distillate thiophene by gas chromatography, and cutting the distillate thiophene into a qualified tank after the purity is more than or equal to 99.5%, wherein the temperature of the top of the tower is 83.5-84.5 ℃. When the temperature of the tower top is close to 85 ℃, the distillate components are detected in time, the unqualified tank is cut into, and the rectification operation is stopped.
Pumping the residue in the distillation tower kettle into a light tar tank through a pump, and selling the residue as a byproduct (accounting for about 40-50% of the feed of the distillation tower)
Packaging: filtering the solution in the qualified tank, and loading the solution into a galvanized iron cylinder.
Referring to material balance, taking 15kg/h thiophene as a benchmark:
feeding: 32kg/h of sulfur
27kg/h of 1, 3-butadiene
Steam 35kg/h
Totaling: 94kg/h
Discharging: thiophene 15kg/h
21kg/h of tail gas
Tar (including light tar and heavy tar) 19kg/h
4kg/h of carbon disulfide and the like
35kg/h of sulfur-containing sewage
Totaling: 94kg/h
Claims (9)
1. Thiophene synthesis process, characterized in that gas phase sulphur and 1, 3-butadiene are reacted, and thiophene is extracted from the reaction gas product.
2. The process of claim 1, wherein the sulfur is reacted with 1, 3-butadiene in the absence of a catalyst at a temperature of 250 to 550 ℃ and a gauge pressure of 0.05 to 0.25 MPa.
3. The process according to claim 2, wherein the reaction temperature of the sulfur and 1, 3-butadiene is 380 to 480 ℃.
4. The process according to claim 2, wherein the linear reaction rate is 1.5 to 3.0m/s and the reaction time is 1 to 3 seconds.
5. The process according to claim 2, wherein the weight ratio of the gas-phase sulfur to 1, 3-butadiene is 1.04 to 1.33: 1.
6. The process as claimed in claim 2, wherein the reaction temperature is controlled by adding a small amount of water vapor during the reaction.
7. The process as claimed in claim 1, wherein the temperature of the reaction gas product is reduced to 250-350 ℃, heavy oil in the reaction by-products is removed, then the reaction gas product is condensed and cooled to 40-50 ℃, tail gas, sulfur-containing sewage and semi-finished product liquid three-phase substances in the reaction product are separated, semi-finished product liquid substances are rectified, and 83.5-84.5 ℃ fractions are collected, namely thiophene.
8. The process as claimed in claim 7, wherein the semi-finished product liquid is carried out in a rectification column, and the temperature of the column bottom is controlled to be 80-120 ℃.
9. The apparatus for producing thiophene according to claim 1, comprising a tubular reactor, a reaction settling tank connected to the tubular reactor, a vertical settling tube connected to the reaction settling tank, and a vertical condensing cooler connected to the vertical settling tube, wherein an outlet of the condensing cooler is connected to a three-phase separator, a semi-finished product storage tank is connected to a lower portion of the three-phase separator, and the storage tank is connected to a batch fractionating tower.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01135132 CN1420116A (en) | 2001-11-20 | 2001-11-20 | Process and apparatus for synthesis of thiophene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01135132 CN1420116A (en) | 2001-11-20 | 2001-11-20 | Process and apparatus for synthesis of thiophene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1420116A true CN1420116A (en) | 2003-05-28 |
Family
ID=4672976
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 01135132 Pending CN1420116A (en) | 2001-11-20 | 2001-11-20 | Process and apparatus for synthesis of thiophene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1420116A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101654449A (en) * | 2009-09-11 | 2010-02-24 | 连云港宏业化工有限公司 | Method and device for producing thiophene and derivant thereof |
| CN101654450B (en) * | 2009-09-11 | 2012-11-21 | 连云港宏业化工有限公司 | Method and device for producing thiophene and derivative thereof in direct-cooled mode |
| CN106946845A (en) * | 2017-03-06 | 2017-07-14 | 山西恒强化工有限公司 | A kind of synthesizer of 2 bromothiophene |
| CN111939849A (en) * | 2020-09-08 | 2020-11-17 | 泰安科赛尔化学科技有限公司 | Thiophene production cyclic recycling system |
| CN111957260A (en) * | 2020-09-08 | 2020-11-20 | 泰安科赛尔化学科技有限公司 | Thiophene production mixer and production mixer assembly thereof |
| CN113801093A (en) * | 2021-10-08 | 2021-12-17 | 湖北特腾新材料技术有限公司 | Production method and equipment of 3-methylthiophene |
| CN114773311A (en) * | 2022-05-12 | 2022-07-22 | 山东省科学院菏泽分院 | Preparation method of thiophene |
-
2001
- 2001-11-20 CN CN 01135132 patent/CN1420116A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101654449A (en) * | 2009-09-11 | 2010-02-24 | 连云港宏业化工有限公司 | Method and device for producing thiophene and derivant thereof |
| CN101654450B (en) * | 2009-09-11 | 2012-11-21 | 连云港宏业化工有限公司 | Method and device for producing thiophene and derivative thereof in direct-cooled mode |
| CN101654449B (en) * | 2009-09-11 | 2013-03-13 | 连云港宏业化工有限公司 | Method and device for producing thiophene and derivant thereof |
| CN106946845A (en) * | 2017-03-06 | 2017-07-14 | 山西恒强化工有限公司 | A kind of synthesizer of 2 bromothiophene |
| CN111939849A (en) * | 2020-09-08 | 2020-11-17 | 泰安科赛尔化学科技有限公司 | Thiophene production cyclic recycling system |
| CN111957260A (en) * | 2020-09-08 | 2020-11-20 | 泰安科赛尔化学科技有限公司 | Thiophene production mixer and production mixer assembly thereof |
| CN113801093A (en) * | 2021-10-08 | 2021-12-17 | 湖北特腾新材料技术有限公司 | Production method and equipment of 3-methylthiophene |
| CN114773311A (en) * | 2022-05-12 | 2022-07-22 | 山东省科学院菏泽分院 | Preparation method of thiophene |
| CN114773311B (en) * | 2022-05-12 | 2022-12-23 | 山东省科学院菏泽分院 | Preparation method of thiophene |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107522602B (en) | Process and system for preparing DMM2 | |
| CN106220532B (en) | A kind of method of separation of extractive distillation acetonitrile and triethylamine | |
| AU2012268914A1 (en) | System and method for continuously producing polyoxymethylene dimethyl ethers | |
| CN106588589A (en) | Purification method for polyoxymethylene dimethyl ether(PODE) | |
| CN102417162B (en) | Recycling method of hydrochloric acid-acetic acid waste liquid | |
| CN106588590B (en) | The refining methd of polyoxymethylene dimethyl ethers | |
| CN102875468A (en) | Method for producing caprolactam through gas phase rearrangement of cyclohexanone-oxime | |
| CN101665474A (en) | Method for recovering epoxy chloropropane from wastewater containing epoxy chloropropane | |
| CN112225650A (en) | Refining method for obtaining high-purity methylal by purifying industrial-grade methylal | |
| CN109928861A (en) | A kind of method of purification recycling methylene chloride from solvent slop | |
| CN100453587C (en) | Recovery and using method of solution and unreaction monomer in process of producting polymer by solution polymerization process | |
| CN1420116A (en) | Process and apparatus for synthesis of thiophene | |
| CN105753649A (en) | Method of recycling isooctanol from waste solvent in production process of isooctyl thioglycolate | |
| CN110437044B (en) | Method and device for preparing polymethoxy dimethyl ether | |
| CN108774100A (en) | A kind of tert-butyl alcohol and methanol prepare the integrated processes of methyl tertiary butyl ether(MTBE) and isobutene | |
| CN106588597A (en) | Method for purifying polyoxyethene dimethyl ether | |
| CN205635422U (en) | Device for separating isopropanol from water-containing acetone hydrogenation product | |
| CN114751812A (en) | Method for producing diethoxymethane from paraformaldehyde | |
| CN103641797B (en) | Preparation method for N-acetyl morpholine | |
| CN103012102A (en) | Method of recovering acetic acid and water in production of aromatic carboxylic acid | |
| CN1613842A (en) | Process for synthesizing ethyl lactate by catalytic rectifying method | |
| CN101463041B (en) | Production method of high-purity triisopropyl borate ester | |
| CN220513452U (en) | Piperidine separation and purification system | |
| CN110668920A (en) | Method for preparing ethanol and co-producing cyclohexanol by using reactive distillation method | |
| CN205616821U (en) | Serialization production system of first ether of cyclopentyl group |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |