CN115108883A - Preparation method of benzyl chloride - Google Patents
Preparation method of benzyl chloride Download PDFInfo
- Publication number
- CN115108883A CN115108883A CN202110287720.0A CN202110287720A CN115108883A CN 115108883 A CN115108883 A CN 115108883A CN 202110287720 A CN202110287720 A CN 202110287720A CN 115108883 A CN115108883 A CN 115108883A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- preparation
- catalyst
- chloride
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/32—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by introduction of halogenated alkyl groups into ring compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/084—Y-type faujasite
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of coproduction benzyl chloride, which utilizes the reaction of HEDP byproduct hydrogen chloride, benzene and paraformaldehyde to generate benzyl chloride under the action of an immobilized catalyst and a filler. The benzyl chloride obtained by the method has the benzyl dichloride content of less than 5 percent, does not need to be separated, and can be directly used for producing the quaternary ammonium salt 1227; the method uses the molecular sieve supported catalyst, prolongs the service life of the catalyst, is convenient for the separation and recovery of the catalyst, greatly increases the reaction contact area under the action of the molecular sieve and the filler, quickly separates the generated water, improves the reaction rate and shortens the reaction time; the method converts low-value hydrogen chloride into high-value benzyl chloride, solves the problem of overstock retention of industrial-grade hydrochloric acid, eliminates potential environmental safety hazards, provides raw materials for the production of the water treatment agent 1227, saves the production and operation cost, and effectively improves the market competitiveness of enterprises.
Description
Technical Field
The invention relates to the technical field of fine chemicals, in particular to a preparation method of benzyl chloride.
Background
The industry is the foundation of national economy, and both heavy industry and light industry almost cover all aspects of social material demand, and the development of the industry promotes social progress and improvement of life quality of people. The industry brings convenience and causes a series of environmental pollution problems, such as generation of waste water, waste gas and waste residues. In recent years, with the enhancement of environmental awareness, the environmental protection requirements of industry in operation are upgraded year by year, and the environmental quality becomes an important industrial survival factor.
In the problem of 'three wastes', wastewater is a main problem which restricts the environmental-friendly development of industry, and in order to solve the problem, a special water treatment industry is generated. It is mainly aimed at the treatment of circulating water and comprehensive treatment of water resource. The method mainly adopts physical, chemical and biological means to treat, remove or add some substances which are not needed or needed for production, life and environment in water so that the water quality meets the requirements of specific environment and recycling. Wherein, the chemical mode of water treatment by the water treatment agent gradually occupies the mainstream water treatment market by the advantages of simpler and more efficient, low cost, easy operation and the like. The water treatment agent products are various, and the main categories of the existing polymers, organic phosphines, quaternary ammonium salts, amino acids and the like. The water treatment agent industry wants to develop continuously and better, and needs to perfect the production and operation structure of the water treatment agent industry, enlarge the market and improve the energy-saving and environment-friendly level of the water treatment agent industry while updating the product types and improving the product quality and yield.
The organic phosphine water treatment agents such as HEDP and other scale and corrosion inhibitors occupy a large share in the market, and no substitute product is developed; quaternary ammonium salts, such as dodecyl dimethyl benzyl ammonium chloride (1227) and other cationic bactericides, are widely applied to circulating cooling water systems in the industries of petroleum, chemical engineering, electric power, textile and the like due to excellent performance of the cationic bactericides. Enterprises can produce industrial-grade hydrochloric acid as a byproduct after hydrogen chloride is melted while HEDP is produced, the industrial-grade hydrochloric acid cannot be used in the fields of food, medicine and the like, the existing market tends to be saturated and is not easy to sell, the hydrochloric acid has potential safety and environmental protection problems, and the enterprises can additionally spend a large amount of capital every year in order to solve the problem of a large amount of surplus hydrochloric acid; the raw material benzyl chloride used by enterprises in the production of 1227 is directly purchased from other enterprises at present, and the cost is high.
In order to comprehensively solve the problems, optimize a product system and dominate the energy conservation and environmental protection, the invention provides a method for producing benzyl chloride by using HEDP byproduct hydrogen chloride as a raw material, which converts low-value products into high-value raw material benzyl chloride while consuming hydrochloric acid, saves cost, eliminates environmental hidden danger and effectively improves the market competitiveness of enterprises.
Disclosure of Invention
Aiming at the problems of improper treatment of HEDP byproduct-industrial grade hydrochloric acid and high market price of benzyl chloride in the prior art, the invention provides a preparation method of coproduction benzyl chloride.
A preparation method of benzyl chloride specifically comprises the following steps:
1) adding benzene, paraformaldehyde, a catalyst and a filler into a reaction kettle;
2) starting a condensation reflux and water separation device, heating the reaction kettle to a reflux state, and introducing hydrogen chloride gas to start reaction;
3) reacting for 3-5 h under a reflux state, transferring the reaction liquid into an external steaming kettle to steam out benzene, and leaving benzyl chloride;
the catalyst is loaded zinc chloride mesoporous molecular sieve and pretreated Y-type zeolite molecular sieve.
The mesoporous molecular sieve is of a spherical structure, the diameter of the mesoporous molecular sieve is 5-10 mm, the Y-type zeolite molecular sieve is of a disc net structure, the diameter of a circular surface of the Y-type zeolite molecular sieve is 5-10 cm, and the thickness of the Y-type zeolite molecular sieve is 1-2 cm.
Wherein the catalyst in the step (1) is formed by mixing a loaded zinc chloride mesoporous molecular sieve and a pretreated Y-type zeolite molecular sieve according to the mass ratio of (1-2) to 1, the dosage of the catalyst is 5-10% of the mass of paraformaldehyde,
the processing method of the zinc chloride loaded mesoporous molecular sieve comprises the steps of adding zinc chloride with equal molar weight into methanol liquid containing 10-15% of dodecyl trimethyl ammonium chloride, carrying out ultrasonic treatment for 2-4 hours at 40-60 ℃, adding a silicon-based mesoporous molecular sieve with 1-2 times of solute mass, carrying out ultrasonic treatment for 12-24 hours at 20-30 ℃, taking out the molecular sieve, carrying out leaching for 3-5 times by using methanol, and drying at 70-75 ℃.
The pretreatment method comprises the steps of adding a molecular sieve with the mass being 1-2 times that of hydrogen chloride into a dilute hydrochloric acid solution with the content being 5-10%, ultrasonically soaking for 1-3 hours, filtering, ultrasonically washing the molecular sieve with distilled water until the pH value is 5-7, drying at 80-90 ℃, slowly steaming with water vapor for 1-3 hours, drying at 90-100 ℃, and cooling to room temperature to obtain the pretreated Y-type zeolite molecular sieve.
Furthermore, the service cycle of the molecular sieve is 80-120 h, and the molecular sieve is recycled after being reprocessed by the method.
Wherein the mass ratio of the benzene to the paraformaldehyde in the step (1) is (5-10) to 1, and the polymerization degree of the paraformaldehyde is 10-50.
Further, in the step (1), the filler is a ceramic annular raschig ring, the diameter of the ring is 25-50 mm, the length of the ring is 30-50 mm, and the using amount of the ring is 10-15% of the volume of the reaction kettle.
Further, the hydrogen chloride in the step (2) is a byproduct of HEDP, and is added at a flow rate of 200-400L/min after being dried by a physical drying agent.
The invention has the beneficial effects
The invention provides a preparation method of benzyl chloride, which utilizes HEDP byproduct hydrogen chloride to react with benzene and paraformaldehyde to generate benzyl chloride under the action of an immobilized catalyst and a filler.
The benzyl chloride obtained by the method has the benzyl dichloride content of less than 5 percent, does not need to be separated, and can be directly used for the subsequent production of high-value quaternary ammonium salt 1227. Meanwhile, the problem of overstock and detention of industrial grade hydrochloric acid is solved, the potential safety hazard of the environment is eliminated, raw materials are provided for production of the water treatment agent 1227, the production and operation cost is saved, and the market competitiveness of enterprises is effectively improved.
The method uses the molecular sieve to carry the catalyst, prolongs the service life of the catalyst, is convenient for the separation and recovery of the catalyst, greatly increases the reaction contact area under the action of the molecular sieve and the filler, quickly separates the generated water, improves the reaction rate and shortens the reaction time.
The problem of overstock detention of industrial-grade hydrochloric acid is solved, the potential safety hazard of the environment is eliminated, raw materials are provided for the production of the water treatment agent 1227, the production and operation cost is saved, and the market competitiveness of enterprises is effectively improved.
Detailed Description
The present invention is described in detail below by way of examples, which are intended to be illustrative only and not to be construed as limiting the scope of the invention, and one skilled in the art will be able to make variations within the scope of the invention based on the disclosure herein, in reagents, catalysts and reaction process conditions. All equivalent changes or modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Molecular sieve and filler specifications used in the examples:
the silicon-based mesoporous molecular sieve loaded with zinc chloride is a spherical individual with the diameter of about 3 cm; the used Y-type zeolite molecular sieve has a silicon-aluminum ratio of 10:1, the diameter of the disc is 5cm, and the thickness of the disc is 1 cm; the used filler is an annular ceramic Raschig ring with the diameter of 3cm and the length of 5 cm.
Pretreatment of the molecular sieve:
treating a zinc chloride-loaded molecular sieve: adding 13.6kg of zinc chloride into 265kg of methanol solution containing 10% of dodecyl trimethyl ammonium chloride, performing ultrasonic treatment at 55 +/-5 ℃ for 3h, adding 50kg of silicon-based mesoporous molecular sieve, performing ultrasonic treatment at 25 +/-2 ℃ for 24h, filtering, leaching the molecular sieve with 20L of methanol, leaching for 3 times, and drying the molecular sieve in an oven at 70-75 ℃ to obtain 74.3kg of loaded zinc chloride molecular sieve.
Treating the Y-type zeolite molecular sieve: putting a 40kgY type zeolite molecular sieve into 250kg of hydrochloric acid with the content of 8%, ultrasonically soaking for 1h, filtering, ultrasonically washing the molecular sieve by using distilled water until the pH value is 6.0, drying at the temperature of 85 +/-5 ℃, continuously slowly steaming for 3h by using water vapor, drying at the temperature of 85 +/-5 ℃, and cooling to room temperature to obtain the 50.2kgY type zeolite molecular sieve.
And mixing the treated loaded zinc chloride molecular sieve and the Y-type zeolite molecular sieve to obtain 124.5kg of the immobilized catalyst.
Example 1
(1) Adding 2500kg of benzene and 500kg of paraformaldehyde into a 5-cubic reaction kettle, and then adding 124.5kg of supported catalyst and 500kg of annular ceramic Raschig ring into the reaction kettle;
(2) starting a condensation reflux and water diversion device at the top of the reaction kettle, heating the reaction kettle to about 80 ℃, keeping benzene in a reflux state, adding dry hydrogen chloride gas from the kettle bottom at the speed of 200L/min for reaction, collecting the generated formaldehyde aqueous solution through the water diversion device, using the formaldehyde aqueous solution for the synthesis of a water treatment agent ATMP, and circularly participating in the reaction after drying the unreacted hydrogen chloride gas again;
(3) after the reaction is carried out for 5 hours under the reflux state, transferring the reaction liquid into an external steaming kettle, steaming out 1249kg of benzene under the pressure of-0.07 MPa, transferring the residual 2062kg of benzyl chloride into a benzyl chloride raw material storage tank for later use, and transferring the benzene steamed out from the external into a transfer tank for continuous use.
The purity of benzyl chloride is 95.01%, the content of benzyl dichloride is 4.73%, and the conversion rate is 93.02% through detection and analysis.
Example 2
(1) Adding 3000kg of benzene and 300kg of paraformaldehyde into a 5-cubic reaction kettle, and then adding 124.5kg of supported catalyst and 750kg of annular ceramic Raschig ring into the reaction kettle;
(2) starting a condensation reflux and water diversion device at the top of the reaction kettle, heating the reaction kettle to about 80 ℃, keeping benzene in a reflux state, adding dry hydrogen chloride gas from the bottom of the reaction kettle at a speed of 400L/min for reaction, collecting the generated formaldehyde water solution through the water diversion device, using the formaldehyde water solution for synthesis of a water treatment agent ATMP, and circularly participating in the reaction after drying the unreacted hydrogen chloride gas again;
(3) after reacting for 3 hours under the reflux state, transferring the reaction liquid into an external steaming kettle, steaming 2238kg of benzene under the pressure of-0.07 MPa, transferring the residual 1255kg of benzyl chloride into a benzyl chloride raw material storage tank for later use, and transferring the benzene steamed out from the external into a transfer tank for continuous use.
The purity of benzyl chloride is 95.56%, the content of benzyl dichloride is 4.28%, and the conversion rate is 94.43% through detection and analysis.
Comparative example 1
Solid particulate anhydrous zinc chloride using conventional technology was used in an amount of 13.6 kg. The other steps and the amounts of the raw materials were the same as in example 2.
After the reaction is carried out for 10 hours under the reflux state, transferring the reaction liquid into an external steaming kettle, steaming out 2265kg of benzene under the pressure of-0.07 MPa, transferring the residual 1193kg of benzyl chloride into a benzyl chloride raw material storage tank for later use, and transferring the benzene steamed out externally into a transfer tank for continuous use.
The purity of benzyl chloride is 94.37%, the content of benzyl dichloride is 4.01%, and the conversion rate is 88.97% by detection and analysis.
Comparative example 2
Only the zinc chloride-loaded molecular sieve was used in an amount of 74.3kg, and the other steps and the raw materials were the same as in example 2.
After reacting for 6 hours under the reflux state, transferring the reaction solution into an external distillation kettle, distilling 2229kg of benzene under the pressure of-0.07 MPa, transferring the residual 1308kg of benzyl chloride into a benzyl chloride raw material storage tank for later use, and transferring the benzene distilled out into a transfer tank for continuous use.
The purity of benzyl chloride is 90.07%, the content of benzyl dichloride is 9.72%, and the conversion rate is 93.07% through detection and analysis.
The benzyl dichloride impurity is too high to be directly used as the raw material of 1277 and needs to be further purified.
Application example (use of benzyl chloride from example 1 to produce 1227 with 80% Activity)
(1) Adding 1320kg of dodecyl dimethyl tertiary amine and 250kg of methanol into a reaction kettle, heating the reaction kettle to about 55 ℃, dropwise adding 750kg of benzyl chloride at the speed of 60kg/min, and controlling the temperature of the reaction kettle to be 55-60 ℃ in the dropwise adding process;
(2) after the dropwise addition, the temperature is kept at 60 +/-1 ℃ for 2 hours, and after the reaction is finished, 200kg of pure water is added for dilution to obtain 2548.6kg of dodecyl dimethyl benzyl ammonium chloride (1227) which is a yellowish transparent liquid product.
The detection shows that the obtained 1227 has the activity of 80.97%, the ammonium salt content of 0.33%, the chroma (hazen) of 45.6 and the pH value (1% aqueous solution) of 7.34, and is a qualified product.
Claims (7)
1. The preparation method of benzyl chloride is characterized by comprising the following steps:
1) adding benzene, paraformaldehyde, a catalyst and a filler into a reaction kettle;
2) starting a condensation reflux and water separation device, heating the reaction kettle to a reflux state, and introducing hydrogen chloride gas to start reaction;
3) reacting for 3-5 h under a reflux state, transferring the reaction liquid into an external steaming kettle to steam out benzene, and leaving benzyl chloride;
the catalyst is loaded zinc chloride mesoporous molecular sieve and pretreated Y-type zeolite molecular sieve.
2. The preparation method according to claim 1, wherein the preparation method of the zinc chloride loaded mesoporous molecular sieve comprises the following steps: adding zinc chloride with equal molar weight into 10-15 wt% of dodecyl trimethyl ammonium chloride methanol solution, performing ultrasonic treatment at 40-60 ℃ for 2-4 hours, adding a silicon-based mesoporous molecular sieve with 1-2 times of solute mass, performing ultrasonic treatment at 20-30 ℃ for 12-24 hours, taking out the molecular sieve, leaching with methanol for 3-5 times, and drying at 70-75 ℃.
3. The preparation method of claim 1, wherein the pretreated Y-type zeolite molecular sieve has a silica-alumina molar ratio of 10-20: 1, and the preparation method comprises the following steps: adding a molecular sieve with the mass being 1-2 times that of hydrogen chloride into a dilute hydrochloric acid solution with the content being 5-10 wt%, ultrasonically soaking for 1-3 hours, filtering, ultrasonically washing the molecular sieve with distilled water until the pH value reaches 5-7, drying at 80-90 ℃, slowly steaming for 1-3 hours with water vapor, drying at 90-100 ℃, and cooling to room temperature to obtain the hydrogen chloride-based catalyst.
4. The preparation method of claim 1, wherein the catalyst is prepared by mixing a loaded zinc chloride mesoporous molecular sieve and a pretreated Y-type zeolite molecular sieve in a mass ratio of 1-2: 1; the dosage of the catalyst is 5-10% of the mass of the paraformaldehyde.
5. The preparation method according to claim 1, wherein the mass ratio of benzene to paraformaldehyde is 5-10: 1, and the polymerization degree of paraformaldehyde is 10-50.
6. The preparation method according to claim 1, wherein the filler is a ceramic annular Raschig ring with a diameter of 25-50 mm and a length of 30-50 mm, and the dosage of the filler is 10-15% of the volume of the reaction kettle.
7. The preparation method according to claim 1, wherein the hydrogen chloride in step (2) is a byproduct of HEDP, and is added at a flow rate of 200-400L/min after being dried by a physical desiccant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110287720.0A CN115108883A (en) | 2021-03-17 | 2021-03-17 | Preparation method of benzyl chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110287720.0A CN115108883A (en) | 2021-03-17 | 2021-03-17 | Preparation method of benzyl chloride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115108883A true CN115108883A (en) | 2022-09-27 |
Family
ID=83323649
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110287720.0A Pending CN115108883A (en) | 2021-03-17 | 2021-03-17 | Preparation method of benzyl chloride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115108883A (en) |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1370767A (en) * | 2001-02-27 | 2002-09-25 | 中国科学院成都有机化学研究所 | Synthesis of optically pure R-and S-2-hydroxyl-4-aryl butyric acid |
| CN1814578A (en) * | 2006-03-02 | 2006-08-09 | 浙江大学 | Method for preparing chloromethyl substituted arene |
| CN101406844A (en) * | 2008-11-20 | 2009-04-15 | 中山大学 | Method for preparing molecular sieve supported nano zinc sulphide |
| CN101830853A (en) * | 2010-04-23 | 2010-09-15 | 武汉工程大学 | Nitroimidazoline derivatives and preparation method thereof and application thereof |
| CN102452893A (en) * | 2010-10-29 | 2012-05-16 | 中国石油化工股份有限公司 | Method for oxidizing cyclic ketone by utilizing zinc-supported Beta molecular sieve |
| CN103342688A (en) * | 2013-07-10 | 2013-10-09 | 浙江工业大学 | Method for preparing furfural by one-step selective catalytic cracking |
| CN103965031A (en) * | 2014-05-13 | 2014-08-06 | 宿迁科思化学有限公司 | Preparation method of floralozone |
| CN103980088A (en) * | 2014-05-13 | 2014-08-13 | 宿迁科思化学有限公司 | Method of preparing floralozone intermediate |
| CN105399600A (en) * | 2015-12-01 | 2016-03-16 | 南京钟腾化工有限公司 | Method for preparing parachlorotoluene |
| CN105418482A (en) * | 2015-11-23 | 2016-03-23 | 东南大学 | Improved preparation method for ropinirole hydrochloride |
| CN106966854A (en) * | 2017-05-05 | 2017-07-21 | 王显权 | A kind of method for preparing benzyl chloride |
| CN110981908A (en) * | 2019-11-08 | 2020-04-10 | 山东泰和水处理科技股份有限公司 | Production method of water treatment agent amino trimethylene phosphonic acid |
| WO2020250018A1 (en) * | 2019-06-14 | 2020-12-17 | Anthea Aromatics Private Limited | An efficient and environment friendly process for chloromethylation of substituted benzenes |
| CN112209806A (en) * | 2020-08-28 | 2021-01-12 | 江苏康爱特环境工程集团有限公司 | Preparation method of ethyl benzyl chloride |
-
2021
- 2021-03-17 CN CN202110287720.0A patent/CN115108883A/en active Pending
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1370767A (en) * | 2001-02-27 | 2002-09-25 | 中国科学院成都有机化学研究所 | Synthesis of optically pure R-and S-2-hydroxyl-4-aryl butyric acid |
| CN1814578A (en) * | 2006-03-02 | 2006-08-09 | 浙江大学 | Method for preparing chloromethyl substituted arene |
| CN101406844A (en) * | 2008-11-20 | 2009-04-15 | 中山大学 | Method for preparing molecular sieve supported nano zinc sulphide |
| CN101830853A (en) * | 2010-04-23 | 2010-09-15 | 武汉工程大学 | Nitroimidazoline derivatives and preparation method thereof and application thereof |
| CN102452893A (en) * | 2010-10-29 | 2012-05-16 | 中国石油化工股份有限公司 | Method for oxidizing cyclic ketone by utilizing zinc-supported Beta molecular sieve |
| CN103342688A (en) * | 2013-07-10 | 2013-10-09 | 浙江工业大学 | Method for preparing furfural by one-step selective catalytic cracking |
| CN103965031A (en) * | 2014-05-13 | 2014-08-06 | 宿迁科思化学有限公司 | Preparation method of floralozone |
| CN103980088A (en) * | 2014-05-13 | 2014-08-13 | 宿迁科思化学有限公司 | Method of preparing floralozone intermediate |
| CN105418482A (en) * | 2015-11-23 | 2016-03-23 | 东南大学 | Improved preparation method for ropinirole hydrochloride |
| CN105399600A (en) * | 2015-12-01 | 2016-03-16 | 南京钟腾化工有限公司 | Method for preparing parachlorotoluene |
| CN106966854A (en) * | 2017-05-05 | 2017-07-21 | 王显权 | A kind of method for preparing benzyl chloride |
| WO2020250018A1 (en) * | 2019-06-14 | 2020-12-17 | Anthea Aromatics Private Limited | An efficient and environment friendly process for chloromethylation of substituted benzenes |
| CN110981908A (en) * | 2019-11-08 | 2020-04-10 | 山东泰和水处理科技股份有限公司 | Production method of water treatment agent amino trimethylene phosphonic acid |
| CN112209806A (en) * | 2020-08-28 | 2021-01-12 | 江苏康爱特环境工程集团有限公司 | Preparation method of ethyl benzyl chloride |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20150087866A1 (en) | Process for the production of olefins and use thereof | |
| CN106631684B (en) | A method of sec-butyl alcohol is prepared with sec-butyl acetate hydrolysis | |
| CN106631699B (en) | A method of preparing sec-butyl alcohol | |
| CN106831315B (en) | Continuous production method of chloroethane | |
| CN112973701A (en) | Iron-sodium carbon material catalyst and preparation method and application thereof | |
| CN108126748B (en) | Alkaline monolithic catalyst with regular pore channels and preparation method and application thereof | |
| CN101914021B (en) | Method for producing high-content and high-optical purity butyl lactate with two-step method | |
| CN111072602A (en) | Preparation of 3-acetamido-5-acetylfuran from chitin monomer N-acetylglucosamine catalyzed by amino acid ionic liquid | |
| CN101724174A (en) | Method for preparing anti-aging agent RD | |
| CN202246142U (en) | Steam stripping system for recycled water containing epoxy chloropropane (ECH) | |
| CN102304055B (en) | Method for preparing ethanolamine hydrochlorides and coproduct ethanolamine | |
| CN115108883A (en) | Preparation method of benzyl chloride | |
| CN108276293A (en) | A kind of separation method of 1,5- pentanediamines | |
| CN103435484A (en) | Preparation technology of high-purity hydroxyalkyl methacrylate | |
| CN110818573B (en) | Preparation method of 3,3 '-dichloro-4, 4' -diaminodiphenylmethane | |
| CN104030925A (en) | Method for catalytically synthesizing mononitrochlorobenzene | |
| CN104045550B (en) | A kind of fumaric acid production technique | |
| CN107235940B (en) | Method for producing furfural by gas-phase acid catalysis in cooperation with ethyl acetate extraction | |
| CN107673970A (en) | A kind of preparation method of tributyrin | |
| CN106146304A (en) | The method producing Ethyl formate | |
| CN101747177A (en) | Device and method for preparing butane diacid by continuously hydrolyzing dialkyl succinate ester | |
| CN1333204A (en) | Method and device for hydrolyzing methyl acetate | |
| CN214693947U (en) | Preparation facilities of coproduction benzyl chlorine | |
| CN111153794A (en) | Method for synthesizing ethyl palmitate by using dodecyl trimethyl ammonium chloride-based eutectic solvent catalyst | |
| CN114835559B (en) | Catalytic method for synthesizing bisphenol F |
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 |