CN1986053A - Liquid phase reaction process of methyl acetate and CO to produce acetic anhydride and its catalyst preparing process - Google Patents

Liquid phase reaction process of methyl acetate and CO to produce acetic anhydride and its catalyst preparing process Download PDF

Info

Publication number
CN1986053A
CN1986053A CN 200610130648 CN200610130648A CN1986053A CN 1986053 A CN1986053 A CN 1986053A CN 200610130648 CN200610130648 CN 200610130648 CN 200610130648 A CN200610130648 A CN 200610130648A CN 1986053 A CN1986053 A CN 1986053A
Authority
CN
China
Prior art keywords
catalyst
methyl acetate
liquid phase
carbon monoxide
aceticanhydride
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.)
Granted
Application number
CN 200610130648
Other languages
Chinese (zh)
Other versions
CN100486701C (en
Inventor
杨世东
张力明
陈庆忠
华超
贾飞
刘素英
高岚
张帆
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
TIANJIN MEIKETAI CHEMICAL INDUSTRY SCIENCE AND TECHNOLOGY Co Ltd
Dehua Design & Research Co Ltd Shandong Hualu Hengsheng Group
Original Assignee
TIANJIN MEIKETAI CHEMICAL INDUSTRY SCIENCE AND TECHNOLOGY Co Ltd
Dehua Design & Research Co Ltd Shandong Hualu Hengsheng Group
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by TIANJIN MEIKETAI CHEMICAL INDUSTRY SCIENCE AND TECHNOLOGY Co Ltd, Dehua Design & Research Co Ltd Shandong Hualu Hengsheng Group filed Critical TIANJIN MEIKETAI CHEMICAL INDUSTRY SCIENCE AND TECHNOLOGY Co Ltd
Priority to CNB2006101306486A priority Critical patent/CN100486701C/en
Publication of CN1986053A publication Critical patent/CN1986053A/en
Application granted granted Critical
Publication of CN100486701C publication Critical patent/CN100486701C/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Landscapes

  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention is the preparation process of acetic anhydride through liquid phase reaction of methyl acetate and CO and the preparation process of its catalyst. The catalyst has Rh-Pd complex with Rh/Pd weight ratio of 4-5 as the active component in 2.0-5.0 wt%, ethyl iodide or methyl bromide as co-catalyst in 0.5-9.5 wt%, and carrier of ZSM or MCM molecular sieve in 30.0-40.0 wt%. The catalyst is prepared through dissolving soluble compound of the catalyst and co-catalyst to obtain solution, soaking the carrier inside the solution, high temperature roasting at 500.0-600.0 deg.c for 1.0-1.5. The catalyst is used in preparing acetic anhydride through liquid phase reaction of methyl acetate and CO and can result in high methyl acetate converting rate and acetic anhydride yield. The present invention provides one new industrial production way.

Description

Methyl acetate and carbon monoxide liquid phase carbonyl generate the preparation method and the Preparation of catalysts method thereof of aceticanhydride
Technical field
The invention belongs to the method for chemical reaction.Relate to preparation technology and method for preparing catalyst thereof that a kind of methyl acetate and carbon monoxide liquid phase carbonyl generate aceticanhydride (acetic anhydride).
Background technology
Aceticanhydride is the abbreviation of acetic anhydride, the formal name used at school acetic anhydride.It is a kind of water white liquid, has penetrating odor, strong tearing property is arranged; it is a kind of important Organic Chemicals; chemical property is very active, is widely used in producing the production of cellulose acetate and as the acetylizing agent in medicine, dyestuff, spices and the organic synthesis.The production of aceticanhydride is the ketene process based on acetic acid and acetone at first, is the oxidation of acetaldehyde co-production method then.Though the ketene process technology maturation, its flow process complexity and side reaction are more, and process energy consumption and equipment investment are all bigger; The oxidation of acetaldehyde co-production method has that flow process is simple, technical maturity but its corrosion of equipment is serious, energy consumption is bigger.Method synthetic with the gas phase carbonyl at present and the synthetic production of liquid phase carbonyl aceticanhydride has the advantages that flow process is simple, the process energy consumption is lower and side reaction is less, and by the calculation of thermodynamics feasibility of course of reaction as can be known, obviously this is a technical process with practicality and novelty, has better industrial application prospect.Following data provides the background information of relevant aceticanhydride synthesis technique.
Chinese patent CN1778468A discloses the catalyst system and the application of catalytic methylester acetate or the synthetic aceticanhydride of dimethyl ether, its active component is a rhodium complex, co-catalyst is alkyl iodide, phosphate and alkali metal salt compounded of iodine, the conversion ratio of methyl acetate is 49.8~51.2%, and the aceticanhydride space-time yield is 12.1~15.5mol/ (L.h).
Chinese patent CN1612850A discloses the integral method that is generated carbonylation acetate, acetic anhydride or coproduction of each by the ethyl acetate accessory substance, be to utilize by-product methyl acetate in the polyvinyl alcohol production process to generate the method for acetate and acetic anhydride, the conversion ratio of methyl acetate is 39.0~43.0%, and the aceticanhydride space-time yield is 13.1~16.5mol/ (L.h).
Chinese patent CN1039410A discloses the synthetic method of acetate and acetic anhydride, generate acetate and acetic anhydride under the catalyst condition that adopts VIII family carbonyls, methyl iodide and alkali metal acetate to form, the conversion ratio of methyl acetate is 38.0~42.0%, and the aceticanhydride space-time yield is 12.1~15.5mol/ (L.h).
Chinese patent CN1039410A discloses under rhodium catalyst and co-catalyst the synthetic method for preparing acetic anhydride or acetic anhydride and acetate mixture of methyl acetate gas phase carbonyl, the conversion ratio of methyl acetate is 34.0~39.0%, and the aceticanhydride space-time yield is 8.1~11.5mol/ (L.h).
Document (the research that the aceticanhydride carbonyl is synthetic, Coal Chemical Industry, 2001,95 (2): 21-25) disclose a kind of novel multidentate quaternary salt and heterodesmic mould assembly rhodium complex catalyst of utilizing and made methyl acetate carry out the technology of the acetic acid synthesized and acetic anhydride of liquid phase carbonyl, its catalytic rate and space-time yield are all greater than external existing industrial level.
United States Patent (USP) UP4618460 discloses a kind of methyl acetate and carbon monoxide of utilizing under the carboxylic acid condition, the process of the composite catalyst synthesis of acetic acid acid anhydride of forming with nickel, methyl iodide and sodium iodide, methyl acetate process conversion ratio can reach 50.0~60.0%, and the aceticanhydride space-time yield is 24.1~37.5mol/ (L.h).
United States Patent (USP) UP4374070 discloses the process of composite catalyst oxo-acetic anhydride under HTHP of forming with rhodium, iodide and lithiumation thing under a kind of hydrogen condition that adds the 2-7% percent by volume in the carbonyl reaction device, the conversion ratio of methyl acetate is 42.0~62.0%, and the aceticanhydride space-time yield is 30.1~45.5mol/ (L.h).
European patent EP 0350635 disclose a kind of methyl acetate in adding the hydrogen of 5% percent by volume under the composite catalyst of rhodium and nickel, alkyl iodide and phosphate composition the process of gas phase carbonyl synthesis acetic acid and aceticanhydride, the conversion ratio of methyl acetate is 44.0~49.2%, and the aceticanhydride space-time yield is 25.1~29.5mol/ (L.h).
Japan Patent JP8-20555 has introduced technology and the catalyst thereof that utilizes methyl acetate and carbon monoxide to generate aceticanhydride under a kind of high pressure under rhodium plutonium catalyst, the conversion ratio of its process methyl acetate is 43.0~56.0%, and the aceticanhydride space-time yield is 31.1~38.5mol/ (L.h).
In the method for the synthetic aceticanhydride of above various liquid phase carbonyls, though some technology is very ripe and industrialization, generally all has following shortcoming: the selection of catalysts of the complicated and preparation of catalyst preparation process and activity is relatively poor and catalyst life is shorter; The methyl acetate conversion ratio is low, side reaction product is more, the methyl acetate space-time yield is lower so that bring difficulty for the subsequent separation process of product, and the process production cost is higher.
Summary of the invention
The object of the present invention is to provide methyl acetate and carbon monoxide liquid phase carbonyl to generate the preparation method and the method for preparing catalyst thereof of aceticanhydride (acetic anhydride), use catalyst provided by the invention can high conversion, high selectivity and high stability ground produces aceticanhydride.
The invention provides the technology and the process thereof of the synthetic aceticanhydride of a kind of methyl acetate and carbon monoxide liquid phase carbonyl, it is characterized in that reaction equation is:
CH 3COOCH 3+CO→(CH 3CO) 2O
The average conversion of this course of reaction methyl acetate is 58.0~78.0%, and aceticanhydride space-time average yield is 45.0~65.0mol/ (L.h).
Methyl acetate provided by the invention and carbon monoxide liquid phase carbonyl generate the method for preparing catalyst of aceticanhydride, comprise active component rhodium palladium complex A, cocatalyst component ethyl group iodine or methyl bromide B and carrier D, wherein the content of active component rhodium palladium complex A is 2.0~5.0% of catalyst weight, and the quality proportioning of rhodium and palladium is 4: 1~5: 1; The content of cocatalyst component ethyl group iodine or methyl bromide B is 0.5~9.5% of catalyst weight; Molecular sieve is ZSM series or MCM series among the carrier D, and its content is 30.0~40.0% of catalyst weight, and all the other components are one or more in kaolin and the silica.
Utilize infusion process that active component A and cocatalyst component B are supported in the solution of soluble metal element on the carrier D, accompany to burn at 500.0~600.0 ℃ of following high temperature to obtain catalyst in 1.0~1.5 hours.
The solution of described soluble metal element is the phosphate of acetate or acetum or containing metal potassium; Liquid phase solvent content is 70.0~80.0% of reaction system gross weight in the reaction system.
Utilize Preparation of Catalyst methyl acetate and carbon monoxide liquid phase carbonyl to generate the method for aceticanhydride, it is characterized in that: reaction temperature is 180.0~220.0 ℃, reaction pressure is 0.2~0.5MPa, and air speed is 2.5~4.8ml/g.h, and the carbon monoxide flow velocity is 800.0~1400.0ml/hr.
Co-catalyst ethyl group iodine that to use an advantage of the present invention be exactly this catalyst system or methyl bromide play good effect to the activity and the stability of catalyst activity component rhodium palladium complex, are convenient in the actual production process process operation parameter be adjusted and optimized.
Advantage of the present invention is exactly that methyl acetate and the carbon monoxide process of carrying out the synthetic aceticanhydride of liquid phase carbonyl has solved the oxidation of acetaldehyde co-production method and the ketene process flow process is complicated and the bigger problem of energy consumption, methyl acetate conversion ratio and aceticanhydride yield are higher in the course of reaction, and simple, the catalyst life of catalyst process of preparation is long, conversion ratio and selectivity height, for its industrial applications provides new approach.
Description of drawings
Fig. 1 is the change curve of methyl acetate conversion ratio and aceticanhydride space-time yield under the different catalysts reaction condition.
The specific embodiment
Below in conjunction with embodiment the present invention is further elaborated, but the present invention is not produced any restriction.
Example 1:
Adopt 500ml titanium pressing pressure reactor to carry out above working of an invention in the laboratory, the logistics composition and the operating parameter that add reactor are:
Methyl acetate addition: 1.20mol; The content of active component rhodium palladium complex A is 2.1%, and its proportioning is 4: 1; Co-catalyst: ethyl group iodine or methyl bromide load on the ZSM-5 molecular sieve, and its percentage by weight is 2.5%; Carrier is the ZSM-5 molecular sieve, and its percentage by weight is 30.0%, and all the other components are 1: 1 kaolin and aktivton for the quality proportioning; The weight ratio of catalyst and methyl acetate, carbon monoxide is 1: 0.65: 0.45; Acetic acid consumption: 0.22L; Carrier impregnation with accompany burning time: 65.0min, accompany that to burn temperature be 550.0 ℃; Reaction system is a liquor kalii acetici, and liquid phase solvent content is 70.0% of reaction system gross weight; Reaction time: 18.0min; Reaction temperature: 195.0 ± 1 ℃; Carbon monoxide pressure of tension: 0.39Ma; The carbon monoxide flow velocity is 1000.0ml/h; Hydrogen partial pressure: 0.3MPa; Methyl acetate conversion ratio: 62.0%; The aceticanhydride space-time yield is: 49.5mol/ (L.h).
Example 2:
Adopt 500ml titanium pressing pressure reactor to carry out above working of an invention in the laboratory, the logistics composition and the operating parameter that add reactor are:
Methyl acetate addition: 1.21mol; The content of active component rhodium palladium complex A is 2.1%, and its proportioning is 4.5: 1; Cocatalyst B ethyl group iodine or methyl bromide load on the ZSM-5 molecular sieve, and its percentage by weight is 2.6%; Carrier is the ZSM-5 molecular sieve, and its percentage by weight is 35.0%, and all the other components are 1: 1.2 kaolin and aktivton for the quality proportioning; The weight ratio of catalyst and methyl acetate, carbon monoxide is 1: 0.68: 0.45; Acetic acid consumption: 0.21L; Carrier impregnation with accompany burning time: 60.0min, accompany that to burn temperature be 560.0 ℃; Reaction system is a liquor kalii acetici, and liquid phase solvent content is 75.0% of reaction system gross weight; Reaction time: 20.0min; Reaction temperature: 198.0 ± 1 ℃; Carbon monoxide pressure of tension: 0.40Ma; The carbon monoxide flow velocity is 900.0ml/h; Hydrogen partial pressure: 0.3MPa; Methyl acetate conversion ratio: 59.2%; The aceticanhydride space-time yield is: 47.1mol/ (L.h).
Example 3:
Adopt 500ml titanium pressing pressure reactor to carry out above working of an invention in the laboratory, the logistics composition and the operating parameter that add reactor are:
Methyl acetate addition: 1.22mol; The content of active component rhodium palladium complex A is 2.1%, and its proportioning is 4.4: 1; Cocatalyst B ethyl group iodine or methyl bromide load on the ZSM-5 molecular sieve, and its percentage by weight is 2.6%; Carrier is the ZSM-5 molecular sieve, and its percentage by weight is 34.9%, and all the other components are 1: 1.2 kaolin and aktivton for the quality proportioning; The weight ratio of catalyst and methyl acetate, carbon monoxide is 1: 0.68: 0.45; Acetic acid consumption: 0.21L; Carrier impregnation with accompany burning time: 58.0min, accompany that to burn temperature be 550.0 ℃; Reaction system is a liquor kalii acetici, and liquid phase solvent content is 75.0% of reaction system gross weight; Reaction time: 20.0min; Reaction temperature: 200.0 ± 1 ℃; Carbon monoxide pressure of tension: 0.41Ma; The carbon monoxide flow velocity is 1200.0ml/h; Hydrogen partial pressure: 0.3MPa; Methyl acetate conversion ratio: 48.5%; The aceticanhydride space-time yield is: 42.3mol/ (L.h).
Example 4:
Adopt 500ml titanium pressing pressure reactor to carry out above working of an invention in the laboratory, the logistics composition and the operating parameter that add reactor are:
Methyl acetate addition: 1.20mol; The content of active component rhodium palladium complex A is 2.2%, and its proportioning is 4: 1; Cocatalyst B ethyl group iodine or methyl bromide load on the MCM-41 molecular sieve, and its percentage by weight is 4.5%; Carrier is the MCM-41 molecular sieve, and its percentage by weight is 35.0%, and all the other components are 1: 3 kaolin and aktivton for the quality proportioning; The weight ratio of catalyst and methyl acetate, carbon monoxide is 1: 0.66: 0.48; Acetic acid consumption: 0.20L; Carrier impregnation with accompany burning time: 60.0min, accompany that to burn temperature be 600.0 ℃; Reaction system is a liquor kalii acetici, and liquid phase solvent content is 80.0% of reaction system gross weight; Reaction time: 22.0min; Reaction temperature: 202.0 ± 1 ℃; Carbon monoxide pressure of tension: 0.41Ma; The carbon monoxide flow velocity is 1100.0ml/h; Hydrogen partial pressure: 0.3MPa; Methyl acetate conversion ratio: 67.1%: the aceticanhydride space-time yield is: 62.4mol/ (L.h).
Example 5:
Adopt 1000ml titanium pressing pressure reactor to carry out above working of an invention in the laboratory, the logistics composition and the operating parameter that add reactor are:
Methyl acetate addition: 2.4mol; The content of active component rhodium palladium complex A is 2.4%, and its proportioning is 4.5: 1; Cocatalyst B ethyl group iodine or methyl bromide load on the MCM-41 molecular sieve, and its percentage by weight is 3.5%; Carrier is the MCM-41 molecular sieve, and its percentage by weight is 36.0%, and all the other components are kaolin; The weight ratio of catalyst and methyl acetate, carbon monoxide is 1: 0.66: 0.48; Acetic acid consumption: 0.42L; Carrier impregnation with accompany burning time: 75.0min, accompany that to burn temperature be 600.0 ℃; Reaction system is a liquor kalii acetici, and liquid phase solvent content is 75.0% of reaction system gross weight; Reaction time: 30.0min reaction temperature: 210.0 ± 1 ℃; Carbon monoxide pressure of tension: 0.40Ma; The carbon monoxide flow velocity is 1000.0ml/h; Hydrogen partial pressure: 0.3MPa; Methyl acetate conversion ratio: 59.8%; The aceticanhydride space-time yield is: 53.2mol/ (L.h).
Example 6:
Adopt 1000ml titanium pressing pressure reactor to carry out above working of an invention in the laboratory, the logistics composition and the operating parameter that add reactor are:
Methyl acetate addition: 2.44mol; The content of active component rhodium palladium complex A is 2.2%, and its proportioning is 4.8: 1; Cocatalyst B ethyl group iodine or methyl bromide load on the ZSM-5 molecular sieve, and its percentage by weight is 2.5%; Carrier is the ZSM-5 molecular sieve, and its percentage by weight is 35.0%, and all the other components are silica; The weight ratio of catalyst and methyl acetate, carbon monoxide is 1: 0.64: 0.48; Acetic acid consumption: 0.47L; Carrier impregnation with accompany burning time: 70.0min, accompany that to burn temperature be 600.0 ℃; Reaction system is a liquor kalii acetici, and liquid phase solvent content is 80.0% of reaction system gross weight; Reaction time: 32.0min; Reaction temperature: 204.0 ± 1 ℃; Carbon monoxide pressure of tension: 0.40Ma; The carbon monoxide flow velocity is 1150.0ml/h; Hydrogen partial pressure: 0.3MPa; Methyl acetate conversion ratio: 65.2%; The aceticanhydride space-time yield is: 57.2mol/ (L.h).
The content of the foregoing description is represented as can be known by Fig. 1, the methyl acetate conversion ratio under different condition and the change curve of aceticanhydride space-time yield, utilize methyl acetate of the present invention and carbon monoxide liquid phase carbonyl to generate the process of aceticanhydride (acetic anhydride) and the catalyst of employing preparation thereof, in the laboratory operating parameter under the different condition is experimentized as can be known, it is average 60.3% that the methyl acetate yield changes, aceticanhydride space-time yield average out to 51.95%.
Methyl acetate that the present invention proposes and carbon monoxide liquid phase carbonyl generate the preparation method and the method for preparing catalyst thereof of aceticanhydride.Be described by preferred embodiment, person skilled obviously can be in not breaking away from content of the present invention, spirit and scope to equipment as herein described and the preparation method changes or suitably change realize the technology of the present invention with combination.Special needs to be pointed out is, the replacement that all are similar and change apparent to those skilled in the artly, they are regarded as being included in spirit of the present invention, scope and the content.

Claims (5)

1. methyl acetate and carbon monoxide liquid phase carbonyl generate the method for preparing catalyst of aceticanhydride, comprise active component rhodium palladium complex A, cocatalyst component ethyl group iodine or methyl bromide B and carrier D, the content that it is characterized in that active component rhodium palladium complex A is 2.0~5.0% of catalyst weight, and the quality proportioning of rhodium and palladium is 4: 1~5: 1; The content of cocatalyst component ethyl group iodine or methyl bromide B is 0.5~9.5% of catalyst weight; Molecular sieve is ZSM series or MCM series among the carrier D, and its content is 30.0~40.0% of catalyst weight, and all the other components are one or more in kaolin and the silica.
2. methyl acetate as claimed in claim 1 and carbon monoxide liquid phase carbonyl generate the method for preparing catalyst of aceticanhydride, it is characterized in that: utilize infusion process that active component A and cocatalyst component B are supported in the solution of soluble metal element on the carrier D, accompany to burn at 500.0~600.0 ℃ of following high temperature to obtain catalyst in 1.0~1.5 hours.
3. methyl acetate as claimed in claim 2 and carbon monoxide liquid phase carbonyl generate the method for preparing catalyst of aceticanhydride, and the solution that it is characterized in that described soluble metal element is the phosphate of acetate or acetum or containing metal potassium; Liquid phase solvent content is 70.0~80.0% of reaction system gross weight in the reaction system.
4. generate the method for aceticanhydride as claim 1,2 or 3 described Preparation of Catalyst methyl acetates and carbon monoxide liquid phase carbonyl, it is characterized in that: the reaction time is 20.0min~30.0min, reaction temperature is 180.0~220.0 ℃, reaction pressure is 0.2~0.5MPa, air speed is 2.5~4.8ml/g.h, and the carbon monoxide flow velocity is 800.0~1400.0ml/hr.
5. generate the method for aceticanhydride as claim 1,2 or 3 described Preparation of Catalyst methyl acetates and carbon monoxide liquid phase carbonyl, it is characterized in that: the weight ratio of catalyst and methyl acetate, carbon monoxide is 1: 0.6~0.75: 0.4~0.55.
CNB2006101306486A 2006-12-28 2006-12-28 Liquid phase reaction process of methyl acetate and CO to produce acetic anhydride and its catalyst preparing process Active CN100486701C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNB2006101306486A CN100486701C (en) 2006-12-28 2006-12-28 Liquid phase reaction process of methyl acetate and CO to produce acetic anhydride and its catalyst preparing process

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB2006101306486A CN100486701C (en) 2006-12-28 2006-12-28 Liquid phase reaction process of methyl acetate and CO to produce acetic anhydride and its catalyst preparing process

Publications (2)

Publication Number Publication Date
CN1986053A true CN1986053A (en) 2007-06-27
CN100486701C CN100486701C (en) 2009-05-13

Family

ID=38183076

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB2006101306486A Active CN100486701C (en) 2006-12-28 2006-12-28 Liquid phase reaction process of methyl acetate and CO to produce acetic anhydride and its catalyst preparing process

Country Status (1)

Country Link
CN (1) CN100486701C (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102266795A (en) * 2011-06-15 2011-12-07 陕西煤业化工技术开发中心有限责任公司 Catalyst used for low water acetic acid synthetic technology and preparation and application method thereof
CN102319587A (en) * 2011-06-15 2012-01-18 陕西煤业化工技术开发中心有限责任公司 Catalyst used in carbonylation synthesis of acetic anhydride coproduced with acetic acid and preparation and application methods thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102266795A (en) * 2011-06-15 2011-12-07 陕西煤业化工技术开发中心有限责任公司 Catalyst used for low water acetic acid synthetic technology and preparation and application method thereof
CN102319587A (en) * 2011-06-15 2012-01-18 陕西煤业化工技术开发中心有限责任公司 Catalyst used in carbonylation synthesis of acetic anhydride coproduced with acetic acid and preparation and application methods thereof
CN102319587B (en) * 2011-06-15 2013-08-28 陕西煤业化工技术开发中心有限责任公司 Catalyst used in carbonylation synthesis of acetic anhydride coproduced with acetic acid and preparation and application methods thereof
CN102266795B (en) * 2011-06-15 2013-09-11 陕西煤业化工技术开发中心有限责任公司 Catalyst used for low water acetic acid synthetic technology and preparation and application method thereof

Also Published As

Publication number Publication date
CN100486701C (en) 2009-05-13

Similar Documents

Publication Publication Date Title
CN101613274B (en) Method for preparing methyl acetate by carbonylating dimethyl ether
CN109453815A (en) The rhodium base catalyst of organic load of polymer support containing phosphine and its preparation and application
TW200631935A (en) Production method of acetic acid
CN100411738C (en) Rhodium catalyst with organometallic lithium salts as ligand
CN109926056A (en) It is a kind of using carbon nanotube as the catalyst of carrier, preparation method and application
CN109453814A (en) Containing sulfonic group and the polymer supported rhodium catalyst of Phosphine ligands multi-stage porous and preparation and application
CN103539665A (en) Succinic acid diester preparation method
CN102863335B (en) Preparation method of diethyl succinate
CN100486701C (en) Liquid phase reaction process of methyl acetate and CO to produce acetic anhydride and its catalyst preparing process
CN108503545B (en) Method for preparing phenylacetate by catalytic oxidation of mandelate
CN101146755B (en) Process for the preparation of p-toluic acid by liquid phase oxidation of p-xylene in water
CN114849786A (en) Imidazole sulfonic acid ionic liquid based palladium-phosphine complex catalyst for synthesizing methyl propionate by ethylene methyl hydrogen esterification
CN115709072B (en) Catalyst for preparing acetic acid by catalyzing methanol carbonylation and preparation method and application thereof
CN110317131A (en) A kind of method that second benzene-like compounds prepare ketone compounds
CN100457706C (en) New technological process of synthesizing acetyl bromide, acetic acid, acetate from methane
CN101411997A (en) Single teeth syn-dicarbonyl rhodium-triphenylphosphine complex catalyst for carbonyl group combined to acetic acid as well as preparation method and use thereof
CN101722047B (en) Homogeneous phase iridium complex catalyst of methanol oxo-synthesis acetic acid, preparation method and application thereof
CN101502805B (en) Catalyst for preparing acetic anhydride as well as preparation method and application
CN103204775B (en) Oxidation method of acetophenone
CN100372608C (en) Catalyst system of catalytic methylester acetate or methylether synthetic acetoanhy dride and use thereof
CN101716522A (en) Complex catalyst for synthesizing acetic acid from methanol carbonyl and preparation method and application thereof
CN114573450B (en) Method for preparing acetic acid by catalyzing levulinic acid through MnCeOx
CN101070332A (en) Rhodium acetic anhydride complex, and its preparing method and use
JP2548590B2 (en) Method for selective oxidative carbonylation of conjugated dienes
CN102218329A (en) Method for preparing C2 and oxygenated chemicals thereof by using synthesis gas

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