CN1185992A - Catalyst for ether pyrolysis isobutylene and applications - Google Patents
Catalyst for ether pyrolysis isobutylene and applications Download PDFInfo
- Publication number
- CN1185992A CN1185992A CN96123535A CN96123535A CN1185992A CN 1185992 A CN1185992 A CN 1185992A CN 96123535 A CN96123535 A CN 96123535A CN 96123535 A CN96123535 A CN 96123535A CN 1185992 A CN1185992 A CN 1185992A
- Authority
- CN
- China
- Prior art keywords
- ether
- heteropolyacid
- dioxide
- catalyzer
- 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.)
- Granted
Links
Abstract
A catalyst used for preparing isobutylene by cracking ether is a heteropoly acid compound carried by SiO2 carrier, which is prepared through drying and calcine. It has the advantages of high transoform rate, selectivity to isobutylene, purity of product and anti-poisoning power when it is used in ether cracking reaction (such as methyl tert-butyl ether-MTBE) to prepare isobutylene.
Description
The present invention relates to a kind of method that ether-splitting is separated the preparing isobutene catalyzer and used this catalyzer that is used for.
At present, the ether-splitting of having developed with exploitation is separated the preparing isobutene catalyzer, mainly is some solid acid catalysts.For example aluminum oxide (USP 3,170,000), (BP 1 for vitriol, 482,883), modified aluminas (USP 4,006,198), (BP 1 for aluminum phosphate, 173,128), (Fr.P 1 for activated carbon (day is openly speciallyyed permit communique, 49-94,602), improved silica (CN 86104617A) and ion exchange resin, 256,388) etc.Some problems below these catalyzer exist:
From reacting itself, methyl tertiary butyl ether (MTBE) cracking is thermo-negative reaction, and high temperature helps reaction, but the temperature height, some catalyzer can cause the secondary side reaction, the methanol dehydration that cracking obtains generates dme, reduce the rate of recovery of methyl alcohol, be unfavorable for the economy of producing; Some catalyzer reacts at a lower temperature, can reduce the generation of dme, but can cause the dimerization or the trimerization of the alkene that generates, and the selectivity of loss iso-butylene reduces the generation of purpose product, also is unfavorable for the economy of producing.
From engineering viewpoint, some catalyzer (as activated carbon catalyst) is when temperature of reaction is higher, and MTBE has avoided the Separation and Recovery of MTBE and recirculation to use near transforming fully, has reduced energy consumption.But owing to the temperature of reaction height, easily make the thermal oil coking and the blocking pipeline of heating system, bring some troubles to operation; Some catalyzer (as modified aluminas) needs control transformation efficiency (70～80%), reaches optionally purpose of raising iso-butylene and methyl alcohol.Yet this kind practice need reclaim MTBE recirculation and use, and has increased separating device and energy consumption.
For example, patent (CN 86104617A) the MTBE cracking preparing isobutene of Italy Snam company application adopts alumina modified SiO 2 catalyst, by add water and control MTBE transformation efficiency (70～80%) to reactive system, reach optionally purpose of raising iso-butylene and methyl alcohol, owing to add water in reactive system, make process complicated, and cause extra extra charge.The patent (CN91102950.8) of France Inst Francais Du Petrole the early 1990s application adopts silica modified catalyzer, and (170～250 ℃) MTBE transformation efficiency about 70% can reduce side reaction under lower temperature conditions, has increased the rate of recovery of iso-butylene and methyl alcohol.Because lower transformation efficiency increases the operating process energy consumption.Japan special permission communique 49--94,602 described activated-carbon catalysts can make MTBE transform near complete, but need higher temperature, bring difficulty to heating operation.
The object of the present invention is to provide a kind of ether-splitting to separate the preparing isobutene catalysts, this catalyzer is used for ether-splitting and separates when reacting preparing isobutene, do not need to add the inert substance of water and so on to reaction system, need not limit the transformation efficiency of ether, (150～270 ℃) can make the transformation efficiency of raw material ether near 100% under lower temperature.
The present invention is a kind of new catalyst that ether-splitting is separated preparing isobutene.Said catalyzer is meant that active constituent is carried on the silica supports, and drying, roasting form.
Said active constituent is meant heteropolyacid or heteropolyacid mixture.Heteropolyacid (HPA) is phospho-wolframic acid, phospho-molybdic acid, silicotungstic acid, Vanadotungstic acid etc.The heteropolyacid mixture contains a kind of compound in basic metal or the alkaline-earth metal at least, as compound of lithium, potassium, caesium, calcium, strontium, barium, magnesium etc.
The weight percentage that heteropolyacid accounts for carrier silicon-dioxide is 0.5～30%, is preferably 1～10%, and the weight percentage that basic metal or alkaline earth metal compound account for carrier silicon-dioxide is 0～10%, is preferably 0～5%.
Silica supports is spherical or amorphous.Particle diameter is 1～10mm, is preferably 3～5mm, and specific surface area is 50～800m
2/ g is preferably 80～300m
2/ g.
Method for preparing catalyst can adopt the method for any introducing active constituent, for example ion exchange method, saturated pickling process, solution soaking method, mechanical mixing and organic compound grafting method.Preferably adopt pickling process.Immersion process for preparing catalyzer process is as follows: at first, the catalyzer that dipping is good is heated to 75 ℃～80 ℃ in water-bath, evaporation moisture content, then in 120 ℃ dry 4 hours down, 200 ℃～500 ℃ roasts 4 hours, be preferably in 300 ℃～400 ℃ roastings 4 hours at last.
According to the present invention, adopt fixed-bed reactor to carry out MTBE cracking preparing isobutene.Temperature of reaction is 150 ℃～300 ℃, preferably 170 ℃～270 ℃; Working pressure is 0～2MPa, is preferably 0～0.6MPa; The liquid air speed is 0.1～10h
-1, be preferably 0.5～5h
-1
This catalyzer is applicable to that ether-splitting separates reaction, the scission reaction of MTBE, Ethyl Tertisry Butyl Ether etc. for example, and purpose is to make highly purified iso-butylene (with methyl alcohol or ethanol etc.).
Use catalyzer of the present invention (150～300 ℃) under moderate moisture, ether-splitting is separated near transforming fully, need not react back Separation and Recovery raw material ether; Simultaneously, this catalyzer also has higher selectivity, and selective isobutene is greater than 99%, and the methyl alcohol selectivity is more than 98.0%, after product is refining, can obtain high-purity isobutylene.
In addition, ether-splitting is separated the not fiat secundum artem processing of raw material ether of usefulness, removes micro-detrimental impurity such as organic amine etc., and the ethers that can directly use the etherificate operation has certain anti-poisoning capability.
The following examples will further specify the present invention.
Embodiment 1: according to preparation method used in the present invention, and the preparation catalyst A
Earlier silica supports is put in the baking oven, drying is 2 hours under 120 ℃, evaporates the moisture content of absorption.The magnesium nitrate of 4g phospho-wolframic acid and 3g six crystal water is dissolved in the 75g distilled water, this solution is heated to 75 ℃～80 ℃, dipping 100g silica supports.Through evaporation, 120 ℃ of dryings are after 4 hours, and 400 ℃ of roastings 4 hours obtain catalyzer.This specific surface area of catalyst 295m
2/ g, pore volume are 0.734cm
2/ g.
The 80g catalyst A, in the fixed-bed reactor of the Φ 20mm diameter of packing into, MTBE liquid air speed is 1h
-1, normal pressure, temperature of reaction is 170 ℃, MTBE transformation efficiency 99%, selective isobutene 99%, methyl alcohol selectivity 98%.
Embodiment 2: according to preparation method used in the present invention, and the preparation catalyst B
With unformed silicon-dioxide (20～40 order) through 120 ℃ of processing, remove moisture content after, it is standby to put into moisture eliminator cooling.7g phospho-molybdic acid and 3g nitrate of baryta are dissolved in the 80g distilled water, in the time of 75～80 ℃, dipping 100g silica supports.According to embodiment 1 same method carry out drying, roasting makes catalyst B.
50g catalyst B catalyzer, in the fixed-bed reactor of the Φ 20mm diameter of packing into, MTBE liquid air speed is 0.5h
-1, temperature of reaction is 230 ℃, MTBE transformation efficiency 99.8%, selective isobutene 99%, methyl alcohol selectivity 98.6%.
Embodiment 3: according to preparation method used in the present invention, and preparation catalyzer C
With the silicon-dioxide (20～40 order) of ball-type, handle through embodiment 1 same method.With 5.5g Vanadotungstic acid and 3g cesium nitrate melt into 80g solution, dipping 80g silica supports.According to embodiment 1 same method carry out drying, roasting makes catalyzer C.
50g catalyzer C, in the fixed-bed reactor of the Φ 20mm diameter of packing into, MTBE liquid air speed is 0.5h
-1, temperature of reaction is 240 ℃, MTBE transformation efficiency 99.9%, selective isobutene 99%, methyl alcohol selectivity 98%.
Embodiment 4: according to preparation method used in the present invention, and preparation catalyzer D
The 75ml solution that will contain the 5g phospho-wolframic acid, the spherical silica carrier of dipping 80g Φ 2.5mm diameter, according to embodiment 1 same method carry out drying, roasting makes catalyzer D.
50g catalyzer D, in the fixed-bed reactor of the Φ 20mm diameter of packing into, MTBE liquid air speed is 0.5h
-1, temperature of reaction is 150 ℃, MTBE transformation efficiency 95%, selective isobutene 98%, methyl alcohol selectivity 98%.
Embodiment 5: use the embodiment of the invention 4 prepared catalyst D to carry out the MTBE scission reaction, reaction pressure is 0.6MPa, and MTBE liquid air speed is 0.5h
-1, temperature of reaction is 240 ℃, MTBE transformation efficiency 98%, selective isobutene 99%, methyl alcohol selectivity 98%.
Embodiment 6: adopt the catalyst A of example 1 method preparation, carry out the scission reaction of Ethyl Tertisry Butyl Ether, produce highly purified iso-butylene and ethanol.With the 50g catalyst A, in the fixed-bed reactor of the Φ 20mm diameter of packing into, the liquid air speed is 0.3h
-1, temperature of reaction is 260 ℃, and normal pressure, Ethyl Tertisry Butyl Ether transformation efficiency are greater than 98%, and iso-butylene and ethanol selectivity are more than 99%.
Claims (9)
1, a kind of ether-splitting that is used for is separated the new catalyst that reacts preparing isobutene, it is characterized in that catalyst activity component is heteropolyacid or heteropolyacid mixture, and load carriers is a silicon-dioxide.
2,, be the mixture of heteropolyacid and at least a basic metal or alkaline earth metal compound according to the said heteropolyacid mixture of claim 1.
3, be phospho-wolframic acid, phospho-molybdic acid, silicotungstic acid, Vanadotungstic acid according to claim 1 or 2 described heteropolyacids.
4, described according to claim 1～2, the weight percentage that heteropolyacid accounts for carrier silicon-dioxide is 0.5～30%.
5, described according to claim 1～2, the weight percentage that basic metal or alkaline earth metal compound account for carrier silicon-dioxide is 0～10%.
6, described according to claim 4, the weight percentage that heteropolyacid accounts for carrier silicon-dioxide is preferably 1～10%,
7, described according to claim 5, the weight percentage that basic metal or alkaline earth metal compound account for carrier silicon-dioxide is preferably 0～5%.
8, a kind of ether-splitting of separating in the presence of the catalyzer at ether-splitting is separated the method for preparing iso-butylene, and required processing condition are: pressure 0～2MPa, and temperature of reaction is 150～300 ℃, the liquid air speed is 0.1～10h
-1
9, in accordance with the method for claim 8, required optimum process condition is pressure 0～0.6MPa, and temperature of reaction is 170～270 ℃, liquid air speed 0.5～5h
-1
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96123535A CN1093000C (en) | 1996-12-27 | 1996-12-27 | Catalyst for ether pyrolysis isobutylene and applications |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96123535A CN1093000C (en) | 1996-12-27 | 1996-12-27 | Catalyst for ether pyrolysis isobutylene and applications |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1185992A true CN1185992A (en) | 1998-07-01 |
| CN1093000C CN1093000C (en) | 2002-10-23 |
Family
ID=5127680
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96123535A Expired - Lifetime CN1093000C (en) | 1996-12-27 | 1996-12-27 | Catalyst for ether pyrolysis isobutylene and applications |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1093000C (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100420518C (en) * | 2006-09-08 | 2008-09-24 | 华东理工大学 | Catalyst of solid acid in use for preparing isobutene, and preparation method |
| CN100441495C (en) * | 2003-12-19 | 2008-12-10 | 华东师范大学 | Silicon gel coated poly metal oxygen-containing cluster compound nano particle material and its preparing method |
| CN100448534C (en) * | 2003-12-31 | 2009-01-07 | 科学与工业研究委员会 | Catalyst for synthesis of 2-and 4-picolines, process for preparing 2- and 4-picoline and process for preparing the catalyst |
| CN101896269B (en) * | 2007-12-13 | 2013-06-19 | 英国石油有限公司 | Catalyst recovery process |
| CN106890673A (en) * | 2015-12-18 | 2017-06-27 | 中国石油天然气股份有限公司 | A kind of catalyst for cracking isobutene by methyl-tert-butyl ether and preparation method thereof |
| US10792642B2 (en) | 2014-12-03 | 2020-10-06 | China Petroleum & Chemical Corporation | Catalyst and preparation method thereof, and method for preparing isobutylene by applying the same |
| CN112759499A (en) * | 2019-10-21 | 2021-05-07 | 中国石油化工股份有限公司 | Process for preparing isobutene by high-efficiency decomposition of methyl tert-butyl ether |
| CN115532314A (en) * | 2021-06-29 | 2022-12-30 | 中国石油化工股份有限公司 | Catalyst for preparing isobutene by methyl tert-butyl ether hydrolysis, preparation method and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1188179B (en) * | 1985-07-05 | 1988-01-07 | Snam Progetti | PROCEDURE FOR PRODUCING TERTIARY OLEFINS BY DECOMPOSITION OF ALCHIL-TER-ALCHIL-ETERI |
| CN1029611C (en) * | 1990-10-16 | 1995-08-30 | 三井石油化学工业株式会社 | Process for producing alkyl-substituted aromatic hydrocarbon |
| JPH0776540A (en) * | 1993-09-09 | 1995-03-20 | Sumitomo Chem Co Ltd | Production of alkyl t-alkyl ether |
-
1996
- 1996-12-27 CN CN96123535A patent/CN1093000C/en not_active Expired - Lifetime
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100441495C (en) * | 2003-12-19 | 2008-12-10 | 华东师范大学 | Silicon gel coated poly metal oxygen-containing cluster compound nano particle material and its preparing method |
| CN100448534C (en) * | 2003-12-31 | 2009-01-07 | 科学与工业研究委员会 | Catalyst for synthesis of 2-and 4-picolines, process for preparing 2- and 4-picoline and process for preparing the catalyst |
| CN100420518C (en) * | 2006-09-08 | 2008-09-24 | 华东理工大学 | Catalyst of solid acid in use for preparing isobutene, and preparation method |
| CN101896269B (en) * | 2007-12-13 | 2013-06-19 | 英国石油有限公司 | Catalyst recovery process |
| US10792642B2 (en) | 2014-12-03 | 2020-10-06 | China Petroleum & Chemical Corporation | Catalyst and preparation method thereof, and method for preparing isobutylene by applying the same |
| CN106890673A (en) * | 2015-12-18 | 2017-06-27 | 中国石油天然气股份有限公司 | A kind of catalyst for cracking isobutene by methyl-tert-butyl ether and preparation method thereof |
| CN112759499A (en) * | 2019-10-21 | 2021-05-07 | 中国石油化工股份有限公司 | Process for preparing isobutene by high-efficiency decomposition of methyl tert-butyl ether |
| CN112759499B (en) * | 2019-10-21 | 2023-10-20 | 中国石油化工股份有限公司 | Process for preparing isobutene by decomposing high-efficiency methyl tertiary butyl ether |
| CN115532314A (en) * | 2021-06-29 | 2022-12-30 | 中国石油化工股份有限公司 | Catalyst for preparing isobutene by methyl tert-butyl ether hydrolysis, preparation method and application thereof |
| CN115532314B (en) * | 2021-06-29 | 2024-01-05 | 中国石油化工股份有限公司 | Catalyst for preparing isobutene by methyl tertiary butyl ether and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1093000C (en) | 2002-10-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1093000C (en) | Catalyst for ether pyrolysis isobutylene and applications | |
| JPH05507495A (en) | Catalyzed continuous gas phase dimer cyclic ester process | |
| CN106470963B (en) | Method for producing isobutylene, method for producing methacrylic acid, and method for producing methyl methacrylate | |
| KR20150056645A (en) | Method and device for coproducing cyclohexanol and alkanol | |
| CA1117986A (en) | Process for the preparation of tertiary olefins | |
| MX2013003910A (en) | Process for production of methacrylic acid ester. | |
| CN1123556C (en) | Process for preparing ketone by dehydrogenating para-alcohol | |
| GB2048247A (en) | Process for preparing methyl tertiary-butyl ether | |
| MX2012007463A (en) | Process for preparing ethylbenzene. | |
| CN112206820B (en) | Composite metal oxide catalyst for preparing isobutyl isobutyrate by using isobutyraldehyde one-step method and preparation method thereof | |
| CN1181919C (en) | Catalyst for cracking ether to prepare tert-olefine and its prepn and application | |
| CN110170327B (en) | Mesoporous C/SiO2Supported heteropolyacid catalyst and preparation method and application thereof | |
| JP2911244B2 (en) | Method for producing lower olefins | |
| CN100467124C (en) | Catalyst for producing isobutene by cracking methyl tert-butyl ether | |
| CN111995494B (en) | Preparation method of 2-methallyl alcohol | |
| CN1380140A (en) | Catalyst for synthesizing dimethyl carbonate and its application | |
| CN1134410A (en) | Process for producing isopropyl alcohol | |
| CN1178740C (en) | Catalytic rectification and reaction method and apparatns | |
| CN112441866A (en) | Method for producing n-butene from isobutene | |
| WO2008069983A2 (en) | Process for making dibutyl ethers from dry ethanol | |
| CN114950503B (en) | Preparation method and application of regenerated acid catalyst | |
| CN1202051C (en) | Method of producing isobutene joint producing dimetylether and dipolyisobutene | |
| Kuno et al. | Lactonization of hydroxy ester over hydrous zirconium (IV) oxide modified by trimethylsilyl chloride | |
| CN1085108C (en) | Superfine catalyst for preparing methyl formate by carbonylating methanol | |
| CN110743580A (en) | Catalyst for preparing methyl ethyl ketone by dehydrating 2, 3-butanediol and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: CHINA PETROLEUM CO., LTD. Free format text: FORMER OWNER: INST. OF JILIN CHEMICAL INDUSTRY CO. Effective date: 20021220 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20021220 Address after: 100011 Beijing city Dongcheng District No. 16 Andrew intercontinental building Patentee after: China Petroleum & Natural Gas Co., Ltd. Address before: 132021 No. 27 East Zunyi Road, Jilin, Jilin Patentee before: Research Inst. of Jilin Chem. Ind. Corp. |
|
| CX01 | Expiry of patent term |
Granted publication date: 20021023 |
|
| EXPY | Termination of patent right or utility model |