CN1238314C - Process and catalyst for cracking methyl tert-amyl ether to prepare test-amyl olefine - Google Patents
Process and catalyst for cracking methyl tert-amyl ether to prepare test-amyl olefine Download PDFInfo
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- CN1238314C CN1238314C CN 00129388 CN00129388A CN1238314C CN 1238314 C CN1238314 C CN 1238314C CN 00129388 CN00129388 CN 00129388 CN 00129388 A CN00129388 A CN 00129388A CN 1238314 C CN1238314 C CN 1238314C
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Abstract
The present invention relates to a method and a catalyst for cracking methyl tert-amyl ether to prepare tert-pentene. The active component of a catalyst is heteropoly acid, or salt of heteropoly acid or a mixture of the heteropoly acid, the salt of heteropoly acid and metal salt; a carrier is silicon dioxide with a specified specific surface area and hole distribution. The conversion rate of methyl tert-amyl ether is more than 98.5%, and the selectivities of methanol and tert-pentene are more than 99.5% under the conditions that the temperature is between 130 DEG C and 300 DEG C, the space velocity of raw material liquid is between 0.1 h<-1> and 10 h<-1>, the reaction pressure keeps a reaction system in the form of gas.
Description
The present invention relates to a kind of method that ether-splitting is separated preparing high-purity uncle amylene that is used for.
Tertiary olefin is the particularly very important starting raw materials of polymkeric substance of some Chemicals of preparation, often needs very pure tertiary olefin.
Have suitable acid catalyst in the presence of, the reaction of the mixture of tertiary olefin or tertiary olefin and primary alconol can obtain corresponding ether, formed ether can never be separated in the alkene at an easy rate corresponsively, decomposes then to obtain highly purified tertiary olefin.
The tert-alkyl ether cracking is thermo-negative reaction, and high temperature helps reaction, but the temperature height is easy to cause side reaction, generates the polymkeric substance of dialkyl ether and alkene, has reduced the rate of recovery of methyl alcohol and alkene, is unfavorable for the economy of producing; If temperature of reaction is low, the transformation efficiency of ether is lower, need and recycle the ether Separation and Recovery, has increased separating device and energy consumption.
It is known (US4,006,198) that tert-alkyl ether can take place to decompose on the alumina base catalyst that adds silicon-dioxide, but this catalyzer causes the formation of more dialkyl ether under higher reaction temperatures, cause the loss of alcohol, unfavorable economically.In the presence of the alumina modified SiO 2 catalyst of interpolation (WO87/00166), methyl tertiary butyl ether can decompose, but transformation efficiency is lower, increases the separation costs of having opened product.The patent (CN 86104617A) of Italy Snamprogetti S.P.A. application, adopt alumina modified SiO 2 catalyst, by adding water to reactive system and controlling the methyl tertiary butyl ether transformation efficiency and improve iso-butylene and methyl alcohol selectivity, make process complicated but add water, and cause extra extra charge.
In addition, cracking methyl tert-amyl ether to prepare test-amyl olefine is compared with cracking isobutene by methyl-tert-butyl ether, and technical difficulty is bigger, because tert amyl methyl ether(TAME) easy polymerization under the temperature condition with higher forms tar, and the also easily polymerization of product uncle amylene is therefore higher to the performance requriements of catalyzer.
The object of the present invention is to provide the method for a kind of tert amyl methyl ether(TAME) (TAME) cracking system uncle amylene, under lower temperature of reaction (130～300 ℃), the transformation efficiency that can make TAME is greater than 98.5%, and the selectivity of methyl alcohol and uncle's amylene is all greater than 99.5%.
The said catalyzer of the present invention is meant that active constituent is carried on the silica supports, and drying, roasting form.
Said active constituent is meant the mixture of heteropolyacid or heteropolyacid salt or they and metal-salt.Said heteropolyacid or heteropolyacid salt are that central atom is a kind of element among P, the Si, heteropolyacid or heteropolyacid salt or their mixture that ligating atom is at least a element among W, Mo, the V.As heteropolyacid or its salt or their mixtures such as phospho-wolframic acid, phospho-molybdic acid, silicotungstic acid, silicomolybdic acid, phosphotungstomolybdic acid, molybdovanaphosphoric acids.Metal-salt is alkali metals such as Li, Na, K, Cs, the inorganic salt of alkali earth metal such as Mg, Ca, Sr, Ba or V, Cr, Mn, Fe, Co, Ni, transition metals such as Cu, Zn or one or more the mixture in the organic salt.
Silicon-dioxide as carrier is generally sphere, and particle diameter is 1-10mm, is preferably 3-6mm; Specific surface area is 50-700m
2/ g; The specific pore volume in the above hole of 22 , aperture (mercurous method mensuration) is 0.3～1.5ml/g, and wherein the pore volume in the above hole of aperture 200 accounts for pore volume 2% or more of aperture in the above hole of 22 , and is best more than 5%.If the specific surface area of carrier silicon-dioxide is excessive, or wide-aperture hole very little, will cause selectivity of catalyst to descend, and the growing amount of dme, uncle's pentene polymer increases.
The weight of heteropolyacid or heteropolyacid salt accounts for the 0.5-25% of carrier silica weight, is preferably 2-12%, and the weight of metal-salt accounts for the 0-15% of carrier silica weight, is preferably 0-7%.
Preparation of catalysts can adopt the method for any introducing active constituent, ion exchange method for example, pickling process, mechanical mixing etc.Preferably adopt pickling process.When adopting the immersion process for preparing catalyzer, can adopt saturated pickling process or solution soaking method.Dipping catalyzer well is dry certain hour under the temperature more than 100 ℃ earlier, then at roasting temperature 1-10 hour of 200-500 ℃, is preferably in 200-450 ℃ of following roasting.
According to the present invention, when adopting fixed-bed reactor to carry out the reaction of TAME cracking system uncle amylene, reaction conditions is: temperature 130-300 ℃, be preferably 160-220 ℃; The raw material liq air speed is 1.1-10h
-1, be preferably 0.3-5h
-1Pressure can adopt and can make reaction system keep any pressure of gasiform.
The invention has the advantages that: use catalyzer of the present invention (130-300 ℃) under moderate moisture, TAME is near transforming fully; This catalyzer also has higher selectivity simultaneously, and uncle's amylene and methyl alcohol selectivity are all greater than 99.5%, and product can obtain high purity uncle amylene after making with extra care.Use in uncle's amylene (mixture of 2-methyl-1-butene alkene and 2-methyl-2-butene) that catalyzer of the present invention makes, the shared ratio of 2-methyl-1-butene alkene is formed with catalyzer and is changed with the different of reaction conditions, is generally 16-40%.
The following examples will illustrate the present invention, but the present invention is not subjected to the restriction of following example.
Embodiment 1: prepare catalyst A-K according to method of the present invention
Use dried surface-area to be 400m
2/ g, specific pore volume are that 0.91ml/g, aperture are that to account for the aperture be carrier at 10.4% silicon-dioxide of the pore volume in the above hole of 22 for the pore volume in the above hole of 200 .The heteropolyacid of required load is dissolved in the distilled water, and the metal-salt (pressing table 1 proportioning) with aequum when needing dissolves together, and the amount of distilled water is joined 1.05 gram water by every gram silicon-dioxide; Silicon-dioxide is added in this solution, is stirred, make dipping evenly; Baking 2 hours under 100 ℃ the temperature in baking oven then, 300 ℃ of following roastings 4 hours in muffle furnace at last make catalyzer.Metal-salt used in the table 1 derives from corresponding FeSO respectively
4, Mg (NO
3)
2, Ni (NO
3)
2, MnCl
2, Zn (NO
3)
2, FeCl
3
The composition of catalyst A-K is as shown in table 1.
Embodiment 2: prepare catalyzer L according to method of the present invention
Use the silicon-dioxide identical to be carrier with embodiment 1.Phospho-wolframic acid and FeSO with required load
4Be dissolved in the distilled water, the amount of distilled water is joined 1.05 gram water by every gram silicon-dioxide; Silicon-dioxide is added in this solution, is stirred, make dipping evenly; In baking oven, dried by the fire 2 hours under 100 ℃ the temperature then; KNO with required load
3Be dissolved in the distilled water, the amount of distilled water has been carried phospho-wolframic acid and FeSO by every gram
4Silicon-dioxide join 1.05 gram water meters, will carry phospho-wolframic acid and FeSO
4Silicon-dioxide be added in this solution, stirred, make dipping evenly; Baking 2 hours under 100 ℃ the temperature in baking oven then, 300 ℃ of following roastings 4 hours in muffle furnace at last make catalyzer L.The weight of phospho-wolframic acid accounts for 5% of silica weight, K among the catalyzer L
+/ Fe
2+With the mol ratio of phospho-wolframic acid be 0.5/1: 1.
The composition of table 1 catalyst A-K
| Catalyzer | Heteropolyacid | Heteropolyacid/SiO 2 m/m | Metal ion: heteropolyacid mol: mol | Metal-salt/SiO 2 m/m |
| A B C D E F G H I J K | Phosphomolybdic acid phosphotungstic acid phosphotungstic acid phosphotungstic acid phosphotungstic acid phosphotungstic acid phosphotungstic acid phosphotungstic acid phosphomolybdic acid phosphomolybdic acid phosphotungstic acid | 5％ 2.5％ 5％ 5％ 5％ 5％ 5％ 5％ 5％ 5％ 12％ | / / / Fe 2+ 1.5∶1 Mg 2+ 1.5∶1 Ni 2+ 1.5∶1 Mg 2+/Ni 2+ 1.5/1.5∶1 Mn 2+ 2∶1 Mg 2+/Zn 2+ 1/1∶1 Mg 2+/Fe 2+ 1.5/1.5∶1 Fe 3+ 6∶1 | / / / 0.67％ 0.61％ 0.70％ 1.31％ 0.63％ 1.83％ 2.15％ 6.21％ |
Embodiment 3: prepare catalyzer M according to method of the present invention
Use dried specific surface area to be 349m
3/ g, specific pore volume be the pore volume in 0.41ml/g, the above hole of 200 , aperture to account for the aperture be carrier at 3.5% silicon-dioxide of the pore volume in the above hole of 22 , a load phosphotungstic acid, phospho-wolframic acid/SiO
2(m/m) be 5%, other preparation process are identical with embodiment 1, preparation catalyzer M.
Embodiment 4: the catalytic performance of catalyst A-M of the present invention to the tert amyl methyl ether(TAME) scission reaction is described.
The 40ml catalyzer is packed in the fixed-bed reactor of internal diameter 15mm, is 0.3-1h in TAME liquid air speed
-1, temperature of reaction is that 160-200 ℃, reaction pressure are to estimate under the condition of 0.3MPa, what obtain the results are shown in table 2.
Table 2 catalyst A-M is for TAME cracked catalytic performance
| Catalyzer | Temperature ℃ | Liquid air speed h -1 | X TAME ％ | S Methyl alcohol ％ | S Uncle's amylene ％ | R 2MIB ％ |
| A A B C C D D E F G H I J K L M | 180 180 200 180 200 180 200 200 180 200 200 200 180 190 180 160 | 0.3 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.43 0.5 0.5 0.5 0.5 0.5 0.5 0.5 | 99.2 98.8 99.3 99.1 99.6 99.3 99.5 99.1 99.0 99.4 99.3 98.8 98.8 98.8 99.1 98.7 | 100 100 100 100 99.9 100 100 100 100 100 100 99.8 99.8 99.5 100 100 | 99.9 99.9 99.9 99.8 99.7 99.9 99.7 99.9 99.9 99.9 99.7 99.9 99.9 99.6 99.8 99.6 | 20.0 22.7 26.5 19.2 19.3 18.6 19.0 21.5 22.1 21.7 18.2 31.0 19.5 20.9 18.1 16.6 |
X in the table
TAMERefer to the TAME transformation efficiency, S
Methyl alcoholRefer to generate the selectivity of methyl alcohol, S
Uncle's amyleneRefer to generate the selectivity of uncle's amylene, R
2MIBRefer to the ratio that 2-methyl-1-butene alkene accounts in the uncle's amylene that generates.Table 3 together
Comparative Examples 1: the preparation catalyst n illustrates the influence of specific pore volume and wide-aperture hole proportion
Use dried specific surface area to be 567m
2/ g, specific pore volume be the pore volume in 0.15ml/g, the above hole of 200 , aperture to account for the aperture be carrier at 4.2% silicon-dioxide of the pore volume in the above hole of 22 , a load phosphotungstic acid, phospho-wolframic acid/SiO
2(m/m) be 5%, other preparation process are identical with embodiment 1, the preparation catalyst n.
Comparative Examples 2: the catalytic performance of catalyst n to the tert amyl methyl ether(TAME) scission reaction is described.
Press the catalytic performance of the method evaluate catalysts N of embodiment 4, the results are shown in table 3 the TAME scission reaction.
Table 3 catalyst n is for TAME cracked catalytic performance
| Catalyzer | Temperature ℃ | Liquid air speed h -1 | X TAME ％ | S Methyl alcohol ％ | S Uncle's amylene ％ | R 2MIB ％ |
| N N | 160 160 | 0.5 1.0 | 98.9 98.7 | 97.4 99.3 | 86.5 88.0 | 16.7 16.7 |
Claims (6)
1, a kind of method with cracking methyl tert-amyl ether to prepare test-amyl olefine, it is characterized in that the used catalyst activity component of scission reaction is the mixture of heteropolyacid and metal-salt, carrier is a silicon-dioxide, described metal-salt is inorganic salt or the organic salt of V, Cr, Mn, Fe, Co, Ni, Cu or Zn, the weight of heteropolyacid accounts for 2～12% of carrier silica weight, in the carrier silicon-dioxide, the pore volume in the hole of aperture more than 200 accounts for pore volume 2% or more of aperture in the above hole of 22 , and the specific pore volume in the hole of aperture more than 22 is 0.3～1.5ml/g.
2, in accordance with the method for claim 1, it is characterized in that described heteropolyacid is that central atom is that a kind of element, ligating atom among P, the Si is the heteropolyacid of at least a element among W, Mo, the V.
3,, it is characterized in that described heteropolyacid is phospho-wolframic acid, phospho-molybdic acid or silicotungstic acid according to claim 1 or 2 described methods.
4, in accordance with the method for claim 1, the specific surface area that it is characterized in that described silicon-dioxide is 50～70m
2/ g.
5, in accordance with the method for claim 1, it is characterized in that in the described carrier silicon-dioxide that the pore volume in the hole of aperture more than 200 accounts for more than 5% of pore volume of aperture in the above hole of 22 .
6, in accordance with the method for claim 1, it is characterized in that the scission reaction temperature is 130～300 ℃, the raw material liq air speed is 0.1～10h
-1, reaction pressure keeps any pressure of gasiform for making reaction system.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00129388 CN1238314C (en) | 2000-12-08 | 2000-12-08 | Process and catalyst for cracking methyl tert-amyl ether to prepare test-amyl olefine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00129388 CN1238314C (en) | 2000-12-08 | 2000-12-08 | Process and catalyst for cracking methyl tert-amyl ether to prepare test-amyl olefine |
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| Publication Number | Publication Date |
|---|---|
| CN1357522A CN1357522A (en) | 2002-07-10 |
| CN1238314C true CN1238314C (en) | 2006-01-25 |
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| CN 00129388 Expired - Lifetime CN1238314C (en) | 2000-12-08 | 2000-12-08 | Process and catalyst for cracking methyl tert-amyl ether to prepare test-amyl olefine |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103846098B (en) * | 2014-03-25 | 2016-05-18 | 华东理工大学 | Tert amyl methyl ether(TAME) cracking is for catalyst and preparation method and the application of iso-amylene |
| CN104689853B (en) * | 2015-03-20 | 2017-07-28 | 华东理工大学 | A kind of preparation method and application for being used to prepare the catalyst of iso-amylene |
| CN106622382B (en) * | 2015-11-04 | 2020-05-19 | 中国石油化工股份有限公司 | Catalyst for synthesizing dimethyl carbonate and preparation method and application thereof |
| 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 |
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Owner name: CHINA PETROLEUM & CHEMICAL CORPORATION; QILU PETR Free format text: FORMER OWNER: QILU PETROCHEMICAL GROUP CO., CHINA PETROCHEMICAL CORP. Effective date: 20070615 |
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Effective date of registration: 20070615 Address after: 100029, No. 6, Xin Xin Street East, Beijing, Chaoyang District Co-patentee after: Qilu Petrochemical Co., China Petrochemical Group Corp. Patentee after: Sinopec Corp. Address before: 124 mailbox 255408, Shandong City, Zibo Province Patentee before: Qilu Petrochemical Co., China Petrochemical Group Corp. |
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Owner name: CHINA PETROLEUM & CHEMICAL CORPORATION Free format text: FORMER OWNER: CHINA PETROLEUM + CHEMICAL CORPORATION; QILU PETROCHEMICAL GROUP CO., CHINA PETROCHEMICAL CORP. Effective date: 20071228 |
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Effective date of registration: 20071228 Address after: 6, Xin Xin Dong Street, Beijing, Chaoyang District, China: 100029 Patentee after: Sinopec Corp. Address before: 6, Xin Xin Dong Street, Beijing, Chaoyang District, China: 100029 Co-patentee before: Qilu Petrochemical Co., China Petrochemical Group Corp. Patentee before: China Petroleum Chemical Co |
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