CN103071520B - Preparation method for catalyst used in production of isobutene through cracking of methyl tert-butyl ether - Google Patents
Preparation method for catalyst used in production of isobutene through cracking of methyl tert-butyl ether Download PDFInfo
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Abstract
The invention discloses a preparation method for a catalyst used in production of isobutene through cracking of methyl tert-butyl ether (MTBE). According to the method, aluminum hydroxide colloid and Silicalite-1 molecular sieve crystallization liquid are mixed and molded and then undergo hydro-thermal treatment, and a resultant is used as the catalyst; preferably, the catalyst is loaded with a proper amount of active metal components; and the catalyst is used for cracking of MTBE for production of isobutene. The catalyst prepared in the invention has good catalysis performance, enables good selectivity on methanol and isobutene and a high conversion rate of MTBE to be obtained and inhibits generation of dimethyl ether, a reaction by-product.
Description
Technical field
The present invention relates to a kind of for cracking isobutene by methyl-tert-butyl ether Catalysts and its preparation method.
Background technology
Isobutene is important Organic Chemicals, high-purity isobutylene is widely used in producing the products such as butyl rubber, polyisobutene, and methyl tertiary butyl ether(MTBE) (MTBE) cracking high-purity isobutylene is advanced technology in many method for makings, a kind of method of better economy.The accessory substance dimethyl ether of MTBE cracking is the principal element that affects product isobutene purity, product isobutene for the production of butyl rubber time, particularly strict to the requirement of its dimethyl ether content.Therefore develop MTBE cracking conversion ratio and selective isobutene all excellent catalyst make that dimethyl ether is as far as possible few to be generated or do not generate, reduce the burden of MTBE cracker later separation, be the core of this technology.
At present, being applied to the better catalyst of MTBE cracking performance has: alumina series catalyst, silicon oxide series catalyst, ion-exchange resin catalyst is (as DE 3509292A1, DE 3210435A1, US 4447668A, GB 1482883A, US 4570026A, US 4551567A), sulfate catalyst (as JP7626401), activated-carbon catalyst (as JP7494602), solid phosphoric acid catalyst (as CN 96123535.7, EP 0118085A1) etc.
From aspects such as catalyst activity, stability, Possibility of Regeneration and costs, consider, adopting alumina series, silicon oxide series catalyst is preferably to select as MTBE catalyst for cracking.Alumina series catalyst is because a large amount of existence of aluminium oxide reduce catalyst activity, and reaction temperature is higher.The methyl alcohol that particularly cracking generates can not only make methyl alcohol yield reduce by dehydration generation dimethyl ether under reaction condition, product separation is brought to adverse effect simultaneously.
For reducing or eliminate the generation of dimethyl ether, in adopting course of reaction, water injection technology, select suitable catalyst, as silica-based catalyst or contain the catalyst of aluminium oxide and silica simultaneously, be the main selection that improves MTBE cracking accessory substance.
In CN 96115213.3, catalyst carries out roasting by silica gel and prepared by hydrothermal treatment consists, roasting 1 ~ 6h at 350 ~ 550 ℃, at 200 ~ 400 ℃, with saturated vapor, process 1 ~ 6h and.This catalyst is at 180 ~ 260 ℃, 0.1 ~ 0.8MPa, MTBE weight (hourly) space velocity (WHSV) 2 ~ 6h
-1reaction condition under, selectively can reaching of the conversion ratio of methyl tertiary butyl ether(MTBE) and isobutene is close to 100%, the amount of the accessory substance dimethyl ether simultaneously generating is 0.3%.
< < Speciality Petrochemicals > > the 4th phase in 1997 1st ~ 4 pages of Liu Fu victory wait one piece of exercise question delivering in " progress of MTBE cracking isobutene catalyst ", from " silicon oxide series catalyst system and catalyzing " joint, when adopting silicon oxide series catalyst, with silica, almost there is no catalytic activity separately.And add a small amount of aluminium oxide or with a small amount of alumina modified after, although its activity and selectivity improves a lot, but the impact of the oxidated silicon material purity of catalyst performance is more remarkable, such as WO 8700166A1 be by the soluble-salt solution impregnation of aluminium to highly purified silica, then through super-dry and roasting, make modified catalyst.
156th ~ 160 pages of < < chemistry of fuel journal > > the 31st the 2nd phases of volume in 2003 disclose one piece of article that exercise question is " methyl tertiary butyl ether(MTBE) cracking is for high-purity isobutylene ", in silica-alumina catalyst wherein, silica content is 79wt% ~ 89wt%, alumina content is 9wt% ~ 12wt%, and also adding other auxiliary agent content is 10wt% ~ 12wt%.The preparation method of this silica-alumina catalyst is as follows: be first prepared into silicon-aluminum sol, with ammonia neutralization, then through aging, add auxiliary agent after washing impurity, and then (the unexposed processing method of this article) after treatment, moulding, dry, in 850 ℃ of roastings, make this catalyst.In above-mentioned two kinds of methods, sintering temperature used all just can make the activity and selectivity of catalyst reach best at 700 ℃ above, and sintering temperature is during lower than 700 ℃, the side reactions such as the isobutene polymerisation of gained catalyst or methanol dehydration are active to be increased, thereby affect the selective of catalyst, the deposition due to polymer in accessory substance also can affect the service life of catalyst simultaneously.
At present, for the research work that reduces MTBE cracking accessory substance dimethyl ether, still continuing, but in product, still having at least 0.3% dimethyl ether existence.
Summary of the invention
For weak point of the prior art, the invention provides a kind of preparation method of cracking isobutene by methyl-tert-butyl ether catalyst.This catalyst, keeping good MTBE conversion ratio and higher isobutene and methyl alcohol optionally simultaneously, can significantly reduce the generation of accessory substance dimethyl ether.
The preparation method of cracking isobutene by methyl-tert-butyl ether catalyst of the present invention, comprising:
(1) alumine hydroxide colloid is mixed with Silicalite-1 Crystallization of Zeolite liquid, after moulding, drying and roasting;
(2) material of step (1) gained, through hydrothermal treatment consists, obtains catalyst of the present invention;
In the inventive method step (1), the butt mass ratio of alumine hydroxide colloid and Silicalite-1 Crystallization of Zeolite liquid is 1:10 ~ 1:40, is preferably 1:15 ~ 1:25.
In the inventive method, the described mixing of step (1) adopts mechanical mixing, and moulding can adopt the forming methods such as compressing tablet, extrusion, spin.The described drying condition of step (1) is as follows: at 90 ~ 120 ℃ of dry 2 ~ 5h, roasting condition is as follows: at 450 ~ 600 ℃ of roasting 3 ~ 6h.
In the inventive method, step (2) is that the material that step (1) is obtained is processed with saturated vapor, and temperature is 100 ~ 600 ℃, and the time is 1 ~ 10h, and optimum condition is that temperature is 100 ~ 300 ℃, and the time is 4 ~ 8h.After hydrothermal treatment consists step (2) Suo Shu, can pass through drying steps, also can be without drying steps.Described drying condition is as follows: at 90 ~ 120 ℃ of dry 2 ~ 6h.
In catalyst of the present invention, described alumine hydroxide colloid can be prepared by conventional method, such as in Alchlor process, aluminum nitrate method, aluminum sulfate-sodium metaaluminate method, sodium metaaluminate-carbon dioxide process, one or more make.Character through 3 ~ 6 hours gained aluminium oxide of 350 ~ 650 ℃ of roastings is as follows: specific area is 200 ~ 500m
2/ g, pore volume is 0.40 ~ 0.75mL/g.
The character of Silicalite-1 molecular sieve of the present invention is as follows: specific area is 300 ~ 400m
2/ g, pore volume is 0.15 ~ 0.20mL/g.
In the inventive method, the Silicalite-1 molecular sieve that step (1) adopts is not containing the silica zeolite with MFI pore passage structure of aluminium, has special ten-ring pore passage structure, good heat endurance, chemical stability and hydrophobicity.This Crystallization of Zeolite liquid can take hydro-thermal method synthetic, specific as follows; The TPAOH solution that is 20wt% ~ 40wt% by concentration at normal temperatures joins in ethyl orthosilicate, or the Ludox that is 20wt% ~ 30wt% by silica concentration mixes with 4-propyl bromide, NaOH; Above-mentioned mixed serum stirs 2 ~ 4h under 70 ~ 90 ℃ of conditions, and then crystallization 36 ~ 96h under 140 ~ 160 ℃ of self-generated pressures, obtains Silicalite-1 Crystallization of Zeolite liquid.
In catalyst of the present invention, can also contain amorphous aluminum silicide, the weight content in catalyst is 5% ~ 95%.In described amorphous aluminum silicide, SiO
2content is 60wt% ~ 99wt%, preferably 80wt% ~ 95wt%, preferably 87wt% ~ 93wt%; Al
2o
3content is 1wt% ~ 40wt%, preferably 5wt% ~ 20wt%, preferably 7 wt% ~ 13wt%.The character of amorphous aluminum silicide of the present invention is as follows: specific area is 240 ~ 450m
2/ g, pore volume is 0.4 ~ 0.9mL/g; Be preferably: specific area is 270 ~ 410m
2/ g, pore volume is 0.5 ~ 0.7mL/g.In the inventive method, amorphous aluminum silicide is introduced the method in catalyst, can in step (1), add amorphous aluminum silicide and other mixing of materials, wherein amorphous aluminum silicide can adopt method preparation conventional in prior art, as coprecipitation, step-by-step precipitation method and mechanical mixing.Generally, prepare the sintering temperature of amorphous aluminum silicide lower than 700 ℃, preferably at 200 ~ 600 ℃.It is raw material that the present invention's amorphous aluminum silicide used also can adopt silica-alumina gel, carries out roasting 3 ~ 8 hours and obtain at 200 ~ 600 ℃ of temperature.
In catalyst of the present invention, can also contain active metal component, this active metal is selected from one or more in IIA family and group VIII metal, and the weight content of active metal in catalyst is 0.3wt% ~ 2.0wt%.In the present invention, described IIA family metal is selected from one or more in Be, Mg, Ca.Described group VIII metal is selected from one or more in Ni, Pd, Pt.In the inventive method, the mode in active metal component introducing catalyst can adopt one or more in infusion process, mixing method.Described infusion process can adopt saturated infusion process, sprays method, supersaturation infusion process etc., detailed process is as follows: the material that step (2) can be obtained immerses the aqueous solution containing solubility active metal salt, then drying and roasting, make catalyst of the present invention, the material that also step (1) can be obtained immerses the aqueous solution containing solubility active metal salt, then drying and roasting, then carry out step (2), make catalyst of the present invention; Wherein soluble metallic salt can be nitrate or chloride; Wherein, described drying condition is as follows: at 90 ~ 120 ℃ of dry 2 ~ 6h; Roasting condition is as follows: at 200 ~ 600 ℃ of roasting 3 ~ 8h.Described mixing method is to join in step (1) and mix with alumine hydroxide colloid, Silicalite-1 Crystallization of Zeolite liquid in the mode of solid or solution containing the compound of active metal component, then completing steps (1) and step (2).
In catalyst of the present invention, introduced Silicalite-1 molecular sieve component, and aluminium oxide and the molecular sieve molded thing of Silicalite-1 are through hydrothermal treatment consists, so not only improved the pore structure of catalyst, the diffusion of more suitable MTBE and pyrolysis product, also improved the polarity of catalyst surface, especially the polarity on Silicalite-1 molecular sieve surface, makes catalyst surface hydrophobic lipophile stronger, absorption affinity to water obviously weakens, and makes the absorption of reactant and the desorption of product easier simultaneously.Therefore, catalyst of the present invention is for MTBE cracking isobutene process, not only improved the selective of the lytic activity of MTBE and product isobutene, and reduced the growing amount of accessory substance dimethyl ether.
The specific embodiment
In the present invention, material purity and product form in the above-mentioned catalyst of employing gc analysis, described specific area adopts low temperature liquid nitrogen determination of adsorption method according to ASTM D3663-2003 standard, and pore volume adopts low temperature liquid nitrogen determination of adsorption method according to ASTM D4222-2003 standard.In the present invention, wt% is mass fraction.
The character of aluminium hydroxide AH1 roasting 4h gained aluminium oxide at 450 ℃ that the embodiment of the present invention adopts is as follows: specific area is 488m
2/ g, pore volume is 0.65mL/g.
The character of aluminium hydroxide AH2 roasting 4h gained aluminium oxide at 450 ℃ that the embodiment of the present invention adopts is as follows: specific area is 253m
2/ g, pore volume is 0.45mL/g.
Employing silica-alumina gel is raw material, and at 450 ℃, roasting 4h obtains amorphous aluminum silicide (SA), wherein SiO
2content is 92.0 wt%, Al
2o
3content is 8.0 wt%, and specific area is 277m
2/ g, pore volume is 0.59mL/g.
The TPAOH solution that is 30wt% by concentration at normal temperatures joins in ethyl orthosilicate, mixed serum stirs 3h at 80 ℃ respectively, then at 150 ℃, crystallization 48h takes out, obtain Silicalite-1 Crystallization of Zeolite liquid (Si-1-A), as follows through the character of 550 ℃ of roasting 4h gained Silicalite-1 molecular sieves: specific area is 333m
2/ g, pore volume is 0.17mL/g.
Embodiment 1
Aluminium hydroxide AH1 is mixed with the butt weight ratio of 1:10 with Silicalite-1 Crystallization of Zeolite liquid Si-1-A, and roller forming, 110 ℃ of dry 3h, 500 ℃ of roasting 4h, obtain H-1.H-1 saturated vapor at 200 ℃ is processed to 5h, and 110 ℃ of dry 3h, obtain catalyst C-1, and its physico-chemical property is in Table 1.
Embodiment 2
Aluminium hydroxide AH1 is mixed with the butt weight ratio of 1:25 respectively with Silicalite-1 Crystallization of Zeolite liquid Si-1-A, and roller forming, 110 ℃ of dry 3h, 500 ℃ of roasting 4h, obtain H-2.H-2 saturated vapor at 200 ℃ is processed to 5h, and 110 ℃ of dry 3h, obtain catalyst C-2, and its physico-chemical property is in Table 1.
Embodiment 3
Aluminium hydroxide AH2 is mixed with the butt weight ratio of 1:20 with Silicalite-1 Crystallization of Zeolite liquid Si-1-A, and roller forming, 110 ℃ of dry 3h, 500 ℃ of roasting 4h, obtain H-3.H-3 saturated vapor at 200 ℃ is processed to 5h, and 110 ℃ of dry 3h, obtain catalyst C-3, and its physico-chemical property is in Table 1.
Embodiment 4
Aluminium hydroxide AH2 is mixed with the butt weight ratio of 1:40 with Silicalite-1 Crystallization of Zeolite liquid Si-1-A, and roller forming, 110 ℃ of dry 3h, 500 ℃ of roasting 4h, obtain H-4.H-4 saturated vapor at 200 ℃ is processed to 5h, and 110 ℃ of dry 3h, obtain catalyst C-4, and its physico-chemical property is in Table 1.
Embodiment 5
C-1 adopts saturated infusion process carried metal active metal component, then, at 110 ℃ of dry 3h, obtains catalyst C-5, and its physico-chemical property and active metallic content are in Table 1.
Embodiment 6
C-2 adopts saturated infusion process carried metal active metal component, then, at 110 ℃ of dry 3h, obtains catalyst C-6, and its physico-chemical property and active metallic content are in Table 1.
Embodiment 7
By aluminium hydroxide AH1, Silicalite-1 Crystallization of Zeolite liquid Si-1-A, containing the compound of active metal component, wherein the butt weight ratio of aluminium oxide AH1 and Silicalite-1 molecular sieve Si-1-A crystallization liquid is 1:20, and roller forming, 110 ℃ of dry 3h, 500 ℃ of roasting 4h, obtain H-5.H-5 saturated vapor at 300 ℃ is processed to 4h, and 110 ℃ of dry 3h, obtain catalyst C-7, and its physico-chemical property and active metallic content are in Table 1.
Embodiment 8
Aluminium hydroxide AH1, amorphous aluminum silicide SA are mixed with 1:20:5 butt weight ratio with Silicalite-1 Crystallization of Zeolite liquid Si-1-A, and roller forming, 110 ℃ of dry 3h, 500 ℃ of roasting 4h, obtain H-6.H-6 saturated vapor at 200 ℃ is processed to 5h, and 110 ℃ of dry 3h, obtain catalyst C-8, and its physico-chemical property and active metallic content are in Table 1.
Comparative example 1
For comparing, by SA roller forming, 110 ℃ of dry 3h, 500 ℃ of roasting 4h, then at 200 ℃, saturated vapor is processed 5h, then adopts saturated infusion process supported active metal and at 110 ℃ of dry 3h, obtains catalyst C-0.The physico-chemical property of C-0 and active metallic content are in Table 1.
The character of table 1 embodiment prepared catalyst
| Catalyst numbering | C-0 | C-1 | C-2 | C-3 | C-4 |
| Ni,wt% | 1.2 | - | - | - | - |
| Pd,wt% | - | - | - | - | - |
| Pt,wt% | - | - | - | - | - |
| Mg,wt% | 0.5 | - | - | - | - |
| Be,wt% | - | - | - | - | - |
| Ca,wt% | - | - | - | - | - |
| Specific area, m 2/g | 260 | 347 | 336 | 325 | 328 |
| Pore volume, mL/g | 0.65 | 0.26 | 0.24 | 0.23 | 0.22 |
Table 1 is continuous
| Catalyst numbering | C-5 | C-6 | C-7 | C-8 |
| Ni,wt% | 1.2 | - | - | - |
| Pd,wt% | - | 0.2 | - | - |
| Pt,wt% | - | - | 0.25 | - |
| Mg,wt% | 0.5 | - | - | - |
| Be,wt% | - | - | - | - |
| Ca,wt% | - | 0.5 | - | - |
| Specific area, m 2/g | 340 | 330 | 343 | 324 |
| Pore volume, mL/g | 0.25 | 0.23 | 0.22 | 0.36 |
Embodiment 9
Catalyst C-1, C-3, C-5, C-7, C-8 are investigated in micro-test of carrying out MTBE cracking isobutene on anti-.Reaction condition is as follows: during MTBE liquid, volume space velocity is 2.5 h
-1, during the liquid of water, volume space velocity is 0.5 h
-1, temperature is 225 ℃, pressure is 0.2MPa.Result of the test is as shown in table 2.
Comparative example 2
Under the process conditions identical with embodiment 2, investigated the MTBE cracking performance of comparative catalyst C-0, result is as shown in table 2.
Comparative example 3
Under the process conditions identical with embodiment 2, investigated the MTBE cracking performance of comparative catalyst H-1, result is as shown in table 2.
Comparative example 4
By aluminium hydroxide AH1 and ZSM-5 molecular sieve crystallization liquid Si-1-A (SiO
2: Al
2o
3mol ratio is 95:5) with the butt weight ratio of 1:10, mix, and roller forming, 110 ℃ of dry 3h, 500 ℃ of roasting 4h, obtain H-0.H-0 saturated vapor at 200 ℃ is processed to 5h, and 110 ℃ of dry 3h, obtain catalyst C-00.
Under the process conditions identical with embodiment 2, investigated the MTBE cracking performance of comparative catalyst C-00, result is as shown in table 2.
The MTBE cracking isobutene result of the test of table 2 catalyst
| Catalyst | MTBE conversion ratio, wt% | Selective isobutene, wt% | Dimethyl ether content in product, wt% |
| H-1 | 91.9 | 99.9 | 2.86 |
| C-1 | 99.9 | 99.9 | 0.26 |
| C-3 | 99.9 | 99.9 | 0.24 |
| C-5 | 99.9 | 99.9 | 0.19 |
| C-7 | 99.9 | 99.9 | 0.20 |
| C-8 | 99.9 | 99.9 | 0.17 |
| C-0 | 99.6 | 99.8 | 0.36 |
| C-00 | 76.9 | 92.8 | 0.76 |
As can be seen from Table 2, employing is MTBE cracking isobutene prepared by carrier at amorphous aluminum silicide, the catalyst that is relatively carrier at amorphous aluminum silicide and Silicalite-1 molecular sieve, MTBE conversion ratio, selective isobutene and methyl alcohol are selectively all slightly poor, its by-product dimethyl ether particularly, the catalyst of preparing far above the inventive method, illustrates the interpolation of Silicalite-1 molecular sieve, not only having improved the activity and selectivity of catalyst, is fairly obvious to reducing the effect of by-product dimethyl ether.Find simultaneously, add the control for accessory substance after activating agent to there is positive effect, can make the content of dimethyl ether further reduce.
Claims (12)
1. a preparation method for cracking isobutene by methyl-tert-butyl ether catalyst, comprising:
(1) alumine hydroxide colloid is mixed with Silicalite-1 Crystallization of Zeolite liquid, after moulding, drying and roasting; Wherein, the butt mass ratio of alumine hydroxide colloid and Silicalite-1 Crystallization of Zeolite liquid is 1:10～1:40; Described alumine hydroxide colloid is as follows through the character of 3～6 hours gained aluminium oxide of 350～650 ℃ of roastings: specific area is 200～500m
2/ g, pore volume is 0.40～0.75mL/g; The character of described Silicalite-1 molecular sieve is as follows: specific area is 300～400m
2/ g, pore volume is 0.15～0.20mL/g; Described drying condition is as follows: at 90～120 ℃ of dry 2～5h, roasting condition is as follows: at 450～600 ℃ of roasting 3～6h;
(2) material of step (1) gained, through hydrothermal treatment consists, obtains catalyst, and wherein hydrothermal treatment consists condition is as follows: with saturated vapor, process, temperature is 100～600 ℃, and the time is 1～10h.
2. in accordance with the method for claim 1, it is characterized in that in step (1), the butt mass ratio of alumine hydroxide colloid and Silicalite-1 Crystallization of Zeolite liquid is 1:15～1:25.
3. in accordance with the method for claim 1, it is characterized in that one or more make described alumine hydroxide colloid in Alchlor process, aluminum nitrate method, aluminum sulfate-sodium metaaluminate method, sodium metaaluminate-carbon dioxide process.
4. in accordance with the method for claim 1, it is characterized in that Silicalite-1 Crystallization of Zeolite liquid that step (1) adopts takes hydro-thermal method synthetic, specific as follows: the TPAOH solution that is 20wt%～40wt% by concentration at normal temperatures joins in ethyl orthosilicate, or the Ludox that is 20wt%～30wt% by silica concentration mixes with 4-propyl bromide, NaOH; Above-mentioned mixed serum stirs 2～4h under 70～90 ℃ of conditions, and then crystallization 36～96h under 140～160 ℃ of self-generated pressures, obtains Silicalite-1 Crystallization of Zeolite liquid.
5. in accordance with the method for claim 1, it is characterized in that step (2) is that the material that step (1) is obtained is processed with saturated vapor, temperature is 100～300 ℃, and the time is 4～8h.
6. in accordance with the method for claim 1, it is characterized in that after hydrothermal treatment consists step (2) Suo Shu, through drying steps; Described drying condition is as follows: at 90～120 ℃ of dry 2～6h.
7. in accordance with the method for claim 1, it is characterized in that containing amorphous aluminum silicide in described catalyst, in described amorphous aluminum silicide, SiO
2content is 60wt%～99wt%, Al
2o
3content is 1wt%～40wt%.
8. in accordance with the method for claim 7, it is characterized in that in described amorphous aluminum silicide SiO
2content is 80wt%～95wt%, Al
2o
3content is 5wt%～20wt%.
9. in accordance with the method for claim 7, it is characterized in that the character of described amorphous aluminum silicide is as follows: specific area is 240～450m
2/ g, pore volume is 0.4～0.9mL/g.
10. in accordance with the method for claim 7, it is characterized in that the method in described amorphous aluminum silicide introducing catalyst, in step (1), add and other mixing of materials.
11. in accordance with the method for claim 1, it is characterized in that containing active component in described catalyst, this active metal is selected from one or more in IIA family and group VIII metal, and the weight content of active metal in catalyst is 0.3wt%～2.0wt%; Compound containing active metal component adds in step (1) or step (2).
12. in accordance with the method for claim 11, it is characterized in that described IIA family metal is selected from one or more in Be, Mg, Ca; Described group VIII metal is selected from one or more in Ni, Pd, Pt.
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| CN1665911A (en) * | 2002-05-23 | 2005-09-07 | 托塔尔石油化学产品研究弗吕公司 | Production of olefins |
| CN1853772A (en) * | 2005-04-27 | 2006-11-01 | 中国石油化工股份有限公司 | Catalyst in preparation of isobutene by methyl tertbutyl ether pyrolysis |
| CN1871191A (en) * | 2003-08-19 | 2006-11-29 | 托塔尔石油化学产品研究弗吕公司 | Production of olefins |
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| CN1665911A (en) * | 2002-05-23 | 2005-09-07 | 托塔尔石油化学产品研究弗吕公司 | Production of olefins |
| CN1871191A (en) * | 2003-08-19 | 2006-11-29 | 托塔尔石油化学产品研究弗吕公司 | Production of olefins |
| CN1853772A (en) * | 2005-04-27 | 2006-11-01 | 中国石油化工股份有限公司 | Catalyst in preparation of isobutene by methyl tertbutyl ether pyrolysis |
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