CN103071518B - Catalyst used in production of isobutene through cracking of methyl tert-butyl ether and preparation method thereof - Google Patents
Catalyst used in production of isobutene through cracking of methyl tert-butyl ether and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a catalyst used in production of isobutene through cracking of methyl tert-butyl ether (MTBE) and a preparation method thereof. The catalyst comprises amorphous silica-alumina and a Silicalite-1 molecular sieve; amorphous silica-alumina and the Silicalite-1 molecular sieve 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, and high-purity isobutylene is widely used in producing the product such as butyl rubber, polyisobutene.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, and product isobutene is during for the production of butyl rubber, 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.
Consider from aspects such as catalyst activity, stability, Possibility of Regeneration and costs, 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 eliminating 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 ℃, process 1 ~ 6h with saturated vapor 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 accessory substance dimethyl ether simultaneously generating is 0.3%.
One piece of exercise question that " Speciality Petrochemicals " the 4th phase in 1997 1st ~ 4 pages of Liu Fu victory wait to deliver is in " progress of MTBE cracking isobutene catalyst ", from " silicon oxide series catalyst system and catalyzing " joint, in the time 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 said method, sintering temperature used all just can make the activity and selectivity of catalyst reach best more than 700 ℃, and sintering temperature is during lower than 700 ℃, active the increasing of the side reaction such as isobutene polymerisation or methanol dehydration of gained catalyst, thereby affect the selective of catalyst, also can affect the service life of catalyst simultaneously due to the deposition of polymer in accessory substance.
CN1853772A discloses a kind of modified silicon Al catalysts for cracking isobutene by methyl-tert-butyl ether and preparation method thereof.This catalyst is processed amorphous aluminum silicide with saturated vapor and is obtained, owing to adopting separately amorphous aluminum silicide specific area less, and in weak acid, L acid amount is relatively high, not only affected the reactivity of catalyst and optionally improved, and the content of MTBE cracking accessory substance dimethyl ether is still higher.
Summary of the invention
For weak point of the prior art, the invention provides a kind of cracking isobutene by methyl-tert-butyl ether Catalysts and its preparation method.This catalyst, for cracking isobutene by methyl-tert-butyl ether process, keeping good methyl tertiary butyl ether(MTBE) conversion ratio and higher isobutene and optionally while of methyl alcohol, can significantly reduce the generation of accessory substance dimethyl ether.
The invention provides a kind of cracking isobutene by methyl-tert-butyl ether catalyst, described catalyst comprises amorphous aluminum silicide and Silicalite-1 molecular sieve, in catalyst, the infrared total acid content of weak acid is 0.020 ~ 0.080 mmol/g, and B acid/L acid of weak acid is 2.5 ~ 4.0.
The infrared total acid content that the infrared total acid content that the infrared total acid content of weak acid of the present invention records while referring to 160 ℃ records while deducting 250 ℃, the ratio of the difference that the L acid that the L acid amount that the difference of the B acid amount that B that the B acid/L acid in weak acid records while referring to 160 ℃ acid amount records during with 250 ℃ records during with 160 ℃ records during with 250 ℃ is measured.Described infrared total acid content, B acid and L acid are to adopt infrared spectroscopic determination, take pyridine as probe molecule.Infrared total acid content described in the present invention and B acid/L acid (mol ratio) are the acid amount in weak acid.
In above-mentioned catalyst, the mass ratio of described amorphous aluminum silicide and Silicalite-1 is 9.5:1 ~ 1:1, is preferably 9:1 ~ 4:1.
In above-mentioned catalyst, in described amorphous aluminum silicide, SiO
2content be 60 wt% ~ 99wt%, be preferably 80 wt% ~ 95wt%, most preferably 87 wt% ~ 93wt%; Al
2o
3content be 1wt% ~ 40wt%, be preferably 5 wt% ~ 20wt%, most preferably 7 wt% ~ 13wt%.
Above-mentioned catalyst, described Silicalite-1 molecular sieve is the silica zeolite with MFI structure that does not contain aluminium, has special ten-ring pore passage structure, good heat endurance, chemical stability and hydrophobicity.
In above-mentioned catalyst, described catalyst also comprises active metal component, and described active metal component is selected from least one in IIA family and group VIII metal.Take metallic element, the content in catalyst is 0.3wt% ~ 2.0wt% to described active metal component.Described IIA family metal is selected from least one in Be, Mg, Ca; Described group VIII metal is selected from least one in Ni, Pd, Pt.
In above-mentioned catalyst, the specific area of described catalyst is 240 ~ 400 m
2/ g, pore volume is 0.3 ~ 0.8 mL/g.
In above-mentioned catalyst, 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.Raw purity of the present invention and product composition adopt gc analysis.
The present invention also provides a kind of method of preparing above-mentioned catalyst, comprising:
A, amorphous aluminum silicide and Silicalite-1 molecular sieve are mixed, after moulding, dry and roasting;
The material of b, step a gained, through hydrothermal treatment consists, obtains catalyst.
In said method, in step a, described 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, roasting 3 ~ 8h at 200 ~ 600 ℃ and obtaining.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; Be preferably: specific area is 270 ~ 410m
2/ g, pore volume is 0.5 ~ 0.7mL/g.
In said method, in step a, described Silicalite-1 molecular sieve can take hydro-thermal method synthetic, specific as follows: the TPAOH solution that is 20 ~ 40wt% by concentration at normal temperatures joins in ethyl orthosilicate, or be that the Ludox of 20 ~ 30wt % mixes with 4-propyl bromide, NaOH by silica concentration; Above-mentioned mixed serum stirs 2 ~ 4h under 70 ~ 90 ℃ of conditions, and then crystallization 36 ~ 96h under 140 ~ 160 ℃ of self-generated pressures, through cooling, separation, washing, through 90 ~ 120 ℃ of dry 2 ~ 6h, at 450 ~ 600 ℃ of roasting 2 ~ 6h, obtains Silicalite-1 molecular sieve.The specific area of described Silicalite-1 molecular sieve is 300 ~ 400m
2/ g, pore volume is 0.15 ~ 0.20mL/g.Described Silicalite-1 molecular sieve is the silica zeolite with MFI structure that does not contain aluminium.
In said method, the mixing described in step a adopts mechanical mixing, and moulding can adopt the forming methods such as compressing tablet, extrusion, spin.In step a, be dried 2 ~ 5h at 90 ~ 120 ℃, at 450 ~ 600 ℃ of roasting 3 ~ 6h.
In said method, in step b, use saturated vapor processing, temperature is 100 ~ 600 ℃, and the time is 1 ~ 10h, and preferably temperature is 100 ~ 300 ℃, and the time is 4 ~ 8h.After hydrothermal treatment consists, preferred drying step, obtains catalyst of the present invention.Wherein said drying condition is as follows: at 90 ~ 120 ℃ of dry 2.0 ~ 6.0h.
In said method, the compound containing active metal component is added in a step or b step.By will comprising one or more in infusion process, mixing method containing the mode in catalyst of adding of the compound of active metal component.Described infusion process can adopt saturated infusion process, sprays method, supersaturation infusion process etc.Described active metal component is selected from least one in IIA family and group VIII metal.Described IIA family metal is selected from least one in Be, Mg, Ca; Described group VIII metal is selected from least one in Ni, Pd, Pt.In a step, add fashionablely, can adopt mixing method, as the compound containing active metal component is joined in step a in the mode of solid or solution, mixes with amorphous aluminum silicide and Silicalite-1 molecular sieve, then moulding, be dried and roasting; Also can adopt infusion process, as the material that in a step, moulding obtains immerses containing in the aqueous solution of solubility active metal salt, and then dry, roasting.Described solubility active metal salt can be nitrate or halide.In b step, add fashionablely, can adopt infusion process, as the material after hydrothermal treatment consists immerses containing in the aqueous solution of solubility active metal salt, then at 90 ~ 120 ℃ of dry 2 ~ 6h, at 200 ~ 600 ℃ of roasting 3 ~ 8h, Kaolinite Preparation of Catalyst.
The present invention also provides a kind of method of cracking isobutene by methyl-tert-butyl ether, and methyl tertiary butyl ether(MTBE) carries out cracking reaction and makes isobutene under the existence of above-mentioned catalyst.
In said method, described reaction condition is that when methyl tertiary butyl ether(MTBE) liquid, volume space velocity is 0.7 ~ 6.0h
-1, when the liquid of water, volume space velocity is 0 ~ 1.0 h
-1, temperature is 180 ~ 360 ℃, pressure is that normal pressure is to 1.0MPa.Preferably, volume space velocity is 2.0 ~ 4.0 h when described methyl tertiary butyl ether(MTBE) liquid
-1, when the liquid of water, volume space velocity is 0.1 ~ 0.5h
-1, temperature is 210 ~ 270 ℃, pressure is normal pressure to 0.6 MPa.
Catalyst of the present invention can be used for MTBE cracking isobutene process.This catalyst has shown good catalytic performance, methyl alcohol and isobutene selectively good, and MTBE conversion ratio is high, and the generation of inhibitory reaction accessory substance dimethyl ether preferably of this catalyst.
In the present invention, the Silicalite-1 molecular sieve of employing is the silica zeolite that does not contain aluminium, has MFI structure, there is no acidity, has good heat endurance, chemical stability and hydrophobicity.And Si-Al molecular sieve as in Y zeolite, beta-molecular sieve, ZSM-5 molecular sieve owing to there being the existence of aluminium, not only can affect the Acidity of catalyst, also can improve the hydrophily of catalyst, these are unfavorable to MTBE cracking reaction.
In catalyst of the present invention, employing is not compound containing Silicalite-1 molecular sieve and the amorphous aluminum silicide of aluminium, acid strength and the acid that can improve catalyst distribute, and due to the coordinative role of Silicalite-1 molecular sieve and amorphous aluminum silicide, be conducive to the Acidity that hydrothermal treatment consists further regulates catalyst, make the B acid site in catalyst weak acid more, and L acid site is less, the ratio that is B acid/L acid in weak acid is high, improve on the other hand the pore structure of catalyst, the diffusion of more suitable MTBE and pyrolysis product.In addition, also improved the polarity of catalyst surface by the hydrothermal treatment consists in method provided by the invention, especially the polarity on Silicalite-1 molecular sieve surface, make catalyst surface hydrophobic lipophile stronger, absorption affinity to water obviously weakens, and makes the absorption of reactant and the desorption of product easier simultaneously.In catalyst, introduce after active metal component, be conducive to further improve weak acid total amount and B acid/L acid ratio of catalyst, thereby improve the character of catalyst, reduce the growing amount of accessory substance dimethyl ether.
For cracking isobutene by methyl-tert-butyl ether, show good catalytic performance by catalyst provided by the invention, 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
Below in conjunction with embodiment, the present invention is further described, but does not form any limitation of the invention.
The concrete assay method of the infrared total acid of the present invention, B acid and L acid publishes in July, 2000 according to publishing house of Northeastern University that the infrared acidity assay method of 90-92 page in " catalyst analysis " book measures, specific as follows:
1. the preparation of sample: get 20 milligrams, levigate rear sample (granularity is less than 200 orders), being pressed into diameter is that 20 millimeters of thin slices are placed in cell for infrared absorption, quartz spring lower end hang cup in add 200 milligrams of samples, system pump down to 1 × 10
-2pa, is heated to 500 ℃ of constant temperature 1 hour, purifies sample, removes the adsorbate and the water etc. that cover on specimen surface;
2. drop to room temperature in the above-mentioned condition of finding time, Adsorption of Pyridine 5 minutes, is then warmed up to 160 ℃, balance 1 hour, the pyridine of desorption physical absorption, utilizes pyridine weight adsorption to try to achieve total acid content, record the infrared spectrogram of gained under above-mentioned condition, wherein bands of a spectrum 1545cm corresponding to B acid
-1, bands of a spectrum 1455cm corresponding to L acid
-1, thus, total acid content, B acid amount and L acid amount while obtaining 160 ℃;
3. continue to be warming up to 250 ℃, balance 1 hour, the pyridine of desorption physical absorption, record the infrared spectrogram of gained under above-mentioned condition, utilize pyridine weight adsorption to try to achieve total acid content, record the infrared spectrogram of gained under above-mentioned condition, wherein bands of a spectrum 1545cm corresponding to B acid
-1, bands of a spectrum 1455cm corresponding to L acid
-1, thus, total acid content, B acid amount and L acid amount while obtaining 250 ℃.
embodiment 1
the preparation of catalyst
Heavy content with silicon and aluminium compares with SiO
2and Al
2o
3the silica-alumina gel of counting 92.0:8.0 is raw material, and at 450 ℃, roasting 4h obtains amorphous aluminum silicide SA, and the specific area of SA is 277m
2/ g, pore volume is 0.59mL/g, SiO
2content is 92.0 wt%, Al
2o
3content is 8.0 wt%.
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, and obtains silica zeolite Silicalite-1 at 550 ℃ of roasting 4h, and its character is as follows: specific area is 333m
2/ g, pore volume is 0.17mL/g.
Amorphous aluminum silicide SA is mixed with 9:1 weight ratio with Silicalite-1 molecular sieve, and roller forming, 110 ℃ of dry 3h, 500 ℃ of roasting 4h, then material saturated vapor at 200 ℃ is processed 5h, and 110 ℃ of dry 3h, obtain catalyst C-1.Catalyst characterization data are in table 1.
cracking isobutene by methyl-tert-butyl ether
On microreactor, carry out cracking reaction research.Reaction condition is as follows, and when methyl tertiary butyl ether(MTBE) (MTBE) liquid, volume space velocity is 2.5 h
-1, when 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.
embodiment 2
With embodiment 1, difference is, amorphous aluminum silicide SA mixes with 4:1 weight ratio with Silicalite-1 molecular sieve, obtains catalyst C-2, and data are in table 1.The result data of cracking reaction is in table 2.
embodiment 3
With embodiment 1, difference is, amorphous aluminum silicide SB mixes with 1:1 weight ratio with Silicalite-1 molecular sieve, the SiO in amorphous aluminum silicide SB
2content is 83.0 wt%, Al
2o
3content is 17.0 wt%, and specific area is 320m
2/ g, pore volume is 0.61mL/g.Obtain catalyst C-3, data are in table 1.The result data of cracking reaction is in table 2.
embodiment 4
with embodiment 3, difference is, amorphous aluminum silicide SB mixes with 5:1 weight ratio with Silicalite-1 molecular sieve, saturated vapor treatment conditions: at 300 ℃, saturated vapor is processed 4h, obtains catalyst C-4, and data are in table 1.The result data of cracking reaction is in table 2.
embodiment 5
With embodiment 1, difference is to adopt saturated infusion process, and steam treatment dry material are immersed in the aqueous solution of nickel chloride and magnesium chloride, then, at 110 ℃ of dry 3h, obtains catalyst C-5, and data are in table 1.The result data of cracking reaction is in table 2.
embodiment 6
With embodiment 2, difference is to adopt saturated infusion process, and steam treatment dry material are immersed in the aqueous solution of solution palladium nitrate and calcium chloride, then, at 110 ℃ of dry 3h, obtains catalyst C-6, tables of data 1.The result data of cracking reaction is in table 2.
embodiment 7
With embodiment 2, difference is amorphous aluminum silicide SA, Silicalite-1 molecular sieve to mix with beryllium oxide, and wherein the consumption of beryllium oxide is counted 1.8wt% with beryllium.Obtain catalyst C-7, data are in table 1.The result data of cracking reaction is in table 2.
comparative example 1
With embodiment 1, difference is not pass through saturated steam processing, obtains catalyst H-1, and data are in table 1.The result data of cracking reaction is in table 2.
comparative example 2
With embodiment 5, difference is, in catalyst without Silicalite-1-A molecular sieve.The catalyst H-2 obtaining, data are in table 1.The result data of cracking reaction is in table 2.
Table 1 catalyst
| ? | Catalyst numbering | The weight ratio of amorphous aluminum silicide and molecular sieve | Total acid content, mmol/g | B acid/L acid |
| Embodiment 1 | C-1 | 9:1 | 0.058 | 3.14 |
| Embodiment 2 | C-2 | 4:1 | 0.055 | 2.76 |
| Embodiment 3 | C-3 | 1:1 | 0.049 | 2.75 |
| Embodiment 4 | C-4 | 5:1 | 0.054 | 2.85 |
| Embodiment 5 | C-5 | 9:1 | 0.061 | 3.15 |
| Embodiment 6 | C-6 | 4:1 | 0.058 | 2.78 |
| Embodiment 7 | C-7 | 4:1 | 0.057 | 3.16 |
| Comparative example 1 | H-1 | 9:1 | 0.091 | 0.28 |
| Comparative example 2 | H-2 | - | 0.071 | 2.16 |
Table 1 is continuous
| ? | Catalyst numbering | Specific area, m 2/g | Pore volume, mL/g | Active metal, in metallic element, wt% |
| Embodiment 1 | C-1 | 280 | 0.56 | 0 |
| Embodiment 2 | C-2 | 292 | 0.53 | 0 |
| Embodiment 3 | C-3 | 313 | 0.54 | 0 |
| Embodiment 4 | C-4 | 315 | 0.58 | 0 |
| Embodiment 5 | C-5 | 265 | 0.53 | Ni 1.2,Mg 0.5 |
| Embodiment 6 | C-6 | 290 | 0.55 | Pd 0.2, Ca 0.5 |
| Embodiment 7 | C-7 | 272 | 0.50 | Be 1.8 |
| Comparative example 1 | H-1 | 289 | 0.54 | 0 |
| Comparative example 2 | H-2 | 260 | 0.65 | Ni 1.2,Mg 0.5 |
Comparative example 3
By amorphous aluminum silicide SA and ZSM-5 molecular sieve (SiO
2: Al
2o
3mol ratio is 95:5) mix with 9:1 weight ratio, and roller forming, 110 ℃ of dry 3h, 500 ℃ of roasting 4h, obtain catalyst H-3.The result data of cracking reaction is in table 2.
Comparative example 4
The catalyst H-3 of comparative example 3 gained saturated vapor at 200 ℃ is processed to 5h, and 110 ℃ of dry 3h, obtain catalyst H-4.The result data of cracking reaction is in table 2.
The data of table 2 cracking isobutene by methyl-tert-butyl ether
| ? | Catalyst | Methyl tertiary butyl ether(MTBE) conversion ratio, wt% | Selective isobutene, wt% | The content of dimethyl ether in product, wt% |
| Embodiment 1 | C-1 | 99.9 | 99.9 | 0.27 |
| Embodiment 2 | C-2 | 99.9 | 99.9 | 0.27 |
| Embodiment 3 | C-3 | 99.9 | 99.9 | 0.29 |
| Embodiment 4 | C-4 | 99.9 | 99.9 | 0.24 |
| Embodiment 5 | C-5 | 99.9 | 99.9 | 0.20 |
| Embodiment 6 | C-6 | 99.9 | 99.9 | 0.19 |
| Embodiment 7 | C-7 | 99.9 | 99.9 | 0.21 |
| Comparative example 1 | H-1 | 87.2 | 99.9 | 0.40 |
| Comparative example 2 | H-2 | 99.6 | 99.8 | 0.39 |
| Comparative example 3 | H-3 | 80.2 | 96.5 | 0.44 |
| Comparative example 4 | H-4 | 85.1 | 97.8 | 0.41 |
As can be seen from Table 2, adopt the catalyst that comprises amorphous aluminum silicide and Silicalite-1 molecular sieve provided by the invention for MTBE cracking isobutene, compare with prior art, not only improved MTBE conversion ratio, selective isobutene, and fairly obvious to the effect of reduction by-product dimethyl ether.This illustrates that catalyst provided by the invention has higher activity and selectivity.Meanwhile, side reaction can be more effectively controlled in adding of active metal component, further reduces the content of accessory substance dimethyl ether.
Claims (18)
1. a cracking isobutene by methyl-tert-butyl ether catalyst, described catalyst comprises amorphous aluminum silicide and Silicalite-1 molecular sieve, and in catalyst, the infrared total acid content of weak acid is 0.020 ~ 0.080 mmol/g, and B acid/L acid of weak acid is 2.5 ~ 4.0; The character of described amorphous aluminum silicide is as follows: specific area is 240 ~ 450m2/g, and pore volume is 0.4 ~ 0.9mL/g.
2. catalyst according to claim 1, is characterized in that, the character of described amorphous aluminum silicide is as follows: specific area is 270 ~ 410m2/g, and pore volume is 0.5 ~ 0.7mL/g.
3. catalyst according to claim 1, is characterized in that, the mass ratio of described amorphous aluminum silicide and Silicalite-1 is 9.5:1 ~ 1:1.
4. catalyst according to claim 3, is characterized in that, the mass ratio of described amorphous aluminum silicide and Silicalite-1 is 8:1 ~ 4:1.
5. according to the catalyst described in any one in claim 1 ~ 4, it is characterized in that, in described amorphous aluminum silicide, SiO
2content be 60wt% ~ 99wt%, Al
2o
3content be 1wt% ~ 40wt%.
6. catalyst according to claim 4, is characterized in that, in described amorphous aluminum silicide, and SiO
2content be 80wt% ~ 95wt%, Al
2o
3content be 5wt% ~ 20wt%.
7. catalyst according to claim 1, is characterized in that, described catalyst also comprises active metal component, and described active metal is selected from least one in IIA family and group VIII metal.
8. catalyst according to claim 7, is characterized in that, described IIA family metal is selected from least one in Be, Mg, Ca; Described group VIII metal is selected from least one in Ni, Pd, Pt.
9. according to the catalyst described in claim 7 or 8, it is characterized in that, take metallic element, the content in catalyst is 0.3wt% ~ 2.0wt% to described active metal component.
10. prepare in claim 1 ~ 9 method for catalyst described in any one, comprising:
A, amorphous aluminum silicide and Silicalite-1 molecular sieve are mixed, after moulding, dry and roasting;
The material of b, step a gained, through hydrothermal treatment consists, obtains catalyst;
In step b, hydrothermal treatment consists condition: use saturated vapor processing, temperature is 100 ~ 600 ℃, and the time is 1 ~ 10h.
11. methods according to claim 10, is characterized in that, in step b, use saturated vapor processing, and temperature is 100 ~ 300 ℃, and the time is 4 ~ 8h.
12. methods according to claim 10, is characterized in that, after hydrothermal treatment consists, through drying steps, described drying condition is as follows: at 90 ~ 120 ℃ of dry 2.0 ~ 6.0h.
13. methods according to claim 10, is characterized in that, the compound containing active metal component is added in a step or b step, and described active metal component is selected from least one in IIA family and group VIII metal.
14. methods according to claim 13, is characterized in that, described IIA family metal is selected from least one in Be, Mg, Ca; Described group VIII metal is selected from least one in Ni, Pd, Pt.
15. methods according to claim 10, is characterized in that, are dried 2 ~ 5h, at 450 ~ 600 ℃ of roasting 3 ~ 6h in step a at 90 ~ 120 ℃.
The method of 16. 1 kinds of cracking isobutene by methyl-tert-butyl ether, is characterized in that, carries out cracking reaction and make isobutene under the existence of methyl tertiary butyl ether(MTBE) catalyst described in any one in claim 1 ~ 8.
17. methods according to claim 16, is characterized in that, described reaction condition is that when methyl tertiary butyl ether(MTBE) liquid, volume space velocity is 0.7 ~ 6.0h
-1, when the liquid of water, volume space velocity is 0 ~ 1.0 h
-1, temperature is 180 ~ 360 ℃, pressure is that normal pressure is to 1.0MPa.
18. methods according to claim 17, is characterized in that, described reaction condition is that when methyl tertiary butyl ether(MTBE) liquid, volume space velocity is 2.0 ~ 4.0 h
-1, when the liquid of water, volume space velocity is 0.1 ~ 0.5h
-1, temperature is 210 ~ 270 ℃, pressure is normal pressure to 0.6 MPa.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110325817.2A CN103071518B (en) | 2011-10-25 | 2011-10-25 | Catalyst used in production of isobutene through cracking of methyl tert-butyl ether and preparation method thereof |
| PCT/CN2012/083397 WO2013060262A1 (en) | 2011-10-25 | 2012-10-24 | Isobutene catalyst prepared by splitting methyl tert-butyl ether, preparation method and use thereof |
| US14/353,366 US9708229B2 (en) | 2011-10-25 | 2012-10-24 | Catalyst for preparing isobutene by dissociation of methyl tert-butyl ether, preparation method and use thereof |
| KR1020147013089A KR102010938B1 (en) | 2011-10-25 | 2012-10-24 | Isobutene catalyst prepared by splitting methyl tert-butyl ether, preparation method and use thereof |
| TW101139238A TWI586429B (en) | 2011-10-25 | 2012-10-24 | Catalyst for the preparation of isobutene from methyl tertiary butyl ether and its preparation and application |
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|---|---|---|---|
| CN201110325817.2A CN103071518B (en) | 2011-10-25 | 2011-10-25 | Catalyst used in production of isobutene through cracking of methyl tert-butyl ether and preparation method thereof |
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|---|---|
| CN103071518A CN103071518A (en) | 2013-05-01 |
| CN103071518B true CN103071518B (en) | 2014-05-21 |
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| CN106673946B (en) * | 2015-11-10 | 2019-06-11 | 中国石油化工股份有限公司 | A kind of method that MTBE and TBA mixture prepares isobutene |
| CN108409517B (en) * | 2018-02-24 | 2020-10-20 | 安徽海德化工科技有限公司 | Method for preparing isobutene by catalytic cracking of methyl tert-butyl ether |
| CN113713850B (en) * | 2020-05-26 | 2023-08-15 | 中国石油化工股份有限公司 | MTBE cracking propylene preparation catalyst and preparation method and application thereof |
| CN116459863A (en) * | 2022-01-11 | 2023-07-21 | 中国石油化工股份有限公司 | Molded carrier, preparation method and application thereof, and dehydrogenation molded catalyst |
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| 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 |
| FR2894851A1 (en) * | 2005-12-15 | 2007-06-22 | Total France Sa | CATALYTIC COMPOSITION AND PROCESS FOR CATALYTIC CRACKING IN FLUIDIZED BED USING SUCH A COMPOSITION |
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| 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 |
| FR2894851A1 (en) * | 2005-12-15 | 2007-06-22 | Total France Sa | CATALYTIC COMPOSITION AND PROCESS FOR CATALYTIC CRACKING IN FLUIDIZED BED USING SUCH A COMPOSITION |
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