CN1721073A - Catalyst suitable for butylene oligomerization - Google Patents
Catalyst suitable for butylene oligomerization Download PDFInfo
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- CN1721073A CN1721073A CNA2004100527266A CN200410052726A CN1721073A CN 1721073 A CN1721073 A CN 1721073A CN A2004100527266 A CNA2004100527266 A CN A2004100527266A CN 200410052726 A CN200410052726 A CN 200410052726A CN 1721073 A CN1721073 A CN 1721073A
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- catalyst
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- molecular sieve
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The present invention relates to catalyst fit to butylene oligomerisation reaction to solve the problems in past that the catalyst is easy to pelitization, with low active and poor selectivity of oct-alkene. It uses the scheme to achieve purpose that uses heteroatom ZSM-5 molecular sieve as main body of catalyst with YO2/M2O3 of mole rate 50~200 and M and Y are separately triad and quadravalence, and fits to practical production.
Description
Technical field
The present invention relates to a kind of suitable butene oligomerization catalyst for reaction.
Background technology
The butene oligomerization reaction can be made into high-knock rating gasoline and multiple chemical products with high added-value, and this not only can find a way out for superfluous day by day carbon four resources, also can be the refinery and creates tangible economic benefit.Industrial widely used catalyst is phosphoric acid/diatom scholar catalyst at present.This catalyst is easy to the argillization caking, stops up reactor, though people have carried out many-sided improvement to such catalyst, this problem is solved eventually at all.
U.S. Pat 4100220, US4463211 has reported with cation exchange resin catalyst as the butene oligomerization catalyst for reaction, but the HMW oligomer easily blocks the reaction duct, and resin matrix alkylation meeting causes its active decline comparatively fast, the temperature tolerance of resin is relatively poor in addition, also restricts its application.
MOGD technology (US4150062 and US4254298) the employing silica alumina ratio of Mobil company exploitation is 79 ZSM-5 molecular sieve catalyst, obtained product by changing process conditions based on gasoline or diesel oil, but owing to oligomerisation in the course of reaction, cracking copolyreaction coexistence, the product carbon number distribution is too wide, and selectivity is relatively poor.
Summary of the invention
Technical problem to be solved by this invention is that the catalyst that uses in the process of butene oligomerization reaction in the conventional art exists easy argillization, and catalytic activity is low, and the problem that carbon eight olefine selectives are low provides a kind of new butene oligomerization catalyst for reaction that is suitable for.This catalyst has the argillization of being difficult for, catalytic activity height, the characteristics that product carbon eight olefine selectives are high when being used for the butene oligomerization reaction.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of suitable butene oligomerization catalyst for reaction comprises following component by weight percentage:;
A) 50～80%YO
2/ M
2O
3Mol ratio is 50～200 hetero atom ZSM-5 molecular sieve, and wherein M is a triad, and Y is a quadrivalent element;
B) 20～50% binding agent.
In the technique scheme, triad M preferred version is selected from least a among Fe, Cr, Ga or the V, and more preferably scheme is Fe; Quadrivalent element Y preferred version is selected from Si or Ge, and more preferably scheme is selected from Si.The consumption preferable range of hetero atom ZSM-5 molecular sieve is 60～70% by weight percentage, and the consumption preferable range of binding agent is 20～30%, and binding agent is selected from Al
2O
3, SiO
2Or its mixture.
The preparation method of the hetero atom ZSM-5 molecular sieve that uses among the present invention is as follows: its raw material is formed and mol ratio is M3
+: SiO
2: Na
2O: Na
+: R: H
2O=1: (50～200): (8～15): (15～25): (25～40): (2500～4000) wherein M are selected from Fe, Cr, Ga or V, and R is organic amine or quaternary ammonium salt.
Above-mentioned M-ZSM-5 molecular screen primary powder adopts hydro-thermal method synthetic, and its preparation method is as follows: the oxyacid or the oxysalt of hetero atom M source chosen from Fe, chromium, gallium, vanadium are ferric nitrate or ferric trichloride as source of iron, and the chromium source is compounds such as chromic nitrate; The silicon source is selected from waterglass, white carbon black, silicon-containing compounds such as Ludox; The template agent of using is generally ethamine, ethylenediamine, 1, organic amines such as 6-hexamethylene diamine, 4-propyl bromide, with each reaction mass according to the desired amount of proportioning, be mixed with solution, mix then, crystallization is 24～120 hours under 100～150 ℃ of conditions, after cooling is taken out, filtration washing, 80～120 ℃ of oven dry obtain hetero atom M-ZSM-5 molecular screen primary powder.
Preparation of catalysts method of the present invention is as follows:
After above-mentioned molecular sieve adopts ion-exchange to change Hydrogen into, can be directly used in the butene oligomerization reaction by compressing tablet as catalyst, also can add an amount of binding agent such as white carbon black or aluminium oxide, binding agent is generally 20～50% of molecular screen primary powder amount, and an amount of shaping assistant, as extrusion aid or peptizing agent, shaping assistant is generally 10～20% of molecular screen primary powder amount, mix, mediate, extruded moulding obtains the molecular sieve of strip, the catalyst of forming is through oven dry, at 300～550 ℃ of roasting removed template methods and some additive.Last crushing screening obtains the catalyst finished product.
The present invention is because the hetero atom ZSM-5 molecular sieve catalyst that uses, be that hetero atom ZSM-5 molecular sieves such as iron silicon, chrome-silicon, gallium silicon, vanadium silicon are catalyst, by the different metal hetero atom is introduced framework of molecular sieve, can regulate the acidity and the microcellular structure in molecular sieve activated centre within the specific limits, to reduce the surface acidity of molecular sieve catalyst, the acidity that has overcome Si-Al molecular sieve causes the too wide shortcoming of product carbon number distribution more by force, and problems such as catalyst argillization caking do not take place.This catalyst is used for the butene oligomerization reaction, has very high conversion, and conversion ratio can reach 90%, C
8 =Selectivity can reach 80%, obtained better technical effect.
The invention will be further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
With 9.8 gram ferric nitrates, after the 20 gram concentrated sulfuric acids add 100 gram deionized water for stirring dissolvings, add 4.0 gram anhydrous sodium sulfates, stir and make A solution, 262.7 gram waterglass are added 100 gram water dilutions to be stirred evenly and makes B solution, to make C solution in 20.8 gram 4-propyl bromides addings, the 50 gram water, brute force stirred 20 minutes after stirring dropwise added B solution A solution formation gel down, add C solution, regulate pH value to 10 with 10 mol sodium hydroxide solutions at last, continue to stir after 20 minutes and insert in 1 liter of crystallizing kettle, under 150 ℃ and self-generated pressure, left standstill crystallization 72 hours, cooled and filtered, washing, filter cake obtains sodium type molecular screen primary powder in 100～120 ℃ of oven dry.Make hydrogen type molecular sieve with ion-exchange.Get 20 gram molecules sieve, add 6 white carbon blacks of gram and 3 gram sesbania powder, with 25 gram SiO
2(40% weight) Ludox is as binding agent, extruded moulding, and pelletizing, 120 ℃ of dryings 12 hours 550 ℃ of following roastings 3 hours, make the catalyst finished product, SiO
2/ Fe
2O
3Mol ratio is 90.
[embodiment 2]
Method for preparing catalyst is with embodiment 1, and metal M nitrate is gallium nitrate, makes the Ga-ZSM-5 molecular sieve catalyst at last, gets hydrogen type molecular sieve through exchange system, SiO
2/ Ga
2O
3Mol ratio is 50.Get molecular sieve 20 grams, add 6 gram aluminium oxide and 3 gram sesbania powder, mix, with the HNO of 1 mol
3Moulding, extrusion, pelletizing, 120 ℃ of dryings 12 hours 550 ℃ of following roastings 4 hours, make the catalyst finished product.
[embodiment 3]
Method for preparing catalyst is with embodiment 1, and metal M nitrate is chromic nitrate, makes the Cr-ZSM-5 molecular sieve catalyst at last, gets hydrogen type molecular sieve through exchange system, SiO
2/ Cr
2O
3Mol ratio is 150.Get 20 gram molecules sieve, add 6 gram aluminium oxide and 3 gram sesbania powder, mix, with the HNO of 1 mol
3Moulding, extrusion, pelletizing, 120 ℃ of dryings 12 hours 550 ℃ of following roastings 4 hours, make the catalyst finished product.
[embodiment 4]
Method for preparing catalyst is with embodiment 1, and the sulfate of metal M is vanadic sulfate, and hydro-thermal method is synthesized the V-ZSM-5 molecular sieve, is exchanged into Hydrogen, SiO
2/ V
2O
3Mol ratio is 90.Get 20 gram molecules sieves, add 6 white carbon blacks of gram and 3 gram sesbania powder, mix, use the Ludox moulding, extrusion, pelletizing, 120 ℃ of dryings 12 hours 550 ℃ of following roastings 4 hours, make the catalyst finished product.
[embodiment 5]
The catalyst finished product of embodiment 1～4 is checked and rated on fixed bed reactors respectively, and loaded catalyst is 10 milliliters, and reaction temperature is 300 ℃, and reaction pressure is 4.0MPa, and volume space velocity is 1.0 hours during liquid
-1, raw material adopts mixed c 4, and wherein the alkene weight content is 42%, and appraisal result is listed in table 1.
Table 1
| Embodiment number | The catalyst numbering | Feed stock conversion % | C 8 ＝Selectivity % |
| Embodiment 1 | Fe-ZSM-5 | 91.5 | 82.0 |
| Embodiment 2 | Ga-ZSM-5 | 85.5 | 75.2 |
| Embodiment 3 | Cr-ZSM-5 | 86.5 | 80.5 |
| Embodiment 4 | V-ZSM-5 | 75 | 80.5 |
[embodiment 6]
According to each step and the operating condition of embodiment 1, just changing Fe-ZSM-5 molecular sieve consumption is 24 grams, and reaction temperature is 250 ℃, and reaction pressure is 4.5MPa, and air speed is 2.0 hours
-1, its reaction result is: the raw material butene conversion is 84.6%, the selectivity of carbon eight alkene is 86.7%.
[embodiment 7]
According to each step and the operating condition of embodiment 1, just changing Fe-ZSM-5 molecular sieve consumption is 34 grams, and reaction pressure is 5.0MPa, and air speed is 1.5 hours
-1, its reaction result is: the raw material butene conversion is 90.4%, the selectivity of carbon eight alkene is 83.7%.
Claims (5)
1, a kind of suitable butene oligomerization catalyst for reaction comprises following component by weight percentage:
A) 50～80%YO
2/ M
2O
3Mol ratio is 50～200 hetero atom ZSM-5 molecular sieve, and wherein M is a triad, and Y is a quadrivalent element;
B) 20～50% binding agent.
2,, it is characterized in that triad M is selected from least a among Fe, Cr, Ga or the V according to the described suitable butene oligomerization catalyst for reaction of claim 1; Quadrivalent element Y is selected from Si or Ge.
3, according to the described suitable butene oligomerization catalyst for reaction of claim 1, it is characterized in that the consumption of hetero atom ZSM-5 molecular sieve is 60～70% by weight percentage.
4, according to the described suitable butene oligomerization catalyst for reaction of claim 1, it is characterized in that the consumption of binding agent is 20～30% by weight percentage, binding agent is selected from Al
2O
3, SiO
2Or its mixture.
5, according to the described suitable butene oligomerization catalyst for reaction of claim 2, it is characterized in that triad M is selected from Fe, quadrivalent element Y is Si.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2004100527266A CN1721073A (en) | 2004-07-12 | 2004-07-12 | Catalyst suitable for butylene oligomerization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2004100527266A CN1721073A (en) | 2004-07-12 | 2004-07-12 | Catalyst suitable for butylene oligomerization |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1721073A true CN1721073A (en) | 2006-01-18 |
Family
ID=35911892
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2004100527266A Pending CN1721073A (en) | 2004-07-12 | 2004-07-12 | Catalyst suitable for butylene oligomerization |
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|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107286983A (en) * | 2016-04-12 | 2017-10-24 | 中国石油化工股份有限公司 | The method of C 4 olefin oligomerisation gasoline component |
| CN112316974A (en) * | 2020-11-06 | 2021-02-05 | 东华工程科技股份有限公司 | Bifunctional catalyst and preparation method and application thereof |
-
2004
- 2004-07-12 CN CNA2004100527266A patent/CN1721073A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107286983A (en) * | 2016-04-12 | 2017-10-24 | 中国石油化工股份有限公司 | The method of C 4 olefin oligomerisation gasoline component |
| CN107286983B (en) * | 2016-04-12 | 2019-02-19 | 中国石油化工股份有限公司 | The method of C 4 olefin oligomerisation gasoline component |
| CN112316974A (en) * | 2020-11-06 | 2021-02-05 | 东华工程科技股份有限公司 | Bifunctional catalyst and preparation method and application thereof |
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