CN1704388A - Process for preparing octaene by butene oligomerization - Google Patents
Process for preparing octaene by butene oligomerization Download PDFInfo
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- CN1704388A CN1704388A CN 200410024725 CN200410024725A CN1704388A CN 1704388 A CN1704388 A CN 1704388A CN 200410024725 CN200410024725 CN 200410024725 CN 200410024725 A CN200410024725 A CN 200410024725A CN 1704388 A CN1704388 A CN 1704388A
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Abstract
The invention relates to a process for preparing octaene by butene oligomerizatio through using butene as raw material, using M-ZSM-5 molecular sieve as the catalyst for the reactive main body, and employing a reaction temperature of 250-350 deg. C, reaction pressure 4.0-5.0 MPa, liquid phase volume hourly space velocity of 0.5-3h-1, the prepared octaene can be used in the industrial production of octaene through butylenes oligomerization reaction.
Description
Technical field
The present invention relates to a kind of method of butene oligomerization prepared in reaction carbon eight alkene.
Background technology
By-product C in naphtha cracking and catalytic cracking (FCC)
4In the component, butene content is higher, can make the blend component and the multiple chemical products with high added-value of stop bracket gasoline by butene oligomerization.Therefore the butylene comprehensive utilization based on oligomerisation has tangible effect to improving refinery and chemical plant economic benefit.
Industrial widely used butene oligomerization catalyzer is phosphoric acid/diatom scholar catalyzer at present.This catalyzer is phosphoric acid and acid carrier effect generation phosphoric acid salt etc. under reaction conditions, easily makes catalyzer argillization, caking stop up reactor.Though people have carried out many-sided improvement to such catalyzer, do not deal with problems all the time at all.
U.S. Pat 4100220, US4463211 has reported with cation exchange resin catalyst as the butene oligomerization catalyst for reaction, but the high molecular oligopolymer 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 processing condition based on gasoline or diesel oil, but owing to oligomerisation in the reaction process, 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 to exist in butene oligomerization in the conventional art to prepare the easy argillization of catalyzer in carbon eight olefin hydrocarbons, and catalytic activity is low, and the problem that selectivity of product is low provides a kind of new butene oligomerization to prepare the method for carbon eight alkene.This method has at butene oligomerization and prepares in carbon eight olefin hydrocarbons, and catalyzer is difficult for argillization, and the catalyst activity height, the characteristics that product carbon eight olefine selectives are high.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of butene oligomerization prepared in reaction carbon eight alkene is a raw material with the butylene, is 250～350 ℃ in temperature of reaction, reaction pressure is 4.0～5.0MPa, and volume space velocity is 0.5～3 hour during liquid
-1Under the condition, raw material contacts with catalyzer and generates carbon eight alkene, and wherein employed catalyzer comprises following component by weight percentage: a) 50～80% heteroatoms M-ZSM-5 molecular sieve, and M is selected from least a among Fe, Cr, Ga or the V; B) 20～50% binding agent.
In the technique scheme, the temperature of reaction preferable range is 250～300 ℃, and the volume space velocity preferable range is 1～2 hour-1 during liquid.Butene feedstock is selected from least a in butene-1, iso-butylene, maleic-2 or the anti-butene-2; The consumption preferable range of heteroatoms M-ZSM-5 molecular sieve is 60～70% by weight percentage, and binding agent consumption preferable range is 20～30%, and the binding agent preferred version is aluminum oxide or silicon-dioxide.
The method for preparing catalyst of the M-ZSM-5 molecular sieve that uses in the inventive method is as follows:
At first adopt the M-ZSM-5 molecular sieve, after adopting ion exchange method to change Hydrogen into, can be directly used in the butene oligomerization reaction by compressing tablet as catalyzer, also can add an amount of binding agent such as white carbon black or aluminum oxide, binding agent is generally 20～50% of molecular screen primary powder weight, and an amount of shaping assistant, as extrusion aid or peptizing agent, shaping assistant is generally 1～10% of molecular screen primary powder weight, mixes, and mediates, extruded moulding, obtain the molecular sieve catalyst of strip, the catalyzer of forming is through oven dry, at 300～550 ℃ of roasting removed template methods and some additive.Last crushing screening obtains the catalyzer finished product of certain particle size.
The preparation feed molar of M-ZSM-5 molecular sieve is composed as follows:
M
3+: SiO
2: Na
2O: Na
+: R: H
2O=1: (60～150): (8～15): (15～25): (25～40): (2500～4000) wherein M are Fe, Cr, Ga or V, and R is organic amine or quaternary ammonium salt, and crystallization obtained in 24～120 hours under 100～150 ℃ of crystallization temperatures.Organic amine is generally ethamine, quadrol, 1,6-hexanediamine or 4-propyl bromide.
Molecular sieve catalyst in the inventive method is used for butene oligomerization and prepares carbon eight alkene, the catalyst activity examination is carried out in fixed-bed reactor, raw material adopts at least a in butene-1, iso-butylene, maleic-2 or the anti-butene-2, butane is as thinner, loaded catalyst is 10 milliliters, temperature of reaction is 250～350 ℃, and pressure is 4.0～5.0MPa, and volume space velocity is 0.5～3 hour during stock liquid
-1, raw material olefin is contacted with catalyzer in the inventive method butene oligomerization reaction, reacted liquid product and tail gas takes place, pass through gas-liquid separator separates, liquid product enters collector, and time sampling is analyzed the liquid phase hydrocarbon composition, and tail gas enters on-line chromatograph and analyzes its composition situation.
In the inventive method, owing to used heteroatoms ZSM-5 molecular sieve catalyst, be that iron silicon, chrome-silicon, gallium silicon or vanadium sila atom ZSM-5 molecular sieve are catalyzer, by the different metal heteroatoms is introduced framework of molecular sieve, can regulate the acidity and the microvoid structure in molecular sieve active 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 problem such as catalyzer argillization caking does not take place.Under above-mentioned processing condition, C 4 olefin has very high conversion, can reach 90%, C
8 =The selectivity of alkene can reach 80%, and catalyst life was obtained better technical effect greater than 600 hours.
The invention will be further elaborated below by embodiment.
Embodiment
[embodiment 1]
Get the Fe-ZSM-5 molecular sieve 20 gram (SiO of Hydrogen
2/ Fe
2O
3Mol ratio is 90), add 6 white carbon blacks of gram and 3 gram sesbania powder, with 25 gram SiO
2(40% weight) silicon sol is as binding agent, extruded moulding, and pelletizing, 120 ℃ of dryings 12 hours 550 ℃ of following roastings 3 hours, make the catalyzer finished product, SiO
2/ Fe
2O
3Mol ratio is 90, and catalyzer is checked and rated on fixed-bed reactor, and 10 milliliters of loadings, temperature of reaction are 300 ℃, reaction pressure 4.0MPa, and air speed is 1 hour
-1, raw material adopts mixed c 4, and wherein the alkene weight content is 42%, and appraisal result shows that the raw material olefin transformation efficiency is 91.5%, and the selectivity of carbon eight alkene is 82%.
[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, SiO
2/ Ga
2O
3Mol ratio is 50.Get molecular sieve 20 grams, add aluminum oxide and mix, with 1 mol salpeter solution moulding, catalyzer is made in the drying roasting, loads 10 milliliters to fixed-bed reactor, and condition is with example 1, the result is 85.5% for the raw material olefin transformation efficiency, and the selectivity of carbon eight alkene is 75.2%.
[embodiment 3]
Method for preparing catalyst makes the Cr-ZSM-5 molecular sieve catalyst, SiO at last with embodiment 1
2/ Cr
2O
3Mol ratio is 150.Operational condition is the same.The result is: the raw material olefin transformation efficiency is 86.5%, and the selectivity of carbon eight alkene is 80.5%.
[embodiment 4]
Method for preparing catalyst is with embodiment 1, and the raw material of metal M is a vanadylic sulfate, and other operational condition is the same.The result is: the raw material olefin transformation efficiency is 80.0%, and the selectivity of carbon eight alkene is 75.5%.
[embodiment 5]
According to each step and the operational condition of embodiment 1, just changing Fe-ZSM-5 molecular sieve consumption is 24 grams, and temperature of reaction 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 6]
According to each step and the operational 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 method of butene oligomerization prepared in reaction carbon eight alkene is a raw material with the butylene, is 250～350 ℃ in temperature of reaction, and reaction pressure is 4.0～5.0MPa, and volume space velocity is 0.5～3 hour during liquid
-1Under the condition, raw material contacts with catalyzer and generates carbon eight alkene, it is characterized in that employed catalyzer comprises following component by weight percentage: a) 50～80% heteroatoms M-ZSM-5 molecular sieve, and M is selected from least a among Fe, Cr, Ga or the V; B) 20～50% binding agent.
2, according to the method for the described butene oligomerization prepared in reaction of claim 1 carbon eight alkene, it is characterized in that temperature of reaction is 250～300 ℃, volume space velocity is 1～2 hour-1 during liquid.
3,, it is characterized in that butene feedstock is selected from least a in butene-1, iso-butylene, maleic-2 or the anti-butene-2 according to the method for the described butene oligomerization prepared in reaction of claim 1 carbon eight alkene.
4,, it is characterized in that the consumption of heteroatoms M-ZSM-5 molecular sieve is 60～70% by weight percentage according to the method for the described butene oligomerization prepared in reaction of claim 1 carbon eight alkene.
5, according to the method for the described butene oligomerization prepared in reaction of claim 1 carbon eight alkene, it is characterized in that the binding agent consumption is 20～30% by weight percentage, binding agent is selected from aluminum oxide or silicon-dioxide.
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|---|---|---|---|
| CNB2004100247250A CN1298684C (en) | 2004-05-28 | 2004-05-28 | Process for preparing octaene by butene oligomerization |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100247250A CN1298684C (en) | 2004-05-28 | 2004-05-28 | Process for preparing octaene by butene oligomerization |
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| CN1704388A true CN1704388A (en) | 2005-12-07 |
| CN1298684C CN1298684C (en) | 2007-02-07 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101537369B (en) * | 2008-03-21 | 2012-02-15 | 上海宝钢化工有限公司 | ZSM-5 catalyst and preparation thereof and use thereof |
| CN112264106A (en) * | 2020-11-20 | 2021-01-26 | 中化泉州石化有限公司 | Ethylene selective oligomerization catalyst composition and application thereof |
| CN113145162A (en) * | 2021-04-19 | 2021-07-23 | 江西西林科股份有限公司 | Si/M/ZSM-5 molecular sieve and preparation method and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5202513A (en) * | 1987-07-15 | 1993-04-13 | Research Association For Utilization Of Light Oil | Process for producing aromatic hydrocarbons |
| RU2056399C1 (en) * | 1990-02-21 | 1996-03-20 | Воробьев Борис Львович | Method for producing benzene and xylenes |
| FI96320C (en) * | 1994-12-29 | 1996-06-10 | Neste Oy | Method for oligomerization of alkenes |
-
2004
- 2004-05-28 CN CNB2004100247250A patent/CN1298684C/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101537369B (en) * | 2008-03-21 | 2012-02-15 | 上海宝钢化工有限公司 | ZSM-5 catalyst and preparation thereof and use thereof |
| CN112264106A (en) * | 2020-11-20 | 2021-01-26 | 中化泉州石化有限公司 | Ethylene selective oligomerization catalyst composition and application thereof |
| CN113145162A (en) * | 2021-04-19 | 2021-07-23 | 江西西林科股份有限公司 | Si/M/ZSM-5 molecular sieve and preparation method and application thereof |
| CN113145162B (en) * | 2021-04-19 | 2023-09-26 | 江西西林科股份有限公司 | Si/M/ZSM-5 molecular sieve and preparation method and application thereof |
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|---|---|
| CN1298684C (en) | 2007-02-07 |
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