CN102600886A - Catalyst for preparing iso-olefins by isomerizing straight-chain olefins and preparation method of catalyst - Google Patents
Catalyst for preparing iso-olefins by isomerizing straight-chain olefins and preparation method of catalyst Download PDFInfo
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Abstract
The invention discloses a catalyst for preparing iso-olefins by isomerizing straight-chain olefins and a preparation method of the catalyst. The catalyst uses the FER (ferrierite) zeolite raw powder as a main active body, wherein the silica-alumina ratio (SiO2/Al2O3) (molar ratio) is less than 50. The preparation method comprises the following steps: mixing FER zeolite raw powder, silica sol and/or alumina sol, organic acid and water evenly; carrying out molding, drying and calcinaton, and soaking in a VIII group metal oxide solution; and carrying out drying and calcination to obtain the catalyst. For the isomerization of straight-chain olefins, the catalyst is good in activity and stability, high in both conversion rate of straight-chain olefins and selectivity to iso-olefins and can be applied to the field of industrial production of the iso-olefins, such as the industrial production of isobutene and isoamylene.
Description
Technical field
The present invention relates to the Catalysts and its preparation method that a kind of isomerizating straight-chain prepares different olefine.
Background technology
Different olefine such as isobutene and iso-amylene are important basic organic.Isobutene is mainly used in the production of gasoline additive methyl tertiary butyl ether(MTBE) (MTBE), polyisobutene etc.; Isobutene also is the primary raw material of synthetic rubber such as butyl rubber, and simultaneously isobutene still is the raw material of multiple Organic Chemicals such as the tert-butyl alcohol, methacrylonitrile, antioxidant etc.Iso-amylene then is one of main intermediate of producing by agricultural chemicals, medicine and spices.
Different olefine generally separates acquisition from the accessory substance of steam cracking device or plant catalytic cracking unit (FCC), then from mix carbon five, separate obtaining from mixed c 4, iso-amylene like isobutene.According to the difference of different olefine relative volatility, divide the method for divorce olefine also to be not quite similar.Can be through usual manners such as conventional distillation and extracting rectifyings, also can through with separate again after alcohols such as methyl alcohol generates ether compound, as isobutene can through with methyl alcohol reaction generation methyl tertiary butyl ether(MTBE) (MTBE) after separate again.
Linear alkene or mixture of linear olefins mainly come from the accessory substance of steam cracking device or refinery's device.According to the difference of raw material, reaction depth and catalyst, accessory substance composition and output that steam cracking device or refinery's device are produced are also different.For example the mixed c 4 of steam cracking device by-product composition (weight) is about under the usual conditions: alkane: isobutene 3%: butene-1 22%: butene-2 14%: butadiene 11%: 50%.The mixed c 4 of plant catalytic cracking unit by-product is formed (weight) and is about: iso-butane: 34%, and normal butane: 10%, isobutene: 15%, butene-1: 13%, butene-2: 28%.On total amount, the mixed c 4 of catalytic cracking unit by-product is approximately the 9%-12% (weight) of device fresh feed generally speaking, and the mixed c 4 of steam cracking device by-product is approximately about 40% of ethene ability.
In China; In the mixed c 4 of steam cracking device or plant catalytic cracking unit by-product and the mixing carbon five; Except that butadiene, isobutene, iso-amylene etc. obtained preferably chemical utilization, all the other major parts comprised that linear alkene etc. is used as fuel and uses, and the chemical industry added value is lower.
By the end of the year 2009, Chinese crude oil time processing ability reaches 4.77 hundred million tons, and over the past two years, China be constructed and put into operation can reach 5000 with the refining capacity of building surplus ten thousand tons, building or the steam cracking device scale of planning construction also considerable.Therefore, a large amount of mixed c 4s will be arranged future and mix carbon five appearance, the chemical utilization that how to improve linear alkene wherein is worth has high realistic meaning, particularly under the environment of soaring oil prices.
Document US 5648585 has been introduced a kind of catalyst for preparing different olefine from linear alkene.It is catalyst body that this catalyst adopts zeolite such as ferrierite, ZSM-22 or the ZSM-23 of one dimension pore structure, and aluminium oxide is the binding agent of catalyst; Catalyst comprises metal such as palladium or the platinum that is up to 15% (weight) in addition.The isomerisation temperature of this technology is about 200-650 ℃, and the dividing potential drop of linear alkene is greater than 0.5Bar in the charging; Hydrogen in the charging is 0-30 (mole) with the ratio of hydrocarbon mixture.The embodiment of this document shows that adopting n-butene is raw material, and the obtainable selective isobutene of this catalyst is up to 88% (butene conversion of this moment is 40%), and the conversion ratio of butylene is up to 50% (selective isobutene of this moment is 75%); The one way life-span of catalyst is about 100-300 hour.This catalyst can obtain the conversion ratio of different preferably olefine selectivity and linear alkene, but has adopted the modified with noble metals catalyst of higher concentration, and cost is higher; Possibly face hydrogen in the reaction feed simultaneously, increase technology operating cost.
It is linear alkene such as n-butene skeletal isomerization the catalyst of different olefine that document US 5449851 has been introduced a kind of highly selective.This catalyst is ZSM-35, is preferably through the HZSM-35 like the rare earth ion modification.The isomerisation temperature of this catalyst is about 390-550 ℃, and the dividing potential drop of linear alkene is 50-150KPa in the charging, and the weight (hourly) space velocity (WHSV) of charging is 30-250 hour 1.The embodiment of this document shows that adopting n-butene is raw material, and the butene conversion of this catalyst is about 30%-40% (weight), and the selectivity of isobutene is about 90-99%; The catalyst line duration that embodiment shows is very short, and several hrs only can't be explained the stability of this catalyst.Though the catalyst of this document introduction can obtain higher different olefine selectivity, the conversion ratio of linear alkene is lower in the raw material, and the stability of catalyst can't be described.
Summary of the invention
The present invention relates to the Catalysts and its preparation method that a kind of isomerizating straight-chain prepares different olefine, be mainly used in the production of different olefine.
Problem to be solved by this invention be in the past in the technology isomerizating straight-chain be that the catalyst reaction activity of different olefine is lower, the purpose selectivity of product is not high and technical problem such as poor catalyst stability, a kind of new Catalysts and its preparation method is provided.It is active with stability, higher one way linear alkene conversion ratio with to the advantages such as selectivity of different olefine that this catalyst has good isomerizating straight-chain.
In order to solve the problems of the technologies described above, the technical scheme that the present invention adopts is following: a kind of isomerizating straight-chain prepares the Catalysts and its preparation method of different olefine, it is characterized in that this catalyst is with silica alumina ratio (SiO
2/ Al
2O
3) (mole) be active main body less than 50 FER zeolite powder; FER zeolite powder, Ludox and/or aluminium colloidal sol, organic acid and water are evenly mixed; After moulding, the dry also roasting, impregnated in the VIII family metal oxide solution, after drying, roasting, make again.
In the technique scheme, the FER zeolite powder is preferably ferrierite, ZSM-35, FU-9 or ISI-6, more preferably silica alumina ratio (SiO
2/ Al
2O
3) (mole) less than 30 ferrierite or ZSM-35.
The mixed proportion (weight) of Ludox and/or aluminium colloidal sol and FER zeolite powder is preferably 1: 1-10.
Organic acid is preferably formic acid, acetate, citric acid, oxalic acid or maleic acid.The mixed proportion of organic acid and FER zeolite powder (weight) is preferably 1: 10-300.
The mixed proportion of water and FER zeolite powder (weight) is preferably 1: 1-10.
VIII family metal oxide solution is preferably the inorganic salt solution of Metal Palladium, platinum, cobalt or nickel.
This Preparation of catalysts is preferably and may further comprise the steps:
Step 1: FER zeolite powder, Ludox and/or aluminium colloidal sol, organic acid and water are mixed in proportion, stir 10 minutes to 60 minutes aftershapings, then in 80 ℃-120 ℃ dry 10-20 hour down, under 450 ℃ of-650 ℃ of conditions roasting 2-6 hour again.
Step 2: the catalyst soakage that step 1 is obtained in VIII family metal oxide solution 1-6 hour, the ratio of catalyst and metal oxide solution (weight) is 3-1: 1.
Step 3: with the mixture heating evaporation of step 2, then 80 ℃-120 ℃ dry 10-20 hour down, under 450 ℃ of-650 ℃ of conditions roasting 2-6 hour again.
VIII family metal oxide solution metal content is preferably 0.1-10% (weight).
This Application of Catalyst condition is preferably: reaction raw materials is preferably and contains C
4 +The hydrocarbon mixture of linear alkene, wherein C
4 +The content of linear alkene is preferably more than 30% (weight); Reactor is preferably one or more snippets fixed bed reactors, and reaction temperature is preferably 250 ℃-450 ℃, and reaction pressure is preferably 0.05-0.5MPa, and weight (hourly) space velocity (WHSV) is preferably 5-100 hour
-1
The present invention adopts the FER zeolite catalyst, has unique one dimension pore structure, and different olefine is had higher selectivity; It is more even that organic acid helps catalyst granules to disperse, and removes the impurity in the catalyst duct simultaneously, improves activity of such catalysts and stability; The existence of VIII family metal ion has improved the carbon accumulation resisting ability of catalyst, helps keeping the long period stability of catalyst.The linear alkene conversion per pass of catalyst of the present invention is greater than 43% (weight), simultaneously to the selectivity of different olefine greater than 86%, obtained the good technical effect.
Through embodiment the present invention is done further elaboration below.
The specific embodiment
Catalyst sample to all embodiment obtained adopts identical appreciation condition, and appreciation condition is:
Catalyst: 5.0 grams; Raw material is butene-1 and normal butane mixture, and wherein the content of butene-1 (weight) is 80%, and feed rate is 200 Grams Per Hours; Reaction temperature is 400 ℃, and the reactor inlet stagnation pressure is 0.20MPa, adopts individual layer axial restraint bed bioreactor.
The evaluation result of all catalyst samples sees Table 1.
[embodiment 1]
With silica alumina ratio (SiO
2/ Al
2O
3) (mole) be former powder 901 grams of 20 ferrierite, aluminium colloidal sol 107 grams, citric acid 15 grams; Deionized water 203 grams mix; At the uniform velocity stir 30 minutes aftershapings, under 100 ℃ of conditions dry 20 hours then, roasting obtained catalyst sample 1 after 2 hours under 500 ℃ of conditions again.
[embodiment 2]
With silica alumina ratio (SiO
2/ Al
2O
3) (mole) be former powder 885 grams of 20 ferrierite, aluminium colloidal sol 93 grams, citric acid 16 grams, deionized water 196 grams mix, and at the uniform velocity stir 30 minutes aftershapings, and under 100 ℃ of conditions dry 20 hours then, roasting 2 hours under 500 ℃ of conditions again.With the catalyst that obtains after the roasting in palladium nitrate aqueous solution (weight concentration of palladium is 5%) in 60 ℃ the dipping 3 hours, wherein the ratio of catalyst and palladium nitrate aqueous solution (weight) is 2; The mixture of heating evaporation catalyst and palladium nitrate solution descended dry 20 hours at 100 ℃ then, and roasting obtains catalyst sample 2 after 2 hours under 500 ℃ of conditions again.
[embodiment 3]
With silica alumina ratio (SiO
2/ Al
2O
3) (mole) be former powder 916 grams of 20 ferrierite, aluminium colloidal sol 111 grams, citric acid 18 grams, deionized water 213 grams mix, and at the uniform velocity stir 30 minutes aftershapings, and under 100 ℃ of conditions dry 20 hours then, roasting 2 hours under 500 ℃ of conditions again.With the catalyst that obtains after the roasting in cobalt nitrate aqueous solution (weight concentration of cobalt is 5%) in 60 ℃ the dipping 3 hours, wherein the ratio of catalyst and cobalt nitrate aqueous solution (weight) is 2; The mixture of heating evaporation catalyst and cobalt nitrate solution descended dry 20 hours at 100 ℃ then, and roasting obtains catalyst sample 3 after 2 hours under 500 ℃ of conditions again.
[embodiment 4]
With silica alumina ratio (SiO
2/ Al
2O
3) (mole) be former powder 966 grams of 25 ZSM-35, aluminium colloidal sol 118 grams, acetate 11 grams; Deionized water 200 grams mix; At the uniform velocity stir 30 minutes aftershapings, under 100 ℃ of conditions dry 20 hours then, roasting obtained catalyst sample 4 after 2 hours under 500 ℃ of conditions again.
[embodiment 5]
With silica alumina ratio (SiO
2/ Al
2O
3) (mole) be former powder 953 grams of 25 ZSM-35, aluminium colloidal sol 117 grams, acetate 13 grams, deionized water 220 grams mix, and at the uniform velocity stir 30 minutes aftershapings, and under 100 ℃ of conditions dry 20 hours then, roasting 2 hours under 500 ℃ of conditions again.With the catalyst that obtains after the roasting in palladium nitrate aqueous solution (weight concentration of palladium is 5%) in 60 ℃ the dipping 3 hours, wherein the ratio of catalyst and palladium nitrate aqueous solution (weight) is 2; The mixture of heating evaporation catalyst and palladium nitrate solution descended dry 20 hours at 100 ℃ then, and roasting obtains catalyst sample 5 after 2 hours under 500 ℃ of conditions again.
[embodiment 6]
With silica alumina ratio (SiO
2/ Al
2O
3) (mole) be former powder 989 grams of 25 ZSM-35, aluminium colloidal sol 123 grams, acetate 20 grams, deionized water 208 grams mix, and at the uniform velocity stir 30 minutes aftershapings, and under 100 ℃ of conditions dry 20 hours then, roasting 2 hours under 500 ℃ of conditions again.With the catalyst that obtains after the roasting in nickel nitrate aqueous solution (weight concentration of nickel is 5%) in 60 ℃ the dipping 3 hours, wherein the ratio of catalyst and nickel nitrate aqueous solution (weight) is 2; The mixture of heating evaporation catalyst and nickel nitrate solution descended dry 20 hours at 100 ℃ then, and roasting obtains catalyst sample 6 after 2 hours under 500 ℃ of conditions again.
Table 1 catalyst sample test result
Claims (10)
1. an isomerizating straight-chain prepares the Catalysts and its preparation method of different olefine, and this catalyst is with silica alumina ratio (SiO
2/ Al
2O
3) (mole) be active main body less than 50 FER zeolite powder; FER zeolite powder, Ludox and/or aluminium colloidal sol, organic acid and water are evenly mixed; After moulding, the dry also roasting, impregnated in the VIII family metal oxide solution, after drying, roasting, make again.
2. the catalyst for preparing different olefine according to the said isomerizating straight-chain of claim 1 is characterized in that the FER zeolite powder is ferrierite, ZSM-35, FU-9 or ISI-6, more preferably silica alumina ratio (SiO
2/ Al
2O
3) (mole) less than 30 ferrierite or ZSM-35.
3. the catalyst for preparing different olefine according to the said isomerizating straight-chain of claim 1 is characterized in that the mixed proportion (weight) of Ludox and/or aluminium colloidal sol and FER zeolite powder is 1: 1-10.
4. the catalyst for preparing different olefine according to the said isomerizating straight-chain of claim 1 is characterized in that organic acid is formic acid, acetate, citric acid, oxalic acid or maleic acid.
5. the catalyst for preparing different olefine according to the said isomerizating straight-chain of claim 4 is characterized in that the mixed proportion (weight) of organic acid and FER zeolite powder is 1: 10-300.
6. the catalyst for preparing different olefine according to the said isomerizating straight-chain of claim 1 is characterized in that the mixed proportion (weight) of water and FER zeolite powder is 1: 1-10.
7. the catalyst for preparing different olefine according to the said isomerizating straight-chain of claim 1 is characterized in that VIII family metal oxide solution is the inorganic salt solution of Metal Palladium, platinum, cobalt or nickel.
8. the catalyst for preparing different olefine according to the said isomerizating straight-chain of claim 1 is characterized in that this Preparation of catalysts method is:
Step 1: FER zeolite powder, Ludox and/or aluminium colloidal sol, organic acid and water are mixed in proportion, stir 10 minutes to 60 minutes aftershapings, then in 80 ℃-120 ℃ dry 10-20 hour down, under 450 ℃ of-650 ℃ of conditions roasting 2-6 hour again.
Step 2: the catalyst soakage that step 1 is obtained in VIII family metal oxide solution 1-6 hour, the ratio of catalyst and metal oxide solution (weight) is 3-1: 1.
Step 3: with the mixture heating evaporation of step 2, then 80 ℃-120 ℃ dry 10-20 hour down, under 450 ℃ of-650 ℃ of conditions roasting 2-6 hour again.
9. said according to Claim 8 isomerizating straight-chain prepares the catalyst of different olefine, it is characterized in that VIII family metal oxide solution metal content is 0.1-10% (weight).
10. the catalyst for preparing different olefine according to the said isomerizating straight-chain of claim 1, it is characterized in that this Application of Catalyst condition is: reaction raw materials is for containing C
4 +The hydrocarbon mixture of linear alkene, wherein C
4 +The content of linear alkene is greater than 30% (weight); Reactor is one or more snippets fixed bed reactors, and reaction temperature is 250 ℃-450 ℃, and reaction pressure is 0.05-0.5MPa, and weight (hourly) space velocity (WHSV) is 5-100 hour
-1
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105709715A (en) * | 2014-12-03 | 2016-06-29 | 中国石油化工股份有限公司 | Catalyst used for preparing isobutene, and preparation method thereof |
| CN108246352A (en) * | 2016-12-28 | 2018-07-06 | 中国石油天然气股份有限公司 | A kind of C5, C6 linear chain olefin skeleton isomerism catalyst and its preparation method and application |
| CN109701607A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | Skeletal isomerisation catalyst, preparation method and applications |
| CN109701606A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | Skeletal isomerisation catalyst, preparation method and its usage |
| CN109851464A (en) * | 2017-11-30 | 2019-06-07 | 中国石油化工股份有限公司 | A kind of method and device of n-butene isomerization |
| CN109851465A (en) * | 2017-11-30 | 2019-06-07 | 中国石油化工股份有限公司 | A kind of method and device of n-butene isomerization |
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| US5510560A (en) * | 1993-08-30 | 1996-04-23 | Texaco Inc. | Skeletal isomerization of n-olefins to iso-olefins on binded ferrierite zeolites |
| CN1491888A (en) * | 1995-06-07 | 2004-04-28 | Process for preparing magnesium basic zeolite |
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2012
- 2012-02-07 CN CN2012100265465A patent/CN102600886A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5510560A (en) * | 1993-08-30 | 1996-04-23 | Texaco Inc. | Skeletal isomerization of n-olefins to iso-olefins on binded ferrierite zeolites |
| CN1491888A (en) * | 1995-06-07 | 2004-04-28 | Process for preparing magnesium basic zeolite |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105709715A (en) * | 2014-12-03 | 2016-06-29 | 中国石油化工股份有限公司 | Catalyst used for preparing isobutene, and preparation method thereof |
| CN105709715B (en) * | 2014-12-03 | 2017-11-24 | 中国石油化工股份有限公司 | It is a kind of to be used to prepare catalyst of isobutene and preparation method thereof |
| CN108246352A (en) * | 2016-12-28 | 2018-07-06 | 中国石油天然气股份有限公司 | A kind of C5, C6 linear chain olefin skeleton isomerism catalyst and its preparation method and application |
| CN109701607A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | Skeletal isomerisation catalyst, preparation method and applications |
| CN109701606A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | Skeletal isomerisation catalyst, preparation method and its usage |
| CN109851464A (en) * | 2017-11-30 | 2019-06-07 | 中国石油化工股份有限公司 | A kind of method and device of n-butene isomerization |
| CN109851465A (en) * | 2017-11-30 | 2019-06-07 | 中国石油化工股份有限公司 | A kind of method and device of n-butene isomerization |
| CN109851464B (en) * | 2017-11-30 | 2021-11-19 | 中国石油化工股份有限公司 | Method and device for isomerizing n-butene |
| CN109851465B (en) * | 2017-11-30 | 2021-11-19 | 中国石油化工股份有限公司 | Method and device for isomerizing n-butene |
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