CN102069007A - Catalyst for use in preparation of propylene by olefin cracking - Google Patents
Catalyst for use in preparation of propylene by olefin cracking Download PDFInfo
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Abstract
The invention discloses a catalyst for use in the preparation of propylene by olefin cracking, and a preparation method thereof. The catalyst is prepared by using molecular sieve raw powder of which the silicon to aluminum (molar) ratio is smaller than 300 as an active main body and by uniformly mixing the molecular sieve raw powder, silica sol and/or alumina sol and a template agent, forming by crystallization, drying, roasting, performing hydro-thermal treatment with high-temperature water vapor, and modifying by using rare earth metal and/or phosphorus as a modifier. The modifier comprises the following components in percentage by weight: 0.2 to 8 percent of rare earth metal, 0.1 to 5 percent of non-metal phosphorus and the balance of molecular sieve. The catalyst has high activity and stability and high propylene selectivity, and can be used in the field of propylene production industry.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method of olefin cracking system propylene.
Background technology
Propylene is one of basic Organic Chemicals, is mainly used in many products such as producing polypropylene, isopropylbenzene, expoxy propane, acrylonitrile, acrylic acid, to the national economy important influence.In recent years, propylene year demand in continuous growth, its annual growth has surpassed the important light olefin of another one: the annual growth of ethene.Propylene mainly still obtains by preparing ethylene by steam cracking device and catalytic cracking unit, accounts for about 65% of propylene source.In addition, developed the technology of many production propylene both at home and abroad, for example technology such as dehydrogenating propane, preparing propylene from methanol.
C from steam cracking device and catalytic cracking unit
4-C
8Contain a large amount of olefines in the mixture.According to the difference of raw material, reaction depth and catalyst, C
4-C
8The composition difference of mixture is apparent in view.For example generally, the C of steam cracking device by-product
4Mixture is formed (weight) and is about: alkane: isobutene 3%: butene-1 22%: butene-2 14%: 11, butadiene: 50%; And the C of catalytic cracking unit by-product
4Mixture is formed (weight) and is about: iso-butane 34%, normal butane: isobutene 10%: butene-1 15%: 13, butene-2: 28%.And on total amount, the C of catalytic cracking unit by-product generally speaking
4Mixture is approximately the 9%-12% (weight) of device fresh feed, and the C of steam cracking device by-product
4Mixture is approximately the 40-50% of ethylene production capacity.At present, C
4-C
8Seldom component in the mixture is C for example
4Butadiene in the mixture, the separated utilization of isobutene, other most components are used as fuel and use, and 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 and the refining capacity of building can reach 5000 surplus ten thousand tons, building or the steam cracking device scale of planning construction also considerable.Therefore, future a large amount of C will be arranged
4-C
8Mixture occurs, and the comprehensive utilization ratio and the chemical utilization value that how to improve them have great realistic meaning.Utilize C
4-C
8Olefin catalytic cracking to produce propylene in the mixture is to have one of solution than hi-tech economy, and particularly under the background environment of soaring oil prices, the method has not only improved C
4-C
8The chemical industry added value of mixture, and satisfied market to the ever-increasing demand of propylene.
Document US 2006116544A1 has introduced a kind of technology of utilizing preparing olefin by catalytic cracking.This process using SiO
2/ Al
2O
3Be the pentasil type zeolite of 25-800 (mole), supported rare earth element and a kind of element among Mn, the Zr at least on it.The atomic ratio of aluminium is 0.1-20 in rare earth element and the molecular sieve, and the mol ratio of aluminium is 0.1-20 in the summation of Mn and Zr and the molecular sieve.In addition, molecular sieve is the nonmetal phosphorus of load also, and its content is 0.1%-5%.This catalyst need be used under the water vapour existence condition, and the yield of product propylene is about 15% (weight), and the yield of ethene is about 35% (weight).
Document EP 109059 has been introduced a kind of C
4-C
12Mixed olefins prepares the technology of propylene and ethylene, and the catalyst of this process using is ZSM-5 or ZSM-11 molecular sieve, SiO
2/ Al
2O
3Smaller or equal to 300, binding agent is SiO
2Molecular sieve is through phosphorus, calcium, copper, zinc or magnesium-modified.At reaction temperature 400-600, reaction velocity was greater than 50 hours
-1Condition under, this catalyst is about 38.5% to the selectivity of propylene, and to C
5The selectivity of above cut is greater than 33.5%.
Documents such as CN1506342A, CN1611471A, CN1915515A, CN1927785A have been introduced the catalyst that is used for olefin catalytic cracking to produce propylene, ethene.The catalyst that is adopted all is preferably the ZSM-5 molecular sieve catalyst, and the ZSM-5 molecular sieve is carried out modification by different method of modifying, the binding agent that shaping of catalyst adopts is silica, aluminium oxide or both mixtures, and binding agent shared ratio in catalyst is 10-70% (weight).The propene yield that the described catalyst of these several documents obtains is about 36%, and yield of ethene is about 12%.
The disclosed catalyst of above-mentioned document has all adopted a certain amount of binding agent, help molecular sieve molded, though obtained better physical intensity, the activated centre that has reduced the surface area of molecular sieve simultaneously and then reduced molecular sieve, and increased diffusional resistance, influence the purpose product selectivity.
Summary of the invention
The present invention relates to a kind of Catalysts and its preparation method of olefin cracking system propylene, be mainly used in by big molecular olefine catalytic cracking for producing propylene using.
The problem that technical problem to be solved by this invention is that the catalyst reaction activity of olefin cracking system propylene in the conventional art is lower, the purpose selectivity of product is not high and carbon accumulation resisting ability is strong etc. provides a kind of new Catalysts and its preparation method.This catalyst has bigger surface area, reactivity height, to the selectivity of purpose product propylene better and have preferably an advantage such as carbon accumulation resisting ability.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of catalyst of olefin cracking system propylene, it is characterized in that this catalyst is active main body with silica alumina ratio (mole) less than 300 molecular screen primary powder, molecular screen primary powder, Ludox and/or aluminium colloidal sol and template agent are evenly mixed, after crystallization forming, drying and roasting, using the high-temperature water vapor hydrothermal treatment consists, is that modifier carries out modification with rare earth metal and/or phosphorus again.By weight percentage: rare earth metal content is 0.2-8%, and the content of nonmetal phosphorus is 0.1-5%, and remaining set becomes molecular sieve.
Molecular screen primary powder is preferably ZSM-5, ZSM-11 or ZSM-35 type molecular sieve, and the silica alumina ratio of molecular screen primary powder (mole) is 20-250 more preferably.
The mixed proportion of Ludox and/or aluminium colloidal sol and molecular screen primary powder (weight) is preferably 1: 1-10.
The template agent is preferably cyclohexylamine, C
2-C
4Alkyl quaternary ammonium salts or their mixture, the mixed proportion of template agent and molecular screen primary powder (weight) is preferably 1: 1-10.
Rare earth metal is preferably at least a in lanthanum, cerium, praseodymium, the neodymium, and rare earth metal content is 0.5-5% more preferably.
The content of nonmetal phosphorus is 0.5-2.5% more preferably.
The temperature of hydrothermal treatment consists is preferably 250 ℃-550 ℃, and the processing time was preferably 3 hours-36 hours.
This Preparation of catalysts method is preferably the employing following steps:
Step 1: molecular screen primary powder, Ludox and/or aluminium colloidal sol, template agent are mixed, crystallization certain hour aftershaping, then 60 ℃-160 ℃ dry 5-15 hour down, and in 450 ℃-650 ℃ roasting 2-6 hour.
Step 2: under 250 ℃ of-550 ℃ of conditions, step 1 gained catalyst was carried out hydrothermal treatment consists 3-36 hour, the thermal source of employing is that (volume ratio is 1: 10-20) for the mixture of water vapour and nitrogen.
Step 3: with the catalyst after the hydrothermal treatment consists in containing the aqueous solution of nonmetal phosphorus in 60 ℃-100 ℃ following dippings 3-8 hour, heating evaporation, then 60 ℃-160 ℃ dry 5-15 hour down, and in 450 ℃-650 ℃ roasting 2-6 hour.
Step 4: the catalyst that step 3 is obtained in containing the aqueous solution of rare earth metal in 60 ℃-100 ℃ dippings 3-8 hour down, heating evaporation, then 60 ℃-160 ℃ dry 5-15 hour down, and in 450 ℃-650 ℃ roasting 2-6 hour.
Step 5: the passivation of catalyst.The catalyst that step 4 is obtained under 550 ℃, nitrogen environment passivation 3-8 hour, the catalyst after the passivation is last catalyst prod.
Crystallization temperature is preferably 120 ℃-180 ℃, and crystallization time is preferably 20-120 hour.
This Application of Catalyst condition is preferably: reaction raw materials is preferably and contains C
4-C
8The hydrocarbon mixture of alkene, reactor are preferably fixed bed or fluid bed, more preferably fixed bed; Reaction temperature is preferably 450 ℃-600 ℃, and reaction pressure is preferably 0.08-0.28MPa, and weight space velocity is preferably 2.5-25 hour
-1
The present invention adopts molecular screen primary powder, binding agent to mix with the agent of molecular sieve template, through crystallization forming, drying and roasting, make binding agent and molecular sieve be combined into the new molecular sieve catalyst that has the Different Silicon aluminum ratio, effectively increased the surface area of molecular sieve catalyst, reduce diffusional resistance, increase the activity of such catalysts center, reduced the generation of side reaction.Simultaneously, utilize rare earth element, can improve the carbon accumulation resisting ability and the stability of catalyst catalyst modification; Utilize nonmetal phosphorus that catalyst is carried out modification, the acidity that can regulate catalyst can and strengthen the hydrothermal stability of catalyst.This catalyst can reach 50% to the selectivity of purpose product propylene, has obtained the good technical effect.
The invention will be further elaborated below by embodiment.
The specific embodiment
The catalyst sample that all embodiment obtained is adopted identical appreciation condition, for:
Catalyst: 1.0 grams; Raw material is C
4-C
5Mixture, olefin(e) centent wherein (weight) is 55%, material flow is 20 Grams Per Hours; Reaction temperature is 530 ℃, and reaction pressure is 0.18MPa, adopts fixed bed reactors.
The evaluation result of all catalyst samples sees Table 1.
[embodiment 1-3]
With silica alumina ratio (mole) is that 60 ZSM-5 molecular screen primary powder, 100 grams, Ludox 20 grams, tetraethyl ammonium hydroxide 10 grams and cyclohexylamine 10 grams mix, the difference crystallization is 36 hours, 72 hours, 120 hours under 160 ℃ of conditions, moulding, descend dry 10 hours at 100 ℃ then, and in 550 ℃ of roastings 3 hours.Under 550 ℃ of conditions, the mixture of catalyzer with water steam after the roasting and nitrogen was carried out hydrothermal treatment consists 3 hours (volume ratio of water vapour and nitrogen is 1: 10).With the catalyst after the hydrothermal treatment consists at (NH
4)
2HPO
4In the aqueous solution in 100 ℃ of dippings 4 hours, behind the heating evaporation 120 ℃ dry 8 hours down, then in 550 ℃ of roastings 3 hours.With the catalyst after the phosphorus modification at La (NO
3)
3The aqueous solution in 100 ℃ of dippings 4 hours, behind the heating evaporation 100 ℃ dry 10 hours down, and in 550 ℃ of roastings 3 hours.Through modification, the content of nonmetal phosphorus is 0.5% (weight) in the catalyst, and the content of La is 0.5% (weight).Existing down in 550 ℃, nitrogen the catalyst after the modification, passivation obtained catalyst sample 1-3 in 5 hours.
[embodiment 4-6]
With silica alumina ratio (mole) is that 100 ZSM-11 molecular screen primary powder, 100 grams, Ludox 20 grams, aluminium colloidal sol 10 grams, cyclohexylamine 20 grams mix, the difference crystallization is 48 hours, 96 hours, 144 hours under 120 ℃ of conditions, moulding, descend dry 8 hours at 120 ℃ then, and in 500 ℃ of roastings 5 hours.Under 550 ℃ of conditions, the mixture of catalyzer with water steam after the roasting and nitrogen was carried out hydrothermal treatment consists 3 hours (volume ratio of water vapour and nitrogen is 1: 20).With the catalyst after the hydrothermal treatment consists at (NH
4)
2HPO
4In the aqueous solution in 80 ℃ of dippings 8 hours, behind the heating evaporation 100 ℃ dry 10 hours down, then in 500 ℃ of roastings 5 hours.With the catalyst after the phosphorus modification at Ce (NO
3)
3The aqueous solution in 80 ℃ of dippings 8 hours, behind the heating evaporation 120 ℃ dry 8 hours down, and in 500 ℃ of roastings 5 hours.Through modification, the content of nonmetal phosphorus is 1.5% (weight) in the catalyst, and the content of Ce is 1.5% (weight).Existing down in 550 ℃, nitrogen the catalyst after the modification, passivation obtained catalyst sample 4-6 in 5 hours.
[embodiment 7-9]
With silica alumina ratio (mole) is that 200 ZSM-35 molecular screen primary powder, 100 grams, Ludox 60 grams, TPAOH 30 grams and cyclohexylamine 10 grams mix, the difference crystallization is 36 hours, 72 hours, 120 hours under 180 ℃ of conditions, moulding, descend dry 10 hours at 100 ℃ then, and in 600 ℃ of roastings 3 hours.Under 450 ℃ of conditions, the mixture of catalyzer with water steam after the roasting and nitrogen was carried out hydrothermal treatment consists 24 hours (volume ratio of water vapour and nitrogen is 1: 15).With the catalyst after the hydrothermal treatment consists at (NH
4)
2HPO
4In the aqueous solution in 60 ℃ of dippings 10 hours, behind the heating evaporation 120 ℃ dry 8 hours down, then in 600 ℃ of roastings 3 hours.With the catalyst after the phosphorus modification at La (NO
3)
3The aqueous solution in 60 ℃ of dippings 10 hours, behind the heating evaporation 100 ℃ dry 10 hours down, and in 600 ℃ of roastings 3 hours.Through modification, the content of nonmetal phosphorus is 3.0% (weight) in the catalyst, and the content of La is 3.0% (weight).Existing down in 550 ℃, nitrogen the catalyst after the modification, passivation obtained catalyst sample 7-9 in 5 hours.
[embodiment 10-12]
With silica alumina ratio (mole) is that 160 ZSM-5 molecular screen primary powder, 100 grams, Ludox 30 grams, aluminium colloidal sol 30 grams, TBAH 20 grams and cyclohexylamine 20 grams mix, the difference crystallization is 36 hours, 72 hours, 120 hours under 120 ℃ of conditions, moulding, descend dry 10 hours at 100 ℃ then, and in 550 ℃ of roastings 3 hours.Under 300 ℃ of conditions, the mixture of catalyzer with water steam after the roasting and nitrogen was carried out hydrothermal treatment consists 36 hours (volume ratio of water vapour and nitrogen is 1: 20).With the catalyst after the hydrothermal treatment consists at (NH
4)
2HPO
4In the aqueous solution in 80 ℃ of dippings 8 hours, behind the heating evaporation 120 ℃ dry 8 hours down, then in 550 ℃ of roastings 3 hours.With the catalyst after the phosphorus modification at Ce (NO
3)
3The aqueous solution in 80 ℃ of dippings 8 hours, behind the heating evaporation 120 ℃ dry 8 hours down, and in 550 ℃ of roastings 3 hours.Through modification, the content of nonmetal phosphorus is 1.5% (weight) in the catalyst, and the content of Ce is 1.5% (weight).Existing down in 550 ℃, nitrogen the catalyst after the modification, passivation obtained catalyst sample 10-12 in 5 hours.
Table 1 catalyst sample test result
| Sample | The C 4 olefin conversion ratio, % | The propylene selectivity, % | Ethylene selectivity, % | ?C 5 +Selectivity, % |
| 1 | 71.1 | 48.6 | 15.6 | 22.3 |
| 2 | 68.3 | 51.0 | 17.1 | 19.1 |
| 3 | 73.5 | 48.0 | 14.4 | 23.8 |
| 4 | 67.6 | 53.1 | 17.6 | 19.6 |
| 5 | 68.4 | 51.3 | 16.8 | 20.8 |
| 6 | 73.8 | 47.8 | 15.3 | 23.1 |
| 7 | 80.5 | 45.5 | 14.6 | 23.6 |
| 8 | 73.4 | 48.1 | 15.1 | 22.6 |
| 9 | 69.0 | 53.3 | 17.9 | 18.8 |
| 10 | 68.9 | 55.0 | 17.4 | 17.6 |
| 11 | 70.5 | 49.3 | 16.8 | 20.3 |
| 12 | 70.3 | 50.1 | 16.1 | 20.8 |
Claims (10)
1. the catalyst of an olefin cracking system propylene, it is characterized in that this catalyst is active main body with silica alumina ratio (mole) less than 300 molecular screen primary powder, molecular screen primary powder, Ludox and/or aluminium colloidal sol and template agent are evenly mixed, after crystallization forming, drying and the roasting, through the high-temperature water vapor hydrothermal treatment consists, be that modifier carries out modification with rare earth metal and/or phosphorus again.By weight percentage: rare earth metal content is 0.2-8%, and the content of nonmetal phosphorus is 0.1-5%, and remaining set becomes molecular sieve.
2. according to the catalyst of the described olefin cracking system propylene of claim 1, it is characterized in that molecular screen primary powder is ZSM-5, ZSM-11 or ZSM-35 type molecular sieve, the silica alumina ratio of molecular screen primary powder (mole) is 20-250.
3. according to the catalyst of the described olefin cracking system propylene of claim 1, it is characterized in that the mixed proportion (weight) of Ludox and/or aluminium colloidal sol and molecular screen primary powder is 1: 1-10.
4. according to the catalyst of the described olefin cracking system propylene of claim 1, it is characterized in that the template agent is cyclohexylamine, C
2-C
4Alkyl quaternary ammonium salts or their mixture, the mixed proportion of template agent and molecular screen primary powder (weight) is 1: 1-10.
5. according to the catalyst of the described olefin cracking system propylene of claim 1, it is characterized in that rare earth metal is at least a in lanthanum, cerium, praseodymium, the neodymium, rare earth metal content is preferably 0.5-5%.
6. according to the catalyst of the described olefin cracking system propylene of claim 1, it is characterized in that the content of nonmetal phosphorus is preferably 0.5-2.5%.
7. according to the catalyst of the described olefin cracking system propylene of claim 1, it is characterized in that the hydrothermal treatment consists temperature is 250 ℃-550 ℃, the processing time is 3 hours-36 hours.
8. according to the catalyst of the described olefin cracking system propylene of claim 1, it is characterized in that this Preparation of catalysts method is:
Step 1: molecular screen primary powder, Ludox and/or aluminium colloidal sol, template agent are mixed, crystallization certain hour aftershaping, then 60 ℃-160 ℃ dry 5-15 hour down, and in 450 ℃-650 ℃ roasting 2-6 hour.
Step 2: under 250 ℃ of-550 ℃ of conditions, step 1 gained catalyst was carried out hydrothermal treatment consists 3-36 hour, the thermal source of employing is that (volume ratio is 1: 10-20) for the mixture of water vapour and nitrogen.
Step 3: with the catalyst after the hydrothermal treatment consists in containing the aqueous solution of nonmetal phosphorus in 60 ℃-100 ℃ following dippings 3-8 hour, heating evaporation, then 60 ℃-160 ℃ dry 5-15 hour down, and in 450 ℃-650 ℃ roasting 2-6 hour.
Step 4: the catalyst that step 3 is obtained in containing the aqueous solution of rare earth metal in 60 ℃-100 ℃ dippings 3-8 hour down, heating evaporation, then 60 ℃-160 ℃ dry 5-15 hour down, and in 450 ℃-650 ℃ roasting 2-6 hour.
Step 5: the passivation of catalyst.The catalyst that step 4 is obtained under 550 ℃, nitrogen environment passivation 3-8 hour, the catalyst after the passivation is last catalyst prod.
9. the method for preparing catalyst of according to Claim 8 described olefin cracking system propylene is characterized in that crystallization temperature is 120 ℃-180 ℃, and crystallization time is 20-120 hour.
10. according to the catalyst of the described olefin cracking system propylene of claim 1, it is characterized in that this Application of Catalyst condition is: reaction raw materials is the hydrocarbon mixture that contains C4-C8 alkene, and reactor is fixed bed or fluidized-bed reactor, is preferably fixed bed reactors; Reaction temperature is 450 ℃-600 ℃, and reaction pressure is 0.08-0.28MPa, and weight space velocity is 2.5-25 hour
-1
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104549437A (en) * | 2013-10-12 | 2015-04-29 | 中国石油化工股份有限公司 | ZSM-5 molecular sieve based catalyst modified by phosphor and rear earth as well as preparation method and application of ZSM-5 molecular sieve based catalyst |
| CN110639602A (en) * | 2018-06-27 | 2020-01-03 | 中国石油化工股份有限公司 | Catalyst for producing monoethanolamine and diethanolamine |
| CN110813367A (en) * | 2019-11-20 | 2020-02-21 | 延安大学 | Phosphorus and rare earth synergistically modified ZSM-5 and method for increasing propylene yield through catalytic cracking of ZSM-5 |
| CN113751057A (en) * | 2021-10-18 | 2021-12-07 | 深圳科冠华太新材料技术有限公司 | Preparation and application of Silicalite-1 and silica-coated ZSM-5 catalyst |
| CN115594196A (en) * | 2022-10-27 | 2023-01-13 | 陕西煤业化工技术研究院有限责任公司（Cn） | Modified SAPO-34 molecular sieve, and preparation method and application thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104549437A (en) * | 2013-10-12 | 2015-04-29 | 中国石油化工股份有限公司 | ZSM-5 molecular sieve based catalyst modified by phosphor and rear earth as well as preparation method and application of ZSM-5 molecular sieve based catalyst |
| CN110639602A (en) * | 2018-06-27 | 2020-01-03 | 中国石油化工股份有限公司 | Catalyst for producing monoethanolamine and diethanolamine |
| CN110639602B (en) * | 2018-06-27 | 2022-07-08 | 中国石油化工股份有限公司 | Catalyst for producing monoethanolamine and diethanolamine |
| CN110813367A (en) * | 2019-11-20 | 2020-02-21 | 延安大学 | Phosphorus and rare earth synergistically modified ZSM-5 and method for increasing propylene yield through catalytic cracking of ZSM-5 |
| CN113751057A (en) * | 2021-10-18 | 2021-12-07 | 深圳科冠华太新材料技术有限公司 | Preparation and application of Silicalite-1 and silica-coated ZSM-5 catalyst |
| CN115594196A (en) * | 2022-10-27 | 2023-01-13 | 陕西煤业化工技术研究院有限责任公司（Cn） | Modified SAPO-34 molecular sieve, and preparation method and application thereof |
| CN115594196B (en) * | 2022-10-27 | 2024-02-20 | 陕西煤业化工技术研究院有限责任公司 | A modified SAPO-34 molecular sieve and its preparation method and application |
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| CN102069007B (en) | 2016-03-16 |
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