CN102069007B - The Catalysts and its preparation method of olefin cracking preparation of propylene - Google Patents
The Catalysts and its preparation method of olefin cracking preparation of propylene Download PDFInfo
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Abstract
A kind of Catalysts and its preparation method of olefin cracking preparation of propylene, this catalyst is less than the molecular screen primary powder of 300 for active main body with silica alumina ratio (mole), first molecular screen primary powder, Ludox and/or Alumina gel and template Homogeneous phase mixing is made, after crystallization forming, dry also roasting, through high-temperature water vapor hydrothermal treatment consists, then with rare earth metal and/or phosphorus for modifier carries out modification.By weight percentage: rare earth metal content is 0.2-8%, the content of nonmetal phosphorus is 0.1-5%, and remaining set becomes molecular sieve.This catalyst has good activity and stability, selective higher to propylene, can be applicable to the industrial circle producing propylene.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method of olefin cracking preparation of propylene.
Background technology
Propylene is one of basic organic chemical industry raw material, mainly for the production of all multi-products such as polypropylene, isopropylbenzene, expoxy propane, acrylonitrile, acrylic acid, has important impact to national economy.In recent years, propylene year demand in continuous growth, its annual growth has exceeded the important light olefin of another one: the annual growth of ethene.Propylene is main or obtained by preparing ethylene by steam cracking device and catalytic cracking unit, accounts for about 65% of propylene source.In addition, many technique of producing propylene is developed both at home and abroad, the such as technology such as dehydrogenating propane, preparing propylene from methanol.
From the C of steam cracking device and catalytic cracking unit
4-C
8containing a large amount of olefines in mixture.According to the difference of raw material, reaction depth and catalyst, C
4-C
8the composition comparison in difference of mixture is obvious.Such as under normal circumstances, the C of steam cracking device by-product
4mixture composition (weight) is about: alkane: 3%, isobutene: 22%, butene-1: 14%, butene-2: 11, butadiene: 50%; And the C of catalytic cracking unit by-product
4mixture composition (weight) is about: iso-butane 34%, normal butane: 10%, isobutene: 15%, butene-1: 13, butene-2: 28%.And from total amount, the generally C of catalytic cracking unit by-product
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
8little component such as C in mixture
4the separated utilization of butadiene in mixture, isobutene, other most components are used by as fuel, and added value is lower.
By the end of the year 2009, Chinese crude oil time processing ability will reach 4.77 hundred million tons, and over the past two years, and China is constructed and put into operation and the refining capacity of building can reach more than 5,000 ten thousand tons, building or the steam cracking device scale of planning construction also considerable.Therefore, following will have a large amount of C
4-C
8mixture occurs, 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 mixture has one of the solution compared with hi-tech economy, and particularly under the background environment of soaring oil prices, the method not only increases C
4-C
8the chemical industry added value of mixture, and meet market to the ever-increasing demand of propylene.
Document US2006116544A1 describes a kind of technique utilizing preparing olefin by catalytic cracking.This technique adopts SiO
2/ Al
2o
3for the pentasil type zeolite of 25-800 (mole), supported rare earth element and a kind of element at least in Mn, Zr on it.In rare earth element and molecular sieve, the atomic ratio of aluminium is that in the summation of 0.1-20, Mn and Zr and molecular sieve, the mol ratio of aluminium is 0.1-20.In addition, molecular sieve is the nonmetal phosphorus of load also, and its content is 0.1%-5%.This catalyst needs to apply under water vapour existence condition, and the yield of product propylene is about 15% (weight), and the yield of ethene is about 35% (weight).
Document EP109059 describes a kind of C
4-C
12mixed olefins prepares the technique of propylene and ethylene, and the catalyst that this technique adopts is ZSM-5 or ZSM-11 molecular sieve, SiO
2/ Al
2o
3be less than or equal to 300, binding agent is SiO
2.Molecular sieve is through phosphorus, calcium, copper, zinc or magnesium-modified.At reaction temperature 400-600, reaction velocity is greater than 50 hours
-1condition under, this catalyst is about 38.5% to the selective of propylene, and to C
5the selective of above cut is greater than 33.5%.
The documents such as CN1506342A, CN1611471A, CN1915515A, CN1927785A describe the catalyst for olefin catalytic cracking to produce propylene, ethene.The catalyst adopted all is preferably ZSM-5 molecular sieve catalyst, and by different method of modifying, modification is carried out to ZSM-5 molecular sieve, the binding agent that shaping of catalyst adopts is silica, aluminium oxide or both mixtures, and the shared in the catalyst ratio of binding agent is 10-70% (weight).The propene yield that catalyst described in these documents obtains is about 36%, and yield of ethene is about 12%.
Disclosed in above-mentioned document, catalyst all have employed a certain amount of binding agent, help molecular sieve molded, although obtain good physical strength, reduce the surface area of molecular sieve simultaneously and then decrease the activated centre of molecular sieve, and add diffusional resistance, affect the selective of object product.
Summary of the invention
The present invention relates to a kind of Catalysts and its preparation method of olefin cracking preparation of propylene, be mainly used in by large molecular olefine catalytic cracking for producing propylene.
Technical problem to be solved by this invention is active lower, object selectivity of product is not high and carbon accumulation resisting ability is strong etc. the problem of the catalyst reaction of olefin cracking preparation of propylene in conventional art, provides a kind of new Catalysts and its preparation method.This catalyst have larger surface area, reactivity high, to object product propylene selective better and there is the advantages such as good 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 preparation of propylene, it is characterized in that this catalyst is less than the molecular screen primary powder of 300 for active main body with silica alumina ratio (mole), first molecular screen primary powder, Ludox and/or Alumina gel and template Homogeneous phase mixing is made, after crystallization forming, drying and roasting, use high-temperature water vapor hydrothermal treatment consists, then with rare earth metal and/or phosphorus for modifier carries out modification.By weight percentage: rare earth metal content is 0.2-8%, 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 (mole) of molecular screen primary powder is more preferably 20-250.
The mixed proportion (weight) of Ludox and/or Alumina gel and molecular screen primary powder is preferably 1: 1-10.
Template is preferably cyclohexylamine, C
2-C
4alkyl quaternary ammonium salts or their mixture, the mixed proportion (weight) of template and molecular screen primary powder is preferably 1: 1-10.
Rare earth metal is preferably at least one in lanthanum, cerium, praseodymium, neodymium, and rare earth metal content is more preferably 0.5-5%.
The content of nonmetal phosphorus is more preferably 0.5-2.5%.
The temperature of hydrothermal treatment consists is preferably 250 DEG C-550 DEG C, and the processing time is preferably 3 hours-36 hours.
The preparation method of this catalyst preferably adopts following steps:
Step one: molecular screen primary powder, Ludox and/or Alumina gel, template are mixed, crystallization certain hour aftershaping, then dry 5-15 hour at 60 DEG C-160 DEG C, and in 450 DEG C-650 DEG C roasting 2-6 hour.
Step 2: under 250 DEG C of-550 DEG C of conditions, carries out hydrothermal treatment consists 3-36 hour by step one gained catalyst, and the thermal source of employing is the mixture of water vapour and nitrogen (volume ratio is 1: 10-20).
Step 3: the catalyst after hydrothermal treatment consists is flooded 3-8 hour, heating evaporation, then dry 5-15 hour at 60 DEG C-160 DEG C in containing the aqueous solution of nonmetal phosphorus at 60 DEG C-100 DEG C, and in 450 DEG C-650 DEG C roasting 2-6 hour.
Step 4: catalyst step 3 obtained floods 3-8 hour, heating evaporation, then dry 5-15 hour at 60 DEG C-160 DEG C in containing the aqueous solution of rare earth metal at 60 DEG C-100 DEG C, and in 450 DEG C-650 DEG C roasting 2-6 hour.
Step 5: the passivation of catalyst.Catalyst step 4 obtained is in 550 DEG C, passivation 3-8 hour under nitrogen environment, and the catalyst after passivation is last catalyst prod.
Crystallization temperature is preferably 120 DEG C-180 DEG C, and crystallization time is preferably 20-120 hour.
The application conditions of this catalyst is preferably: reaction raw materials is preferably containing C
4-C
8the hydrocarbon mixture of alkene, reactor is preferably fixed bed or fluid bed, is more preferably fixed bed; Reaction temperature is preferably 450 DEG C-600 DEG C, 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 Molecular Sieves as Template agent, through crystallization forming, drying and roasting, binding agent and molecular sieve is made to be combined into the new molecular sieve catalyst having Different Silicon aluminum ratio, effectively increase the surface area of molecular sieve catalyst, reduce diffusional resistance, add the activated centre of catalyst, decrease the generation of side reaction.Meanwhile, utilize rare earth element to catalyst modification, carbon accumulation resisting ability and the stability of catalyst can be improved; Utilize nonmetal phosphorus to carry out modification to catalyst, the acidity of adjustable catalyst can and strengthen the hydrothermal stability of catalyst.This catalyst reaches 50% to the selective of object product propylene, achieves good technique effect.
Below by embodiment, the invention will be further elaborated.
Detailed description of the invention
Identical appreciation condition is adopted to the catalyst sample that all embodiments obtain, for:
Catalyst: 1.0 grams; Raw material is C
4-C
5mixture, olefin(e) centent (weight) is wherein 55%, and material flow is 20 Grams Per Hours; Reaction temperature is 530 DEG C, and reaction pressure is 0.18MPa, adopts fixed bed reactors.
The evaluation result of all catalyst samples is in table 1.
[embodiment 1-3]
Be that 100 grams, the former powder of ZSM-5 molecular sieve of 60, Ludox 20 grams, tetraethyl ammonium hydroxide 10 grams and cyclohexylamine 10 grams mix by silica alumina ratio (mole), difference crystallization 36 hours, 72 hours, 120 hours under 160 DEG C of conditions, shaping, then at 100 DEG C dry 10 hours, and in 550 DEG C of roastings 3 hours.Under 550 DEG C of conditions, the mixture of the catalyzer with water steam after roasting and nitrogen is carried out hydrothermal treatment consists 3 hours (volume ratio of water vapour and nitrogen is 1: 10).By the catalyst after hydrothermal treatment consists at (NH
4)
2hPO
4in 100 DEG C of dippings 4 hours in the aqueous solution, after heating evaporation at 120 DEG C dry 8 hours, then in 550 DEG C of roastings 3 hours.By the catalyst after P Modification at La (NO
3)
3the aqueous solution in 100 DEG C of dippings 4 hours, after heating evaporation at 100 DEG C dry 10 hours, and in 550 DEG C of roastings 3 hours.Through modification, in catalyst, the content of nonmetal phosphorus is 0.5% (weight), and the content of La is 0.5% (weight).By modified catalyst in 550 DEG C, there is lower passivation and obtain catalyst sample 1-3 in 5 hours in nitrogen.
[embodiment 4-6]
Be the ZSM-11 molecular screen primary powder 100 grams of 100 by silica alumina ratio (mole), Ludox 20 grams, Alumina gel 10 grams, cyclohexylamine 20 grams mix, difference crystallization 48 hours, 96 hours, 144 hours under 120 DEG C of conditions, shaping, then at 120 DEG C dry 8 hours, and in 500 DEG C of roastings 5 hours.Under 550 DEG C of conditions, the mixture of the catalyzer with water steam after roasting and nitrogen is carried out hydrothermal treatment consists 3 hours (volume ratio of water vapour and nitrogen is 1: 20).By the catalyst after hydrothermal treatment consists at (NH
4)
2hPO
4in 80 DEG C of dippings 8 hours in the aqueous solution, after heating evaporation at 100 DEG C dry 10 hours, then in 500 DEG C of roastings 5 hours.By the catalyst after P Modification at Ce (NO
3)
3the aqueous solution in 80 DEG C of dippings 8 hours, after heating evaporation at 120 DEG C dry 8 hours, and in 500 DEG C of roastings 5 hours.Through modification, in catalyst, the content of nonmetal phosphorus is 1.5% (weight), and the content of Ce is 1.5% (weight).By modified catalyst in 550 DEG C, there is lower passivation and obtain catalyst sample 4-6 in 5 hours in nitrogen.
[embodiment 7-9]
Be that 100 grams, the former powder of ZSM-35 molecular sieve of 200, Ludox 60 grams, TPAOH 30 grams and cyclohexylamine 10 grams mix by silica alumina ratio (mole), difference crystallization 36 hours, 72 hours, 120 hours under 180 DEG C of conditions, shaping, then at 100 DEG C dry 10 hours, and in 600 DEG C of roastings 3 hours.Under 450 DEG C of conditions, the mixture of the catalyzer with water steam after roasting and nitrogen is carried out hydrothermal treatment consists 24 hours (volume ratio of water vapour and nitrogen is 1: 15).By the catalyst after hydrothermal treatment consists at (NH
4)
2hPO
4in 60 DEG C of dippings 10 hours in the aqueous solution, after heating evaporation at 120 DEG C dry 8 hours, then in 600 DEG C of roastings 3 hours.By the catalyst after P Modification at La (NO
3)
3the aqueous solution in 60 DEG C of dippings 10 hours, after heating evaporation at 100 DEG C dry 10 hours, and in 600 DEG C of roastings 3 hours.Through modification, in catalyst, the content of nonmetal phosphorus is 3.0% (weight), and the content of La is 3.0% (weight).By modified catalyst in 550 DEG C, there is lower passivation and obtain catalyst sample 7-9 in 5 hours in nitrogen.
[embodiment 10-12]
Be that 100 grams, the former powder of ZSM-5 molecular sieve of 160, Ludox 30 grams, Alumina gel 30 grams, TBAH 20 grams and cyclohexylamine 20 grams mix by silica alumina ratio (mole), difference crystallization 36 hours, 72 hours, 120 hours under 120 DEG C of conditions, shaping, then at 100 DEG C dry 10 hours, and in 550 DEG C of roastings 3 hours.Under 300 DEG C of conditions, the mixture of the catalyzer with water steam after roasting and nitrogen is carried out hydrothermal treatment consists 36 hours (volume ratio of water vapour and nitrogen is 1: 20).By the catalyst after hydrothermal treatment consists at (NH
4)
2hPO
4in 80 DEG C of dippings 8 hours in the aqueous solution, after heating evaporation at 120 DEG C dry 8 hours, then in 550 DEG C of roastings 3 hours.By the catalyst after P Modification at Ce (NO
3)
3the aqueous solution in 80 DEG C of dippings 8 hours, after heating evaporation at 120 DEG C dry 8 hours, and in 550 DEG C of roastings 3 hours.Through modification, in catalyst, the content of nonmetal phosphorus is 1.5% (weight), and the content of Ce is 1.5% (weight).By modified catalyst in 550 DEG C, there is lower passivation and obtain catalyst sample 10-12 in 5 hours in nitrogen.
Table 1 catalyst sample test result
| Sample | C 4 olefin conversion ratio, % | Propylene Selectivity, % | Ethylene selectivity, % | C 5 +Selective, % |
| 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 (9)
1. the catalyst of an olefin cracking preparation of propylene, it is characterized in that this catalyst is less than the molecular screen primary powder of 300 for active main body with silica alumina ratio (mole), first molecular screen primary powder, Ludox and/or Alumina gel and template Homogeneous phase mixing is made, after crystallization forming, drying and roasting, through high-temperature water vapor hydrothermal treatment consists, then with rare earth metal and/or phosphorus for modifier carries out modification; By weight percentage: rare earth metal content is 0.2-8%, the content of nonmetal phosphorus is 0.1-5%, and remaining set becomes molecular sieve.
2. the catalyst of olefin cracking preparation of propylene according to 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 (mole) of molecular screen primary powder is 20-250.
3. the catalyst of olefin cracking preparation of propylene according to claim 1, is characterized in that the mixed proportion (weight) of Ludox and/or Alumina gel and molecular screen primary powder is 1: 1-10.
4. the catalyst of olefin cracking preparation of propylene according to claim 1, is characterized in that template is cyclohexylamine, C
2-C
4alkyl quaternary ammonium salts or their mixture, the mixed proportion (weight) of template and molecular screen primary powder is 1: 1-10.
5. the catalyst of olefin cracking preparation of propylene according to claim 1, it is characterized in that rare earth metal is at least one in lanthanum, cerium, praseodymium, neodymium, rare earth metal content is 0.5-5%.
6. the catalyst of olefin cracking preparation of propylene according to claim 1, is characterized in that the content of nonmetal phosphorus is 0.5-2.5%.
7. the catalyst of olefin cracking preparation of propylene according to claim 1, it is characterized in that hydrothermal treatment consists temperature is 250 DEG C-550 DEG C, the processing time is 3-36 hour.
8. the catalyst of olefin cracking preparation of propylene according to claim 1, is characterized in that the preparation method of this catalyst is:
Step one: molecular screen primary powder, Ludox and/or Alumina gel, template are mixed, crystallization certain hour aftershaping, then dry 5-15 hour at 60 DEG C-160 DEG C, and in 450 DEG C-650 DEG C roasting 2-6 hour; Wherein crystallization temperature is 120 DEG C-180 DEG C, and crystallization time is 20-120 hour;
Step 2: under 250 DEG C of-550 DEG C of conditions, carries out hydrothermal treatment consists 3-36 hour by step one gained catalyst, and the thermal source of employing is the mixture of water vapour and nitrogen, and the mixed proportion (volume) of water vapour and nitrogen is 1: 10-20;
Step 3: the catalyst after hydrothermal treatment consists is flooded 3-8 hour, heating evaporation, then dry 5-15 hour at 60 DEG C-160 DEG C in containing the aqueous solution of nonmetal phosphorus at 60 DEG C-100 DEG C, and in 450 DEG C-650 DEG C roasting 2-6 hour;
Step 4: catalyst step 3 obtained floods 3-8 hour, heating evaporation, then dry 5-15 hour at 60 DEG C-160 DEG C in containing the aqueous solution of rare earth metal at 60 DEG C-100 DEG C, and in 450 DEG C-650 DEG C roasting 2-6 hour;
Step 5: catalyst step 4 obtained is in 550 DEG C, passivation 3-8 hour under nitrogen environment, and the catalyst after passivation is last catalyst prod.
9. the catalyst of olefin cracking preparation of propylene according to claim 1, is characterized in that the application conditions of this catalyst is: reaction raw materials is for containing C
4-C
8the hydrocarbon mixture of alkene, reactor is fixed bed or fluidized-bed reactor; Reaction temperature is 450 DEG C-600 DEG C, and reaction pressure is 0.08-0.28MPa, and weight space velocity is 2.5-25 hour
-1.
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| CN104549437B (en) * | 2013-10-12 | 2017-05-31 | 中国石油化工股份有限公司 | A kind of phosphorus and the rare earth modified molecular sieve catalysts of ZSM 5 and its preparation method and application |
| 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 |
| 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 | Modified SAPO-34 molecular sieve, and preparation method and application thereof |
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|---|---|---|---|---|
| CN1915925A (en) * | 2005-08-15 | 2007-02-21 | 中国石油化工股份有限公司 | Method for producing propylene, ethene by using catalytic cracking olefin through fluid bed |
| CN1927714A (en) * | 2005-09-07 | 2007-03-14 | 中国石油化工股份有限公司 | Preparation method of ZSM-type molecular sieve without binding agent |
| CN101259424A (en) * | 2008-03-18 | 2008-09-10 | 南京工业大学 | Preparation of toluene shape-selective disproportionation without adhesive |
| CN101531918A (en) * | 2008-12-22 | 2009-09-16 | 洛阳瑞泽石化工程有限公司 | Method for improving liquid hydrocarbon yield of catalytic cracking and catalyst thereof |
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| US7629498B2 (en) * | 2007-06-28 | 2009-12-08 | Exxonmobil Chemical Patents, Inc. | Process of manufacturing para-xylene |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1915925A (en) * | 2005-08-15 | 2007-02-21 | 中国石油化工股份有限公司 | Method for producing propylene, ethene by using catalytic cracking olefin through fluid bed |
| CN1927714A (en) * | 2005-09-07 | 2007-03-14 | 中国石油化工股份有限公司 | Preparation method of ZSM-type molecular sieve without binding agent |
| CN101259424A (en) * | 2008-03-18 | 2008-09-10 | 南京工业大学 | Preparation of toluene shape-selective disproportionation without adhesive |
| CN101531918A (en) * | 2008-12-22 | 2009-09-16 | 洛阳瑞泽石化工程有限公司 | Method for improving liquid hydrocarbon yield of catalytic cracking and catalyst thereof |
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