CN100475337C - Catalyst of naphtha catalytic pyrolysis preparing ethylene and propylene - Google Patents
Catalyst of naphtha catalytic pyrolysis preparing ethylene and propylene Download PDFInfo
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- CN100475337C CN100475337C CNB2006100250996A CN200610025099A CN100475337C CN 100475337 C CN100475337 C CN 100475337C CN B2006100250996 A CNB2006100250996 A CN B2006100250996A CN 200610025099 A CN200610025099 A CN 200610025099A CN 100475337 C CN100475337 C CN 100475337C
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- propylene
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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
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- 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
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Abstract
A catalyst for preparing ethene and propene by catalytic cracking of naphtha with low reaction temp and high selectivity and output is composed of ZSM-5 zeolite and mordenite.
Description
Technical field
The present invention relates to a kind of catalyst of naphtha catalytic pyrolysis preparing ethylene propylene.
Background technology
Along with the development of society, the market demand of China's ethylene, propylene sharply increases, and the import volume of ethylene, propylene and downstream product thereof increases year by year, and the home products occupation rate of market is less than half.Whole world ethene is raw material with naphtha (or ethane) mainly at present, adopts steam heat cracking technique (under the temperature about 800 ℃) production, and its output surpasses 90% of total output.Catalytic pyrolysis is compared with the steam heat cracking, and this process reaction temperature is than low 50～200 ℃ approximately of standard cracking reactions, and therefore than common steam cracking less energy consumption, cracking furnace pipe inwall coking rate will reduce, thereby but prolong operation cycle increases the boiler tube life-span; CO2 emission also can reduce, and can adjust the product mix flexibly, can increase the total recovery of ethene and propylene, and production cost of ethylene reduces significantly.
Japan's Asahi Chemical Industry's patent (CN1274342A) has announced that a kind of high silica alumina ratio, the aperture molecular sieve between 0.5～0.65 is a catalyst, be the feedstock production ethylene, propylene with the light hydrocarbons that contains alkene, but the ethylene, propylene yield is lower.
Exxon Mobil (Chinese patent application 00816642.0) announces that a kind of aperture of a kind of usefulness contains the hydrocarbon raw material of naphtha less than the zeolite treatment of 0.7 nanometer, produces ethylene, propylene between 550～600 ℃, and conversion of raw material is lower.
Mobil Oil Corporation (CN1413244A) has announced that a kind of mesopore phosphate material with modification is that catalyst and elementary catalytic pyrolysis material combine, the hydrocarbon raw material of catalytic pyrolysis sulfur-bearing prepares micromolecular hydrocarbon mixture, and the serviceability temperature of its catalyst and conversion of raw material are all lower.
Summary of the invention
Technical problem to be solved by this invention is problems such as the catalyst activity selectivity of using in the existing catalytic pyrolysis lower or ethylene, propylene is relatively poor, serviceability temperature height, and a kind of catalyst of new naphtha catalytic pyrolysis preparing ethylene propylene is provided.This catalyst has active height, ethylene, propylene selectivity height, advantage that reaction temperature is low.
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 naphtha catalytic pyrolysis preparing ethylene propylene is characterized in that catalyst is SiO
2/ Al
2O
3Mol ratio is 12～100 the ZSM-5 and the composite molecular screen of modenite.
In the technique scheme, the SiO of composite molecular screen
2/ Al
2O
3The mol ratio preferable range is 14～40, in the composite molecular screen by weight percentage the content of ZSM-5 molecular sieve be preferable range 20%～99.5%, more preferably scope is 60%～99%.
At least a as in silicate, metasilicate sodium or the Ludox of the preparation composite molecular screen silicon source of using, aluminium source are at least a in aluminium salt or the aluminate, and the template agent is at least a in ethylenediamine or the ethamine, with the pH value of diluted acid adjusting colloidal sol.
The synthetic method of composite molecular screen is by silicon source and the aluminium source that material proportion is got aequum, to make solution with dissolved in distilled water respectively, then two kinds of solution are mixed, the powerful stirring adds the template agent of aequum then, stirs with rare acid for adjusting pH value in 9～13 scopes.Colloidal sol is put into autoclave, control 150～220 ℃ of temperature crystallization after 10～100 hours, take out washing, oven dry, roasting, can obtain the composite molecular screen of ZSM-5 and modenite.With concentration is 5% ammonium nitrate solution, and 70 ℃ of exchanges twice, roasting then makes hydrogen type molecular sieve after repeating twice, then compressing tablet, break into pieces, sieve, get 20～40 purpose particles and put into fixed bed reactors and check and rate.
Catalyst involved in the present invention, owing to adopted the composite molecular screen that contains ZSM-5 molecular sieve and modenite simultaneously, this molecular sieve is owing to contain acid strong modenite, so its acid amount is bigger, acidity is stronger, be suitable for the higher alkane cracking of cracking energy, because composite molecular screen contains multistage pore canal, can handle the different mixture material of molecular diameter, because the degree that comes to the surface of composite molecular screen, acid, having of duct and specific surface and two kinds of molecular sieve mechanical mixture than big difference, so catalytic performance is preferably arranged, is used for the naphtha catalytic pyrolysis preparing ethylene propylene reaction, with C
4～C
10Naphtha be raw material [the raw material weight percentage composition is as follows: alkane 65.2% (wherein n-alkane is 32.5%), cycloalkane is 28.4%, alkene is 0.17%, aromatic hydrocarbons is 6.2%], with the examination down of fixed bed reactors normal pressure, range of reaction temperature is 600～700 ℃, and air speed is 0.25～2 hour
-1, water/weight of oil is than being to react under 1～4 the condition, ethene, propylene total recovery reach as high as 50%, have obtained better technical effect.
The invention will be further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
Get 284 gram sodium metasilicates, become solution A with 300 gram dissolved in distilled water, get 33.3 gram aluminum sulfate, make solution B with 100 gram distilled water, B solution is slowly poured in the A solution, the powerful stirring, add 24.4 gram ethylenediamines then, stir down, regulate the pH value 11.5 with dilute sulfuric acid, the mole proportioning of control colloidal sol is: Si: Al: ethylenediamine: H
2O=1: 0.1: 0.4: 40, mixed solution is put into autoclave, 180 ℃ of insulations 40 hours, take out washing, oven dry, roasting then, make the composite molecular screen of ZSM-5 and modenite, quantitatively contain the modenite of the ZSM-5 and 14.5% (weight) of 85.5% (weight) with the XRD diffraction as can be known in the composite molecular screen.With concentration is 5% ammonium nitrate solution, and 70 ℃ of exchanges twice, roasting then makes hydrogen type molecular sieve after repeating twice, then compressing tablet, break into pieces, sieve, get 20～40 purpose particles and put into fixed bed reactors, 650 ℃, air speed 0.5 hour
-1, water/weight of oil ratio is to check and rate under 3: 1 the condition, the results are shown in Table 4.
[embodiment 2～8]
Get the different composite molecular screen of ZSM-5 molecular sieve weight percentage, make catalyst, be designated as FH-2 respectively, FH-3, FH-4, FH-5, FH-6, FH-7, FH-8 by the mode of embodiment 1.The weight content of ZSM-5 molecular sieve sees Table 1 in the composite molecular screen, and appraisal result sees Table 4.
Table 1
| Embodiment | Contain ZSM-5 ratio (weight %) | Sample number into spectrum |
| Embodiment 2 | 99.5 | FH-2 |
| Embodiment 3 | 97.5 | FH-3 |
| Embodiment 4 | 95.5 | FH-4 |
| Embodiment 5 | 90.5 | FH-5 |
| Embodiment 6 | 81.2 | FH-6 |
| Embodiment 7 | 72.4 | FH-7 |
| Embodiment 8 | 61.5 | FH-8 |
[embodiment 9～13]
Get the composite molecular screen of Different Silicon aluminum ratio,, make catalyst, count FH-9 respectively, FH-10, FH-11, FH-12, FH-13, the SiO of composite molecular screen according to the method for embodiment 1
2/ Al
2O
3Mol ratio sees Table 2, and appraisal result sees Table 4.
Table 2
| Embodiment | SiO 2/Al 2O 3(mol ratio) | Sample number into spectrum |
| Embodiment 9 | 14 | FH-9 |
| Embodiment 10 | 25 | FH-10 |
| Embodiment 11 | 30 | FH-11 |
| Embodiment 12 | 40 | FH-12 |
Table 4
| Sample number into spectrum | Yield of ethene (weight %) | Propene yield (weight %) | Total recovery (weight %) |
| FH-1 | 21.76 | 27.09 | 48.85 |
| FH-2 | 26.38 | 22.41 | 48.79 |
| FH-3 | 22.83 | 26.61 | 49.08 |
| FH-4 | 23.32 | 26.61 | 49.93 |
| FH-5 | 19.61 | 26.3 | 45.91 |
| FH-6 | 24.95 | 21.57 | 46.52 |
| FH-7 | 21.12 | 22.64 | 43.77 |
| FH-8 | 18.99 | 22.45 | 41.44 |
| FH-9 | 17.25 | 24.15 | 41.40 |
| FH-10 | 26.98 | 23.51 | 50.49 |
| FH-11 | 25.12 | 20.91 | 46.03 |
| FH-12 | 19.4 | 26.43 | 45.83 |
[comparative example 1]
With the synthetic pure ZSM-5 molecular sieve of the mode of embodiment 1, making the catalyst postscript is C-1, and checks and rates by the mode of embodiment 1, the results are shown in Table 5.
[comparative example 2]
With the synthetic pure modenite of the mode of embodiment 1, making the catalyst postscript is C-2, and checks and rates by the mode of embodiment 1, the results are shown in Table 5.
[comparative example 3]
In the ratio preparation mechanical impurity of ZSM-5 among the embodiment 1 and modenite, make catalyst, be designated as C-3, check and rate by the mode of embodiment 1, the results are shown in Table 5.
Table 6
| Sample | Yield of ethene (weight %) | Propene yield (weight %) | Total recovery (weight %) |
| C-1 | 20.64 | 22.60 | 43.24 |
| C-2 | 11.32 | 2027 | 31.59 |
| C-3 | 15.38 | 29.28 | 44.65 |
Claims (4)
1, a kind of catalyst of naphtha catalytic pyrolysis preparing ethylene propylene is characterized in that catalyst is SiO
2/ Al
2O
3Mol ratio is 12～100 the ZSM-5 and the composite molecular screen of modenite.
2,, it is characterized in that the SiO of composite molecular screen according to the catalyst of the described naphtha catalytic pyrolysis preparing ethylene propylene of claim 1
2/ Al
2O
3Mol ratio 14～40.
3,, it is characterized in that in the composite molecular screen that the content of ZSM-5 molecular sieve is 20%～99.5% by weight percentage according to the catalyst of the described naphtha catalytic pyrolysis preparing ethylene propylene of claim 1.
4,, it is characterized in that in the composite molecular screen that the content of ZSM-5 molecular sieve is 60%～99% by weight percentage according to the catalyst of the described naphtha catalytic pyrolysis preparing ethylene propylene of claim 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CNB2006100250996A CN100475337C (en) | 2006-03-27 | 2006-03-27 | Catalyst of naphtha catalytic pyrolysis preparing ethylene and propylene |
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|---|---|---|---|
| CNB2006100250996A CN100475337C (en) | 2006-03-27 | 2006-03-27 | Catalyst of naphtha catalytic pyrolysis preparing ethylene and propylene |
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|---|---|
| CN101045212A CN101045212A (en) | 2007-10-03 |
| CN100475337C true CN100475337C (en) | 2009-04-08 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101428233B (en) * | 2007-11-07 | 2011-04-27 | 中国石油化工股份有限公司 | Catalyst for catalytic pyrolysis |
| CN102372553B (en) * | 2010-08-23 | 2013-10-16 | 中国石油化工股份有限公司 | Method for producing olefin by catalytically cracking |
| CN103055929B (en) * | 2011-10-24 | 2015-04-08 | 中国石油化工股份有限公司 | Fluid bed catalyst for preparing olefin through catalytic cracking and preparation method thereof |
| CN103964460B (en) * | 2013-01-30 | 2016-01-20 | 中国石油天然气股份有限公司 | A kind of micropore comprehensive silicon aluminum molecular screen and preparation method thereof |
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