CN101703943A - Catalyst for preparing ethylene and propylene through catalytic cracking of hydrocarbon - Google Patents
Catalyst for preparing ethylene and propylene through catalytic cracking of hydrocarbon Download PDFInfo
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- CN101703943A CN101703943A CN200910154608A CN200910154608A CN101703943A CN 101703943 A CN101703943 A CN 101703943A CN 200910154608 A CN200910154608 A CN 200910154608A CN 200910154608 A CN200910154608 A CN 200910154608A CN 101703943 A CN101703943 A CN 101703943A
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
The invention discloses a catalyst for preparing ethylene and propylene through catalytic cracking of hydrocarbon. A ZRP-1 molecular sieve is used a carrier; a rare-earth metal oxide is used as a catalyst of active components; and the weight of the rare-earth metal oxide accounts for 0.1 to 8.0 percent of the total weight of the catalyst. The catalyst is modified by a proper amount of the rare-earth metal oxide, so the catalyst has good catalytic performance; and the preparation process has simple operation. The catalyst uses the ZRP-1 molecular sieve as the carrier; and as the ZRP-1 molecular sieve has multilevel pore canals, raw materials or mixture materials with different molecular diameters can be processed in the reaction for preparing ethylene and propylene through the catalytic cracking of hydrocarbon. After the catalyst is adopted, high conversion rate of hydrocarbon and high once through yield of ethylene and propylene can be achieved.
Description
Technical field
The present invention relates to a kind of catalyst of preparing ethylene and propylene through catalytic cracking of hydrocarbon.
Background technology
Ethene, propylene play a part very important in petro chemical industry as the important foundation raw material of petrochemical industry.In numerous hydrocarbon cracking production technologies, the pyrolysis in tubular furnace method is occupied an leading position in world's olefin yield.But the pyrolysis method technology exists energy consumption and equipment investment is too high, the cracking stock range of choice is narrower, reaction temperature height shortcomings such as (under the temperature about 800 ℃, producing), and the yield of propylene is lower, has restricted its further development.
Catalytic pyrolysis also is one of important method of producing ethylene, propylene, and catalytic pyrolysis is under the condition that catalyst exists, and petroleum hydrocarbon is carried out the process that low-carbon alkenes such as ethene, propylene are produced in cracking.Compare with the pyrolysis technology of routine, not only can reduce reaction temperature, obtain high selectivity of light olefin, and be easier to regulate the distribution that product is formed.The key of catalytic pyrolysis technology is catalyst, and therefore researching and developing the catalyst with good catalytic more and more becomes the problem that people are concerned about.
United States Patent (USP) (US7381678) has been announced a kind of catalyst that is used for catalytic cracking to prepare lower carbon olefin and aromatic hydrocarbons mixture, and this catalyst deposits to a kind of metal or metal oxide on the surface of zeolite molecular sieve by chemical liquid deposition.This catalyst can improve the yield of ethene in the catalytic naphtha process, but is unfavorable for that propylene optionally improves.
United States Patent (USP) (US6211104) provides a kind of catalyst that is used for catalytic thermal cracking process to prepare lower olefine, catalyst is made up of 10～70% clay, 5～85% inorganic oxide and 1～50% zeolite, its mesolite is the phosphorous and aluminium of 0～25% y-type zeolite and 75～100% or the five-membered ring structure high-silicon zeolite of magnesium or calcium, in catalytic pyrolysis process, this catalyst has demonstrated the activity that well is converted into light olefin, especially ethene, but the ethylene, propylene selectivity of catalyst and yield are not high.
Chinese patent (CN1676213A) has been announced the catalyst of a kind of C4～C7 olefin cracking production propylene, the group vib metal oxide and the Zirconia carrier of average size of microcrystal that comprise 1～20 quality % in the catalyst in 10～100 nanometers, this catalyst helps improving the yield of propylene, but the conversion of olefines rate is relatively low.
Summary of the invention
Lower at the catalyst activity that uses in the existing preparing ethylene and propylene through catalytic cracking of hydrocarbon reaction, the problem that the yield of ethylene, propylene is low, the catalyst that the purpose of this invention is to provide a kind of new preparing ethylene and propylene through catalytic cracking of hydrocarbon, this catalyst activity is higher, helps improving the ethylene, propylene yield.
The catalyst of preparing ethylene and propylene through catalytic cracking of hydrocarbon of the present invention is to be carrier with the ZRP-1 molecular sieve, is the catalyst of active component with the rare-earth oxide, and the weight of rare-earth oxide accounts for 0.1～8.0% of total catalyst weight.The weight of preferred rare earth metal oxides accounts for 0.1～2.0% of total catalyst weight.
Among the present invention, rare-earth oxide is at least a in yittrium oxide, cerium oxide and the lanthana.
Used rare-earth oxide raw material is the soluble compound of yittrium oxide, cerium oxide, lanthana, as nitrate, chloride, carbonate or acetate.Above-mentioned ZRP-1 molecular sieve is provided by Sinopec research institute.
Preparation of catalysts method among the present invention is as follows: a certain amount of ZRP-1 molecular sieve is fully mixed with the soluble compound solution of the rare earth metal of requirement, slowly evaporate redundant moisture behind the dipping, drying, 600～700 ℃ of temperature roasting a few hours, obtain containing the molecular sieve catalyst of rare-earth oxide.
Catalyst of the present invention have catalytic performance preferably, and preparation process is easy and simple to handle after an amount of rare-earth oxide modification.Catalyst is a carrier with the ZRP-1 molecular sieve, because the ZRP-1 molecular sieve itself has multistage pore canal, therefore in the preparing ethylene and propylene through catalytic cracking of hydrocarbon reaction, can handle different raw material of molecular diameter or mixture material.Experiment shows, adopts the ethene that catalyst reaction of the present invention obtains and the total recovery of propylene can reach 53%.
The specific embodiment
The invention will be further elaborated below by embodiment.
Embodiment 1
10g ZRP-1 molecular sieve (being labeled as A) is immersed in the aqueous solution that 15g contains yttrium nitrate, fully mixes, flood after 8 hours, rest solution is evaporated by Rotary Evaporators under 80 ℃ of temperature.120 ℃ of dried overnight, catalyst places Muffle furnace to be warming up to 700 ℃ then, roasting 4 hours.Taking-up is cooled to room temperature, and it is standby to put into drier in mortar behind the pulverize.The catalyst that obtains is labeled as A1, and among this embodiment, yittrium oxide content is 0.3wt%, by weight percentage.Get the 0.1g catalyst and put into fixed bed reactors, 650 ℃, mass space velocity 1 hour
-1, water/normal heptane mol ratio is to check and rate under 3: 1 the condition, the results are shown in Table 1.
Embodiment 2-4
Change the content of yittrium oxide, prepare catalyst, be labeled as A2 respectively, A3, A4 by the mode of embodiment 1.Wherein yittrium oxide content is respectively 0.8wt%, 3.0wt%, and 8.0wt%, by weight percentage, appraisal result sees Table 1.
Table 1
| Sample number into spectrum | Yield of ethene (%) | Propene yield (%) | Total recovery (%) |
| ??A | ??25.1 | ??24.1 | ??49.2 |
| ??A1 | ??27.6 | ??25.4 | ??53.0 |
| ??A2 | ??26.8 | ??25.7 | ??52.5 |
| ??A3 | ??25.3 | ??24.2 | ??49.5 |
| ??A4 | ??25.4 | ??21.3 | ??46.7 |
Embodiment 5-7
With the identical preparation process of embodiment 1, change rare-earth oxide and content thereof, obtain flooding the cerium oxide catalyst that contains different content respectively.Be labeled as B1 respectively, B2, B3.Wherein cerium oxide content is respectively 0.3wt%, 2.0wt%, and 6.0wt%, by weight percentage, appraisal result sees Table 2.
Table 2
| Sample number into spectrum | Yield of ethene (%) | Propene yield (%) | Total recovery (%) |
| ??A | ??25.1 | ??24.1 | ??49.2 |
| ??B1 | ??26.3 | ??25.8 | ??52.1 |
| ??B2 | ??26.5 | ??25.3 | ??51.8 |
| ??B3 | ??24.7 | ??24.2 | ??48.9 |
Embodiment 8
With the identical preparation process of embodiment 1, change rare-earth oxide, obtain flooding the lanthanum oxide catalyst that content is 0.5% (by weight percentage).Be labeled as C1.Appraisal result sees Table 3.
Table 3
| Sample number into spectrum | Yield of ethene (%) | Propene yield (%) | Total recovery (%) |
| ??A | ??25.1 | ??24.1 | ??49.2 |
| ??C1 | ??26.2 | ??24.7 | ??50.9 |
Claims (3)
1. the catalyst of a preparing ethylene and propylene through catalytic cracking of hydrocarbon is characterized in that it is is carrier with the ZRP-1 molecular sieve, is the catalyst of active component with the rare-earth oxide, and the weight of rare-earth oxide accounts for 0.1～8.0% of total catalyst weight.
2. the catalyst of preparing ethylene propylene from catalytic pyrolysis according to claim 1 is characterized in that described rare-earth oxide is at least a in yittrium oxide, cerium oxide and the lanthana.
3. the catalyst of preparing ethylene propylene from catalytic pyrolysis according to claim 1 is characterized in that the weight of catalyst middle rare earth metal oxide accounts for 0.1～2.0% of total catalyst weight.
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| Application Number | Priority Date | Filing Date | Title |
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| CN200910154608A CN101703943A (en) | 2009-11-19 | 2009-11-19 | Catalyst for preparing ethylene and propylene through catalytic cracking of hydrocarbon |
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| Application Number | Priority Date | Filing Date | Title |
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| CN200910154608A CN101703943A (en) | 2009-11-19 | 2009-11-19 | Catalyst for preparing ethylene and propylene through catalytic cracking of hydrocarbon |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113322093A (en) * | 2020-02-28 | 2021-08-31 | 中国石油化工股份有限公司 | Catalytic cracking method |
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2009
- 2009-11-19 CN CN200910154608A patent/CN101703943A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113322093A (en) * | 2020-02-28 | 2021-08-31 | 中国石油化工股份有限公司 | Catalytic cracking method |
| CN113322093B (en) * | 2020-02-28 | 2023-06-09 | 中国石油化工股份有限公司 | Catalytic cracking method |
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Open date: 20100512 |