CN1313268A - Process for preparing ethylene and propylene - Google Patents
Process for preparing ethylene and propylene Download PDFInfo
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- CN1313268A CN1313268A CN 00103425 CN00103425A CN1313268A CN 1313268 A CN1313268 A CN 1313268A CN 00103425 CN00103425 CN 00103425 CN 00103425 A CN00103425 A CN 00103425A CN 1313268 A CN1313268 A CN 1313268A
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Abstract
A process for preparing ethylene and propylene features that the C2-C5 gas hydrocarbon and catalyst containing laminated column clay molecular sieve take part in reaction at 650-750 deg.C and 150000-400000 Pa for 0.2-1 second. said catalyst contains aluminium cross-linked laminated coloum clay molecular sieve (30-75 wt.%), inorganic oxide adhesive containing Al, Si, or Zr (10-40), high-Si zeolite with five-membered ring structure (0-30), modifier chosen from Mg, Al, P, Sn and polyglycol or their mixtur (0-10) and gaolin clay (0-50).
Description
The invention relates to the preparation method of ethene and propylene.Exactly, the invention relates to containing C
2～C
5Hydro carbons be raw material is produced ethene and propylene in the presence of the clay molecular sieve with layer structure catalyzer method.
As everyone knows, ethene and propylene are the main raw materials of organic chemistry and petrochemical industry, and their preparation method mainly is by the catalytic cracking of the dehydrogenation of ethane and propane, petroleum hydrocarbon or catalytic pyrolysis.
CN1124467A and CN1124468A disclose with C
1～C
4Lower hydrocarbon is the method that raw material is produced ethene as methane, Sweet natural gas or liquefied petroleum gas (LPG).Used the loaded catalyst that contains VIII class precious metal in the method, at 500～980 ℃, preferred 670～850 ℃, 1～10 normal atmosphere, under the condition that preferred 1～5 normal atmosphere and thinner nitrogen exist catalyzer is contacted with lower hydrocarbon, can obtain to be up to 12.1% transformation efficiency and 11.0% ethylene yield.
CN86103900A discloses a kind of with the C in the Sweet natural gas
3And C
4Hydrocarbon is converted into the method for ethene and propylene.This method is that the oxide compound with magnesium and manganese is a catalyzer, add or do not add the cocatalytic element that is selected from calcium, strontium, barium, tin and antimony, at 625～850 ℃, preferred 650～775 ℃, 0.69～690KPa, under the condition that preferred 6.9～414KPa and steam exist Sweet natural gas is contacted with catalyzer, can obtain to be up to 84% transformation efficiency, 33.0% ethylene selectivity and 22.2% propylene selectivity.
The objective of the invention is on the basis of above-mentioned prior art, to provide a kind of new to contain C
2～C
5Hydrocarbon gas be the method that raw material is produced ethene and propylene.
Method provided by the invention is: at 650～750 ℃, 1.5～4 * 10
5Make under the condition in Pa, 0.2～1 second reaction times and contain C
2～C
5Hydrocarbon gas contact with the catalyzer that contains clay molecular sieve with layer structure.Consisting of of this catalyzer: the modified component that being selected from of the inorganic oxide binder that contains aluminium or silicon or zirconium of the aluminium cross-linked clay molecular sieve with layer structure of 30～75 heavy %, 10～40 heavy %, the five-membered ring structure high-silicon zeolite of 0～30 heavy %, 0～10 heavy % contains magnesium, aluminium, phosphorus, tin, polyoxyethylene glycol or its mixture and kaolin group's clay of 0～50 heavy %.
According to method provided by the invention, contain C
2～C
5The gaseous hydrocarbon feedstock hydrocarbon that can contain following weight percentage form: 0.2～1.0% ethane; 0～0.6% ethene; 2.0～15.0% propane; 0～45% propylene; 0～30% butane; 0～40% butylene; 0～5% pentane.The hydrocarbon of going up is according to this formed, and the raw material that is applicable to the inventive method both can be Sweet natural gas, liquefied petroleum gas (LPG) or catalytic cracked gas, also can be remaining gaseous fraction after separating alkene by liquefied petroleum gas (LPG) or catalytic cracked gas.
The used catalyzer that contains clay molecular sieve with layer structure is a disclosed catalyzer among the CN1221015A in the inventive method.This catalyzer is characterised in that:
(1) has following composition: kaolin group's clay of the modified component of the inorganic oxide binder of the clay molecular sieve with layer structure of 30～75 heavy %, 10～40 heavy %, the five-membered ring structure high-silicon zeolite of 0～30 heavy %, 0～10 heavy % and 0～50 heavy %;
(2) wherein clay molecular sieve with layer structure is the aluminium cross-linked laminated clay that polymerization aluminium chlorohydroxide or aluminium colloidal sol with high-basicity are interlayer support thing predecessor;
(3) wherein binding agent is to be selected from the inorganic oxide that forms after the colloidal sol that contains aluminium, silicon, zirconium or gel or one or more the material drying, roasting in these poly ethyldiol modified materials;
(4) its mesolite is selected from the product after commodity are called ZRP series or ZSM-5 class zeolite or their modifications;
(5) wherein the precursor of modified component is selected from the compound that contains magnesium, aluminium, phosphorus or tin or one or more the material in the polyoxyethylene glycol.
This Preparation of catalysts method is as follows: the laminated clay of sodium type or rare-earth type and binding agent precursor, zeolite, kaolin group's clay are mixed making beating and are spray dried to microballoon by the predetermined proportion of catalyst prod; By the feed ratio of every gram clay microballoon is added in the aluminum crosslinker of basicity OH/Al about 2.5, uses NH with 2.0～10.0mmol Al linking agent
4OH regulates and keeps its pH5～6, reacts 2～3 hours down at 65～75 ℃; Filtration, washing, drying, 650 ℃ of roastings 1～3 hour.
Method provided by the invention can also can be produced ethene and propylene to replenish as the matching method of the heavy-oil catalytic thermal cracking process of using above-mentioned catalyzer as the method for producing ethene and propylene separately.Under one situation of back, need not change device, need not increase equipment, need not change operational condition yet and both can implement the present invention.
Below example will illustrate further the present invention, but not thereby limiting the invention.
Example and comparative example
Used hydrocarbon feed weight consists of: 0.63% ethane; 0.41% ethene; 5.61% propane; 11.92% propylene; The butane of surplus, butylene and pentane.
Used catalyzer is to make according to the example among the CN1221015A 1 in the example.This catalyzer consists of: 50 heavy % layer post rectorite lengs, 15 heavy % weigh % from the Al that intends thin water-aluminum hydroxide colloidal sol through phosphorus and magnesium-modified ZRP-1 zeolite, 30
2O
3The kaolin of binding agent and 5 heavy %.
Test is carried out in little anti-fixed bed.Reactor inside diameter is 3 millimeters, and the catalyzer loading amount is 60 milligrams.The reaction procatalyst is through 500 ℃, 40 minutes pre-treatment of nitrogen purging.Adopt the pulse mode charging during reaction, each inlet amount is 70 microlitres.Be 0.3 second the duration of contact of raw material hydrocarbon and catalyzer.Reaction pressure is 2.5 * 10
5Pa.The reaction product gas chromatographic analysis.
Comparative Examples has been listed under the identical condition of operation condition the heat scission reaction result with quartz sand alternative catalysts gained.The consumption of quartz sand is all identical with catalyzer with granularity.
Under the differential responses temperature, the gained reaction result is as shown in the table.Listed product yield is meant the weight percentage to raw material hydrocarbon in the table.
Claims (7)
1. the preparation method of ethene and propylene is at 650～750 ℃, 1.5～4 * 10
5Under the condition in Pa, 0.2～1 second reaction times, make to contain C
2～C
5Hydrocarbon gas contact with the catalyzer that contains clay molecular sieve with layer structure.
2. in accordance with the method for claim 1, it is characterized in that said hydrocarbon gas can contain the hydrocarbon composition of following weight percentage: 0.2～1.0% ethane; 0～0.6% ethene; 2.0～15.0% propane; 0～45% propylene; 0～30% butane; 0～40% butylene; 0～5% pentane.
3. in accordance with the method for claim 1, it is characterized in that the said catalyzer that contains clay molecular sieve with layer structure has following composition: kaolin group's clay of the modified component of the inorganic oxide binder of the clay molecular sieve with layer structure of 30～75 heavy %, 10～40 heavy %, the five-membered ring structure high-silicon zeolite of 0～30 heavy %, 0～10 heavy % and 0～50 heavy %.
4. in accordance with the method for claim 3, it is characterized in that said clay molecular sieve with layer structure is the aluminium cross-linked laminated clay that polymerization aluminium chlorohydroxide or aluminium colloidal sol with high-basicity are interlayer support thing predecessor.
5. in accordance with the method for claim 3, it is characterized in that said binding agent is to be selected from the inorganic oxide that forms after the colloidal sol that contains aluminium, silicon, zirconium or gel or one or more the material drying, roasting in these poly ethyldiol modified materials.
6. in accordance with the method for claim 3, it is characterized in that said zeolite is selected from the product after commodity are called ZRP series or ZSM-5 class zeolite or their modifications.
7. in accordance with the method for claim 3, the precursor that it is characterized in that said modified component is selected from the compound that contains magnesium, aluminium phosphorus or tin or one or more the material in the polyoxyethylene glycol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00103425 CN1125006C (en) | 2000-03-10 | 2000-03-10 | Process for preparing ethylene and propylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00103425 CN1125006C (en) | 2000-03-10 | 2000-03-10 | Process for preparing ethylene and propylene |
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| Publication Number | Publication Date |
|---|---|
| CN1313268A true CN1313268A (en) | 2001-09-19 |
| CN1125006C CN1125006C (en) | 2003-10-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00103425 Expired - Fee Related CN1125006C (en) | 2000-03-10 | 2000-03-10 | Process for preparing ethylene and propylene |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6670490B1 (en) | 2002-12-23 | 2003-12-30 | E. I. Du Pont De Nemours And Company | Platinum-rhenium-tin catalyst for hydrogenation in aqueous solution |
| US6908544B2 (en) | 2001-12-25 | 2005-06-21 | China Petroleum & Chemical Corporation | Cracking catalyst comprising layered clays and a process for cracking hydrocarbon oils using the same |
| CN107511167A (en) * | 2016-06-17 | 2017-12-26 | 神华集团有限责任公司 | The method of organic oxygen-containing compound olefin hydrocarbon molecules sieve catalyst and preparation method thereof and organic oxygen-containing compound alkene |
-
2000
- 2000-03-10 CN CN 00103425 patent/CN1125006C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6908544B2 (en) | 2001-12-25 | 2005-06-21 | China Petroleum & Chemical Corporation | Cracking catalyst comprising layered clays and a process for cracking hydrocarbon oils using the same |
| US6670490B1 (en) | 2002-12-23 | 2003-12-30 | E. I. Du Pont De Nemours And Company | Platinum-rhenium-tin catalyst for hydrogenation in aqueous solution |
| CN107511167A (en) * | 2016-06-17 | 2017-12-26 | 神华集团有限责任公司 | The method of organic oxygen-containing compound olefin hydrocarbon molecules sieve catalyst and preparation method thereof and organic oxygen-containing compound alkene |
| CN107511167B (en) * | 2016-06-17 | 2021-11-05 | 国家能源投资集团有限责任公司 | Molecular sieve catalyst for preparing olefin from organic oxygen-containing compound, preparation method of molecular sieve catalyst and method for preparing olefin from organic oxygen-containing compound |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1125006C (en) | 2003-10-22 |
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Applicant after: China Petrochemical Group Corp. Applicant after: Sinopec Research Institute of Petroleum Processing Applicant before: China Petrochemical Group Corp. Applicant before: Chinese petrochemical industry Research Institute of Petro-Chemical Engineering of group company |
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Free format text: CORRECT: APPLICANT; FROM: CHINA PETROCHEMICAL CORPORATION; CHINA PETROLEUM + CHEMICAL CORPORATION, PETROLEUM CHEMICAL ENGINEERING INSTITUTE TO: CHINA PETROCHEMICAL CORPORATION; CHINA PETROCHEMICAL GROUP PETROCHEMICAL SINCE INSTITUTE |
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