CN108689788B - Method for preparing propylene by catalytic cracking of carbon tetraolefin - Google Patents
Method for preparing propylene by catalytic cracking of carbon tetraolefin Download PDFInfo
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- CN108689788B CN108689788B CN201810358245.XA CN201810358245A CN108689788B CN 108689788 B CN108689788 B CN 108689788B CN 201810358245 A CN201810358245 A CN 201810358245A CN 108689788 B CN108689788 B CN 108689788B
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- molecular sieve
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/06—Catalytic processes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
Abstract
The invention discloses a method for preparing propylene by catalytic cracking of carbon tetraenes, which comprises the step of contacting carbon tetraenes with a catalyst to react under the catalytic cracking condition to generate the propylene, wherein the active component of the catalyst is an inactivated titanium silicalite molecular sieve with an MFI structure or a mixture of the inactivated titanium silicalite molecular sieve with the MFI structure and a phosphorus modified ZSM-5 molecular sieve. The method adopts the inactivated titanium silicalite molecular sieve as the active component of the catalyst, is beneficial to the selective generation of propylene in the catalytic cracking process of the carbon tetraene, utilizes the waste, fully utilizes the resources and reduces the emission; the catalyst has stable quality and good repeatability; the reaction process is simple, the operation is convenient, the process is stable, and the industrial production is easy.
Description
Technical Field
The invention belongs to the technical field of organic chemical industry, relates to a method for preparing propylene by catalytic cracking of carbon tetraolefin, and particularly relates to a method for preparing propylene by catalytic cracking of carbon tetraolefin by taking deactivated titanium silicalite molecular sieve with an MFI structure as an active component of a catalyst.
Background
Propylene is an important chemical industry basic raw material, is mainly used for producing polypropylene, acrylonitrile, propylene oxide, isopropanol, epichlorohydrin, acrylic acid, acetone and derivatives thereof, and the like, and the demand of the propylene is in a rapidly increasing trend. The carbon tetraolefin is a byproduct of an FCC device in an ethylene production plant and an oil refinery, and is generally used as a low-added-value product such as liquefied gas fuel. Meanwhile, with the rapid development of the technology of preparing olefin (MTO) from methanol, a large amount of carbon tetraolefin is also produced as a byproduct in the MTO production process. Therefore, the by-product and low-value carbon tetraolefin are used as raw materials, propylene and ethylene are generated through catalytic cracking reaction, the by-product olefin resource is fully facilitated, the economic value is important, and the atomic economy principle of green chemistry is met.
The method for preparing propylene by using carbon four olefin as a raw material or a method for preparing propylene by catalytic cracking olefin with carbon four or above is a technical scheme that the raw material is contacted with a molecular sieve catalyst under a catalytic cracking condition for reaction, the core of the molecular sieve catalyst is an active component molecular sieve of the molecular sieve catalyst, the commonly used molecular sieve is ZSM-5, ZSM-11, FER, ZSM-48, SAPO-34 or a mixture of the above and the like, and in order to further promote the stability of the reaction process and/or improve the selectivity of the propylene, the technical scheme frequently adopted is further modification treatment of the molecular sieve, such as high-temperature hydrothermal treatment, phosphorus modification, metal ion modification and the like, so as to inhibit series side reactions such as olefin superposition, hydrogen transfer, aromatization and the like in the catalytic cracking reaction process.
CN1284109A and CN1413966 disclose a method for producing propylene by catalytic cracking of olefins with four or more carbon atoms, wherein the active component of the catalyst is a ZSM-5 molecular sieve modified by hydrothermal method. CN1676499 discloses a method for preparing low-carbon olefin by catalytic cracking, wherein the active component of the catalyst is ZSM-5 molecular sieve modified by rare earth metal, alkaline earth metal and phosphorus oxide. US6049017 discloses a process for preparing propylene by catalytically cracking carbon tetraolefin with a small-pore aluminophosphate molecular sieve as an active component of a catalyst. CN106608789A discloses a method for producing propylene by catalytic cracking of carbon tetraene, wherein a molecular sieve of an active component of a catalyst is a ZSM-5 molecular sieve with a cyclic index of 3-100. CN106673945A discloses a method for preparing propylene from n-butene, wherein the active component of the catalyst is a mixture of FER molecular sieve and modified ZSM-5 molecular sieve.
Disclosure of Invention
The invention aims to provide a method for preparing propylene by catalytic cracking of carbon tetraenes, which adopts an inactivated titanium silicalite molecular sieve as an active component of a catalyst, utilizes wastes, fully utilizes resources and reduces emission.
The purpose of the invention is realized as follows:
a method for preparing propylene by catalytic cracking of carbon tetraenes is characterized in that the carbon tetraenes are used as raw materials, the reaction temperature is 400-600 ℃, the reaction pressure is 0-0.5 MPa, and the weight space velocity is 1-10 h-1Under the condition, the raw materials are subjected to catalytic cracking reaction through a catalyst bed layer to generate propylene, wherein the used catalyst comprises 20-80% of a molecular sieve and a balanced binder in percentage by weight, the molecular sieve is a deactivated titanium silicalite molecular sieve with an MFI structure or a mixture of the deactivated titanium silicalite molecular sieve with the MFI structure and a phosphorus modified ZSM-5 molecular sieve, and the binder is at least one of silicon dioxide, aluminum oxide and aluminum phosphate; the deactivated titanium silicalite molecular sieves having the MFI structure are present in the molecular sieve mixture in an amount of at least 10 weight percent.
Experiments show that the inactivated titanium silicalite molecular sieve in the ammoximation process for synthesizing oxime under the catalysis of the titanium silicalite molecular sieve as a catalyst has the catalytic action of preparing propylene and ethylene by catalytic cracking of carbon tetraene, and shows the catalytic activity equivalent to that of a modified ZSM-5 molecular sieve as a catalyst and higher propylene selectivity. The fresh titanium-silicon molecular sieve which is not inactivated basically has no catalytic action of preparing propylene and ethylene by catalytic cracking of carbon tetraenes.
The catalyst of the present invention is prepared by molding methods well known to those skilled in the art, for example, by kneading metered amounts of the molecular sieve and the binder, extruding the kneaded mixture to form a molded catalyst, and then performing conventional drying, calcination, etc. to obtain the catalyst.
Compared with the prior art, the invention has the following remarkable advantages:
1. the deactivated titanium-silicon molecular sieve is used as an active component of the catalyst, so that wastes are utilized, resources are fully utilized, and emission is reduced.
2. The catalyst has stable quality, high propylene/ethylene ratio in the product and good repeatability.
3. The reaction process is simple, the operation is convenient, the process is stable, and the industrial production is easy.
Detailed Description
All the embodiments are operated according to the operation steps of the technical scheme.
The inactivated titanium-silicon molecular sieve with MFI structure is obtained by conventional drying and roasting after reaction inactivation in the industrial production process of cyclohexanone oxime production from cyclohexanone ammoximation. The phosphorus modified ZSM-5 molecular sieve can be a commercial product or prepared according to the existing literature. The phosphorus modified ZSM-5 molecular sieve in the technical embodiment of the invention is prepared by taking ZSM-5 with a silicon-aluminum molecular ratio of 42 as a parent according to a method of a document (Journal of Catalysis 309(2014)136-145) to obtain the phosphorus modified ZSM-5 molecular sieve with the phosphorus content of 1.9 wt%.
In the technical embodiment of the invention, butene is used as a carbon tetraene probe molecule, and a fixed bed reactor is used for reaction to illustrate the technical effect of the invention.
Example 1
Using butylene as raw material, at the reaction temperature of 500 ℃, the reaction pressure of 0.1MPa and the weight space velocity of 6h-1Under the condition of (1), the raw materials are subjected to catalytic cracking reaction through a catalyst bed layer to generate propylene, wherein the used catalyst is prepared from 70 wt% of deactivated titanium silicalite molecular sieve with MFI structure and balance weight of alumina, and the catalyst is obtained by extrusion molding after kneading, conventional drying and roasting.
The reaction was carried out stably for 1.5 hours, and the results are shown in the table.
Example 2
The procedure was as in example 1 except that:
the reaction was carried out at a reaction temperature of 450 ℃.
The reaction results are shown in the table.
Example 3
The procedure was as in example 1 except that:
the reaction was carried out at a reaction temperature of 550 ℃.
The reaction results are shown in the table.
Example 4
The procedure was as in example 1 except that:
the catalyst consists of 50 wt% of deactivated titanium-silicon molecular sieve with MFI structure and balanced silica, and is prepared through kneading, extruding to form, drying and roasting.
The reaction results are shown in the table.
Example 5
The procedure was as in example 1 except that:
the catalyst is prepared from 35 wt% of deactivated titanium-silicon molecular sieve with MFI structure, 35 wt% of phosphorus-modified ZSM-5 molecular sieve and balance aluminum phosphate by mixing, kneading, extruding, drying and roasting.
The reaction results are shown in the table.
Example 6
The procedure was as in example 1 except that:
the reaction results are shown in the table when the reaction proceeded stably for 100 hours.
Comparative example 1
The procedure was as in example 1 except that:
the active component of the catalyst is a phosphorus modified ZSM-5 molecular sieve, wherein the phosphorus content is 1.9 wt%, and the molecular ratio of silicon to aluminum is 42.
The reaction results are shown in the table.
Comparative example 2
The procedure was as in example 1 except that:
the active component of the catalyst is an inactivated titanium silicalite molecular sieve with an MFI structure.
The reaction results are shown in the table.
Comparative example 3
The procedure was as in comparative example 1 except that:
the reaction was carried out at a reaction temperature of 450 ℃.
The reaction results are shown in the table.
Comparative example 4
The procedure was as in comparative example 1 except that:
the reaction was carried out at a reaction temperature of 550 ℃.
The reaction results are shown in the table.
Results of the evaluation of the Table reaction
From the evaluation of the reaction results of examples 1 to 4, it can be seen that the catalyst of the present invention, which uses the deactivated titanium silicalite molecular sieve with MFI structure as the active component, has the catalytic effect of catalytically cracking carbon tetraolefin to generate propylene and ethylene, while the comparative example 2 shows that the catalyst, which uses the non-deactivated titanium silicalite molecular sieve with MFI structure as the active component, does not have the catalytic effect of catalytically cracking carbon tetraolefin to generate propylene and ethylene. Meanwhile, compared with the reaction performance of the catalyst taking the conventional phosphorus modified ZSM-5 molecular sieve as the active component, the catalyst of the invention taking the inactivated titanium silicalite molecular sieve with the MFI structure as the active component has a higher propylene/ethylene ratio of the product under the same reaction temperature condition, for example, when the temperature is 500 ℃, compared with the technical effects of the embodiment 1 and the comparative embodiment 1, the propylene/ethylene ratio of the product of the invention is far higher than 4.15 of the comparative embodiment, which shows that the technology of the invention has a better effect of being beneficial to producing propylene. When the technical catalyst of the present invention using the deactivated titanium silicalite molecular sieve having MFI structure and the phosphorus-modified ZSM-5 molecular sieve as active components has the technical effects as shown in example 6, it can be seen that the catalyst has higher butene conversion rate compared to comparative example 1 under the condition of equivalent propylene/ethylene ratio of the product.
From the results of the above examples, it can be seen that the catalyst of the present invention, which uses the deactivated titanium silicalite molecular sieve with MFI structure or the mixture of the deactivated titanium silicalite molecular sieve with MFI structure and the phosphorus-modified ZSM-5 molecular sieve as active components, has the catalytic effect of catalytically cracking carbon tetraolefin to produce propylene and ethylene, and has high reaction activity and selectivity and good stability.
Claims (1)
1. A method for preparing propylene by catalytic cracking of carbon tetraolefin is characterized in that,using carbon tetraene as a raw material, and reacting at the temperature of 400-600 ℃, the reaction pressure of 0-0.5 MPa and the weight space velocity of 1-10 h-1Under the condition of (1), the raw materials are subjected to catalytic cracking reaction through a catalyst bed layer to generate propylene; the catalyst comprises 20-80 wt% of a molecular sieve and a balance binder, wherein the molecular sieve is a deactivated titanium-silicon molecular sieve with an MFI structure or a mixture of the deactivated titanium-silicon molecular sieve with the MFI structure and a phosphorus-modified ZSM-5 molecular sieve, and the binder is at least one of silicon dioxide, aluminum oxide and aluminum phosphate; the weight percentage of deactivated titanium silicalite molecular sieves with MFI structure in the molecular sieve mixture is at least 10%; the inactivated titanium-silicon molecular sieve with MFI structure is obtained by carrying out conventional drying and roasting after reaction inactivation in the industrial production process of cyclohexanone oxime production from cyclohexanone ammoximation.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6777582B2 (en) * | 2002-03-07 | 2004-08-17 | Abb Lummus Global Inc. | Process for producing propylene and hexene from C4 olefin streams |
| CN102266793A (en) * | 2011-06-21 | 2011-12-07 | 西北大学 | Catalyst for producing propylene and producing method and application thereof |
| CN103301875A (en) * | 2013-06-14 | 2013-09-18 | 华东师范大学 | MFI-type silicon aluminum molecular sieve/aluminum fiber composite material, as well as preparation method and application thereof |
| CN104250190A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Propylene preparation method |
| CN104557396A (en) * | 2013-10-23 | 2015-04-29 | 中国石油化工股份有限公司 | Method for producing propylene by catalytic cracking of n-butene |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6777582B2 (en) * | 2002-03-07 | 2004-08-17 | Abb Lummus Global Inc. | Process for producing propylene and hexene from C4 olefin streams |
| CN102266793A (en) * | 2011-06-21 | 2011-12-07 | 西北大学 | Catalyst for producing propylene and producing method and application thereof |
| CN103301875A (en) * | 2013-06-14 | 2013-09-18 | 华东师范大学 | MFI-type silicon aluminum molecular sieve/aluminum fiber composite material, as well as preparation method and application thereof |
| CN104250190A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Propylene preparation method |
| CN104557396A (en) * | 2013-10-23 | 2015-04-29 | 中国石油化工股份有限公司 | Method for producing propylene by catalytic cracking of n-butene |
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