CN114515595B - Catalyst for preparing propylene by cracking carbon tetraolefin containing titanium-silicon ordered pore material, preparation method thereof and application thereof in catalytic cracking reaction - Google Patents

Catalyst for preparing propylene by cracking carbon tetraolefin containing titanium-silicon ordered pore material, preparation method thereof and application thereof in catalytic cracking reaction Download PDF

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CN114515595B
CN114515595B CN202011301833.3A CN202011301833A CN114515595B CN 114515595 B CN114515595 B CN 114515595B CN 202011301833 A CN202011301833 A CN 202011301833A CN 114515595 B CN114515595 B CN 114515595B
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catalyst
oxide
silicon
titanium
molecular sieve
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CN114515595A (en
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亢宇
刘红梅
王定博
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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    • C07C4/08—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule
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Abstract

The invention relates to the field of novel material preparation, and discloses a catalyst for preparing propylene by cracking carbon tetraolefin of a titanium-silicon-containing ordered pore material, a preparation method thereof and application of the catalyst in catalytic cracking reaction. The catalyst comprises ZSM-5 molecular sieve and titanium-silicon ordered pore material, wherein the titanium-silicon ordered pore material is nearly spherical, the average particle diameter is 0.1-0.4 mu m, and the specific surface area is 50-500m 2 Per gram, the pore volume is 0.3-2 m/g, and the average pore diameter is 0.5-7nm. The catalyst provided by the invention is used for C 4 The reaction for preparing propylene by olefin pyrolysis can obviously improve C 4 The conversion rate of olefin and the selectivity of propylene are improved, and the stability of the catalyst is improved effectively.

Description

Catalyst for preparing propylene by cracking carbon tetraolefin containing titanium-silicon ordered pore material, preparation method thereof and application thereof in catalytic cracking reaction
Technical Field
The invention relates to the field of novel material preparation, in particular to a catalyst for preparing propylene by cracking carbon tetraolefin of a titanium-silicon-containing ordered pore material, a preparation method thereof and application thereof in catalytic cracking reaction.
Background
Propylene is an important chemical raw material and can be used for synthesizing chemical products such as polypropylene, acrylonitrile and the like. With the development of economy, the demand for propylene derivatives is year by yearThe increase resulted in a larger global propylene gap. The traditional propylene production process mainly comes from the co-production or byproducts of steam cracking and catalytic cracking devices. In recent years, the emerging yield-increasing propylene production processes such as olefin catalytic cracking, olefin disproportionation, propylene preparation from methanol, propylene preparation from propane dehydrogenation and the like are attracting great attention, and have more and more propylene production share. Wherein, zeolite molecular sieve is used as catalyst to crack C 4 C (C) 4 The above olefin-rich raw material is a very effective propylene yield-increasing technical route to obtain high yield propylene. At present, the olefin cracking technology mainly adopts ZSM-5 molecular sieve with a 10-membered ring channel structure as a catalyst, and comprises two processes of a fluidized bed and a fixed bed. Representative of the fluidized bed process are the MOI process from Mobile company and the Superflex process from ARCO chemistry company. Representative of the fixed bed process are mainly the Propylur process by Lurgi, the ATOFINA/UOP processes by ATOFINA and UOP, the Omega process by Asahi chemical industry Co., japan, and the OCC process by China petrochemical industry. The fluidized bed process has no report of industrial application at present; in the fixed bed process, the Omega process realizes industrial application in Japanese water island in 2006, and the OCC process realizes industrial application in original petrochemical industry in 2009.
The ZSM-5 molecular sieve has the characteristics of three-dimensional crisscross pore structure, larger specific surface area, unique pore structure, hydrothermal stability and the like, and has good catalytic performance in the aspect of producing more propylene by the catalytic pyrolysis of low-carbon olefin. The research on ZSM-5 molecular sieve for olefin catalytic cracking reaction is mainly focused on the aspect of catalyst modification. The phosphorus modified ZSM-5 molecular sieve pair C was studied by Zhu Xiangxue and Xue Yang et al 4 The effect of the catalytic cracking reaction of olefins has been found to increase the yield of propylene to some extent after phosphorus modification (Catalysis Letters,2005, 103 (3/4): 201-210; industrial catalysis, 2014, 22 (5): 357-362). Zhao Guoliang and the like study the acid modulation effect and the hydrothermal stability of the ZSM-5 molecular sieve by phosphorus modification, and found that the acid strength and the acid amount of the ZSM-5 molecular sieve after phosphorus modification are reduced, and the hydrothermal stability of the ZSM-5 molecular sieve is enhanced (industrial catalysis, 2005, 12 (10): 5-7).
Although zeolite molecular sieve activates C 4 Olefins are more powerful but because of their pore sizeThe small size is easy to influence the diffusion of reaction raw materials and products, thereby leading to lower propylene selectivity and poorer catalyst stability. Researchers modify and modify the surface characteristics of zeolite molecular sieves to improve the propylene selectivity and stability of the catalyst to a certain extent. However, the modification and modification of zeolite molecular sieves can only change the surface characteristics, but cannot change the basic framework structure of the molecular sieves, and the problem of diffusion of raw materials and products is difficult to solve.
Therefore, it is difficult to greatly increase C by modifying zeolite molecular sieve 4 Propylene selectivity of olefin cracking catalyst.
Disclosure of Invention
The invention aims to overcome the problems in the prior art that the C is difficult to be greatly improved by improving the zeolite molecular sieve 4 Propylene selectivity problem for olefin cracking catalysts and existing C 4 The invention provides a catalyst for preparing propylene by cracking carbon tetraolefin, which contains titanium-silicon ordered pore material, a preparation method and application in catalytic cracking reaction, wherein the catalyst provided by the invention is used for C 4 The reaction for preparing propylene by olefin pyrolysis can obviously improve C 4 The conversion rate of olefin and the selectivity of propylene are improved, and the stability of the catalyst is improved effectively.
To achieve the above object, the first aspect of the present invention provides a C containing a titanium-silicon ordered pore material 4 The catalyst for increasing propylene yield by olefin pyrolysis comprises a ZSM-5 molecular sieve and a titanium silicon ordered pore material, wherein the titanium silicon ordered pore material is nearly spherical, the average particle diameter is 0.1-0.4 mu m, and the specific surface area is 50-500m 2 Per gram, the pore volume is 0.3-2mL/g, and the average pore diameter is 0.5-7nm. In a second aspect, the invention provides a C containing the titanium-silicon ordered pore material 4 A method for preparing a propylene catalyst for olefin cracking yield increase, wherein the method comprises the following steps:
(1) Mixing a ZSM-5 molecular sieve, a titanium silicon ordered pore material, an adhesive and an extrusion aid in the presence of dilute nitric acid, extruding to form, and performing first roasting treatment to obtain a catalyst precursor;
(2) Immersing the catalyst precursor in the aqueous solution of the modified oxide precursor and performing a second roasting treatment to obtain C containing the titanium-silicon ordered pore material 4 Propylene catalyst for olefin cracking and increasing yield.
In a third aspect, the invention provides a C containing the titanium-silicon ordered pore material 4 The application of the olefin cracking yield-increasing propylene catalyst in catalytic cracking reaction.
Through the technical scheme, the technical scheme provided by the invention has the following advantages:
(1) C of the ordered pore material containing titanium and silicon provided by the invention 4 The main components of the catalyst for preparing propylene by olefin pyrolysis are ZSM-5 zeolite molecular sieve with high silicon-aluminum ratio and near spherical titanium-silicon ordered pore material, and the catalyst has low raw material cost and simple preparation method.
(2) C of the ordered pore material containing titanium and silicon provided by the invention 4 Catalyst for preparing propylene by cracking olefin 4 The mono-olefin cracking reaction not only effectively improves C 4 Olefin conversion and propylene selectivity, while being able to effectively improve the stability of the catalyst.
(3) C of the ordered pore material containing titanium and silicon 4 The preparation method of the catalyst for preparing propylene by olefin pyrolysis has the advantages of simple process, easy control of conditions and good product repeatability.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
FIG. 1 is a scanning electron microscope image of a nearly spherical titanium-silicon ordered pore material used in example 1 of the present invention.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In a first aspect of the invention, there is provided a C comprising a titanium-silicon ordered pore material 4 The catalyst for increasing propylene yield by olefin pyrolysis comprises a ZSM-5 molecular sieve and a titanium silicon ordered pore material, wherein the titanium silicon ordered pore material is nearly spherical, the average particle diameter is 0.1-0.4 mu m, and the specific surface area is 50-500m 2 Per gram, the pore volume is 0.5-2mL/g, and the average pore diameter is 0.5-7nm.
In the present invention, "nearly spherical" means spherical and/or ellipsoidal, and is strictly nearly spherical.
The inventors of the present invention found by study that: zeolite molecular sieves are various in variety, and the pore channel structures are in short-range order, so that the zeolite molecular sieves have good shape selection effect in small molecule catalytic reaction and adsorption separation. Therefore, the zeolite molecular sieve is widely applied in various fields such as chemical industry, environmental protection and the like. In the prior art, typical C 4 The catalyst for preparing propylene by olefin pyrolysis adopts zeolite molecular sieve (mainly ZSM-5 molecular sieve) as main component. Although ZSM-5 molecular sieve activates C 4 The olefin has stronger capability, but has more side reactions and poorer propylene selectivity. Researchers modify and modify the surface characteristics of zeolite molecular sieves in order to improve the catalytic performance, and can improve the propylene selectivity of the catalyst to a certain extent. Unfortunately, the modified ZSM-5 molecular sieve catalyst also has the disadvantages of easy carbon deposition and low propylene selectivity.
The inventors of the present invention conducted C 4 In the preparation research of a propylene catalyst prepared by olefin pyrolysis, if a nearly spherical titanium-silicon ordered pore material is mixed with a ZSM-5 molecular sieve and modified to prepare C 4 Olefin cracking catalyst capable of effectively improving the diffusion performance of the catalyst, thereby effectively improving C 4 Cracking speed of olefin and inhibiting side reaction, thereby greatly improving C 4 Conversion of olefin, selectivity to propylene, and stability of the catalyst.
According to the invention, the titanium-silicon ordered pore materialThe specific surface area of the material is 0.1-0.4 mu m, and the specific surface area is 387-400m 2 Per gram, the pore volume is 0.34-0.4mL/g, and the average pore diameter is 0.57-7nm. In the invention, the titanium-silicon ordered pore material with specific parameters is adopted, and is mixed with ZSM-5 molecular sieve and modified to enable the prepared catalyst to be used for C 4 The reaction for preparing propylene by olefin pyrolysis can obviously improve C 4 The conversion rate of olefin and the selectivity of propylene are improved, and the stability of the catalyst is improved effectively.
In the invention, the titanium-silicon ordered pore material is purchased from Nanjing pioneer nanometer limited company, is nearly spherical, has small particles with the size of 0.1-0.4 mu m and the specific surface area of 387m 2 Per g, pore volume was 0.34ml/g and average pore diameter was 0.57nm.
According to the invention, the content of the ZSM-5 molecular sieve is 40-80 wt% and the content of the titanium silicon ordered pore material is 10-30 wt% based on the total weight of the catalyst; preferably, the ZSM-5 molecular sieve is present in an amount of 55 to 65 wt% and the titanium silicalite ordered pore material is present in an amount of 18 to 23 wt% based on the total weight of the catalyst. In the invention, the near-spherical titanium silicon ordered pore material with the specific content defined before is mixed with ZSM-5 molecular sieve with the specific content defined before and modified to prepare C 4 Olefin cracking catalyst capable of effectively improving the diffusion performance of the catalyst, thereby effectively improving C 4 Cracking speed of olefin and inhibiting side reaction, thereby greatly improving C 4 Conversion of olefin, selectivity to propylene, and stability of the catalyst.
According to the invention, the ZSM-5 molecular sieve is a hydrogen type ZSM-5 molecular sieve; preferably, the ZSM-5 molecular sieve is SiO 2 With Al 2 O 3 The molar ratio of (2) is from 100 to 1000, preferably from 200 to 500.
According to the invention, the weight ratio of the ZSM-5 molecular sieve to the titanium silicon ordered pore material is (1-8): 1, preferably (2-3.8): 1, more preferably (2.39-3.6): 1.
according to the invention, the catalyst further comprises a first oxide; preferably, the first oxide is an oxide obtained by roasting a binder, preferably silicon oxide and/or aluminum oxide; more preferably, the binder is selected from one or more of silica sol, alumina sol, pseudo-boehmite and diaspore.
According to the invention, the catalyst further comprises a second oxide; preferably, the second oxide is selected from one or more of alkaline earth metal oxides, transition metal oxides, rare earth metal oxides and non-metal oxides; more preferably, the second oxide is selected from one or more of beryllium oxide, calcium oxide, magnesium oxide, strontium oxide, zirconium dioxide, cerium oxide, lanthanum oxide, boron oxide, and phosphorus-containing oxide.
According to the invention, the first oxide is present in an amount of 10 to 25 wt% and the second oxide is present in an amount of 3 to 9 wt% based on the total weight of the catalyst; preferably, the first oxide is present in an amount of 12 to 16 wt% and the second oxide is present in an amount of 5 to 7 wt% based on the total weight of the catalyst.
In the present invention, the content of the second oxide means the total content of all oxides.
In the present invention, the sum of the content of the ZSM-5 molecular sieve, the content of the titanium silicalite ordered pore material, the content of the first oxide and the content of the second oxide is one hundred percent.
In the invention, C of ordered pore material containing titanium and silicon 4 The shape of the catalyst for preparing propylene by olefin pyrolysis can be spherical, granular, strip-shaped, cylindrical and the like.
According to the invention, the catalyst is 50-300m 2 Per gram, the pore volume is 0.5-2mL/g, and the average pore diameter is 0.5-7nm; preferably, the specific surface area of the catalyst is 100-250m 2 Per gram, the pore volume is 0.5-1.8mL/g, and the average pore diameter is 1-6nm.
In a second aspect, the invention provides a C containing the titanium-silicon ordered pore material 4 A method for preparing a propylene catalyst for olefin cracking yield increase, wherein the method comprises the following steps:
(1) Mixing a ZSM-5 molecular sieve, a titanium silicon ordered pore material, an adhesive and an extrusion aid in the presence of dilute nitric acid, extruding to form, and performing first roasting treatment to obtain a catalyst precursor;
(2) Immersing the catalyst precursor in the aqueous solution of the modified oxide precursor and performing a second roasting treatment to obtain C containing the titanium-silicon ordered pore material 4 Propylene catalyst for olefin cracking and increasing yield.
According to the present invention, the modified oxide precursor is selected from one or more of alkaline earth metal nitrate, transition metal nitrate, rare earth metal nitrate, boric acid and phosphoric acid; preferably, the modified oxide precursor is selected from one or more of beryllium nitrate, calcium nitrate, magnesium nitrate, strontium nitrate, zirconium nitrate, cerium nitrate, lanthanum nitrate, boric acid and phosphoric acid.
According to the invention, the extrusion aid is selected from one or more of sesbania powder, polyacrylamide, cellulose, polyethylene glycol and polyvinyl alcohol, more preferably sesbania powder.
According to the invention, the mass ratio of the ZSM-5 molecular sieve, the titanium silicon ordered pore material, the adhesive, the extrusion aid, the dilute nitric acid and the modified oxide precursor is 1: (0.5-2): (0.5-2): (0.5-2): (0.5-2): (0.5-5).
Preferably, the mass concentration of the dilute nitric acid is 1-10%.
According to a preferred embodiment of the invention, the method is operated as follows:
(1) Uniformly mixing a ZSM-5 molecular sieve with high silicon-aluminum ratio, a titanium-silicon ordered pore material, an adhesive and an extrusion aid, adding dilute nitric acid, uniformly stirring, extruding and forming, and performing first drying at 70-150 ℃ for 3-16h and first roasting at 400-600 ℃ for 3-15h to obtain a catalyst precursor;
(2) Immersing the catalyst precursor in the aqueous solution of the second oxide precursor, drying the solid product at 70-150 deg.C for 3-20h, and calcining at 500-600 deg.C for 4-12h to obtain the ordered pore material C containing titanium and silicon 4 A catalyst for preparing propylene by olefin pyrolysis.
According to the present invention, preferably, the conditions of the first firing include: the temperature is 560-580 ℃ and the time is 6-7h; preferably, the conditions of the second firing include: the temperature is 500-550 ℃ and the time is 6-7h.
In a third aspect, the invention provides a C containing the titanium-silicon ordered pore material 4 The application of the olefin cracking yield-increasing propylene catalyst in catalytic cracking reaction.
According to the invention, the application comprises: at a temperature of 450-560 ℃ and a pressure of 0.02-0.5MPa and a weight hourly space velocity of 0.5-30h -1 Under the conditions of (1) will contain C 4 -C 8 C of a feedstock of a Mono-olefin with a titanium-containing silicon ordered pore Material in a fixed bed reactor 4 Contact of propylene catalyst for increasing yield by cracking olefin.
In the invention, C of ordered pore material containing titanium and silicon 4 Application method of olefin cracking propylene yield increasing catalyst, wherein the catalyst contains C 4 The feedstock for the mono-olefin may be selected from:
(1) A carbon four raffinate I of an ethylene plant, namely a product obtained by extracting butadiene in a carbon four fraction;
(2) A carbon four fraction obtained by the catalytic cracking device;
(3) And preparing a fraction with four or more carbon atoms of olefin by methanol.
Preferably C is used 4 Raffinate I or C for preparing olefin by methanol 4 C (C) 5 The above fractions were used as the feedstock in the present invention.
The method provided by the invention can be used as a method for independently preparing propylene, and can also be combined with steam cracking ethylene preparation and an FCC unit in a refinery.
Zeolite molecular sieve catalyst for C 4 The olefin cracking reaction is characterized by fast conversion speed, poor selectivity and short service period. The zeolite molecular sieve catalyst with high silicon-aluminum ratio has improved selectivity and service cycle, but is easy to form carbon in the reaction process and has poor selectivity to propylene if a modifying component is not added. C of the ordered pore material containing titanium and silicon provided by the invention 4 Olefin cracking catalyst adopts ZSM-5 zeolite molecular sieve with high silica-alumina ratio and ordered pore material containing titanium and silicon as main active components, and proper amount of oxide as modifying component, and can raise cracking speed obviouslyCatalyst C 4 Olefin conversion, propylene selectivity, and catalyst stability.
In the following examples and comparative examples:
pore structure parameter analysis was performed on an ASAP2020-M+C adsorbent available from Micromeritics, inc., USA; the specific surface area and pore volume of the sample are calculated by the BET method; scanning electron microscope pictures of the samples are obtained on an XL-30 type field emission environment scanning electron microscope manufactured by FEI company in the United states; elemental analysis experiments of the samples were performed on an Eagle III energy dispersive X-ray fluorescence spectrometer manufactured by EDAX, inc. of America.
ZSM-5 zeolite molecular sieves were purchased from Shanghai Fuxu molecular sieves Co., ltd; the titanium silicon ordered pore material is purchased from Nanjing pioneer nanometer limited company; aluminum sol and silica sol are available from Zibo good wetting chemical Co., ltd; pseudo-boehmite was purchased from new materials, inc. of the body Ji Fen, boheng; other reagents were purchased from national pharmaceutical group chemical reagent limited, purity was analytically pure.
Example 1
(1) Preparation of the catalyst
200g of titanium silicalite ordered pore material was combined with 590g of ZSM-5 molecular sieve (SiO 2 /Al 2 O 3 300), 200g of pseudo-boehmite and 20g of sesbania powder are mixed uniformly, 500ml of 5% nitric acid is added, stirred uniformly, extruded and cut into cylinders with the diameter of 2mm and the length of 2-3 mm; drying at 100℃for 10 hours and finally calcining at 580℃for 6 hours, gives catalyst precursor A. 93g of the catalyst precursor A was taken, impregnated with 90ml of an aqueous solution in which 12.5 g of magnesium nitrate and 5.6 g of lanthanum nitrate hexahydrate were dissolved, dried at 80℃for 6 hours, then impregnated with 80ml of an aqueous solution in which 2.1 g of phosphoric acid was dissolved, and after removal of water, the solid product was dried at 120℃for 15 hours and calcined at 550℃for 6 hours to give catalyst A.
C is calculated according to the weight percentage 4 The propylene catalyst A for increasing yield by olefin cracking comprises the following components: 59% of ZSM-5 molecular sieve, 20% of titanium-silicon mesoporous material, 14% of alumina from a binder, 3.4% of MgO and La 2 O 3 2.1％，P 2 O 5 1.5％。
Fig. 1 is an SEM scanning electron microscope image of the microscopic morphology of the titanium silicon mesoporous material. As can be seen from the graph, the microstructure of the material is nearly spherical, and the particle diameter is between 0.1 and 0.4 mu m.
(2) Catalyst at C 4 Performance testing in olefin cracking reactions
The reaction raw materials are etherified carbon four mixture, and the mixture after partial isobutane is separated is provided by the company of Roche refining macrochemistry industry Co., ltd.): isobutane 11.92, n-butane 26.10, trans-2-butene 22.02, 1-butene 23.48, isobutene 0.38, cis-2-butene 15.29, C 5 The above component 0.76.
The specific test method is as follows: c of the catalyst carried out on a fixed-bed reactor 4 And (5) evaluating the catalytic cracking reaction performance of the olefin. Catalyst loading 5.0 g, reaction temperature 500 ℃, reaction pressure 0.05MPa, raw material weight space velocity 16h -1 After cooling and gas-liquid separation of the product, the gas composition is prepared with Al 2 O 3 -agilent 6890 gas chromatograph analysis of S capillary chromatography column and hydrogen flame detector (FID), quantitative analysis with correction factor using temperature programming; the liquid composition was analyzed with an Agilent 6890 gas chromatograph equipped with a PONA column. The reaction results are shown in Table 2.
Examples 2 to 3
By varying the parameters in the catalyst preparation process in example 1, catalysts B and C were obtained by carrying out examples 2 and 3, respectively. The composition of the catalyst is shown in table 1.
Catalysts B and C were C by the procedure of step (2) in example 1 4 Performance testing in olefin cracking reactions, the reaction results are shown in table 2.
Example 4
The parameters during the preparation of the catalyst in example 1 were changed to obtain catalyst E in example 4. The composition of the catalyst is shown in table 1.
Catalyst E was carried out in C as in step (2) of example 1 4 Performance testing in olefin cracking reactions, the reaction results are shown in table 2.
Comparative example 1
Catalyst D1 was prepared by the method of example 1, step (1), except that 200g of commercially available silica was used in place of the titanium silicalite ordered pore material.
Catalyst D1 was prepared as in step (2) of example 1 at C 4 Performance testing in olefin cracking reactions, the reaction results are shown in table 2.
Comparative example 2
Catalyst D2 was prepared as in step (1) of example 1, except that no titanium silicalite ordered pore material was used and 790g ZSM-5 molecular sieve (SiO 2 /Al 2 O 3 300).
Catalyst D2 was prepared as in step (2) of example 1 at C 4 Performance testing in olefin cracking reactions, the reaction results are shown in table 2.
Comparative example 3
Catalyst D3 was prepared by the method of example 1, step (1), except that a high silica ZSM-5 zeolite molecular sieve (SiO 2 /Al 2 O 3 300) is replaced by low-silicon ZSM-5 zeolite molecular Sieve (SiO) 2 /Al 2 O 3 25).
Catalyst D3 was prepared as in step (2) of example 1 at C 4 Performance testing in olefin cracking reactions, the reaction results are shown in table 2.
Comparative example 4
Catalyst D4 was prepared by the method of example 1, step (1), except that C 4 The propylene catalyst D4 for increasing yield by olefin cracking comprises the following components: 73% of ZSM-5 molecular sieve, 6% of titanium-silicon mesoporous material, 14% of alumina from a binder, 3.4% of MgO and La 2 O 3 2.1％，P 2 O 5 1.5％。
TABLE 1
TABLE 2
As can be seen from Table 2, the present invention was employedC of obviously provided ordered pore material containing titanium and silicon 4 Catalyst for preparing propylene by olefin pyrolysis and used for catalyzing C 4 The performance of the catalyst is excellent in olefin cracking reaction.
Titanium-silicon ordered pore materials in the catalyst A, the titanium-silicon ordered pore materials are not added in the catalyst D1 and the catalyst D2, the conventional silicon dioxide is used for replacing the titanium-silicon ordered pore materials in the catalyst D1, and the zeolite molecular sieve is only used in the catalyst D2. Compared with the catalyst D1 and the catalyst D2, the carbon tetraolefin conversion rate, the propylene selectivity and the catalyst stability of the catalyst A are all obviously improved. The results show that the catalyst provided by the invention has excellent performance because of containing the titanium silicon ordered pore material.
As can be seen from the data of the catalyst A and the catalyst D3, the carbon tetraolefin cracking catalyst prepared by using the low-silicon ZSM-5 zeolite molecular sieve has poor performance, low conversion rate of the carbon tetraolefin, low propylene selectivity and poor catalyst stability. The catalyst prepared by the high-silicon ZSM-5 zeolite molecular sieve has obviously improved performances.
As can be seen from the data of the catalyst A and the catalyst D4, the content of the ZSM-5 molecular sieve and the titanium silicon mesoporous material is not in the range defined by the invention, and the prepared carbon tetraolefin cracking catalyst has poor performance, low conversion rate of the carbon tetraolefin, low propylene selectivity and poor catalyst stability.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims (18)

1. C containing titanium-silicon ordered pore material 4 The catalyst for increasing propylene yield by olefin pyrolysis is characterized by comprising a ZSM-5 molecular sieve and a titanium silicon ordered pore material, wherein the ZSM-5 molecular sieve is a hydrogen type ZSM-5 molecular sieve; siO of the ZSM-5 molecular sieve 2 With Al 2 O 3 The molar ratio of (2) is 100-1000; the titanium-silicon ordered pore material is nearly spherical, the average grain diameter is 0.1-0.4 mu m, and the specific surface area is 50-500m 2 Per gram, the pore volume is 0.3-2mL/g, and the average pore diameter is 0.5-7nm; the catalyst further comprises a first oxide, wherein the first oxide is silicon oxide and/or aluminum oxide; the catalyst further comprises a second oxide selected from one or more of alkaline earth metal oxides, transition metal oxides, rare earth metal oxides, and non-metal oxides;
the content of the ZSM-5 molecular sieve is 40-80 wt% based on the total weight of the catalyst, and the content of the titanium silicon ordered pore material is 10-30 wt%; the first oxide is contained in an amount of 10 to 25 wt% and the second oxide is contained in an amount of 3 to 9 wt%.
2. The catalyst of claim 1, wherein the titanium silicalite ordered pore material has a specific surface area of 387-400m 2 Per gram, the pore volume is 0.34-0.4mL/g, and the average pore diameter is 0.57-7nm.
3. The catalyst of claim 1, wherein the ZSM-5 molecular sieve is present in an amount of 55-65 wt% and the titanium silicalite ordered pore material is present in an amount of 18-23 wt%, based on the total weight of the catalyst.
4. The catalyst of claim 1, wherein the ZSM-5 molecular sieve is SiO 2 With Al 2 O 3 The molar ratio of (2) is 200-500.
5. The catalyst of claim 1, wherein the weight ratio of the ZSM-5 molecular sieve to the titanium silicalite ordered pore material is (2-3.8): 1.
6. the catalyst according to claim 1, wherein the first oxide is an oxide obtained by baking a binder.
7. The catalyst of claim 6, wherein the binder is selected from one or more of silica sol, alumina sol, pseudo-boehmite, and diaspore.
8. The catalyst of claim 1, wherein the second oxide is selected from one or more of beryllium oxide, calcium oxide, magnesium oxide, strontium oxide, zirconium dioxide, cerium oxide, lanthanum oxide, boron oxide, and phosphorus-containing oxides.
9. The catalyst according to any one of claims 1 to 8, wherein the specific surface area of the catalyst is 50 to 300m 2 Per gram, the pore volume is 0.5-2mL/g, and the average pore diameter is 0.5-7nm.
10. A C comprising a titanium silicalite ordered pore material according to any one of claims 1-9 4 The preparation method of the propylene catalyst for olefin cracking yield increase is characterized by comprising the following steps:
(1) Mixing a ZSM-5 molecular sieve, a titanium silicon ordered pore material, an adhesive and an extrusion aid in the presence of dilute nitric acid, extruding to form, and performing first roasting treatment to obtain a catalyst precursor;
(2) Immersing the catalyst precursor in the aqueous solution of the modified oxide precursor and performing a second roasting treatment to obtain C containing the titanium-silicon ordered pore material 4 Propylene catalyst for olefin cracking and increasing yield.
11. The method of claim 10, wherein the modified oxide precursor is selected from one or more of alkaline earth metal nitrate, transition metal nitrate, rare earth metal nitrate, boric acid, and phosphoric acid.
12. The method of claim 11, wherein the modified oxide precursor is selected from one or more of beryllium nitrate, calcium nitrate, magnesium nitrate, strontium nitrate, zirconium nitrate, cerium nitrate, lanthanum nitrate, boric acid, and phosphoric acid.
13. The method of claim 10, wherein the extrusion aid is selected from one or more of sesbania powder, polyacrylamide, cellulose, polyethylene glycol, and polyvinyl alcohol.
14. The method of claim 13, wherein the extrusion aid is sesbania powder.
15. The method of claim 10, wherein the ZSM-5 molecular sieve, titanium silicalite ordered pore material, binder, extrusion aid, dilute nitric acid and the modified oxide precursor are present in a mass ratio of 1: (0.5-2): (0.5-2): (0.5-2): (0.5-2): (0.5-5).
16. The method of claim 10, wherein the first firing conditions comprise: the temperature is 400-600 ℃ and the time is 3-15h.
17. The method of claim 10, wherein the second firing conditions comprise: the temperature is 500-600 ℃ and the time is 4-12h.
18. C containing titanium silicalite ordered pore material according to any one of claims 1-9 4 The application of the olefin cracking yield-increasing propylene catalyst in catalytic cracking reaction.
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