CN112742463A - Catalyst containing silicoaluminophosphate molecular sieve, preparation method thereof and gasoline catalytic conversion method - Google Patents

Catalyst containing silicoaluminophosphate molecular sieve, preparation method thereof and gasoline catalytic conversion method Download PDF

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CN112742463A
CN112742463A CN202010905269.XA CN202010905269A CN112742463A CN 112742463 A CN112742463 A CN 112742463A CN 202010905269 A CN202010905269 A CN 202010905269A CN 112742463 A CN112742463 A CN 112742463A
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catalyst
oxide
molecular sieve
gasoline
content
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CN112742463B (en
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王丽霞
严加松
田辉平
孙敏
林伟
王鹏
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates [SAPO compounds]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/04—Ethylene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/08—Alkenes with four carbon atoms
    • 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
    • C07C4/04—Thermal processes
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/40—Special temperature treatment, i.e. other than just for template removal
    • 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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  • Thermal Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
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Abstract

The invention relates to the field of petrochemical industry, and discloses a catalyst containing a silicoaluminophosphate molecular sieve and a preparation method thereofThe catalyst comprises natural mineral substances, inorganic oxides, a silicoaluminophosphate molecular sieve and noble metals, wherein the content of the natural mineral substances is 10-70 wt%, the content of the inorganic oxides is 10-60 wt%, the content of the silicoaluminophosphate molecular sieve is 10-70 wt%, and the content of the noble metals is 0.01-10 wt% calculated by elements, based on the total weight of the catalyst. The method for catalytically converting gasoline comprises the following steps: gasoline, carbon dioxide are contacted and reacted with the catalyst provided by the invention and optionally a diluent gas. The catalyst containing the silicoaluminophosphate molecular sieve provided by the invention not only can effectively improve the selectivity of low-carbon olefin, but also can realize CO under mild conditions2The effective utilization of the water is realized.

Description

Catalyst containing silicoaluminophosphate molecular sieve, preparation method thereof and gasoline catalytic conversion method
Technical Field
The invention relates to the field of petrochemical industry, in particular to a catalyst containing a silicoaluminophosphate molecular sieve, a preparation method of the catalyst and a gasoline catalytic conversion method.
Background
The low-carbon olefin is an indispensable chemical raw material and comprises ethylene, propylene and butylene. Wherein, ethylene is mainly used for producing polyethylene, ethylene oxide, dichloroethane and the like, and propylene is mainly used for producing polypropylene, acrylonitrile, propylene oxide and other products.
In recent years, the demand of low-carbon olefins is rapidly increased, and the productivity is continuously improved. At present, the main modes for producing low-carbon olefins include steam cracking, catalytic cracking, propane dehydrogenation, MTO, catalytic reforming and the like. Wherein, the proportion of the products of the low-carbon olefin produced by adopting a steam cracking mode can not be flexibly adjusted, the reaction temperature is up to 840-860 ℃, and the energy consumption is about 40 percent of the energy consumption of the petrochemical industry. Therefore, the method for increasing the yield of the low-carbon olefin in large quantity by catalytic cracking is an efficient way for meeting the increase of demand, wherein the catalytic cracking of gasoline fractions such as naphtha and the like is promising due to the advantages of low reaction temperature, flexible and easily-adjustable product distribution, small product pollution, environmental friendliness and the like. However, from the current results, further improvements and enhancements in process and catalyst performance are still needed.
As is well known, CO2Is an important greenhouse gas, the greenhouse effect of the greenhouse gas causes a series of problems such as land desertification, aggravation of plant diseases and insect pests, climate change, glacier melting and the like, and therefore, the international society calls for CO2And (5) emission reduction. But on the other hand, CO2It is also a cheap and rich C1 resource, which can react with hydrogen to produce CO, methanol, dimethyl ether, low carbon hydrocarbon, gasoline, etc., and can react with methane to produce synthetic gas and ethane to produce ethylene, etc. However, these reactions generally need to be carried out under high pressure, and the reaction conditions are relatively severe.
Disclosure of Invention
The invention aims to overcome the defect that the selectivity of a catalyst used in the catalytic conversion process of gasoline in the prior art to low-carbon olefin is to be further improved, and provides a catalyst containing a silicoaluminophosphate molecular sieve, a preparation method of the catalyst and a catalytic conversion method of gasoline. The catalyst containing the silicoaluminophosphate molecular sieve provided by the invention not only can effectively improve the selectivity of low-carbon olefin, but also can realize CO under mild conditions2The effective utilization of the water is realized.
In order to achieve the above object, the first aspect of the present invention provides a catalyst containing a silicoaluminophosphate molecular sieve, the catalyst comprising a natural mineral, an inorganic oxide, a silicoaluminophosphate molecular sieve and a noble metal, wherein the natural mineral content is 10 to 70 wt%, the inorganic oxide content is 10 to 60 wt%, the silicoaluminophosphate molecular sieve content is 10 to 70 wt%, and the noble metal content is 0.01 to 10 wt% calculated by elements, based on the total weight of the catalyst.
The second aspect of the present invention provides a method for preparing the above catalyst containing a silicoaluminophosphate molecular sieve, the method comprising:
(1) mixing, pulping and spray-drying a silicoaluminophosphate molecular sieve, a natural mineral substance, an inorganic oxide and/or an inorganic oxide precursor to obtain a solid product a;
(2) the noble metal is loaded on the solid product a and then calcined.
In a third aspect, the invention provides a catalyst containing a silicoaluminophosphate molecular sieve prepared by the above preparation method.
In a fourth aspect, the present invention provides a method for catalytic conversion of gasoline, the method comprising: gasoline, carbon dioxide and catalyst and optional diluent gas are contacted and reacted, and the catalyst comprises the catalyst containing the silicoaluminophosphate molecular sieve.
The catalyst containing the silicoaluminophosphate molecular sieve is obtained by matching the silicoaluminophosphate molecular sieve with natural mineral substances, inorganic oxides and noble metals, can improve the selectivity of low-carbon olefin when being used in the catalytic conversion process of gasoline, and is used in the catalytic conversion process of gasoline, carbon dioxide, diluent gas are in contact reaction with the catalyst, and CO is utilized2The weak oxidation performance of the catalyst can be coupled with the catalytic cracking/thermal cracking reaction of the gasoline fraction, and the yield of chemical raw materials such as ethylene, propylene, butylene and the like and chemical products can be improved in a normal pressure range. In addition, the method for catalytically converting the gasoline can also fully utilize CO under mild conditions2Resources, reduces the problems caused by greenhouse gases, and has very good economic value and industrial application value.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a catalyst containing a silicoaluminophosphate molecular sieve, which comprises natural minerals, inorganic oxides, silicoaluminophosphate molecular sieves and noble metals, wherein the content of the natural minerals is 10-70 wt%, the content of the inorganic oxides is 10-60 wt%, the content of the silicoaluminophosphate molecular sieves is 10-70 wt%, and the content of the noble metals is 0.01-10 wt% calculated by elements.
Preferably, the content of the natural mineral matter is 20-60 wt%, the content of the inorganic oxide is 10-50 wt%, the content of the silicoaluminophosphate molecular sieve is 10-55 wt%, and the content of the noble metal is 0.1-5 wt% calculated by elements based on the total weight of the catalyst.
More preferably, the content of the natural mineral matter is 25-50 wt%, the content of the inorganic oxide is 10-44 wt%, the content of the silicoaluminophosphate molecular sieve is 30-45 wt%, and the content of the noble metal is 1-3.5 wt% calculated by element, based on the total weight of the catalyst.
In the present invention, the noble metal may be selected from one or more of Au, Ag, Ru, Rh, Pd, Pt, Ir, and Os; preferably one or more selected from Au, Ir, Pd and Rh, and more preferably at least one selected from Pd, Ir and Rh.
In the present invention, preferably, the silicoaluminophosphate molecular sieve is selected from one or more of SAPO-11 molecular sieve, SAPO-31 molecular sieve, SAPO-34 molecular sieve and SAPO-47 molecular sieve; further preferably, the silicoaluminophosphate molecular sieve is SAPO-11 and/or SAPO-34, and even more preferably is SAPO-11. The SAPO-11 is adopted to be matched with other components, so that the yield of the target product is improved.
In the present invention, the silicoaluminophosphate molecular sieve can be obtained commercially or can be prepared according to a conventional method in the art, and the present invention is not particularly limited thereto.
In the present invention, the natural mineral may be conventionally selected in the art, and preferably, the natural mineral is selected from one or more of kaolin, montmorillonite, diatomaceous earth, attapulgite, sepiolite, halloysite, hydrotalcite, bentonite and rectorite.
In the present invention, the inorganic oxide may be conventionally selected in the art, and preferably, the inorganic oxide is selected from one or more of silicon oxide, aluminum oxide-silicon oxide, zirconium oxide, titanium oxide, boron oxide, amorphous silica-alumina, aluminum phosphate, tungsten oxide-zirconium oxide, molybdenum oxide-zirconium oxide, molybdenum oxide-titanium oxide, tungsten oxide-titanium oxide, tin oxide, zinc oxide, copper oxide, nickel oxide, cobalt oxide, vanadium oxide, and niobium oxide; more preferably, the inorganic oxide is selected from one or more of alumina, silica and alumina-silica.
In the invention, preferably, the catalyst also contains an auxiliary agent; the promoter may be present in the catalyst in the form of an oxide. The auxiliary is preferably at least one selected from group IIA, group IIIA, group IVA, group VA, lanthanoid, Y, Cr, Mn, Re, Fe, and Cd, more preferably at least one selected from Ca, Fe, Ga, In, Bi, La, and Mn, and still more preferably Ga.
In the present invention, the content of the promoter is preferably 0.5 to 9 wt% in terms of oxide, based on the total weight of the catalyst. The present invention is exemplified by 2.2 wt% in the examples of the present invention, and the present invention is not limited thereto.
The present invention provides a method for producing the catalyst, which is not particularly limited as long as the catalyst having the above composition can be produced, and a method for producing the catalyst is provided to further improve the catalytic performance of the catalyst.
The second aspect of the present invention provides a method for preparing the above catalyst containing a silicoaluminophosphate molecular sieve, which comprises:
(1) mixing, pulping and spray-drying a silicoaluminophosphate molecular sieve, a natural mineral substance, an inorganic oxide and/or an inorganic oxide precursor to obtain a solid product a;
(2) the noble metal is loaded on the solid product a and then calcined.
In the present invention, the inorganic oxide precursor may be a substance that can be converted into an inorganic oxide in a subsequent process (e.g., firing) of the method provided by the present invention, and the inorganic oxide precursor can be properly selected by those skilled in the art based on the disclosure of the present invention. Specifically, the inorganic oxide precursor may be a sol of an inorganic oxide, for example, at least one of a silica sol, an aluminum sol, a peptized pseudo-boehmite, a silica-alumina sol, and a phosphorus-containing aluminum sol.
According to the preparation method provided by the invention, the solid content of the slurry obtained by mixing and beating in the step (1) is preferably 30-40 wt%.
According to the preparation method provided by the invention, preferably, the method further comprises introducing an auxiliary agent into the catalyst, wherein the kind of the auxiliary agent is described in the foregoing, and is not described in detail herein.
Further preferably, the method further comprises introducing an auxiliary agent into the catalyst in step (2); still further preferably, the step (2) includes: and loading the noble metal and the auxiliary agent on the solid product a.
In the step (2) of the present invention, the noble metal may be supported on the solid product a by a conventional method in the art, and specifically, one of an impregnation method, an ion exchange method, a chemical deposition method and a plasma method may be used. The examples of the present invention are illustrated in part by the dipping method and the present invention is not limited thereto.
According to an embodiment of the present invention, step (2) may be carried out by impregnating the solid product a with a solution containing a noble metal salt, followed by drying and calcining. The drying and calcining conditions may be carried out according to conventional conditions, and the present invention will not be described herein.
In the present invention, the noble metal salt may be a water-soluble noble metal salt, for exampleNitrates and/or chlorides of noble metals, e.g. selected from but not limited to PdCl2、(NH4)3RhCl6And IrCl3。
Specifically, the solid product a may be loaded with an auxiliary agent and a noble metal by an impregnation method, the auxiliary agent precursor and the noble metal salt may be impregnated together with the solid product a (co-impregnation) or may be impregnated stepwise into the solid product a (stepwise impregnation), and when the auxiliary agent precursor and the noble metal salt are impregnated stepwise into the solid product a, the order of introduction of the auxiliary agent precursor and the noble metal salt is not particularly limited in the present invention.
In the present invention, the promoter precursor may be converted to a species of promoter oxide during a subsequent process (e.g. calcination) of the process provided herein, and the skilled person will be able to select the promoter precursor correctly on the basis of the present disclosure. May be a water soluble salt of the adjuvant, for example a nitrate and/or chloride of the adjuvant.
The spray drying method provided by the present invention is not particularly limited, and may be carried out according to a conventional technique in the art. Preferably the spray drying conditions are such that the spray dried particles have an average particle size of from 60 to 80 μm and a particle size distribution predominantly in the range of from 40 to 100. mu.m, and more preferably the spray drying conditions are such that more than 50% of the particles having a particle size of from 60 to 80 μm are present in the spray dried particles.
In the above method of the present invention, preferably, the roasting further comprises a step of washing sodium, which means that the catalyst particles obtained by spray drying are contacted with an ammonium salt solution to wash off sodium in the catalyst, wherein the ammonium salt may be an ammonium salt commonly used in the art, and is preferably one or more of ammonium chloride, ammonium sulfate, ammonium carbonate, ammonium bicarbonate, ammonium acetate and ammonium nitrate.
In the present invention, the roasting conditions may be roasting conditions conventional in the art, and preferably, the roasting conditions include: the roasting temperature is 400-800 ℃, preferably 400-600 ℃, and the roasting time is 0.5-8 hours, preferably 1-5 hours.
According to the present invention, the calcination may be performed under an air atmosphere, an inert atmosphere, or a water vapor atmosphere, and preferably the calcination is performed under an air atmosphere.
In the present invention, the inert atmosphere may be provided by at least one of nitrogen, argon, helium and neon, preferably nitrogen.
The third aspect of the invention also provides a catalyst containing the silicoaluminophosphate molecular sieve prepared by the preparation method.
In a fourth aspect, the present invention provides a method for catalytic conversion of gasoline, the method comprising: gasoline, carbon dioxide and catalyst and optional diluent gas are contacted and reacted, and the catalyst comprises the catalyst containing the silicoaluminophosphate molecular sieve provided by the invention.
According to an embodiment of the present invention, the catalyst may be subjected to hydrothermal aging treatment before being used for catalytic conversion of gasoline. In the present invention, the conditions of the hydrothermal aging treatment are not particularly limited, and the hydrothermal aging treatment can be performed according to a conventional technique in the art. The hydrothermal aging treatment is more favorable for improving the stability of the catalyst. In the examples of the present invention, the aging is performed for 17 hours at 800 ℃ under 100% water vapor, but the present invention is not limited thereto.
In the present invention, preferably, the conditions of the contact reaction include: the temperature is 400-800 ℃, the pressure is 0.1-2MPa, and the weight ratio of the carbon dioxide to the gasoline is 0.2-3: 1, the mass airspeed of the gasoline is 0.3-10h-1(ii) a More preferably, the conditions of the contact reaction include: the temperature is 500-650 ℃, the pressure is 0.1-0.3MPa, and the weight ratio of the carbon dioxide to the gasoline is 0.25-2: 1, the mass airspeed of the gasoline is 0.5-5h-1。
In the invention, the gasoline mainly comprises aliphatic hydrocarbons and naphthenic hydrocarbons of C5-C12, and also comprises a certain amount of aromatic hydrocarbons, and specifically comprises one or more of catalytic cracking gasoline, coker gasoline, straight run gasoline, reformed gasoline, laminated gasoline and alkyl gasoline.
In the present invention, the diluent gas may be N2、H2O、O2Air, N2O、NO2、NO、H2And SO2Preferably N, is preferably N2。
According to the present invention, it is preferable that the carbon dioxide is contained in an amount of 10 to 100% by volume, based on the total volume of the carbon dioxide and the diluent gas.
The present invention will be described in detail below by way of examples.
In the following examples:
the various parameters of the gasoline used are shown in table 1 below:
TABLE 1
Parameter(s) Parameter value
Density (20 ℃ C.), g/cm3 0.7494
Vapor pressure/kPa 21.9
Alkane/wt.% 58.6
Cycloalkane/wt% 31.1
Aromatic hydrocarbon/wt% 10.3
C/wt％ 85.50
H/wt％ 14.48
S/wt％ 102
N/wt％ 0.64
Kaolin (purchased from suzhou china kaolin, having a solids content of 75% by weight);
rectorite (75 wt% solid content from Zhongxiang rectorite in Hubei province);
montmorillonite (obtained from red rock bentonite, Gekko city, Kogyo, Liaoning, with a solid content of 75 wt%);
alumina sol (available from zilu catalyst division, alumina content 22.5 wt%);
silica sol (purchased from Qingdao ocean chemical Co., Ltd., silica content of 25.5 wt%, pH 3.0);
SAPO-11 molecular sieves were prepared as disclosed in the reference "Pure apple appl. chem.,58,1351-1358 (1986)".
The contents of the components in the following catalysts are calculated by the feeding amount.
Example 1
This example illustrates the catalyst of the present invention, its preparation and the process for catalytic conversion of gasoline.
Preparing a catalyst:
(1) preparing 66.7g of alumina sol, 58.9g of kaolin and 39.1g of SAPO-11 molecular sieve into slurry with the solid content of 30 weight percent by using decationized water, uniformly stirring, and carrying out spray drying on the slurry to prepare a microspherical catalyst (the average particle size is 65 mu m, and 60-80 mu m particles account for 60 percent, the same below);
(2) with a solution containing 2.8g of PdCl2The microsphere catalyst is impregnated in the aqueous solution, and then the microsphere catalyst is dried for 2 hours at the temperature of 100 ℃ and roasted for 4 hours at the temperature of 450 ℃.
(3) The catalyst was subjected to sodium-wash exchange with ammonium bicarbonate and then dried at 100 ℃ for 2 h. Catalyst C-1 was obtained. The results of the contents of the components in the catalyst are shown in Table 2.
Catalytic conversion of gasoline:
aging the prepared catalyst for 17h at 800 ℃ and 100% of water vapor, and mixing gasoline, carbon dioxide and the catalyst at 605 ℃ and 0.12MPa, wherein the weight ratio of the carbon dioxide to the gasoline is 0.3: 1. the mass space velocity of the gasoline is 0.7h-1The catalytic conversion product of the gasoline is obtained by the contact reaction under the condition of (1). The yields of each product were tested and the results are shown in table 3.
Example 2
This example illustrates the catalyst of the present invention, its preparation and the process for catalytic conversion of gasoline.
Preparing a catalyst:
(1) preparing 66.7g of alumina sol, 49.2g of montmorillonite and 47g of SAPO-11 molecular sieve into slurry with the solid content of 32 weight percent by using decationized water, uniformly stirring, and carrying out spray drying on the slurry to prepare a microspherical catalyst (the average particle size is 65 mu m, the particles with the particle size of 60-80 mu m account for 60 percent, the same below);
(2) with a solution containing 1.8g of PdCl2The microsphere catalyst is impregnated in the aqueous solution, and then the microsphere catalyst is dried for 2 hours at the temperature of 100 ℃ and roasted for 4 hours at the temperature of 450 ℃.
(3) The catalyst was subjected to sodium-wash exchange with ammonium bicarbonate and then dried at 100 ℃ for 2 h. Catalyst C-2 was obtained. The results of the contents of the components in the catalyst are shown in Table 2.
Catalytic conversion of gasoline:
the procedure is as in example 1. The yields of each product were tested and the results are shown in table 3.
Example 3
This example illustrates the catalyst of the present invention, its preparation and the process for catalytic conversion of gasoline.
Preparing a catalyst:
(1) preparing 66.7g of alumina sol, 64.7g of kaolin and 33g of SAPO-11 molecular sieve into slurry with the solid content of 30 weight percent by using decationized water, uniformly stirring, and performing spray drying on the slurry to prepare a microspherical catalyst;
(2) with a solution containing 5.8g of PdCl2The microsphere catalyst is impregnated in the aqueous solution, and then the microsphere catalyst is dried for 2 hours at the temperature of 100 ℃ and roasted for 4 hours at the temperature of 450 ℃.
(3) And (3) carrying out sodium washing exchange on the catalyst and ammonium bicarbonate, and then drying for 2h at 100 ℃ to obtain a catalyst C-3. The results of the contents of the components in the catalyst are shown in Table 2.
Catalytic conversion of gasoline:
the procedure is as in example 1. The yields of each product were tested and the results are shown in table 3.
Example 4
This example illustrates the catalyst of the present invention, its preparation and the process for catalytic conversion of gasoline.
Preparing a catalyst:
(1) preparing 70.7g of alumina sol, 57.0g of montmorillonite and 41.2g of SAPO-11 molecular sieve into slurry with the solid content of 32 weight percent by using decationized water, uniformly stirring, and performing spray drying on the slurry to prepare a microspherical catalyst;
(2) by means of a gas containing IrCl3The microspherical catalyst is impregnated with the aqueous solution (the Ir content is 0.2g), and then dried at 100 ℃ for 2 hours and calcined at 450 ℃ for 4 hours.
(3) And (3) carrying out sodium washing exchange on the catalyst and ammonium bicarbonate, and then drying for 2h at 100 ℃ to obtain a catalyst C-4. The results of the contents of the components in the catalyst are shown in Table 2.
Catalytic conversion of gasoline:
the procedure is as in example 1. The yields of each product were tested and the results are shown in table 3.
Example 5
This example illustrates the catalyst of the present invention, its preparation and the process for catalytic conversion of gasoline.
(1) Preparing 168.6g of silica sol, 36.7g of rectorite and 28g of SAPO-11 molecular sieve into slurry with the solid content of 32 weight percent by using decationized water, uniformly stirring, and performing spray drying on the slurry to prepare a microspherical catalyst;
(2) with a catalyst containing 5.3g of (NH)4)3RhCl6Is dissolved in waterThe microsphere catalyst is soaked in the solution, and then dried for 2h at 100 ℃ and roasted for 4h at 450 ℃.
(3) And (3) carrying out sodium washing exchange on the catalyst and ammonium bicarbonate, and then drying for 2h at 100 ℃ to obtain a catalyst C-5. The results of the contents of the components in the catalyst are shown in Table 2.
Catalytic conversion of gasoline:
the procedure is as in example 1. The yields of each product were tested and the results are shown in table 3.
Example 6
This example illustrates the catalyst of the present invention, its preparation and the process for catalytic conversion of gasoline.
Preparing a catalyst:
(1) preparing 66.7g of alumina sol, 51.1g of kaolin and 43.2g of SAPO-11 molecular sieve into slurry with the solid content of 32 weight percent by using decationized water, uniformly stirring, and performing spray drying on the slurry to prepare a microspherical catalyst;
(2) with a solution containing 2.2g of PdCl2And 2.2g of Ga2O3The microsphere catalyst is impregnated in the aqueous solution, and then the microsphere catalyst is dried for 2 hours at the temperature of 100 ℃ and roasted for 4 hours at the temperature of 450 ℃.
(3) The catalyst was subjected to sodium-wash exchange with ammonium bicarbonate and then dried at 100 ℃ for 2 h. Catalyst C-6 was obtained. The results of the contents of the components in the catalyst are shown in Table 2.
Catalytic conversion of gasoline:
the procedure is as in example 1. The yields of each product were tested and the results are shown in table 3.
Example 7
The process of example 1 was followed except that carbon dioxide gas was not introduced during the catalytic conversion of gasoline. The yields of each product were tested and the results are shown in table 3.
Comparative example 1
This comparative example serves to illustrate a comparative catalyst and a method of making the same, as well as a method of catalytic conversion of gasoline.
Catalyst preparation and gasoline catalytic conversion the same as in example 1, except that no PdCl was added2。
The catalyst obtained was designated D-1. The results of the contents of the components in the catalyst are shown in Table 2. The results of yields of the various products obtained from gasoline catalytic conversion are shown in table 3.
Comparative example 2
This comparative example serves to illustrate a comparative catalyst and a method of making the same, as well as a method of catalytic conversion of gasoline.
Catalyst preparation and gasoline catalytic conversion the same as example 1 except that no SAPO-11 molecular sieve was added. The catalyst obtained was designated D-2. The results of calculating the contents of the components in the catalyst according to the total weight and the amount of the catalyst to be finally obtained are shown in table 2. The results of yields of the various products obtained from gasoline catalytic conversion are shown in table 3.
TABLE 2
Figure BDA0002661190610000131
TABLE 3
Product yield (%) Ethylene + propylene + butene Coke Diesel oil and oil slurry Gasoline (gasoline) Liquefied gas Dry gas
Example 1 34.7 3.0 5.6 43.9 35.2 12.3
Example 2 34.3 3.7 3.9 41.2 35.0 16.3
Example 3 34.1 3.2 5.2 45.0 34.3 12.4
Example 4 31.6 3.1 6.4 43.5 34.7 12.3
Example 5 32.9 2.7 4.2 46.9 34.0 12.2
Example 6 36.0 2.9 5.1 41.9 36.7 13.4
Example 7 31.4 3.0 6.7 43.8 34.4 12.1
Comparative example 1 24.1 2.6 1.5 60.9 27.4 7.6
Comparative example 2 7.0 2.9 1.1 80.4 7.3 8.3
As can be seen from the data results in Table 3, the catalyst provided by the invention can improve the low-carbon olefins (including ethylene, propylene and butylene)) Selectivity of (2). In addition, the catalyst and CO provided by the invention are adopted2Is used in the catalytic conversion process of gasoline in a matching way, is more favorable for improving the selectivity of low-carbon olefin, and realizes CO2Effective utilization under mild conditions.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (11)

1. The catalyst containing the silicoaluminophosphate molecular sieve is characterized by comprising 10-70 wt% of natural mineral substances, 10-60 wt% of inorganic oxides, 10-70 wt% of the silicoaluminophosphate molecular sieve and 0.01-10 wt% of noble metals by taking the total weight of the catalyst as a reference.
2. The catalyst of claim 1, wherein the natural mineral content is 20-60 wt%, the inorganic oxide content is 10-50 wt%, the silicoaluminophosphate molecular sieve content is 10-55 wt%, and the noble metal content is 0.1-5 wt% calculated as element, based on the total weight of the catalyst;
preferably, the content of the natural mineral matter is 25-50 wt%, the content of the inorganic oxide is 10-44 wt%, the content of the silicoaluminophosphate molecular sieve is 30-45 wt%, and the content of the noble metal is 1-3.5 wt% calculated by element based on the total weight of the catalyst.
3. The catalyst according to claim 1 or 2, wherein the noble metal is selected from one or more of Au, Ag, Ru, Rh, Pd, Pt, Ir and Os; preferably one or more selected from Au, Ir, Pd and Rh.
4. The catalyst of any one of claims 1-3, wherein the silicoaluminophosphate molecular sieves are selected from one or more of SAPO-11 molecular sieves, SAPO-31 molecular sieves, SAPO-34 molecular sieves, and SAPO-47 molecular sieves;
preferably, the silicoaluminophosphate molecular sieves are SAPO-11 and/or SAPO-34.
5. The catalyst of any one of claims 1-4, wherein the natural mineral is selected from one or more of kaolin, montmorillonite, diatomaceous earth, attapulgite, sepiolite, halloysite, hydrotalcite, bentonite, and rectorite;
preferably, the inorganic oxide is selected from one or more of silicon oxide, aluminum oxide-silicon oxide, zirconium oxide, titanium oxide, boron oxide, amorphous silicon aluminum, aluminum phosphate, tungsten oxide-zirconium oxide, molybdenum oxide-zirconium oxide, molybdenum oxide-titanium oxide, tungsten oxide-titanium oxide, tin oxide, zinc oxide, copper oxide, nickel oxide, cobalt oxide, vanadium oxide and niobium oxide.
6. The catalyst according to any one of claims 1 to 5, wherein the catalyst further comprises an auxiliary selected from at least one of group IIA, group IIIA, group IVA, group VA, lanthanides, Y, Cr, Mn, Re, Fe and Cd, preferably from at least one of Ca, Fe, Ga, In, Bi, La and Mn;
preferably, the content of the auxiliary agent is 0.5-9 wt% in terms of oxide based on the total weight of the catalyst.
7. A method of making a catalyst comprising a silicoaluminophosphate molecular sieve as claimed in any one of claims 1 to 6, the method comprising:
(1) mixing, pulping and spray-drying a silicoaluminophosphate molecular sieve, a natural mineral substance, an inorganic oxide and/or an inorganic oxide precursor to obtain a solid product a;
(2) the noble metal is loaded on the solid product a and then calcined.
8. The method of claim 7, further comprising introducing a promoter into the catalyst;
preferably, in step (2), an auxiliary is introduced into the catalyst;
further preferably, step (2) comprises: and loading the noble metal and the auxiliary agent on the solid product a.
9. The method of claim 8, wherein the firing conditions include: the roasting temperature is 400-800 ℃, and the roasting time is 0.5-8 hours.
10. The catalyst containing the silicoaluminophosphate molecular sieve prepared by the preparation method of any one of claims 7 to 9.
11. A process for the catalytic conversion of gasoline, the process comprising: contacting gasoline, carbon dioxide and a catalyst comprising the silicoaluminophosphate molecular sieve containing catalyst of any of claims 1-6 and 10, and optionally a diluent gas;
preferably, the conditions of the contact reaction include: the temperature is 400-800 ℃, the pressure is 0.1-2MPa, and the weight ratio of the carbon dioxide to the gasoline is 0.2-3: 1, the mass airspeed of the gasoline is 0.3-10h-1；
More preferably, the conditions of the contact reaction include: the temperature is 500-650 ℃, the pressure is 0.1-0.3MPa, and the weight ratio of the carbon dioxide to the gasoline is 0.25-2: 1, the mass airspeed of the gasoline is 0.5-5h-1。
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CN1972748A (en) * 2004-04-20 2007-05-30 环球油品公司 Catalyst for selective opening of cyclic paraffins and process for using the catalyst
CN1888024A (en) * 2005-06-30 2007-01-03 中国石油化工股份有限公司 Hydrocarbon oil processing method
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