CN111359657A - Regeneration method of molecular sieve catalyst - Google Patents

Regeneration method of molecular sieve catalyst Download PDF

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CN111359657A
CN111359657A CN201811589240.4A CN201811589240A CN111359657A CN 111359657 A CN111359657 A CN 111359657A CN 201811589240 A CN201811589240 A CN 201811589240A CN 111359657 A CN111359657 A CN 111359657A
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molecular sieve
catalyst
topology
hydrogen
sieve catalyst
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赵学斌
田鹏
刘中民
王林英
李冰
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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    • 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
    • B01J29/90—Regeneration or reactivation
    • 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
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/084—Y-type faujasite
    • 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
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • 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
    • 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
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
    • 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
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • 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
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/74—Noble metals
    • 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
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/7815—Zeolite Beta
    • 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
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/80—Mixtures of different zeolites
    • 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)

Abstract

The application discloses a regeneration method of a molecular sieve catalyst, which comprises the following steps: treating the molecular sieve catalyst to be regenerated in a hydrogen-containing atmosphere with the system pressure of 0.5-20 MPa to obtain the regenerated molecular sieve catalyst. By using the method, the regeneration of the carbon deposition deactivated molecular sieve catalyst can be realized at a lower reaction temperature, the requirement of the regeneration process on a reactor is reduced, and the influence of the regeneration process on other components in the catalyst is reduced.

Description

Regeneration method of molecular sieve catalyst
Technical Field
The application relates to a regeneration method of a molecular sieve catalyst, belonging to the field of chemistry and chemical engineering.
Background
The molecular sieve is used as a common solid acid catalyst and an active center component in acid catalytic reaction and is widely applied to catalytic conversion reaction of hydrocarbons, such as catalytic cracking, hydrocracking, methanol-to-olefin reaction and the like. In the reaction catalyzed by the molecular sieve, carbon deactivation is the main mode of molecular sieve deactivation, high-temperature calcination is the regeneration commonly used for the molecular sieve catalyst deactivated by carbon, but the regeneration temperature is higher and is often more than 600 ℃, and simultaneously, a large amount of heat is released in the calcination process, which has higher requirements on the material of a reactor, and meanwhile, the high temperature in the regeneration process often causes influences on other components in the catalyst, such as metal sintering, crystal phase transformation and the like. Therefore, how to reduce the requirements on the reactor material and influence on other components in the molecular sieve in the regeneration process of the molecular sieve is an important problem in the regeneration process.
At present, most molecular sieve regeneration processes are carried out in an oxygen-containing atmosphere, so that carbon and oxygen react to generate carbon dioxide. Patent CN 102836743B discloses a method for multi-stage constant temperature calcination of deactivated catalyst under oxygen-containing atmosphere, wherein the reaction temperature is 300-750 ℃. CN 106179488A discloses a regeneration method of a bifunctional catalyst containing noble metal and molecular sieve, which uses ethanol, benzene, gasoline and other organic solvents to treat the deactivated catalyst, but this method needs to consume a large amount of solvent.
Disclosure of Invention
According to one aspect of the application, a regeneration method of a molecular sieve catalyst is provided, which can realize the regeneration of the carbon deposit deactivated molecular sieve catalyst at a lower reaction temperature, reduce the requirements of the regeneration process on a reactor, and simultaneously reduce the influence of the regeneration process on other components in the catalyst.
The regeneration method of the molecular sieve catalyst comprises the following steps: treating the molecular sieve catalyst to be regenerated in a hydrogen-containing atmosphere with the system pressure of 0.5-20 MPa to obtain the regenerated molecular sieve catalyst.
Optionally, the upper limit of the system pressure is selected from 1.0MPa, 2.0MPa, 3.0MPa, 4.0MPa, 5.0MPa, 6.0MPa, 7.0MPa, 8.0MPa, 10.0MPa, 12.0MPa, 15.0MPa, 18.0MPa, or 20.0 MPa; the lower limit is selected from 0.5MPa, 1.0MPa, 2.0MPa, 3.0MPa, 4.0MPa, 5.0MPa, 6.0MPa, 7.0MPa, 8.0MPa, 10.0MPa, 12.0MPa, 15.0MPa or 18.0 MPa.
Optionally, the system pressure is 2.0-7.0 MPa.
Optionally, the partial pressure of hydrogen in the hydrogen-containing atmosphere is 0.5-20.0 MPa.
Optionally, the upper limit of the partial pressure of hydrogen in the hydrogen-containing atmosphere is selected from 1.0MPa, 1.5MPa, 2.0MPa, 2.5MPa, 3.0MPa, 4.0MPa, 5.0MPa, 6.0MPa, 7.0MPa, 8.0MPa, 10.0MPa, 12.0MPa, 15.0MPa, 18.0MPa, or 20.0 MPa; the lower limit is selected from 0.5MPa, 1.0MPa, 1.5MPa, 2.0MPa, 2.5MPa, 3.0MPa, 4.0MPa, 5.0MPa, 6.0MPa, 7.0MPa, 8.0MPa, 10.0MPa, 12.0MPa, 15.0MPa or 18.0 MPa.
Optionally, the partial pressure of hydrogen in the hydrogen-containing atmosphere is 2.0-7.0 MPa.
Optionally, the hydrogen-containing atmosphere is at least one of pure hydrogen atmosphere or inert gas including hydrogen;
the partial pressure of the inactive gas in the hydrogen-containing atmosphere is 0-15 MPa.
Optionally, the inert gas is selected from N2、H2O and inert gas.
Optionally, the hydrogen-containing atmosphere also comprises N2、He、H2O and the like in inert atmosphere.
Optionally, the temperature of the treatment is 250-600 ℃.
Optionally, the upper temperature limit of the treatment is selected from 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃ or 600 ℃; the lower limit is selected from 300 deg.C, 350 deg.C, 400 deg.C, 450 deg.C, 500 deg.C or 550 deg.C.
Optionally, the temperature of the treatment is 350-500 ℃.
Optionally, the treatment time is 5-200 h.
Optionally, the treatment time is 20-96 h.
Optionally, the upper time limit of the treatment is selected from 8h, 10h, 20h, 24h, 48h, 72h, 96h, 100h, 120h, 150h, 180h or 200 h; the lower limit is selected from 5h, 8h, 10h, 20h, 24h, 48h, 72h, 96h, 100h, 120h, 150h or 180 h.
The method in the present application solves the technical problem and achieves the beneficial effects described above within the above-mentioned processing time range.
Optionally, the molecular sieve catalyst to be regenerated is a carbon deposit deactivated molecular sieve catalyst.
Optionally, the soot in the soot deactivated molecular sieve catalyst reacts with hydrogen.
Optionally, the content of the molecular sieve active component in the molecular sieve catalyst is 5-100 wt%.
Optionally, the molecular sieve catalyst further comprises at least one of a metal, a metal oxide and a binder.
Optionally, the metal comprises Pt.
Optionally, the metal oxide comprises Zn-Cr oxide, aluminum oxide, molybdenum oxide, cobalt oxide.
Optionally, the binder comprises silica sol, alumina, clay.
Optionally, the molecular sieve active component is selected from at least one of molecular sieves having acidic sites.
Optionally, the molecular sieve active component is selected from one or more of a silicoaluminophosphate, a silicoaluminophosphate molecular sieve and other heteroatom molecular sieves.
Optionally, the active component of the molecular sieve is selected from at least one of a molecular sieve having CHA topology, a molecular sieve having AEI topology, a molecular sieve having LEV topology, a molecular sieve having LTA topology, a molecular sieve having AFX topology, a molecular sieve having AFI topology, a molecular sieve having MFI topology, a molecular sieve having FAU topology, a molecular sieve having BEA topology, a molecular sieve having TON topology, a molecular sieve having MWW topology, a molecular sieve having MOR topology, a molecular sieve having FER topology.
Optionally, the molecular sieve catalyst is selected from a methanol-to-olefin catalyst, a synthesis gas direct-to-low-carbon olefin catalyst, a dimethyl ether carbonylation catalyst, a methanol-to-propylene catalyst, a catalytic cracking catalyst, a hydrocracking catalyst, a hydroisomerization catalyst, C8One or more of an aromatic isomerization catalyst and an alkylation catalyst.
As a specific embodiment, the method for regenerating the molecular sieve catalyst comprises: treating a carbon deposition inactivated molecular sieve catalyst under the conditions of a certain reaction temperature and high-pressure hydrogen-containing atmosphere to enable the carbon deposition to react with hydrogen and eliminate the carbon deposition on the molecular sieve catalyst, wherein the reaction temperature is 250-600 ℃, the system pressure is 0.5-20.0MPa, the hydrogen partial pressure is 0.5-20.0MPa, the molecular sieve catalyst is a catalyst containing part or all of molecular sieve active components, and the molecular sieve has an acid site, and specifically is one or more of silicon-aluminum zeolite, a silicon-aluminum phosphate molecular sieve and other heteroatom molecular sieves.
Optionally, the process partially or completely eliminates soot on the soot deactivated molecular sieve catalyst.
Optionally, the amount of carbon deposition of the regenerated molecular sieve catalyst is reduced by more than 50% compared with the amount of carbon deposition of the molecular sieve to be regenerated.
Optionally, the regenerated molecular sieve catalyst has a carbon deposition of no more than 5%.
Optionally, the regenerated molecular sieve catalyst has a carbon deposition of 0%.
The beneficial effects that this application can produce include:
according to the method, the deactivated molecular sieve catalyst can be regenerated at a lower temperature under a high-pressure hydrogen atmosphere, the requirement on the material of a reactor in the regeneration process is reduced, the influence of the regeneration process on other components of the catalyst is avoided, the device investment is reduced, and the method has a huge economic value.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
The analysis method in the examples of the present application is as follows:
the carbon deposition deactivated molecular sieve catalyst in the embodiment of the application refers to the catalyst when the conversion rate of the raw material is reduced to 80% of the highest conversion rate.
Carbon deposition analysis was performed using a Q600SDT synchronous thermal analyzer from TA instruments, usa.
In the embodiment of the application, the carbon deposition amount is calculated by the weight loss amount between 300 ℃ and 700 ℃ in the thermal analysis result.
According to one embodiment of the application, the method for regenerating the carbon deposition deactivated molecular sieve catalyst in the high-pressure hydrogen atmosphere comprises the step of reacting the carbon deposition in the deactivated molecular sieve with hydrogen at the temperature of 250-600 ℃, the pressure of a reaction system of 0.5-20.0MPa and the partial pressure of the hydrogen of 0.5-20.0MPa, so as to partially or completely eliminate the carbon deposition on the molecular sieve catalyst.
Optionally, the molecular sieve catalyst is a catalyst containing 5-100 wt% of molecular sieve active component, and other components may be metal, metal oxide, binder or the like.
Optionally, the molecular sieve has acidic sites, in particular one or more of a silicoaluminophosphate, a silicoaluminophosphate type molecular sieve and other heteroatomic molecular sieves.
Optionally, the molecular sieve is one or more of CHA, AEI, LEV, LTA, AFX, AFI, MFI, FAU, BEA, TON, MWW, MOR, FER, and the like.
Optionally, the reaction temperature is preferably 350-500 ℃, the reaction pressure is preferably 2.0-7.0 MPa, and the hydrogen partial pressure is preferably 2.0-7.0 MPa.
Optionally, the reaction system comprises N in addition to hydrogen2、He、H2O and the like, wherein the partial pressure of the inert atmosphere is 0-15 MPa.
Example 1
The deactivated catalyst is obtained after catalytic reaction of a methanol-to-olefin catalyst formed by 50 wt% of SAPO-34 molecular sieve (CHA topological structure) and 50 wt% of silica sol spray balls. The deactivated catalyst is treated for 20 hours under the conditions that the temperature is 450 ℃, the reaction pressure is 4.0MPa, the hydrogen partial pressure is 1.5MPa and the water partial pressure is 2.5MPa, and the carbon deposition amount on the deactivated catalyst is reduced to 5.0 percent from 16.0 percent before treatment.
Wherein the methanol-to-olefin catalyst is purchased from the new technology of Chinese science, namely GmbH, and the silicon content of the SAPO-34 molecular sieve is 7.2 percent.
The catalytic reaction conditions are 450 ℃, 50 wt% methanol aqueous solution is fed, and the weight space velocity of the methanol is 4h-1And after 4.5h of reaction, the conversion rate of the methanol is lower than 80 percent, and the inactivated molecular sieve catalyst is obtained.
Example 2
For a methanol-to-olefin catalyst consisting of 100 wt% of Zr-SAPO-5 molecular sieve (AFI topological structure), obtaining a deactivated catalyst after catalytic reaction. The deactivated catalyst is treated for 48 hours under the conditions that the temperature is 350 ℃, the reaction pressure is 10.0MPa and the hydrogen partial pressure is 10.0MPa, and the carbon deposition amount on the deactivated catalyst is reduced to 0.5 percent from 8.0 percent before treatment.
Wherein the Zr-SAPO-5 molecular sieve is purchased from the New technology of Chinese medicine, Inc., the Zr content is 1.2 wt%, and the silicon content is 5.2%.
The catalytic reaction conditions are 500 ℃, 50 wt% methanol aqueous solution is fed, and the weight space velocity of the methanol is 4h-1And after 2.3h of reaction, the conversion rate of the methanol is lower than 80 percent, and the inactivated molecular sieve catalyst is obtained.
Example 3
The methanol-to-olefin catalyst consists of 30 wt% of SAPO-42 molecular sieve (LTA topological structure) and 70 wt% of clay, and the deactivated catalyst is obtained after catalytic reaction. The deactivated catalyst is treated for 48 hours under the conditions that the temperature is 450 ℃, the reaction pressure is 3.0MPa, the hydrogen partial pressure is 2.0MPa and the helium partial pressure is 1.0MPa, and the carbon deposition amount on the deactivated catalyst is reduced to 2.3 percent from 10.0 percent before treatment.
The SAPO-42 molecular sieve is purchased from China Clay, New technology, Inc., with the silicon content of 5.2%, and is formed by mixing the SAPO-42 molecular sieve with clay and then performing spray ball molding.
The catalytic reaction conditions are 450 ℃, 50 wt% methanol aqueous solution is fed, and the weight space velocity of the methanol is 4h-1And after 2.7h of reaction, the conversion rate of methanol is lower than 80 percent, and the inactivated molecular sieve catalyst is obtained.
Example 4
The methanol-to-olefin catalyst is composed of 5 wt% of SAPO-56 molecular sieve (AFX topological structure) and 95 wt% of silica sol, and the deactivated catalyst is obtained after catalytic reaction. The deactivated catalyst is treated for 48 hours under the conditions that the temperature is 600 ℃, the reaction pressure is 7.0MPa, the hydrogen partial pressure is 5.0MPa, the helium partial pressure is 1.0MPa and the water partial pressure is 1.0MPa, and the carbon deposition amount on the deactivated catalyst is reduced to 0.1 percent from 2.0 percent before treatment.
The SAPO-56 molecular sieve is purchased from China Classification of New technology, Inc., with silicon content of 8.5%, and is formed by mixing the SAPO-56 molecular sieve with silica sol and then performing ball-spraying molding.
The catalytic reaction conditions are 450 ℃, 50 wt% methanol aqueous solution is fed, and the weight space velocity of the methanol is 4h-1And after 2.7h of reaction, the conversion rate of methanol is lower than 80 percent, and the inactivated molecular sieve catalyst is obtained.
Example 5
The synthesis gas composed of 50 wt% of SSZ-39 molecular sieve (AEI topological structure) and 50 wt% of Zn-Cr oxide is directly used for preparing the low-carbon olefin catalyst, and the deactivated catalyst is obtained after catalytic reaction. The deactivated catalyst is treated for 48 hours under the conditions that the temperature is 400 ℃, the reaction pressure is 5.0MPa, the hydrogen partial pressure is 2.5MPa and the nitrogen partial pressure is 1.5MPa, and the carbon deposition amount on the deactivated catalyst is reduced to 2.0 percent from 10.0 percent before treatment.
Wherein the SSZ-39 molecular sieve is purchased from Nankai catalyst factories and has a silicon-aluminum ratio of 25. The metal oxide is prepared by a method of adding ammonia water into 0.1mol/L aqueous solution of zinc nitrate and chromium nitrate for precipitation, wherein the atomic ratio of Zn to Cr is 1: 1. and mechanically mixing the molecular sieve and the metal oxide, and molding to obtain the catalyst for preparing the low-carbon olefin from the synthesis gas.
The catalytic reaction conditions are 400 ℃, 4.0MPa and H22.5 of/CO and 9828ml/h/g of GHSV, and after the reaction is carried out for 350 hours, the CO conversion rate is lower than 10 percent, thus obtaining the deactivated catalyst.
Example 6
The dimethyl ether carbonylation catalyst is composed of 60 wt% MOR molecular sieve (MOR topological structure) and 40 wt% alumina, and the deactivated catalyst is obtained after catalytic reaction. The deactivated catalyst is treated for 200 hours under the conditions that the temperature is 350 ℃, the reaction pressure is 20.0MPa, the hydrogen partial pressure is 5.0MPa and the nitrogen partial pressure is 15.0MPa, and the carbon deposition amount on the deactivated catalyst is reduced to 0.0 percent from 7.0 percent before treatment.
Wherein the dimethyl ether carbonylation catalyst is purchased from the elongation middle energy science co ltd, wherein the MOR molecular sieve silica to alumina ratio is 15.
The catalytic reaction conditions are 200 ℃, 3.0MPa and H2and/CO is 2, GHSV is 1500ml/g/h, and after 15h of reaction, the CO conversion rate is lower than 20 percent, thus obtaining the deactivated catalyst.
Example 7
The catalyst is a dimethyl ether carbonylation catalyst composed of 70 wt% of ZSM-35 molecular sieve (FER topological structure) and 30 wt% of silica sol, and the deactivated catalyst is obtained after catalytic reaction. The deactivated catalyst is treated for 24 hours under the conditions that the temperature is 250 ℃, the reaction pressure is 5.0MPa and the hydrogen partial pressure is 5.0MPa, and the carbon deposition amount on the deactivated catalyst is reduced to 2.5 percent from 6.0 percent before treatment.
Wherein the dimethyl ether carbonylation catalyst is purchased from elongation middle energy science and technology limited, wherein the ZSM-35 molecular sieve has a silica alumina ratio of 45.
The catalytic reaction conditions are 200 ℃, 3.0MPa and H2And the reaction time is 60 hours, the CO conversion rate is less than 10 percent, and the deactivated catalyst is obtained.
Example 8
The catalyst for preparing propylene from methanol, which is composed of 50 wt% of ZSM-5 molecular sieve (MFI topological structure) and 50 wt% of silica sol, is subjected to catalytic reaction to obtain the deactivated catalyst. The deactivated catalyst is treated for 96 hours under the conditions that the temperature is 450 ℃, the reaction pressure is 2.0MPa and the hydrogen partial pressure is 2.0MPa, and the carbon deposition amount on the deactivated catalyst is reduced to 2.0 percent from 10.0 percent before treatment.
The methanol-to-propylene catalyst is purchased from China catalytic New technology, Inc., wherein the silica-alumina ratio of the ZSM-5 molecular sieve is 125.
The catalytic reaction conditions are 480 ℃, 50 wt% methanol aqueous solution feeding, and the methanol weight space velocity is 4h-1And after 120 hours of reaction, the conversion rate of the methanol is lower than 80 percent, and the deactivated molecular sieve catalyst is obtained.
Example 9
The catalytic cracking catalyst is composed of 50 wt% of Y molecular sieve (FAU topological structure) and 50 wt% of silica sol, and the deactivated catalyst is obtained after catalytic reaction. The carbon deposition amount on the deactivated catalyst is reduced to 0.5 percent from 15.0 percent before treatment under the conditions of 450 ℃, the reaction pressure of 4.0MPa and the hydrogen partial pressure of 4.0MPa on the deactivated catalyst for 96 hours.
Wherein the catalytic cracking catalyst is purchased from a Nankai catalyst factory, and the silica-alumina ratio of the Y molecular sieve is 10.
The catalytic reaction condition is 480 ℃, normal pressure, feeding with vacuum residue, the catalyst-oil ratio is 3.5, and obtaining the deactivated catalyst after 0.3h of reaction.
Example 10
The catalyst is a hydrocracking catalyst consisting of 50 wt% of Beta molecular sieve (BEA topological structure), 45 wt% of alumina, 2.5 wt% of molybdenum oxide and 2.5 wt% of cobalt oxide, and the deactivated catalyst is obtained after catalytic reaction. The carbon deposition amount on the deactivated catalyst is reduced to 0.0 percent from 11.0 percent before treatment under the conditions that the deactivated catalyst is treated for 96 hours at 450 ℃, the reaction pressure is 6.0MPa and the hydrogen partial pressure is 6.0 MPa.
The Beta molecular sieve is purchased from a Nankai catalyst factory, the silica-alumina ratio of the Beta molecular sieve is 12, the Beta molecular sieve and alumina are mixed and molded, and then the Beta molecular sieve and the alumina are soaked in a mixed solution of 0.5mol/l of ammonium molybdate and cobalt nitrate in equal volume, and the mixture is dried at 120 ℃ for 12 hours and roasted at 550 ℃ for 8 hours to obtain the hydrocracking catalyst.
The catalytic reaction conditions are 400 ℃, 8.0MPa, dodecane is used as a model compound for feeding, the catalyst-oil ratio is 2.0, GHSV is 8630ml/g/h, the conversion rate is reduced to 80% after the reaction is 370h, and the inactivated catalyst is obtained.
Example 11
The catalyst is a hydrocracking catalyst consisting of 25 wt% of Beta molecular sieve (BEA topological structure), 25 wt% of Y molecular sieve (FAU topological structure), 45 wt% of alumina, 2.5 wt% of molybdenum oxide and 2.5 wt% of cobalt oxide, and the deactivated catalyst is obtained after catalytic reaction. The carbon deposition amount on the deactivated catalyst is reduced to 0.0 percent from 12.0 percent before treatment under the conditions that the deactivated catalyst is treated for 96 hours at 450 ℃, the reaction pressure is 6.0MPa and the hydrogen partial pressure is 6.0 MPa.
The Beta molecular sieve and the Y molecular sieve are purchased from Nankai catalyst factories, the silicon-aluminum ratio is 12 to 10 respectively, the Beta molecular sieve, the Y molecular sieve and alumina are mixed and molded, and then the Beta molecular sieve, the Y molecular sieve and the alumina are soaked in 0.5mol/l of mixed solution of ammonium molybdate and cobalt nitrate in equal volume, dried at 120 ℃ for 12 hours and roasted at 550 ℃ for 8 hours, so that the hydrocracking catalyst is obtained.
Under the catalytic reaction conditions of 400 ℃ and 8.0MPa, dodecane is used as a model compound for feeding, the catalyst-oil ratio is 2.0, the GHSV is 8630ml/g/h, the conversion rate is reduced to 80% after 270h of reaction, and the inactivated catalyst is obtained. .
Example 12
The catalyst is a hydroisomerization catalyst consisting of 60 wt% of ZSM-22 molecular sieve (TON topological structure), 39.5 wt% of alumina and 0.5 wt% of Pt, and the deactivated catalyst is obtained after catalytic reaction. The carbon deposition amount on the deactivated catalyst is reduced to 1.2 percent from 4.5 percent before treatment under the conditions that the deactivated catalyst is treated for 48 hours at 450 ℃, the reaction pressure is 5.0MPa and the hydrogen partial pressure is 5.0 MPa.
The ZSM-22 molecular sieve is purchased from a Nankai catalyst factory, the silica-alumina ratio of the ZSM-22 molecular sieve is respectively 30, the ZSM-22 molecular sieve and alumina are mixed and molded, and then dipped in 0.01mol/l chloroplatinic acid solution in an equal volume, dried at 120 ℃ for 12h, and roasted at 550 ℃ for 8h to obtain the hydroisomerization catalyst.
The catalytic reaction conditions are 310 ℃, 13MPa, the hydrogen-oil ratio is 500:1, and the volume space velocity is 1.5h-1The hydrocracking tail oil is adopted for feeding, the conversion rate of the n-octadecane in the raw oil is taken as a reference, and when the reaction lasts for 390 hours, the conversion rate is reduced to 30 percent, so that the deactivated catalyst is obtained.
Example 13
C consisting of 60 wt% MOR molecular sieve (MOR topology), 39.5 wt% alumina, 0.5 wt% Pt8And (3) carrying out catalytic reaction on the aromatic hydrocarbon isomerization catalyst to obtain the deactivated catalyst. The carbon deposition amount on the deactivated catalyst is reduced to 0.0 percent from 8.7 percent before treatment under the conditions of 450 ℃, the reaction pressure of 5.0MPa and the hydrogen partial pressure of 5.0MPa for 96 hours.
Wherein the MOR molecular sieve is purchased from the elongation Medium energy science and technology, Inc., wherein the MOR molecular sieve has a silica to alumina ratio of 15. Mixing MOR molecular sieve and alumina, molding, soaking in 0.01mol/l chloroplatinic acid solution in equal volume, drying at 120 deg.C for 12h, and calcining at 550 deg.C for 8h to obtain C8An aromatic isomerization catalyst.
The catalytic reaction conditions are 350 ℃, 5.0MPa, the hydrogen-oil ratio is 200:1, and the volume space velocity is 1.5h-1By mixing C8And (3) feeding aromatic hydrocarbon, and reacting for 200 hours, wherein the conversion rate of the m-xylene is reduced to 30 percent, and thus the catalyst is deactivated.
Example 14
An alkylation catalyst consisting of 60 wt% MCM-22 molecular sieve (MWW topological structure) and 40 wt% alumina is subjected to catalytic reaction to obtain a deactivated catalyst. The carbon deposition amount on the deactivated catalyst is reduced to 4.5 percent from 9.0 percent before treatment under the conditions of 450 ℃, the reaction pressure of 0.5MPa and the hydrogen partial pressure of 0.5MPa for 96 hours.
Wherein the MCM-22 molecular sieve is purchased from Nankai catalyst factories, and the silica-alumina ratio is 55. Mixing an MCM-22 molecular sieve with alumina, molding, drying at 120 ℃ for 12 hours, and roasting at 550 ℃ for 8 hours to obtain the alkylation catalyst.
The catalytic reaction conditions are 450 ℃ and 0.1MPa, mixed feeding of toluene and methanol is adopted, the toluene/methanol ratio is 1/3, and the toluene space velocity is 1.0h-1And when the reaction lasts for 10 hours, the conversion rate of the toluene is reduced to 27 percent, and the catalyst is deactivated.
Example 15
The methanol-to-olefin catalyst consists of 30 wt% of SAPO-35 molecular sieve (LEV topological structure) and 70 wt% of silica sol, and the deactivated catalyst is obtained after catalytic reaction. The deactivated catalyst is treated for 48 hours under the conditions that the temperature is 450 ℃, the reaction pressure is 3.0MPa and the hydrogen partial pressure is 3.0MPa, and the carbon deposition amount on the deactivated catalyst is reduced to 0 percent from 5.0 percent before treatment.
Wherein the SAPO-35 molecular sieve is purchased from China Classification of New technology, Inc., and the silicon content is 10.2%. And mixing the SAPO-35 molecular sieve with silica sol, and extruding into strips for molding.
The catalytic reaction conditions are 450 ℃, 50 wt% methanol aqueous solution is fed, and the weight space velocity of the methanol is 4h-1And after 2.0h of reaction, the conversion rate of methanol is lower than 80 percent, and the inactivated molecular sieve catalyst is obtained.
The catalyst composition, regeneration conditions and regeneration results in each of the above examples are shown in Table 1. TABLE 1 catalyst composition, regeneration conditions and regeneration results in the examples
Figure BDA0001919839360000111
Figure BDA0001919839360000121
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.

Claims (10)

1. A method of regenerating a molecular sieve catalyst, comprising: treating the molecular sieve catalyst to be regenerated in a hydrogen-containing atmosphere with the system pressure of 0.5-20 MPa to obtain the regenerated molecular sieve catalyst.
2. The method according to claim 1, wherein the system pressure is 2.0-7.0 MPa.
3. The method according to claim 1, wherein the hydrogen partial pressure in the hydrogen-containing atmosphere is 0.5 to 20.0 MPa;
preferably, the partial pressure of hydrogen in the hydrogen-containing atmosphere is 2.0-7.0 MPa.
4. The method of claim 1, wherein the hydrogen-containing atmosphere is at least one of a pure hydrogen atmosphere or a gas comprising hydrogen, an inert gas;
the partial pressure of the inactive gas in the hydrogen-containing atmosphere is 0-15 MPa;
preferably, the inert gas is selected from N2、H2O and inert gas.
5. The method according to claim 1, wherein the temperature of the treatment is 250 to 600 ℃;
the treatment time is 5-200 h;
preferably, the temperature of the treatment is 350-500 ℃;
preferably, the treatment time is 20-96 h.
6. The method of claim 1, wherein the molecular sieve catalyst to be regenerated is a carbon-deactivated molecular sieve catalyst;
preferably, the content of the molecular sieve active component in the molecular sieve catalyst is 5-100 wt%.
7. The method of claim 6, wherein the molecular sieve catalyst further comprises at least one of a metal, a metal oxide, and a binder.
8. The method of claim 6, wherein the molecular sieve active component is selected from at least one of molecular sieves having acidic sites;
preferably, the active component of the molecular sieve is selected from at least one of molecular sieves with CHA topology, molecular sieves with AEI topology, molecular sieves with LEV topology, molecular sieves with LTA topology, molecular sieves with AFX topology, molecular sieves with AFI topology, molecular sieves with MFI topology, molecular sieves with FAU topology, molecular sieves with abe topology, molecular sieves with TON topology, molecular sieves with MWW topology, molecular sieves with MOR topology, molecular sieves with FER topology.
9. The method of any one of claims 1 to 8, wherein the amount of soot of the regenerated molecular sieve catalyst is reduced by more than 50% compared to the amount of soot of the molecular sieve to be regenerated.
10. The process of any one of claims 1 to 8, wherein the regenerated molecular sieve catalyst has a carbon deposit amount of not more than 5%;
preferably, the regenerated molecular sieve catalyst has a carbon deposit amount of 0%.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114166696A (en) * 2020-09-11 2022-03-11 中国科学院大连化学物理研究所 Molecular sieve catalyst diffusion property evaluation method
CN114588952A (en) * 2020-12-07 2022-06-07 中国科学院大连化学物理研究所 Method for regenerating catalyst

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1590364A (en) * 2003-09-03 2005-03-09 中国石油化工股份有限公司 Carbon deposition deactivated noble metal loading type catalyst regeneration method
CN101239332A (en) * 2007-01-26 2008-08-13 林德股份公司 Method and device for regenerating a catalytic converter for steam dealkylation reactions
CN101903098A (en) * 2007-12-19 2010-12-01 英国石油化学品有限公司 Regeneration of zeolite carbonylation catalysts
US20110253596A1 (en) * 2010-04-20 2011-10-20 Fina Technology, Inc. Regenerable Composite Catalysts for Paraffin Aromatization
CN102744103A (en) * 2011-04-20 2012-10-24 中国石油化工股份有限公司 Regeneration method of zeolite molecular sieve catalyst
CN105689013A (en) * 2016-03-14 2016-06-22 辽宁石油化工大学 Regeneration method and application of low-alkane dehydrogenation catalyst

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1590364A (en) * 2003-09-03 2005-03-09 中国石油化工股份有限公司 Carbon deposition deactivated noble metal loading type catalyst regeneration method
CN101239332A (en) * 2007-01-26 2008-08-13 林德股份公司 Method and device for regenerating a catalytic converter for steam dealkylation reactions
CN101903098A (en) * 2007-12-19 2010-12-01 英国石油化学品有限公司 Regeneration of zeolite carbonylation catalysts
US20110253596A1 (en) * 2010-04-20 2011-10-20 Fina Technology, Inc. Regenerable Composite Catalysts for Paraffin Aromatization
CN102744103A (en) * 2011-04-20 2012-10-24 中国石油化工股份有限公司 Regeneration method of zeolite molecular sieve catalyst
CN105689013A (en) * 2016-03-14 2016-06-22 辽宁石油化工大学 Regeneration method and application of low-alkane dehydrogenation catalyst

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114166696A (en) * 2020-09-11 2022-03-11 中国科学院大连化学物理研究所 Molecular sieve catalyst diffusion property evaluation method
CN114166696B (en) * 2020-09-11 2023-08-18 中国科学院大连化学物理研究所 Molecular sieve catalyst diffusion property evaluation method
CN114588952A (en) * 2020-12-07 2022-06-07 中国科学院大连化学物理研究所 Method for regenerating catalyst

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