CN114433183B - Catalyst for selective hydrogenation olefin removal of reformed product oil - Google Patents

Catalyst for selective hydrogenation olefin removal of reformed product oil Download PDF

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CN114433183B
CN114433183B CN202011196017.0A CN202011196017A CN114433183B CN 114433183 B CN114433183 B CN 114433183B CN 202011196017 A CN202011196017 A CN 202011196017A CN 114433183 B CN114433183 B CN 114433183B
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catalyst
carrier
hours
molecular sieve
active component
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CN114433183A (en
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刘丽
杨成敏
段为宇
郑步梅
郭蓉
李扬
姚运海
周勇
孙进
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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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
    • B01J29/04—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
    • B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
    • B01J29/106—Y-type faujasite
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
    • B01J29/042—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing iron group metals, noble metals or copper
    • B01J29/044—Iron group metals or copper
    • 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
    • B01J29/42—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 iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
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    • 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
    • B01J29/76—Iron group metals or copper
    • B01J29/7615—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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/038—Precipitation; Co-precipitation to form slurries or suspensions, e.g. a washcoat
    • 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
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
    • C10G45/34—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used
    • C10G45/40—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing platinum group metals or compounds thereof
    • 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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Abstract

The catalyst for selective hydrogenation and olefin removal of the reformed oil comprises a carrier, an active component and an auxiliary agent, wherein the carrier is a mixture of a molecular sieve and alumina, the active component is Pt and/or Pd, and the auxiliary agent is NiO and/or CoO. The noble metal active component is dispersed on the surface of the catalyst carrier, and the auxiliary metal is dispersed on the inner holes and the surface of the catalyst carrier. The invention is obtained by adding molecular sieve into pseudo-boehmite to prepare a mixed carrier, drying, roasting and reducing after loading palladium and/or platinum, and then loading auxiliary metal. The catalyst has strong adsorption capacity to olefin, is favorable for improving the olefin hydrogenation activity and selectivity of the catalyst, has good precious metal dispersibility and high reduction degree, has high catalyst activity, can hydrogenate and de-olefin at a lower temperature, and reduces aromatic saturation.

Description

Catalyst for selective hydrogenation olefin removal of reformed product oil
Technical Field
The invention relates to the technical field of oil product hydrogenation, in particular to a catalyst for selective hydrogenation and olefin removal of reformed generated oil.
Background
The C6 and C7 fractions in the reformed oil need to be extracted and separated. The C6 and C7 fractions contain a certain amount of olefin, and the olefin is easy to accumulate in the reflux aromatic hydrocarbon to affect the aromatic hydrocarbon content in the extraction process, and is easy to polymerize to pollute the extraction solvent, and meanwhile, the olefin is subjected to oxidation reaction to generate organic acid to cause serious corrosion of extraction system equipment. In addition, if the olefin is not removed, the bromine index and the acid washing color of the aromatic hydrocarbon product are possibly failed, and the bromine index and the copper sheet corrosion test of the solvent oil are possibly failed.
CN1394937A discloses a process for the saturated hydrogenation of olefins in reformate, which comprises contacting reformate with hydrogen in the presence of a catalyst at a temperature of 200-320 ℃ and a pressure of not less than 0.7MPa, and at a liquid hourly space velocity of 1-8 h -1 The hydrogen/oil volume ratio is not less than 30. The catalyst contains tungsten oxide and/or molybdenum oxide, nickel oxide and cobalt oxide supported on an alumina carrier. The catalyst prepared by the method has low activity and selectivity, needs to be carried out at a higher reaction temperature, is easy to cause aromatic hydrocarbon loss, and is easy to polymerize at a high temperature to cause poisoning and deactivation of the catalyst.
CN1618932a discloses a method for catalytic refining of reformed aromatic oil under non-hydrogen conditions. The catalyst is prepared by taking alumina or kaolin as a carrierThe subscreens are active components. The molecular sieve can be beta, Y, SAPO, ZSM-5, SRCY or ultrastable molecular sieve. The method is adopted to catalyze and treat the reformed aromatic oil, and the reaction temperature is 100-300 ℃, the reaction pressure is 1.0-2.0 MPa, and the airspeed is 0.5-4.0 h -1 Under the condition, trace olefin in aromatic hydrocarbon can be effectively removed. Although the method has mild operation condition, the space velocity is lower, the treatment capacity is low, the stability of the catalyst is poor, and the operation period is short.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a catalyst for selective hydrodeolefination of reformed generated oil, which has higher hydrodeolefination activity and selectivity.
The technical purpose of the first aspect of the invention is to provide a catalyst for selective hydrodeolefination of reformed oil, which comprises a carrier, an active component and an auxiliary agent, wherein the carrier is a mixture of a molecular sieve and alumina, and the molecular sieve accounts for 5-40wt%, preferably 8-20wt%, based on the total weight of the carrier; the active component is Pt and/or Pd, and the auxiliary agent is NiO and/or CoO; based on the weight of the catalyst, the mass fraction of the active component is 0.05-5.0wt%, preferably 0.1-0.3wt%, the mass fraction of the auxiliary agent is 1-10wt%, preferably 3-6wt%, and the rest is the carrier.
Further, in the above catalyst, the molecular sieve is at least one selected from the group consisting of a Y-type molecular sieve, a ZSM-5 molecular sieve, a beta-type molecular sieve and an MCM-41 molecular sieve.
Further, the noble metal active component is dispersed on the surface of the catalyst carrier, and specifically, the ratio of the radius of the noble metal distribution area to the radius of the catalyst section is A, and the ratio of A is 1-20%, preferably 5-15%, when the electron probe is used for elemental analysis and the section of the catalyst is viewed. For a cylindrical catalyst, the cross-sectional radius is easily determined, and for an irregularly shaped catalyst, the cross-sectional radius is the radius of the circumscribed circle of the cross-section.
Further, the promoter metal is dispersed in the inner pores and surface of the catalyst support.
Further, the dispersion degree of the noble metal active component on the surface of the catalyst is 55% or more, preferably 58% to 80%, more preferably 60% to 75%.
Wherein the dispersity of the noble metal is measured by a hydrogen-oxygen titration method, taking Pt as an example, and the chemical reaction formulas of the hydrogen-oxygen titration are shown as formulas (1) to (3):
Pt+H 2 PtH (catalyst) (1)
PtH+O 2 →PtO+H 2 O (oxygen titration) (2)
PtO+H 2 →PtH+H 2 O (hydrogen titration) (3)
Titration of 1 Pt atom by hydrogen-oxygen titration requires 3 hydrogen atoms to be consumed, and the dispersity of the noble metal can be obtained according to the ratio of the actual hydrogen consumption to the theoretical hydrogen consumption in the measurement process.
Further, the reduction degree of the noble metal active component in the catalyst is more than 75%, preferably 78% -98%, more preferably 80% -96%.
The degree of reduction of the noble metal is determined by H 2 The TPR is quantitatively analyzed, and the reduction degree of the noble metal can be obtained through the ratio of the actual hydrogen consumption to the theoretical hydrogen consumption in the noble metal reduction process.
The technical purpose of the second aspect of the invention is to provide a preparation method of the catalyst, which comprises the following steps:
(1) Adding molecular sieve into pseudo-boehmite sol, performing hydrothermal treatment, filtering, washing and drying to obtain modified pseudo-boehmite powder;
(2) Mixing the modified pseudo-boehmite powder prepared in the step (1) with a peptizing agent, an extrusion aid and alcohols, extruding into strips, forming, and drying to obtain the carrier;
(3) Impregnating the carrier prepared in the step (2) with a solution containing a palladium compound and/or a platinum compound, and drying, roasting and reducing to obtain a catalyst precursor;
(4) Impregnating the catalyst precursor prepared in the step (3) with a solution containing additive metal, and drying and roasting in an inert atmosphere to obtain the catalyst.
Further, in the above preparation method, the pseudo-boehmite sol in step (1) is a pseudo-boehmite preparation methodIn the process of (2), the glue-forming material which is not aged after glue-forming is filtered and washed, and then is mixed with water again to obtain the slurry. Methods of preparing pseudo-boehmite sols in the art are typically aluminum alkoxide hydrolysis or acid-base neutralization. The acid-base neutralization process generally adopts an operation mode of parallel flow of two materials for forming glue, or adopts an operation mode of placing one material in a glue forming tank and continuously adding the other material into the glue forming tank. The gel-forming material generally includes an aluminum source (e.g., al 2 (SO 4 ) 3 、AlCl 3 、Al(NO 3 ) 3 And NaAlO 2 One or more of them), precipitants (such as NaOH, NH) 4 OH or CO 2 One of them) is selected and used according to different glue forming processes. The conventional operation modes mainly comprise: (1) Acidic aluminum salts (e.g. Al 2 (SO 4 ) 3 、AlCl 3 And Al (NO) 3 ) 3 ) With basic aluminium salts (e.g. NaAlO 2 ) Or alkaline precipitants (e.g. NaOH and NH 4 OH) neutralizing to gel; (2) Basic aluminium salts (e.g. NaAlO 2 ) With acidic precipitants (e.g. CO 2 ) Neutralizing to obtain the final product.
Further, the solid content of the pseudo-boehmite sol in the step (1) is 0.1 g/mL-5.0 g/mL in terms of alumina.
Further, the mass ratio of the molecular sieve to the pseudo-boehmite sol in the step (1) is 5: 95-40: 60, preferably 8: 92-20: 80, pseudo-boehmite sol is calculated as alumina.
Further, the hydrothermal treatment of step (1) is performed in a pressure-resistant vessel such as a high-pressure reactor or the like; the conditions of the hydrothermal treatment are as follows: the temperature is 100-200 ℃, preferably 150-200 ℃, and the time is 6-48 hours, preferably 12-36 hours; the pressure is the autogenous pressure of the system.
Further, the drying conditions of step (1) are: the temperature is 60-150 ℃ and the time is 5-12 hours.
Further, the peptizing agent in the step (2) is at least one selected from nitric acid, phosphoric acid or acetic acid, and the extrusion aid is at least one selected from starch and polyethylene glycol.
Further, the alcohol in the step (2) is an alcohol having less than 4 carbon atoms, more specifically at least one selected from the group consisting of methanol, ethanol, propanol, isopropanol, ethylene glycol and glycerol, and more preferably at least one selected from the group consisting of ethanol, propanol, isopropanol and ethylene glycol.
Further, in step (2), the pseudo-boehmite is 5 to 50% by weight, preferably 15 to 30% by weight, based on the mass of alumina, of the alcohol.
Further, the drying conditions in the step (2) are as follows: the temperature is 100-250 ℃, the time is 5-12 hours, and the atmosphere is air or nitrogen.
Further, the palladium-containing compound in the step (3) is at least one selected from palladium chloride, palladium nitrate, palladium acetate, sodium tetrachloropalladate, dichlorotetraammine palladium, palladium trifluoroacetate, palladium diacetylacetonate and palladium hexafluoroacetylacetonate, and the concentration of the solution is 0.001-0.5g/mL calculated by palladium element.
Further, the platinum-containing compound in the step (3) is at least one selected from chloroplatinic acid, tetraamineplatinum dichloride, ammonium chloroplatinate, platinum trichloride, platinum tetrachloride, dicarbonyl platinum dichloride, dinitrodiammine platinum and sodium tetranitroplatinate, and the solution concentration thereof is 0.001-0.5g/mL calculated by platinum element.
Further, the drying in the step (3) is to dry for 3-6 hours at 80-150 ℃; the roasting is carried out at 400-600 ℃ for 3-8h, and the reduction treatment is carried out under the hydrogen atmosphere at 200-600 ℃, preferably 400-600 ℃ and 0.1-3.0MPa for 3-10h.
Further, the solution containing the auxiliary metal in the step (4) is at least one selected from cobalt nitrate, cobalt acetate, nickel nitrate and nickel acetate, and the concentration of the solution is 0.01-1.0g/mL calculated by the auxiliary oxide.
Further, the inert atmosphere in the step (4) is N 2 And one or more of inert gases.
Further, the drying in the step (4) is to dry for 4-16 hours at 20-90 ℃; the calcination is carried out at 200-500 ℃ for 2-5h, preferably 200-350 ℃.
The technical purpose of the third aspect of the invention is to provide the application of the catalyst in the hydrogenation olefin removal reaction of catalytic reforming generated oil.
Further, the temperature of the hydrogenation olefin removal reaction of the oil generated by the catalytic reforming of the catalyst is 130-280 ℃, preferably 130-190 ℃; the pressure is 1.0-3.0MPa.
The catalyst disclosed by the invention can be used for effectively removing olefin in the reformed oil with bromine index higher than 3500mgBr/100g, and has the advantages of good selective olefin removal effect and small aromatic hydrocarbon loss.
Compared with the prior art, the invention has the following advantages:
(1) The catalyst of the invention takes the mixture of the molecular sieve and the alumina as the carrier, which is favorable for the adsorption of olefin in the inner hole and the outer surface of the catalyst, has strong adsorption capacity on olefin, and is favorable for improving the hydrogenation activity and selectivity of olefin of the catalyst.
(2) The noble metal of the active component in the catalyst is dispersed on the surface of the carrier, so that the catalytic effect of the catalyst can be effectively exerted, the activity of the catalyst is improved, olefin is adsorbed on the surface of the catalyst for hydrogenation reaction, and the residence time of aromatic hydrocarbon components in the raw oil is reduced under the condition of high airspeed, so that the saturation of aromatic hydrocarbon is reduced. Meanwhile, the auxiliary agent is dispersed in the inner hole and the surface of the catalyst carrier, so that the auxiliary agent can be conveniently exerted, and the hydrogenation saturation performance of the olefin is improved. In addition, the catalyst has high olefin hydrogenation activity and low reaction temperature, and can reduce the hydrogenation saturation of aromatic hydrocarbon, thereby improving the olefin hydrogenation selectivity of the catalyst.
(3) The catalyst of the invention is prepared by dipping noble metal into a carrier, roasting to improve the dispersity of the noble metal, and reducing at a higher temperature to improve the reduction degree of the noble metal and fully utilize the noble metal; after that, the auxiliary metal is immersed, dried and roasted, so that the auxiliary metal can be prevented from aggregation in the high-temperature reduction process of the noble metal.
(4) In the preparation process of the catalyst, alcohols are added in the step (2), which can block the inner holes of the carrier, thereby being beneficial to the dispersion of noble metals on the surface of the carrier, and meanwhile, the alcohols are beneficial to improving the adsorption capacity of the noble metals on the surface of the carrier, reducing the loss of the noble metals in the preparation process of the catalyst and improving the utilization rate of the noble metals; after a series of roasting reduction, the inner holes of the carrier are exposed, so that the auxiliary metal is fully and uniformly distributed in the carrier and on the surface of the carrier, and the auxiliary catalytic effect of the auxiliary metal on noble metal is improved.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following non-limiting examples will enable those of ordinary skill in the art to more fully understand the invention and are not intended to limit the invention in any way.
The noble metal composition of the catalyst provided by the invention can be represented by inductively coupled plasma ICP, and the auxiliary metal composition in the catalyst can be represented by a chemical colorimetric method. The noble metal active component of the catalyst provided by the invention is dispersed on the surface of the catalyst carrier, the auxiliary metal component is dispersed on the inner hole and the surface of the catalyst carrier, the element distribution and the composition of the catalyst section from inside to outside can be analyzed through an electronic probe, and the ratio A of the distance of the noble metal distribution area to the radius of the catalyst section is measured. The degree of reduction of the noble metal can be controlled by H 2 -quantitative analysis of TPR. The degree of dispersion of the noble metal in the catalyst can be determined by hydrogen-oxygen titration.
Example 1
(1) 1L of deionized water was added to a reaction tank as a base solution, and 1L of an aluminum sulfate solution and 1L of a sodium hydroxide solution were placed in a raw material tank, respectively, and the temperature of the reaction tank was controlled at 60 ℃. The aluminum sulfate solution is injected into the reaction tank at the rate of 10mL/min, meanwhile, the sodium hydroxide solution is injected and the speed is regulated, so that the pH value of the reaction tank solution is kept constant at 8.0, and the neutralization is finished after 120 min. And (3) in a reaction tank, keeping the temperature constant at 85 ℃ and the pH value constant at 8.5, aging for 5 hours, washing with deionized water for 3 times, filtering, mixing a filter cake with the deionized water, and uniformly stirring to obtain the pseudo-boehmite sol, wherein the solid content is 0.5g/mL in terms of alumina. Adding a Y-type molecular sieve into pseudo-boehmite sol, adding the mixture into a high-pressure reaction kettle, performing hydrothermal treatment at 180 ℃ for 24 hours, filtering the mixed solution, washing with deionized water, and drying at 100 ℃ for 8 hours to obtain modified pseudo-boehmite powder.
(2) Uniformly mixing the modified pseudo-boehmite powder prepared in the step (1) with nitric acid, starch, ethanol and deionized water, wherein the modified pseudo-boehmite powder is prepared by the following steps: nitric acid: starch: ethanol: the mass ratio of deionized water is 150:4:3:18:60, then kneading, extruding and molding are carried out, and drying is carried out for 6 hours in an air atmosphere at 150 ℃ to obtain the carrier, wherein the content of the Y-type molecular sieve is 10%, and the balance is aluminum oxide.
(3) Immersing the chloroplatinic acid solution into the carrier prepared in the step (2), drying at 80 ℃ for 6 hours, roasting at 500 ℃ for 5 hours, and then adopting hydrogen for reduction treatment, wherein the reduction temperature is 400 ℃, the reduction pressure is 1.5MPa, and the reduction time is 5 hours, so as to obtain the catalyst precursor.
(4) And (3) immersing nickel nitrate solution in an equal volume into the catalyst precursor prepared in the step (3), and then drying at 60 ℃ for 3 hours and roasting at 250 ℃ for 3 hours in a nitrogen atmosphere to obtain the catalyst C-1.
The catalyst C-1 comprises the following components in percentage by weight: pt 0.5%, nickel oxide 4.1% and the balance of carrier.
Example 2
(1) 1L of deionized water was added to a reaction tank as a base solution, and 1L of an aluminum sulfate solution and 1L of a sodium hydroxide solution were placed in a raw material tank, respectively, and the temperature of the reaction tank was controlled at 70 ℃. The aluminum sulfate solution is injected into the reaction tank at the rate of 10mL/min, meanwhile, sodium hydroxide solution is injected and the speed is regulated, so that the pH value of the reaction tank solution is constant at 7.5, and the neutralization is finished after 120 min. And (3) in a reaction tank, keeping the temperature at 80 ℃ and the pH value at 8.5, aging for 5 hours, washing with deionized water for 3 times, filtering, mixing a filter cake with the deionized water, and uniformly stirring to obtain the pseudo-boehmite sol, wherein the solid content is 0.6g/mL in terms of alumina. Adding a Y-type molecular sieve into pseudo-boehmite sol, adding the mixture into a high-pressure reaction kettle, performing hydrothermal treatment at 200 ℃ for 24 hours, filtering the mixed solution, washing with deionized water, and drying at 100 ℃ for 8 hours to obtain modified pseudo-boehmite powder.
(2) Uniformly mixing the modified pseudo-boehmite powder prepared in the step (1) with nitric acid, starch, ethanol and deionized water, wherein the modified pseudo-boehmite powder is prepared by the following steps: nitric acid: starch: ethanol: the mass ratio of deionized water is 150:4:3:20:60, then kneading and extruding strips for molding, and drying for 6 hours in an air atmosphere at 120 ℃ to obtain the carrier, wherein the content of the Y-type molecular sieve is 15%, and the balance is aluminum oxide.
(3) Immersing the chloroplatinic acid solution into the carrier prepared in the step (2), drying at 90 ℃ for 5 hours, roasting at 600 ℃ for 5 hours, and then adopting hydrogen for reduction treatment, wherein the reduction temperature is 500 ℃, the reduction pressure is 1.5MPa, and the reduction time is 4 hours, so as to obtain the catalyst precursor.
(4) And (3) immersing cobalt nitrate solution in an equal volume into the catalyst precursor prepared in the step (3), and then drying at 80 ℃ for 3h and roasting at 200 ℃ for 3h in a nitrogen atmosphere to obtain the catalyst C-2.
The catalyst C-2 comprises the following components in percentage by weight: pt 0.5%, cobalt oxide 4.2%, and the rest is carrier.
Example 3
(1) 1L of deionized water was added to a reaction tank as a base solution, and 1L of an aluminum sulfate solution and 1L of a sodium hydroxide solution were placed in a raw material tank, respectively, and the temperature of the reaction tank was controlled at 80 ℃. The aluminum sulfate solution is injected into the reaction tank at the rate of 10mL/min, meanwhile, sodium hydroxide solution is injected and the speed is regulated, so that the pH value of the reaction tank solution is constant at 7.5, and the neutralization is finished after 120 min. And (3) in a reaction tank, keeping the temperature constant at 90 ℃ and the pH value constant at 8.0, aging for 5 hours, washing with deionized water for 3 times, filtering, mixing a filter cake with the deionized water, and uniformly stirring to obtain the pseudo-boehmite sol, wherein the solid content is 0.5g/mL in terms of alumina. Adding a Y-type molecular sieve into pseudo-boehmite sol, adding the mixture into a high-pressure reaction kettle, performing hydrothermal treatment at 200 ℃ for 24 hours, filtering the mixed solution, washing with deionized water, and drying at 120 ℃ for 8 hours to obtain modified pseudo-boehmite powder.
(2) Uniformly mixing the modified pseudo-boehmite powder prepared in the step (1) with nitric acid, starch, glycerol and deionized water, wherein the modified pseudo-boehmite powder is prepared by the following steps: nitric acid: starch: glycerol: the mass ratio of deionized water is 150:4:3:25:60, then kneading and extruding strips for molding, and drying for 6 hours in an air atmosphere at 120 ℃ to obtain the carrier, wherein the content of the Y-type molecular sieve is 10%, and the balance is aluminum oxide.
(3) And (3) immersing the palladium chloride solution into the carrier prepared in the step (2), drying at 80 ℃ for 6 hours, roasting at 500 ℃ for 5 hours, and then adopting hydrogen for reduction treatment, wherein the reduction temperature is 400 ℃, the reduction pressure is 1.5MPa, and the reduction time is 5 hours, so as to obtain the catalyst precursor.
(4) And (3) immersing nickel nitrate solution in an equal volume into the catalyst precursor prepared in the step (3), and then drying at 70 ℃ for 3h and roasting at 200 ℃ for 3h in a nitrogen atmosphere to obtain the catalyst C-3.
The catalyst C-3 comprises the following components in percentage by weight: pd is 0.4%, nickel oxide is 4.2%, and the rest is carrier.
Example 4
(1) 1L of deionized water was added to a reaction tank as a base solution, and 1L of an aluminum sulfate solution and 1L of a sodium hydroxide solution were placed in a raw material tank, respectively, and the temperature of the reaction tank was controlled at 80 ℃. The aluminum sulfate solution is injected into the reaction tank at the rate of 10mL/min, meanwhile, the sodium hydroxide solution is injected and the speed is regulated, so that the pH value of the reaction tank solution is kept constant at 8.0, and the neutralization is finished after 120 min. And (3) aging for 5 hours at a constant temperature of 80 ℃ and a constant pH value of 8.0 in a reaction tank, washing with deionized water for 3 times, filtering, mixing a filter cake with the deionized water, and uniformly stirring to obtain the pseudo-boehmite sol, wherein the solid content is 0.7g/mL in terms of alumina. Adding a Y-type molecular sieve into pseudo-boehmite sol, adding the mixture into a high-pressure reaction kettle, performing hydrothermal treatment at 180 ℃ for 24 hours, filtering the mixed solution, washing with deionized water, and drying at 130 ℃ for 8 hours to obtain modified pseudo-boehmite powder.
(2) Uniformly mixing the modified pseudo-boehmite powder prepared in the step (1) with nitric acid, starch, propanol and deionized water, wherein the modified pseudo-boehmite powder is prepared by the following steps: nitric acid: starch: propanol: the mass ratio of deionized water is 150:4:3:30:60, then kneading and extruding strips for molding, and drying for 6 hours in an air atmosphere at 120 ℃ to obtain the carrier, wherein the content of the Y-type molecular sieve is 10%, and the balance is aluminum oxide.
(3) And (3) immersing the palladium chloride solution into the carrier prepared in the step (2), drying at 80 ℃ for 6 hours, roasting at 500 ℃ for 5 hours, and then adopting hydrogen for reduction treatment, wherein the reduction temperature is 400 ℃, the reduction pressure is 1.5MPa, and the reduction time is 5 hours, so as to obtain the catalyst precursor.
(4) And (3) immersing cobalt nitrate solution in an equal volume into the catalyst precursor prepared in the step (3), and then drying at 60 ℃ for 3 hours and roasting at 250 ℃ for 3 hours in a nitrogen atmosphere to obtain the catalyst C-4.
The catalyst C-4 comprises the following components in percentage by weight: pd 0.5%, cobalt oxide 5.1% and the rest is carrier.
Example 5
(1) 1L of deionized water was added to a reaction tank as a base solution, and 1L of an aluminum sulfate solution and 1L of a sodium hydroxide solution were placed in a raw material tank, respectively, and the temperature of the reaction tank was controlled at 80 ℃. The aluminum sulfate solution is injected into the reaction tank at the rate of 10mL/min, meanwhile, the sodium hydroxide solution is injected and the speed is regulated, so that the pH value of the reaction tank solution is kept constant at 8.5, and the neutralization is finished after 120 min. And (3) in a reaction tank, keeping the temperature at 80 ℃ and the pH value at 8.5, aging for 5 hours, washing with deionized water for 3 times, filtering, mixing a filter cake with the deionized water, and uniformly stirring to obtain the pseudo-boehmite sol, wherein the solid content is 0.7g/mL in terms of alumina. Adding ZSM-5 molecular sieve into pseudo-boehmite sol, adding the mixture into a high-pressure reaction kettle, carrying out hydrothermal treatment at 180 ℃ for 24 hours, filtering the mixed solution, washing with deionized water, and drying at 130 ℃ for 8 hours to obtain the modified pseudo-boehmite powder.
(2) Uniformly mixing the modified pseudo-boehmite powder prepared in the step (1) with nitric acid, starch, propanol and deionized water, wherein the modified pseudo-boehmite powder is prepared by the following steps: nitric acid: starch: propanol: the mass ratio of deionized water is 150:4:3:30:60, then kneading and extruding strips for molding, and drying for 6 hours in an air atmosphere at 120 ℃ to obtain the carrier, wherein the content of ZSM-5 molecular sieve is 10%, and the balance is alumina.
(3) Immersing the chloroplatinic acid solution into the carrier prepared in the step (2), drying at 80 ℃ for 6 hours, roasting at 500 ℃ for 5 hours, and then adopting hydrogen for reduction treatment, wherein the reduction temperature is 500 ℃, the reduction pressure is 2.0MPa, and the reduction time is 4 hours, so as to obtain the catalyst precursor.
(4) And (3) immersing nickel nitrate solution in an equal volume into the catalyst precursor prepared in the step (3), and then drying at 90 ℃ for 3h and roasting at 200 ℃ for 3h in a nitrogen atmosphere to obtain the catalyst C-5.
The catalyst C-5 comprises the following components in percentage by weight: pt 0.5%, nickel oxide 5.1%, and the balance being carrier.
Example 6
(1) 1L of deionized water was added to a reaction tank as a base solution, and 1L of an aluminum sulfate solution and 1L of a sodium hydroxide solution were placed in a raw material tank, respectively, and the temperature of the reaction tank was controlled at 70 ℃. The aluminum sulfate solution is injected into the reaction tank at the rate of 10mL/min, meanwhile, the sodium hydroxide solution is injected and the speed is regulated, so that the pH value of the reaction tank solution is kept constant at 8.0, and the neutralization is finished after 120 min. And (3) aging for 5 hours at a constant temperature of 70 ℃ and a constant pH value of 8.0 in a reaction tank, washing with deionized water for 3 times, filtering, mixing a filter cake with the deionized water, and uniformly stirring to obtain the pseudo-boehmite sol, wherein the solid content is 0.6g/mL in terms of alumina. Adding beta-type molecular sieve into pseudo-boehmite sol, adding the mixture into a high-pressure reaction kettle, performing hydrothermal treatment at 180 ℃ for 24 hours, filtering the mixed solution, washing with deionized water, and drying at 130 ℃ for 8 hours to obtain the modified pseudo-boehmite powder.
(2) Uniformly mixing the modified pseudo-boehmite powder prepared in the step (1) with nitric acid, starch, propanol and deionized water, wherein the modified pseudo-boehmite powder is prepared by the following steps: nitric acid: starch: propanol: the mass ratio of deionized water is 150:4:3:30:60, then kneading, extruding and molding are carried out, and drying is carried out for 6 hours in an air atmosphere at 120 ℃ to obtain the carrier, wherein the content of the beta-type molecular sieve is 10%, and the balance is aluminum oxide.
(3) Immersing the chloroplatinic acid solution into the carrier prepared in the step (2), drying at 80 ℃ for 6 hours, roasting at 400 ℃ for 5 hours, and then adopting hydrogen for reduction treatment, wherein the reduction temperature is 450 ℃, the reduction pressure is 2.0MPa, and the reduction time is 5 hours, so as to obtain the catalyst precursor.
(4) And (3) immersing cobalt nitrate solution in an equal volume into the catalyst precursor prepared in the step (3), and then drying at 60 ℃ for 3 hours and roasting at 250 ℃ for 3 hours in a nitrogen atmosphere to obtain the catalyst C-6.
The catalyst C-6 comprises the following components in percentage by weight: pt 0.4%, cobalt oxide 4.6%, and the rest is carrier.
Example 7
(1) 1L of deionized water was added to a reaction tank as a base solution, and 1L of an aluminum sulfate solution and 1L of a sodium hydroxide solution were placed in a raw material tank, respectively, and the temperature of the reaction tank was controlled at 80 ℃. The aluminum sulfate solution is injected into the reaction tank at the rate of 10mL/min, meanwhile, the sodium hydroxide solution is injected and the speed is regulated, so that the pH value of the reaction tank solution is kept constant at 8.0, and the neutralization is finished after 120 min. And (3) aging for 5 hours at a constant temperature of 80 ℃ and a constant pH value of 8.0 in a reaction tank, washing with deionized water for 3 times, filtering, mixing a filter cake with the deionized water, and uniformly stirring to obtain the pseudo-boehmite sol, wherein the solid content is 0.5g/mL in terms of alumina. Adding MCM-41 molecular sieve into pseudo-boehmite sol, adding the mixture into a high-pressure reaction kettle, performing hydrothermal treatment at 180 ℃ for 24 hours, filtering the mixed solution, washing with deionized water, and drying at 130 ℃ for 8 hours to obtain the modified pseudo-boehmite powder.
(2) Uniformly mixing the modified pseudo-boehmite powder prepared in the step (1) with nitric acid, starch, propanol and deionized water, wherein the modified pseudo-boehmite powder is prepared by the following steps: nitric acid: starch: propanol: the mass ratio of deionized water is 150:4:3:20:60, then kneading, extruding and molding are carried out, and drying is carried out for 6 hours in an air atmosphere at 150 ℃ to obtain the carrier, wherein the content of the MCM-41 type molecular sieve is 10%, and the balance is alumina.
(3) And (3) immersing the palladium chloride solution into the carrier prepared in the step (2), drying at 80 ℃ for 6 hours, roasting at 500 ℃ for 5 hours, and then adopting hydrogen for reduction treatment, wherein the reduction temperature is 400 ℃, the reduction pressure is 1.5MPa, and the reduction time is 5 hours, so as to obtain the catalyst precursor.
(4) And (3) immersing cobalt nitrate solution in an equal volume into the catalyst precursor prepared in the step (3), and then drying at 60 ℃ for 3h and roasting at 250 ℃ for 3h in a nitrogen atmosphere to obtain the catalyst C-7.
The catalyst C-7 comprises the following components in percentage by weight: pd is 0.4%, cobalt oxide is 4.6%, and the rest is carrier.
Example 8
(1) 1L of deionized water was added to a reaction tank as a base solution, and 1L of an aluminum sulfate solution and 1L of a sodium hydroxide solution were placed in a raw material tank, respectively, and the temperature of the reaction tank was controlled at 80 ℃. The aluminum sulfate solution is injected into the reaction tank at the rate of 10mL/min, meanwhile, the sodium hydroxide solution is injected and the speed is regulated, so that the pH value of the reaction tank solution is kept constant at 8.0, and the neutralization is finished after 120 min. And (3) aging for 5 hours at a constant temperature of 80 ℃ and a constant pH value of 8.0 in a reaction tank, washing with deionized water for 3 times, filtering, mixing a filter cake with the deionized water, and uniformly stirring to obtain the pseudo-boehmite sol, wherein the solid content is 0.7g/mL in terms of alumina. Adding Y-type and beta-molecular sieves into pseudo-boehmite sol, adding the mixture into a high-pressure reaction kettle, carrying out hydrothermal treatment at 180 ℃ for 24 hours, filtering the mixed solution, washing with deionized water, and drying at 130 ℃ for 8 hours to obtain modified pseudo-boehmite powder.
(2) Uniformly mixing the modified pseudo-boehmite powder prepared in the step (1) with nitric acid, starch, propanol and deionized water, wherein the modified pseudo-boehmite powder is prepared by the following steps: nitric acid: starch: propanol: the mass ratio of deionized water is 150:4:3:30:60, then kneading and extruding strips for molding, and drying for 6 hours in an air atmosphere at 120 ℃ to obtain the carrier, wherein the content of the Y-type molecular sieve is 10%, the content of the beta-type molecular sieve is 8%, and the balance is aluminum oxide.
(3) And (3) immersing palladium chloride and a chloroplatinic acid solution into the carrier prepared in the step (2), drying at 80 ℃ for 6 hours, roasting at 500 ℃ for 5 hours, and then adopting hydrogen for reduction treatment, wherein the reduction temperature is 500 ℃, the reduction pressure is 2.0MPa, and the reduction time is 5 hours, so as to obtain the catalyst precursor.
(4) And (3) immersing nickel nitrate solution in an equal volume into the catalyst precursor prepared in the step (3), and then drying at 70 ℃ for 3h and roasting at 200 ℃ for 3h in a nitrogen atmosphere to obtain the catalyst C-8.
The catalyst C-8 comprises the following components in percentage by weight: pd 0.3%, pt 0.2%, nickel oxide 5.1% and the rest is carrier.
Comparative example 1
(1) 1L of deionized water was added to a reaction tank as a base solution, and 1L of an aluminum sulfate solution and 1L of a sodium hydroxide solution were placed in a raw material tank, respectively, and the temperature of the reaction tank was controlled at 80 ℃. The aluminum sulfate solution is injected into the reaction tank at the rate of 10mL/min, meanwhile, the sodium hydroxide solution is injected and the speed is regulated, so that the pH value of the reaction tank solution is kept constant at 8.0, and the neutralization is finished after 120 min. And (3) aging for 5 hours at the constant temperature of 80 ℃ and the constant pH value of 8.0 in a reaction tank, washing with deionized water for 3 times, filtering, and drying at the temperature of 130 ℃ for 8 hours to obtain pseudo-boehmite powder.
(2) Uniformly mixing the pseudo-boehmite powder prepared in the step (1) with nitric acid, starch and deionized water, wherein the pseudo-boehmite powder is modified: nitric acid: starch: and (3) mixing and kneading deionized water in a mass ratio of 150:4:3:60, extruding to form strips, and drying for 6 hours in an air atmosphere at 120 ℃ to obtain the alumina carrier.
(3) And (3) immersing the palladium chloride solution into the carrier prepared in the step (2), drying at 80 ℃ for 6 hours, roasting at 500 ℃ for 5 hours, and then adopting hydrogen for reduction treatment, wherein the reduction temperature is 400 ℃, the reduction pressure is 1.5MPa, and the reduction time is 5 hours, so as to obtain the catalyst precursor.
(4) And (3) immersing cobalt nitrate solution in an equal volume into the catalyst precursor prepared in the step (3), and then drying at 60 ℃ for 3 hours and roasting at 250 ℃ for 3 hours in a nitrogen atmosphere to obtain the catalyst DC-1.
The catalyst DC-1 comprises the following components in percentage by weight: pd 0.5%, cobalt oxide 4.6% and alumina carrier for the rest.
Comparative example 2
(1) 1L of deionized water was added to a reaction tank as a base solution, and 1L of an aluminum sulfate solution and 1L of a sodium hydroxide solution were placed in a raw material tank, respectively, and the temperature of the reaction tank was controlled at 70 ℃. The aluminum sulfate solution is injected into the reaction tank at the rate of 10mL/min, meanwhile, sodium hydroxide solution is injected and the speed is regulated, so that the pH value of the reaction tank solution is constant at 7.5, and the neutralization is finished after 120 min. And (3) aging for 5 hours at a constant temperature of 70 ℃ and a constant pH value of 8.0 in a reaction tank, washing with deionized water for 3 times, filtering, mixing a filter cake with the deionized water, and uniformly stirring to obtain the pseudo-boehmite sol, wherein the solid content is 0.6g/mL in terms of alumina. Adding a Y-type molecular sieve into pseudo-boehmite sol, adding the mixture into a high-pressure reaction kettle, performing hydrothermal treatment at 180 ℃ for 24 hours, filtering the mixed solution, washing with deionized water, and drying at 130 ℃ for 8 hours to obtain modified pseudo-boehmite powder.
(2) Uniformly mixing the modified pseudo-boehmite powder prepared in the step (1) with nitric acid, starch, propanol and deionized water, wherein the modified pseudo-boehmite powder is prepared by the following steps: nitric acid: starch: propanol: the mass ratio of deionized water is 150:4:3:30:60, then kneading and extruding strips for molding, and drying for 6 hours in an air atmosphere at 120 ℃ to obtain the carrier, wherein the content of the Y-type molecular sieve is 10%, and the balance is aluminum oxide.
(3) And (3) dipping palladium chloride and cobalt nitrate solution into the carrier prepared in the step (2), drying at 80 ℃ for 6 hours, and roasting at 500 ℃ for 5 hours to obtain the catalyst DC-2.
The catalyst DC-2 comprises the following components in percentage by weight: pdO is 0.4%, coO is 4.8%, and the balance is carrier.
Comparative example 3
(1) 1L of deionized water was added to a reaction tank as a base solution, and 1L of an aluminum sulfate solution and 1L of a sodium hydroxide solution were placed in a raw material tank, respectively, and the temperature of the reaction tank was controlled at 70 ℃. The aluminum sulfate solution is injected into the reaction tank at the rate of 10mL/min, meanwhile, sodium hydroxide solution is injected and the speed is regulated, so that the pH value of the reaction tank solution is constant at 7.5, and the neutralization is finished after 120 min. And (3) aging for 5 hours at a constant temperature of 70 ℃ and a constant pH value of 8.0 in a reaction tank, washing with deionized water for 3 times, filtering, mixing a filter cake with the deionized water, and uniformly stirring to obtain the pseudo-boehmite sol, wherein the solid content is 0.6g/mL in terms of alumina. Adding a Y-type molecular sieve into pseudo-boehmite sol, adding the mixture into a high-pressure reaction kettle, performing hydrothermal treatment at 180 ℃ for 24 hours, filtering the mixed solution, washing with deionized water, and drying at 130 ℃ for 8 hours to obtain modified pseudo-boehmite powder.
(2) Uniformly mixing the modified pseudo-boehmite powder prepared in the step (1) with nitric acid, starch, propanol and deionized water, wherein the modified pseudo-boehmite powder is prepared by the following steps: nitric acid: starch: propanol: the mass ratio of deionized water is 150:4:3:30:60, then kneading and extruding strips for molding, and drying for 6 hours in an air atmosphere at 120 ℃ to obtain the carrier, wherein the content of the Y-type molecular sieve is 15%, and the balance is aluminum oxide.
(3) And (3) dipping the palladium chloride solution into the carrier prepared in the step (2), drying at 80 ℃ for 6 hours, and roasting at 500 ℃ for 5 hours to obtain the catalyst precursor.
(4) And (3) immersing cobalt nitrate solution in an equal volume into the catalyst precursor prepared in the step (3), and then drying at 60 ℃ for 3h and roasting at 250 ℃ for 3h in a nitrogen atmosphere to obtain the catalyst DC-3.
The catalyst DC-3 comprises the following components in percentage by weight: pdO is 0.4%, coO is 4.8%, and the balance is carrier.
The catalysts C-1 to C-8 prepared in the above examples, and the catalysts DC-1 to DC-3 prepared in the comparative examples were analyzed for the ratio A of the radius of the noble metal distribution region to the radius of the catalyst cross section, and the results are shown in Table 1.
Table 1.
Example 9
This example illustrates the olefin hydrogenation performance of the catalyst provided by the present invention for reformate.
The adopted evaluation raw oil is reformed oil provided by a certain refinery for medium petrifaction, and the bromine index is 3520mgBr/100g.
The catalysts C-1 to C-8 and comparative examples DC-1 to DC-3 were evaluated for olefin hydrogenation reaction performance using a 200 mL fixed bed hydrogenation apparatus, respectively.
Pre-reduction conditions of the catalyst: reduction with Hydrogen at a space velocity of 2.0h -1 The catalyst was pre-reduced at an operating pressure of 2.0 MPa.
The reaction conditions were evaluated as follows: operating pressure 2.0MPa, reaction temperature 160 ℃, hydrogen/oil volume ratio 80:1, volume space velocity 8.0h -1 The evaluation results are shown in Table 2.
Table 2.
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Claims (20)

1. The catalyst for selective hydrodeolefine of the reformed oil is characterized by comprising a carrier, a noble metal active component and an auxiliary agent, wherein the carrier is a mixture of a molecular sieve and alumina, and the molecular sieve accounts for 5-40wt% based on the total weight of the carrier; the noble metal active component is Pt and/or Pd, and the auxiliary agent is NiO and/or CoO; based on the weight of the catalyst, the mass fraction of the noble metal active component is 0.05-5.0wt%, the mass fraction of the auxiliary agent is 1-10wt%, and the rest is the carrier; the noble metal active component is dispersed on the surface of the catalyst carrier, wherein the surface refers to the ratio of the radius of a noble metal distribution area to the radius of the catalyst section seen from the section of the catalyst by using an electronic probe for elemental analysis, and the ratio of A is 1-20%; the dispersity of the noble metal active component on the surface of the catalyst is more than 55%; the reduction degree of the noble metal active component in the catalyst is more than 75%; the promoter metal is dispersed in the inner pores and surface of the catalyst support.
2. The catalyst of claim 1 wherein a is 5-15%.
3. The catalyst according to claim 1, wherein the molecular sieve accounts for 8-20wt% based on the total weight of the carrier, the mass fraction of the noble metal active component is 0.1-0.3wt% based on the weight of the catalyst, the mass fraction of the auxiliary agent is 3-6wt%, and the rest is the carrier.
4. The catalyst of claim 1 wherein the precious metal active component has a dispersion of 58% to 80% on the catalyst surface.
5. The catalyst of claim 1, wherein the noble metal active component of the catalyst has a degree of reduction of 78% to 98%.
6. The catalyst of claim 1, wherein the molecular sieve is selected from at least one of a Y-type molecular sieve, a ZSM-5 molecular sieve, a beta-type molecular sieve, and an MCM-41 molecular sieve.
7. A process for preparing a catalyst as claimed in any one of claims 1 to 6, comprising the following:
(1) Adding molecular sieve into pseudo-boehmite sol, performing hydrothermal treatment, filtering, washing and drying to obtain modified pseudo-boehmite powder;
(2) Mixing the modified pseudo-boehmite powder prepared in the step (1) with a peptizing agent, an extrusion aid, alcohols and deionized water, extruding into strips, forming, and drying to obtain the carrier;
(3) Impregnating the carrier prepared in the step (2) with a solution containing a palladium compound and/or a platinum compound, and drying, roasting and reducing to obtain a catalyst precursor;
(4) Impregnating the catalyst precursor prepared in the step (3) with a solution containing additive metal, and drying and roasting in an inert atmosphere to obtain the catalyst.
8. The method according to claim 7, wherein the conditions of the hydrothermal treatment of step (1) are: the temperature is 100-200 ℃, the time is 6-48 hours, and the pressure is the autogenous pressure of the system.
9. The method according to claim 7, wherein the alcohol in the step (2) is at least one selected from the group consisting of methanol, ethanol, propanol, isopropanol, ethylene glycol and glycerol.
10. The method according to claim 7, wherein the pseudo-boehmite in the step (2) is in the form of alumina and the alcohol is 5 to 50% by weight based on the mass of alumina.
11. The method according to claim 7, wherein the palladium-containing compound in the step (3) is at least one selected from the group consisting of palladium chloride, palladium nitrate, palladium acetate, sodium tetrachloropalladate, dichlorotetraammine palladium, palladium trifluoroacetate, palladium diacetylacetonate and palladium hexafluoroacetylacetonate.
12. The method according to claim 7, wherein the platinum-containing compound in the step (3) is at least one selected from the group consisting of chloroplatinic acid, tetraamineplatinum dichloride, ammonium chloroplatinate, platinum trichloride, platinum tetrachloride, dicarbonyl platinum dichloride, dinitrodiammineplatinum and sodium tetranitroplatinate.
13. The method according to claim 7, wherein the reduction treatment in the step (3) is reduction in a hydrogen atmosphere at 200 to 600 ℃ and 0.1 to 3.0MPa for 3 to 10 hours.
14. The method according to claim 13, wherein the temperature of the reduction treatment in step (3) is 400 to 600 ℃.
15. The method of claim 7, wherein the additive metal-containing solution of step (4) is at least one selected from the group consisting of cobalt nitrate, cobalt acetate, nickel nitrate and nickel acetate.
16. The method according to claim 7, wherein the firing in the step (4) is performed at 200 to 500 ℃ for 2 to 5 hours.
17. The process of claim 16, wherein the firing temperature in step (4) is 200-350 ℃.
18. Use of the catalyst of any one of claims 1-6 in a hydrodeolefination reaction of a catalytic reformate.
19. The use according to claim 18, wherein the catalyst catalyzes the hydrodeolefination of the oil to be reformed at a temperature of from 130 ℃ to 280 ℃.
20. The use according to claim 18, wherein the catalyst catalyzes the hydrodeolefination of the oil to be reformed at a temperature of from 130 ℃ to 190 ℃.
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