CN112295595A - Supported nickel phosphide catalyst and preparation method thereof - Google Patents

Supported nickel phosphide catalyst and preparation method thereof Download PDF

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CN112295595A
CN112295595A CN201910698176.1A CN201910698176A CN112295595A CN 112295595 A CN112295595 A CN 112295595A CN 201910698176 A CN201910698176 A CN 201910698176A CN 112295595 A CN112295595 A CN 112295595A
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zsm
macroporous
molecular sieve
mesoporous
catalyst
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CN112295595B (en
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李景锋
高海波
柏介军
姚文君
张永泽
杨红强
向永生
王高峰
谢元
常晓昕
边虎
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Petrochina Co Ltd
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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
    • B01J29/40—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
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
    • B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
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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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/651—50-500 nm
    • 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
    • B01J37/28—Phosphorising
    • 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
    • B01J37/30—Ion-exchange
    • 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
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/12—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
    • 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
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
    • C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/10—Lubricating oil
    • 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 invention relates to a nickel phosphide catalyst and a preparation method thereof. The metal active component of the catalyst is nickel phosphide (Ni)2P), the carrier is a compound consisting of a mesoporous-macroporous ZSM-5 molecular sieve and alumina. Firstly, preparing a silicon source, an aluminum source, inorganic acid or inorganic base and deionized water into gel, aging the gel, adding rubber microemulsion into the aged gel, and crystallizingFiltering, washing, drying, roasting and ion exchange to obtain the acidic mesoporous-macroporous ZSM-5 molecular sieve; then adding Ni2+Exchanging to the molecular sieve, mixing with alumina raw powder, molding, drying, roasting, and finally phosphorizing for 24-72h to obtain Ni loaded by the mesoporous-macroporous ZSM-5 molecular sieve2And (3) a P catalyst. Ni contained in the catalyst of the present invention2The P is in a high dispersion state, the aperture and the acidity of the mesoporous-macroporous ZSM-5 molecular sieve are adjustable, and the mesoporous-macroporous ZSM-5 molecular sieve has wide application prospects in a plurality of catalytic fields of catalytic gasoline hydro-upgrading, lubricating oil isodewaxing, diesel oil isodewaxing and the like.

Description

Supported nickel phosphide catalyst and preparation method thereof
Technical Field
The invention relates to a catalyst in the fields of petroleum refining, petrochemical industry, coal chemical industry and the like and a preparation technology thereof, in particular to a supported nickel-based catalyst and a preparation method thereof.
Background
The transition metal phosphide has good catalytic performance in the processes of hydrodesulfurization, hydrodeoxygenation, hydrodechlorination and the like. Wherein nickel (Ni) phosphate2P) has the best catalytic performance, and has become a research hotspot of new catalytic materials in the fields of petroleum refining, petrochemical industry, coal chemical industry and the like.
Oyama et al [ S.T.Oyama, Y.Lee, J.Catal.,2008,2:393]Found in Ni2Ni (2) active site in P unit crystal structureHas high hydrogenation activity and high dispersion Ni2P has more Ni (2) active sites. Due to the body type Ni2The P catalyst has a low specific surface area and a small number of exposed active bits of Ni (2) in order to increase the amount of Ni2The number of Ni (2) active sites of P catalyst, and Ni supported by carrier with high specific surface area2P catalyst and a preparation method thereof. CN101612584A preparation of Ni from nickel nitrate and diammonium phosphate2P catalyst precursor is reduced by hydrogen procedure to obtain TiO2-Al2O3Loaded Ni2The P catalyst shows excellent hydrodesulfurization activity on dibenzothiophene, but the hydrogen programmed reduction requires high temperature (600-700 ℃) and slow (1-2 ℃/min) programmed temperature rise, is difficult to realize large-scale preparation, and is easy to cause Ni2The P dispersity decreases. Thus, the technologist can prepare the supported Ni at a lower temperature2The method of the P catalyst has been studied in large numbers. For example, CN101734633A obtains a supported Ni with good diesel hydrodesulfurization performance at a lower temperature through the solid-phase reaction of ammonium hypophosphite and nickel hypophosphite2A P catalyst; CN2013105585750 uses nickel hypophosphite as a precursor to prepare Ni loaded on mesoporous alumina at a lower temperature (180-300 ℃), and the method is applied to the preparation of Ni-loaded mesoporous alumina2The P catalyst shows excellent activity, selectivity and stability for the dehydrogenation reaction of cyclane to prepare arene. However, these were used to prepare supported Ni at lower temperatures2Method for preparing P catalyst, supported high-dispersion Ni still can not be prepared2And (3) a P catalyst.
Disclosure of Invention
The invention aims to provide a supported nickel phosphide catalyst and a preparation method thereof. The carrier of the catalyst is a mixture of alumina and a mesoporous-macroporous ZSM-5 molecular sieve, and the active metal component of the catalyst is high-dispersion Ni2And P. Wherein, the content of the mesoporous-macroporous ZSM-5 molecular sieve is 70-80 wt%, the content of the alumina is 10-30 wt%, and the metal active component Ni2The content of P is 0.1-2.0 wt% calculated by NiO.
In order to realize the purpose, the invention takes cheap rubber microemulsion as a mesoporous-macroporous template agent to prepareA mesoporous-macroporous ZSM-5 molecular sieve. The molecular sieve has pore size distribution, total specific surface area and silicon/aluminum atomic ratio of 2-100nm and 300-400m2/g, 10:1-100:1, larger pore diameter, higher specific surface area and stronger acidity, and Ni2+After ion exchange reaction, Ni-containing material can be generated2+The mesoporous-macroporous ZSM-5 molecular sieve of the metal cluster. Because O atoms existing in the mesoporous-macroporous ZSM-5 molecular sieve framework (microporous pore canal) and outside the framework (mesoporous-macroporous pore canal) can align to Ni in the pore canal2+The metal cluster size forming a limiting effect on Ni2+The size of the metal clusters does not generally exceed the pore size distribution of the molecular sieves described above, indicating that Ni2+The metal clusters are in a highly dispersed state in the mesoporous-macroporous ZSM-5 molecular sieve. Thus, the Ni2+The metal cluster is phosphine treated by organic phosphine to prepare high-dispersion Ni2P。
The invention also provides a preparation method of the catalyst, which mainly comprises the following steps:
(1) preparation of acidic mesoporous-macroporous ZSM-5 molecular sieve
Preparing a silicon source, an aluminum source, inorganic acid or inorganic base and deionized water into mixture gel, aging the mixture gel, adding a certain amount of rubber microemulsion into the aged mixture gel, and performing crystallization, filtration, washing, drying, roasting and ion exchange to obtain the acidic mesoporous-macroporous ZSM-5 molecular sieve.
(2) Ni of acidic mesoporous-macroporous ZSM-5 molecular sieve2+Switching
Mixing the acidic mesoporous-macroporous ZSM-5 molecular sieve obtained in the step (1) with Ni2+Ion exchange to produce Ni-containing2+The mesoporous-macroporous ZSM-5 molecular sieve of the metal cluster.
(3) Ni loaded by acidic mesoporous-macroporous ZSM-5 molecular sieve2Preparation of P catalyst precursor
Will contain Ni2+Mixing the mesoporous-macroporous ZSM-5 molecular sieve with alumina raw powder, adding an extrusion aid and a peptizing agent aqueous solution, kneading, molding, drying and roasting to obtain Ni loaded on the acidic mesoporous-macroporous ZSM-5 molecular sieve2And (3) P precursor.
(4) Acid meso-macroPore ZSM-5 molecular sieve loaded Ni2Phosphating of P precursors
Ni loaded with acidic macroporous-mesoporous ZSM-5 molecular sieve2Putting the P precursor into a fixed bed reactor, and then phosphorizing the P precursor by using organic phosphine-hydrogenated naphtha under certain conditions to obtain Ni loaded by the mesoporous-macroporous ZSM-5 molecular sieve2And (3) a P catalyst.
Wherein, in the step (1), the composition of the mixture gel is 1.0SiO2:0.005-0.05Al2O3:0.04-0.55Na2O:5-50H2O, the pH value of the mixture gel is 9.5-13.0;
in the step (1), the ratio (R) of the mass of the rubber microemulsion dry basis to the mass of the silicon element in the silicon source is 0.5-50
In the step (1), the mixture gel is aged for about 2 to 48 hours at the temperature of between 60 and 100 ℃ and crystallized for about 12 to 72 hours at the temperature of between 150 and 200 ℃;
in the step (1), the crystallization product is filtered, washed with water, dried at 80-140 ℃ for about 2-12 hours, and roasted at 500-600 ℃ for about 4-10 hours;
in the step (1), the pore size distribution, the total specific surface area and the silicon/aluminum atomic ratio of the mesoporous-macroporous ZSM-5 molecular sieve are respectively 2-100nm and 300-400m2/g、10:1-100:1；
In the step (1), the Ni2+One or more nickel salts selected from nickel nitrate, nickel acetate, nickel carbonate, etc.;
in step (1), Ni is used for ion exchange2+The concentration is 0.05-0.5mol/L, the exchange temperature is 60-100 ℃, the exchange time is 1-4 hours, the drying temperature is 100-150 ℃, and the drying time is 4-12 hours;
in the step (2), the alumina raw powder can be a common aluminum source, such as pseudo-boehmite, aluminum hydroxide powder, SB powder and the like;
in the step (2), in the forming process, in the mixture of the mesoporous-macroporous ZSM-5 molecular sieve and the alumina, the content of the mesoporous-macroporous ZSM-5 molecular sieve is 60-80 wt%, the content of the alumina is 20-40 wt%, and more preferably, the dry basis weight ratio of the mesoporous-macroporous ZSM-5 molecular sieve to the alumina can be controlled to be 3.0-3.7: 1;
in the step (2), in the forming process, the weight contents of the extrusion aid and the peptizing agent are respectively 6-8 wt% and 3-4 wt% based on the total weight of the dry base of the catalyst carrier, the extrusion aid can be sesbania powder, polyacrylamide, graphite, lubricating oil and the like, and the peptizing agent can be nitric acid, hydrochloric acid, acetic acid, citric acid and the like.
In the step (2), after the formation, the Ni loaded on the acidic mesoporous-macroporous ZSM-5 molecular sieve is prepared by drying at the temperature of 100 ℃ and 150 ℃ for about 3-5 hours and roasting at the temperature of 500 ℃ and 550 ℃ for about 3-5 hours2P catalyst precursor.
In the step (3), the organic phosphine may be one or more of organic phosphines such as triphenylphosphine, triphenoxy phosphine, trioctylphosphine, etc.;
in the step (3), the sulfur content of the hydrogenated naphtha is less than 5ppm, and the content of phosphorus atoms in the organic phosphine-hydrogenated naphtha is 4000-20000 ppm;
in the step (3), the phosphating temperature is 180--1The volume ratio of hydrogen to organic phosphine-hydrogenated naphtha is 300-600:1, and the phosphating time is 24-72 hours.
Compared with the prior art, the mesoporous-macroporous ZSM-5 molecular sieve loaded nickel phosphide catalyst and the preparation method thereof provided by the invention have the following characteristics:
1. cheap rubber microemulsion is used as a mesoporous-macroporous template agent to prepare a mesoporous-macroporous ZSM-5 molecular sieve, and Ni is subjected to ion exchange and organic phosphine phosphorization2P is loaded on the carrier composed of the molecular sieve and alumina, thus Ni is contained in the catalyst2P is in a high dispersion state;
2. the catalyst has wide application prospect in a plurality of catalytic fields of catalytic gasoline modification, lubricating oil isomerization dewaxing, diesel oil isomerization pour point depression and the like.
Detailed Description
The following examples further illustrate a nickel phosphide catalyst supported by a mesoporous-macroporous ZSM-5 molecular sieve and a preparation method thereof, but do not limit the scope of the present invention.
Example 1
The catalyst a1 prepared in this example contains 78.0 wt% of mesoporous-macroporous ZSM-5 molecular sieve, 21.9 wt% of alumina, and 0.1 wt% of nickel oxide, based on the weight of the catalyst.
2084g of ethyl orthosilicate, 28g of sodium metaaluminate, 9900g of deionized water and 24g of sodium hydroxide are firstly prepared into components, and the molar ratio of the oxides is 1.0SiO2:0.01Al2O3:0.08Na2O:55.0H2Stirring and refluxing the mixture gel of O in a container at 85 ℃ for 22h, adding styrene-butadiene rubber microemulsion into the mixture gel according to the proportion of R being 5.0 before crystallization, then filtering and washing the synthesized product, drying at 110 ℃ for 7h, roasting at 540 ℃ for 5h, and exchanging with 0.5mol/L ammonium chloride aqueous solution for 4h at 60 ℃ to obtain the acidic mesoporous-macroporous ZSM-5 molecular sieve (the molar ratio of silicon to aluminum atoms is 30, and the specific surface area is 325 m)2In terms of/g). Adding the molecular sieve into 1L nickel nitrate aqueous solution (0.05mol/L), exchanging at 80 deg.C for 2 hr under continuous stirring, filtering, drying at 120 deg.C for 8 hr to obtain Ni-containing solution2+The mesoporous-macroporous ZSM-5 molecular sieve.
Then, the Ni-containing alloy was weighed2+375g of mesoporous-macroporous ZSM-5 molecular sieve, 150g of pseudo-boehmite powder HC-07 (produced by Shandongtongyu chemical Co., Ltd., alumina loss about 30 wt%) and 32.5g of sesbania powder are mixed uniformly, 16.9g of concentrated nitric acid (65 wt%) and 180g of deionized water are added, after full mixing and kneading, the mixture is extruded into a clover strip with the diameter of 1.7mm in an extruding machine, dried at the temperature of 120 ℃ for about 4 hours, roasted at the temperature of 520 ℃ for about 4 hours, cooled and sieved, and the Ni loaded with the acidic mesoporous-macroporous ZSM-5 molecular sieve with the length of 3-10mm is prepared2And (3) P precursor.
The precursor was placed in a fixed bed reactor and then hydrogenated with triphenylphosphine-naphtha (sulfur content) containing 5000ppm phosphorus<5ppm), at the reaction temperature of 250 ℃, the reaction pressure of normal pressure and the volume space velocity of 2.0h-1And under the condition that the volume ratio of hydrogen to triphenylphosphine-hydrogenated naphtha is 400:1, phosphorizing the hydrogen/triphenylphosphine-hydrogenated naphtha for 24 hours to obtain Ni loaded with the mesoporous-macroporous ZSM-5 molecular sieve2And (3) a P catalyst.
Firstly, reducing the catalyst A with hydrogen at 400 ℃ for 3h on a microcalorimeter (SetarmTian-CalvetC-80), and then carrying out CO chemisorption at 35 ℃ to obtain the CO chemisorption quantity of the catalyst A1 of 970 mu mol/g.
Comparative example 1
The catalyst prepared in the comparative example is A2, and the weight of the catalyst is 78.0 wt% of acidic mesoporous ZSM-5 molecular sieve, 21.9 wt% of alumina and 0.1 wt% of nickel oxide.
Firstly, weighing 375g of self-made acidic mesoporous ZSM-5 molecular sieve, 150g of pseudo-boehmite powder HC-07 (produced by Shandong Xingdu chemical Co., Ltd., about 30 wt% of water loss of prepared alumina) and 32.5g of sesbania powder, uniformly mixing, adding 16.9g of concentrated nitric acid (65 wt%) and 180g of deionized water, fully kneading, extruding into a clover strip shape with the length of 1.7mm in a strip extruder, drying at 120 ℃ for about 4 hours, roasting at 520 ℃ for about 4 hours, cooling and screening to prepare the acidic mesoporous-macroporous ZSM-5 molecular sieve carrier with the length of 3-10 mm. The water absorption of the carrier was measured to be 46 wt%. Soaking 1.0g of nickel nitrate hexahydrate and 94 g of deionized water in a soaking solution of 200g of the carrier by adopting a traditional isometric soaking method, drying at 120 ℃ for about 4 hours, roasting at 520 ℃ for about 4 hours to obtain Ni loaded on the acidic mesoporous-macroporous ZSM-5 molecular sieve carrier2And (3) P precursor.
Then, Ni in comparative example 1 was added by the same procedure as in example 12P precursor is phosphorized to obtain Ni loaded by the mesoporous-macroporous ZSM-5 molecular sieve2P catalyst a 2; using the same procedure as in example 1, the chemisorption amount of CO of the catalyst A2 was measured to be 320. mu. mol/g. The catalyst A1 showed a two-fold increase in CO chemisorption compared to catalyst A2, and thus, the present invention produced highly dispersed Ni2And (3) a P catalyst.
Example 2
The catalyst prepared in this example was B1 and was prepared in the same manner as in example 1, except that the ZSM-5 molecular sieve was prepared as follows: 2084g of ethyl orthosilicate, 35g of sodium metaaluminate, 9900g of deionized water and 24g of sodium hydroxide are firstly prepared into components, and the molar ratio of the components to the oxides is 1.0SiO2:0.01Al2O3:0.08Na2O:55.0H2Stirring and refluxing O mixture gel at 90 ℃ for 12h in a container, and adding butyronitrile into the mixture gel according to the proportion of R-6.0 before crystallizationRubber microemulsion, then crystallizing at 190 ℃ for 40h, filtering the synthesized product, washing with water, drying at 120 ℃ for 5h, and roasting at 550 ℃ for 4h to obtain the product with the silicon-aluminum atom molar ratio of 40 and the specific surface area of 322m2A/g mesoporous-macroporous ZSM-5 molecular sieve.
Using the same procedure as in example 1, the CO chemisorption amount of catalyst B1 was measured to be 950. mu. mol/g.
Example 3
The catalyst prepared in this example is C1, and the preparation method is the same as that in example 1, except that the preparation process of the mesoporous-macroporous ZSM-5 molecular sieve is as follows: firstly, 1000g of water glass, 88g of aluminum sulfate, 7640g of deionized water and 200g of concentrated sulfuric acid (95-98 wt%) are prepared into the components of which the molar ratio of oxides is 1SiO2:0.01Al2O3:0.55Na2O:62.4H2Stirring and refluxing the mixture gel of O in a container at 80 ℃ for 24h, adding styrene-butadiene rubber microemulsion into the mixture gel according to the proportion of R2.5 before crystallization, then filtering and washing a synthetic product, drying at 130 ℃ for 4h and roasting at 560 ℃ for 3h when crystallizing at 185 ℃ for 48h to obtain the product with the silicon-aluminum atom molar ratio of 50 and the specific surface area of 318m2A/g mesoporous-macroporous ZSM-5 molecular sieve.
Using the same procedure as in example 1, the chemisorption amount of CO of the catalyst C1 was found to be 935. mu. mol/g.
Example 4
The catalyst prepared in this example was D1, which was prepared in the same manner as in example 1, except that the catalyst was 77.0 wt% of mesoporous-macroporous ZSM-5 molecular sieve, 21.9 wt% of alumina, and 1.1 wt% of nickel oxide, based on the weight of the catalyst.
Using the same procedure as in example 1, the CO chemisorption amount of catalyst D1 was measured to be 963. mu. mol/g.
Example 5
The catalyst prepared in this example was E1, which was prepared in the same manner as in example 1, except that the catalyst was 77.9 wt% of mesoporous-macroporous ZSM-5 molecular sieve, 17.6 wt% of alumina, and 1.5 wt% of nickel oxide, based on the weight of the catalyst.
Using the same procedure as in example 1, the CO chemisorption amount of catalyst E1 was measured to be 953. mu. mol/g.
Example 6
The catalyst prepared in this example was F1, which was prepared in the same manner as in example 1, except that the catalyst contained 78.4 wt% of the mesoporous-macroporous ZSM-5 molecular sieve, 19.6 wt% of alumina, and 2.0 wt% of nickel oxide, based on the weight of the catalyst.
Using the same procedure as in example 1, the CO chemisorption amount of the catalyst F1 was measured to be 983. mu. mol/g.
Example 7
The catalyst prepared in this example was G1, and the preparation method was the same as in example 1, except that Ni supported on acidic mesoporous-macroporous ZSM-5 molecular sieves was used2When the P precursor is phosphorized, the content of phosphorus atoms in the triphenylphosphine-hydrogenated naphtha is 10000 ppm.
Using the same procedure as in example 1, the CO chemisorption amount of catalyst G1 was found to be 975. mu. mol/G.
Example 8
The catalyst prepared in this example was H1, and the preparation method was the same as in example 1, except that Ni supported on acidic meso-macroporous ZSM-5 molecular sieves was used2When P precursor is phosphorized, the content of phosphorus atom in triphenylphosphine-hydrogenated naphtha is 20000 ppm.
Using the same procedure as in example 1, the CO chemisorption amount of the catalyst H1 was measured to be 978. mu. mol/g.
Example 9
The catalyst prepared in this example is I1, and the preparation method is the same as that in example 1, except that Ni is loaded on acidic mesoporous-macroporous ZSM-5 molecular sieve2And when the P precursor is phosphorized, triphenylphosphine oxide is used as a phosphorizing agent.
Using the same procedure as in example 1, the CO chemisorption amount of catalyst I1 was found to be 972. mu. mol/g.
Example 10
The catalyst prepared in this example was J1, which was prepared in the same manner as in example 1, except that Ni supported on acidic meso-macroporous ZSM-5 molecular sieves was used2When the P precursor is phosphorized, trioctylphosphine is used as a phosphorizing agent.
Using the same procedure as in example 1, the CO chemisorption amount of catalyst J1 was determined to be 974. mu. mol/g.
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (13)

1. A supported nickel phosphide catalyst is characterized in that a mixture of alumina and a mesoporous-macroporous ZSM-5 molecular sieve is used as a carrier, and Ni is used as2P is a metal active component, wherein the mesoporous-macroporous ZSM-5 molecular sieve is synthesized by taking rubber microemulsion as a template agent.
2. The supported nickel phosphide catalyst as claimed in claim 1, wherein the mesoporous-macroporous ZSM-5 molecular sieve has a pore size distribution, a total specific surface area and a silicon/aluminum atomic ratio of 2-100nm and 300-400m2/g、10:1-100:1。
3. The supported nickel phosphide catalyst of claim 1, wherein the mesoporous-macroporous ZSM-5 molecular sieve content is 70-80 wt%, the alumina content is 10-30 wt%, and the metal active component Ni is2The content of P is 0.1-2.0 wt% calculated by NiO.
4. The supported nickel phosphide catalyst of claim 3, wherein the weight ratio of the mesoporous-macroporous ZSM-5 molecular sieve to the alumina on a dry basis in the mesoporous-macroporous ZSM-5 molecular sieve and alumina mixture carrier is 3.0-3.7: 1.
5. The supported nickel phosphide catalyst as claimed in claim 1, wherein the rubber microemulsion may be styrene-butadiene rubber emulsion and/or nitrile-butadiene rubber emulsion, and the microemulsion has a particle size of 40-100 nm.
6. The process for preparing a supported nickel phosphide catalyst as claimed in claim 1, which essentially comprises the steps of:
(1) preparation of acidic mesoporous-macroporous ZSM-5 molecular sieve
Preparing a silicon source, an aluminum source, inorganic acid or inorganic base and deionized water into mixture gel, aging the mixture gel, adding rubber microemulsion into the aged mixture gel, and performing crystallization, filtration, washing, drying, roasting and ion exchange to obtain an acidic mesoporous-macroporous ZSM-5 molecular sieve;
(2) ni of acidic mesoporous-macroporous ZSM-5 molecular sieve2+Switching
Mixing the acidic mesoporous-macroporous ZSM-5 molecular sieve obtained in the step (1) with Ni2+Ion exchange to produce Ni-containing2+A mesoporous-macroporous ZSM-5 molecular sieve of the metal cluster;
(3) preparation of catalyst precursor
The Ni content obtained in the step (2)2+Mixing the mesoporous-macroporous ZSM-5 molecular sieve of the metal cluster with alumina raw powder, adding an extrusion aid and a peptizing agent aqueous solution, and preparing a catalyst precursor after kneading, forming, drying and roasting;
(4) phosphating
Putting the product obtained in the step (3) into a fixed bed reactor, and then phosphorizing the product by using organic phosphine-hydrogenated naphtha under certain conditions to obtain Ni loaded by the mesoporous-macroporous ZSM-5 molecular sieve2And (3) a P catalyst.
7. The method for preparing the supported nickel phosphide catalyst according to claim 6, wherein the rubber microemulsion is added in an amount such that the ratio of the mass of the rubber microemulsion on a dry basis to the mass of the silicon element in the silicon source is 0.5-50.
8. The method of claim 6, wherein the Ni is selected from the group consisting of2+Derived from one or more of nickel salts such as nickel nitrate, nickel acetate, nickel carbonate, etc.
9. The method for preparing a supported nickel phosphide catalyst according to claim 6, wherein Ni is used for ion exchange2+The concentration is 0.05-0.5mol/L, the exchange temperature is 60-100 ℃, the exchange time is 1-4 hours, the drying temperature is 100-150 ℃, and the drying time is 4-12 hours.
10. The method for preparing the supported nickel phosphide catalyst according to claim 6, wherein the weight contents of the extrusion aid and the peptizing agent are respectively 6-8 wt% and 3-4 wt% based on the total weight of the catalyst carrier on a dry basis; wherein, the extrusion aid can be sesbania powder, polyacrylamide, graphite and lubricating oil; the peptizing agent can be nitric acid, hydrochloric acid, acetic acid, citric acid.
11. The method of claim 6, wherein the organic phosphine is one or more of triphenylphosphine, triphenoxy phosphine, and trioctylphosphine.
12. The method for preparing the supported nickel phosphide catalyst as claimed in claim 6, wherein the sulfur content of the hydrogenated naphtha is less than 5ppm, and the content of phosphorus atom in the organic phosphine-hydrogenated naphtha is 4000-20000 ppm.
13. The method for preparing the supported nickel phosphide catalyst as claimed in claim 6, wherein the phosphating temperature is 180--1The volume ratio of hydrogen/organic phosphine-hydrogenated naphtha is 300:1-600:1, and the phosphating time is 24-72 hours.
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CN113328071A (en) * 2021-05-14 2021-08-31 昆明理工大学 Lithium vanadium phosphate/carbon battery positive electrode material and preparation method thereof
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