CN112206795A - Supported nickel phosphide catalyst for preparing hydrogenated petroleum resin and preparation method thereof - Google Patents
Supported nickel phosphide catalyst for preparing hydrogenated petroleum resin and preparation method thereof Download PDFInfo
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- 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
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- 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
- B01J37/031—Precipitation
- B01J37/033—Using Hydrolysis
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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
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/28—Phosphorising
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- C08F8/04—Reduction, e.g. hydrogenation
Abstract
The invention discloses a supported nickel phosphide catalyst for preparing hydrogenated petroleum resin by catalytic hydrogenation of petroleum resin and a preparation method thereof, which comprises the steps of preparing carbonate intercalated NiAl-LDHs binary hydrotalcite by urea hydrolysis method, reducing the carbonate intercalated NiAl-LDHs binary hydrotalcite in reducing atmosphere to obtain a nickel-based catalyst precursor as a nickel source, reducing the nickel-based catalyst precursor and a phosphorus source in reducing atmosphere, and passivating the nickel-based catalyst precursor and the phosphorus source in passivating atmosphere at room temperature to obtain the supported nickel phosphide catalystA nickel-based catalyst. The catalyst obtained by the invention has higher catalytic hydrogenation activity and decoloring performance, and can be applied to hydrogenation reaction of C5/C9 petroleum resin to obtain high-quality hydrogenated petroleum resin, and the effect of the catalyst is superior to that of a nickel-based catalyst Ni/Al2O3Therefore, the method has important significance for the preparation of hydrogenated petroleum resin.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a supported nickel phosphide catalyst for preparing Hydrogenated Petroleum Resin (HPR) by hydrogenation of Petroleum Resin (PR) and a preparation method thereof.
Background
The petroleum resin is a thermoplastic synthetic resin generated by the polymerization reaction of a mixture of residual heavy aromatic hydrocarbon and olefin under the action of a catalyst after benzene, toluene and xylene are removed from a liquid product of ethylene prepared by hydrocarbon cracking, and has wide application in the fields of road marking paint, rubber additives, coating, ink and the like.
Hydrogenated petroleum resin is a special material with excellent performance prepared by carrying out catalytic hydrogenation on unsaturated C = C double bonds and benzene rings in the molecular structure of petroleum resin. The hydrogenated petroleum resin prepared by the catalytic hydrogenation technology is water white in color, is obviously superior to non-hydrogenated petroleum resin in the aspects of light and heat resistance stability, weather resistance, compatibility with other organic solvents and the like, and has wide application in the industries of preparing tackifiers, high-grade printing ink, rubber, coatings, papermaking and the like. Therefore, catalytic hydrogenation technology is undoubtedly the most widely used method for improving the quality of conventional petroleum resins. The price of the hydrogenated petroleum resin prepared by the catalytic hydrogenation technology is about 2-3 times of that of the unhydrogenated crude petroleum resin, and the hydrogenated petroleum resin has considerable additional value.
The catalysts reported at present for hydrogenation of petroleum resin mainly comprise palladium-based and nickel-based supported catalysts. Although the palladium catalyst has excellent catalytic hydrogenation activity on petroleum resin and can effectively inhibit the hydrogenation degradation of the petroleum resin, the palladium catalyst is sensitive to sulfur-containing compounds in the petroleum resin, is easy to irreversibly deactivate due to poisoning, and has high cost. Patent CN 102718925A, CN 104525198A reports a catalyst prepared by using Pd as an active component supported on an alumina carrier. Patent CN 102935367a discloses a petroleum resin hydrogenation catalyst, wherein an alumina-titania compound is used as a carrier, metallic palladium is used as an active component, and a metal is doped in a catalytic system for modification. EP 1552881a1 uses a palladium platinum bimetallic supported alumina or zeolite molecular sieve to make a catalyst for the hydrogenation of petroleum resins. The palladium-based catalysts disclosed in the above patents have high catalytic hydrogenation activity, but still have a poisoning deactivation phenomenon.
The nickel catalyst has high loading, easy agglomeration of active components and easy sintering at high temperature, so that the catalytic activity is reduced. Patent CN 104174410a, CN 104174409a reports a petroleum resin hydrogenation catalyst prepared by modifying an alumina-titania composite as a carrier and adding metals such as molybdenum, tungsten, cobalt, cerium and the like as an auxiliary agent to an active component nickel. Therefore, for nickel-based catalysts, the sintering resistance and activity of the nickel-based catalysts are improved by adding an auxiliary agent or changing a carrier, but the problem of sintering and aggregation of nickel particles at high temperature still cannot be solved well. Patent CN 106861730A, CN 107051430a discloses that metal palladium, nickel phosphide and lanthanum oxide are used as active components for hydrogenation reaction of petroleum resin, and the result shows that nickel phosphide has excellent catalytic activity, and therefore, it is feasible to select nickel phosphide as the active component of the petroleum resin hydrogenation catalyst. However, it is difficult to prepare a single crystalline phase of nickel phosphide, and it is also challenging to prepare a pure phase nickel phosphide/alumina catalyst by combining a conventional impregnation method and a temperature-programmed reduction method, because of the high temperature and reducing atmosphereUnder the condition, the phosphate will react with the carrier A12O3Reaction to inert component AlPO4Cause phosphorus loss, and A1PO4The spinel covers the surface of the catalyst, so that the activity of the catalyst is reduced, and the A1 prepared by the temperature programmed reduction method is difficult2O3A supported metal phosphide catalyst.
In conclusion, the key point of developing a petroleum resin hydrogenation catalyst with high hydrogenation activity and high anti-poisoning activity is that the catalyst is prepared from active components with high hydrogenation activity and excellent anti-poisoning performance and is free of A1PO4The single crystal form nickel phosphide/aluminum oxide catalyst generated by spinel simultaneously improves the dispersion degree of active components and the anchoring effect between the active components and a carrier, further improves the catalytic activity and the anti-poisoning property of the catalyst on petroleum resin, and has very important scientific significance and practical value for producing hydrogenated petroleum resin with high added value.
Disclosure of Invention
In order to solve the problems, the invention provides a supported nickel phosphide catalyst for preparing hydrogenated petroleum resin and a preparation method thereof, wherein immobilized metal nanoparticles obtained by reduction of NiAl-LDHs are used as 'active seeds', and a supported nickel phosphide catalyst inheriting the high dispersibility and stability of parent metal nanoparticles is obtained by introducing a phosphorus source and carrying out solid-gas reaction. The catalyst has excellent catalytic hydrogenation performance on C5/C9 petroleum resin, can be used for preparing water white hydrogenated petroleum resin with low bromine number and excellent performance, has a simple hydrogenation process, and is suitable for industrial production.
In order to achieve the purpose, the invention adopts the following technical scheme:
a supported nickel phosphide catalyst for preparing hydrogenated petroleum resin is prepared by reacting carbonate and hydroxyl generated by urea hydrolysis with nickel and aluminum metal salt ions at a certain temperature by adopting a urea hydrolysis method to generate a carbonate intercalated binary hydrotalcite-like precursor (NiAl-LDHs), and reducing the carbonate intercalated binary hydrotalcite-like precursor in a reducing atmosphere to obtain a nickel-based catalyst with highly dispersed active components; and then, the nickel-based catalyst precursor is used as a nickel source, and is placed in a reducing atmosphere with a phosphorus source according to a certain molar ratio for roasting reduction, and the supported nickel phosphide catalyst is obtained after passivation. The preparation method comprises the following steps:
(1) mixing a nickel precursor, an aluminum precursor, ammonium salt and urea according to a certain molar ratio, dissolving in deionized water, and stirring until the mixture is completely dissolved to obtain a mixed suspension;
(2) transferring the mixed suspension prepared in the step (1) into a stainless steel reaction kettle with a polytetrafluoroethylene lining, then placing the stainless steel reaction kettle into an oven, statically crystallizing the mixed suspension for 6 to 36 hours (preferably 18 to 30 hours) at 80 to 180 ℃ (preferably 110-;
(3) placing the binary hydrotalcite precursor obtained in the step (2) in a reducing atmosphere, reducing for 2-8h (preferably 4-8 h) under the conditions of 450-750 ℃ (preferably 500-700 ℃), and keeping the gas flow rate at 50-150 ml/min to obtain a nickel-based catalyst precursor;
(4) and (3) taking the nickel-based catalyst precursor obtained in the step (3) as a nickel source, placing the nickel-based catalyst precursor and a phosphorus source in a reducing atmosphere according to a certain molar ratio, reducing for 2-8h (preferably 4-8 h) under the conditions of 450-650 ℃ (preferably 450-550 ℃), keeping the gas flow rate at 50-150 ml/min, cooling to room temperature, passivating for 0.5-2.5 h (preferably 1.5-2.5 h) in a passivating gas at room temperature, keeping the gas flow rate at 30-70 ml/min, and preparing the supported nickel phosphide catalyst for preparing the hydrogenated petroleum resin by mechanical tabletting and sieving.
The molar ratio of the nickel precursor, the aluminum precursor, and the urea to the ammonium salt used in step (1) is n (Ni): n (Al): n (urea): n (ammonium salt) = (1-3):1:20 (6-9) (preferably (1.5-2.5):1:20 (7-9)). The precursor of the nickel is any one of nickel nitrate, nickel acetate, nickel chloride, nickel oxalate or nickel sulfate, and preferably nickel nitrate; the precursor of the aluminum is any one of aluminum nitrate, aluminum sulfate, aluminum chloride or aluminum hydroxide, and preferably is aluminum nitrate; the ammonium salt is any one of ammonium nitrate, ammonium chloride, ammonium fluoride, ammonium sulfate, ammonium carbonate or ammonium bicarbonate, and ammonium fluoride is preferred.
In the step (3), the reducing atmosphere is a mixed gas of hydrogen and an inert gas, wherein the volume concentration of the hydrogen is 10%, and the inert gas is any one of argon and nitrogen (preferably argon).
The molar ratio of the nickel source to the phosphorus source used in step (4) is such that n (Ni) and n (P) =1:3-3:1 (preferably 1:1-3: 1). The phosphorus source is any one of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, red phosphorus, ammonium hypophosphite and ammonium phosphite. The reducing atmosphere is a mixed gas of hydrogen and inert gas, wherein the volume concentration of the hydrogen is 10%, and the inert gas is any one of argon or nitrogen (preferably argon); the passivation gas is a mixed gas of oxygen and inert gas, wherein the volume concentration of the oxygen is 0.5%, and the inert gas is any one of argon or nitrogen (preferably argon).
The obtained supported nickel phosphide catalyst can be used for preparing hydrogenated petroleum resin by hydrogenating petroleum resin, wherein the petroleum resin is C5 petroleum resin or C9 petroleum resin.
The specific application method comprises the following steps: dissolving petroleum resin in an organic solvent to prepare a petroleum resin solution, and placing the petroleum resin solution in a raw material tank of a fixed bed reactor; loading the supported nickel phosphide catalyst into a stainless steel reaction tube of a fixed bed reactor, purging and replacing air in the reactor and a pipeline by using nitrogen, activating the nickel phosphide catalyst for 1 h at 250 ℃ and at a hydrogen flow rate of 50 ml/min, injecting a petroleum resin solution into the fixed bed reactor through a high-pressure pump for hydrogenation reaction, and distilling a product after the reaction under reduced pressure to obtain solid hydrogenated petroleum resin;
wherein the organic solvent is one or more of cyclohexane, cyclopentane, acetone, methylcyclohexane, toluene or xylene (preferably cyclohexane); the concentration of the petroleum resin solution is 10-20 wt.%; the conditions of the hydrogenation reaction are as follows: temperature 180 ℃ and 280 ℃ (preferably 240 ℃ and 260 ℃), and hydrogen pressure3-8MPa (preferably 4-6 MPa), and the volume space velocity is 0.5-2.5 h-1(preferably 1.0-2.0 h)-1) The hydrogen-oil ratio is 300:1-1000:1 (preferably 500:1-800: 1).
The invention has the beneficial effects that:
(1) the nickel phosphide has catalytic hydrogenation activity comparable to that of noble metals and excellent poisoning resistance, and is mainly characterized in that nickel is equivalent to an electron donor in the nickel phosphide, phosphorus is equivalent to an electron acceptor, nickel provides electrons for phosphorus, so that nickel atoms generate electronic structure defects, surface acid sites near electron-deficient nickel particles adsorb sulfide molecules to inhibit the formation of metal sulfides, and nickel is not easy to bind with sulfur in petroleum resin to cause poisoning inactivation, so that the nickel has excellent poisoning resistance in catalytic reaction. In addition, the crystal structure of the nickel phosphide is similar to a sphere, so that more active sites can be exposed, and the catalytic hydrogenation function of the active center can be exerted to the greatest extent. Therefore, the invention selects the nickel phosphide as the active component of the catalyst, can show excellent catalytic hydrogenation activity for the catalytic hydrogenation of the C5/C9 petroleum resin, can effectively avoid the occurrence of side reactions in the hydrogenation process, reduce the breakage of molecular chains and inhibit the reduction of softening point.
(2) Under the condition of high-temperature reducing atmosphere, phosphate is easy to react with the carrier A12O3Reaction to inert component AlPO4Cause phosphorus loss, and A1PO4The spinel covers the surface of the catalyst, so that the activity of the catalyst is reduced, and the traditional impregnation method and the temperature-programmed reduction method are difficult to prepare A12O3A supported metal phosphide catalyst. The invention obtains Ni/Al by reduction of NiAl-LDHs2O3The precursor is used as a nickel source and is reduced by temperature programming with a phosphorus source according to a certain proportion to obtain the A1-free 1PO 4Spinel generated single crystal type supported Ni2P/Al2O3A catalyst.
(3) The supported nickel phosphide catalyst prepared by the invention is used for catalytic hydrogenation of petroleum resin, and the bromine number of hydrogenated C5 petroleum resin is low (<0.70gBr2100 g), light color (Gardner chroma is less than or equal to 0.7 #); bromine number of hydrogenated C9 Petroleum resin<1.30gBr2100 g, Gardner color number less than or equal to 1.0#, and is superior to Ni/Al of nickel-based catalyst2O3。
(4) The catalyst of the invention has long service life, simple hydrogenation process and higher industrial application value.
Drawings
FIG. 1 is an XRD pattern of NiAl-LDHs hydrotalcite-like compound prepared in example 1.
FIG. 2 shows Ni/Al obtained by reducing NiAl-LDHs hydrotalcite-like compound obtained in example 12O3XRD pattern of the catalyst.
FIG. 3 is a XRD comparison of nickel phosphide catalysts prepared in example 1 and comparative example 2.
FIG. 4 is an SEM photograph of NiAl-LDHs hydrotalcite-like compound prepared in example 1.
FIG. 5 shows Ni/Al prepared in comparative example 12O3SEM image of catalyst.
FIG. 6 shows Ni prepared in example 12P/Al2O3SEM image of catalyst.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
The raw materials used in the examples are all reagent grade. XRD the morphology of the catalyst was observed using an Ultima model X-ray powder diffractometer, manufactured in Japan, and a/Nova NanoSEM 230 field emission scanning electron microscope, manufactured by Czech REPUBLIC S.R.O. And after the reaction is finished, performing physical property analysis on the obtained solid hydrogenated product, determining the bromine value of the product by adopting a domestic BR-1 type bromine value bromine index determinator, determining the softening point of the product by adopting a domestic SYD-2806G full-automatic softening point determinator, and determining the chromaticity of the product by adopting a Gardner colorimeter.
Example 1
0.005 mol of Ni (NO)3)2•6H2O、0.0025mol Al(NO3)3•9H2O, 0.05 mol of urea and 0.02mol of NH4Adding F into 70g of deionized water, stirring uniformly to form a suspension, transferring the suspension into a stainless steel reaction kettle with a polytetrafluoroethylene lining, then placing the suspension into a 110 ℃ oven for static crystallization for 24 hours, then statically aging for 8 hours, cooling to room temperature, carrying out vacuum filtration, washing and precipitating, placing the precipitate into an 85 ℃ oven for drying to constant weight to obtain binary nickel-aluminum hydrotalcite NiAl-LDHs, then placing the obtained binary nickel-aluminum hydrotalcite in a tube furnace, increasing the temperature from room temperature to 600 ℃ at the speed of 2 ℃/min, and reducing for 6 hours (the flow rate is kept at 50-100 ml/min) under the mixed atmosphere of hydrogen and argon (1: 9, v/v) to obtain Ni/Al hydrotalcite2O3A precursor; mixing the obtained Ni/Al2O3Putting the precursor and red phosphorus in a tube furnace according to the initial molar ratio of n (Ni) to n (P) =2:1, reducing for 6h (the flow rate is kept at 50-100 ml/min) under the mixed atmosphere of hydrogen and argon (1: 9, v/v) at 500 ℃, then cooling to room temperature, passivating for 2.0h (the gas flow rate is kept at 30-70 ml/min) under the mixed atmosphere of oxygen and argon (0.5: 99.5, v/v), forming by mechanical tabletting, and sieving (20-40 meshes) to obtain the supported nickel phosphide catalyst Ni catalyst2P/Al2O3。
Example 2
0.00375 mol of Ni (NO)3)2•6H2O、0.0025mol Al(NO3)3•9H2O, 0.05 mol of urea and 0.0175mol of NH4Adding F into 65g of deionized water, stirring uniformly to form a suspension, transferring the suspension into a stainless steel reaction kettle with a polytetrafluoroethylene lining, then placing the suspension into a 130 ℃ oven for static crystallization for 18 h, then statically aging for 6h, cooling to room temperature, carrying out vacuum filtration, washing and precipitating, placing the precipitate into a 95 ℃ oven for drying to constant weight to obtain binary nickel-aluminum hydrotalcite NiAl-LDHs, then placing the obtained binary nickel-aluminum hydrotalcite into a tube furnace, increasing the temperature from room temperature to 500 ℃ at the speed of 2 ℃/min, and reducing for 4 h (the flow rate is kept at 50-100 ml/min) under the mixed atmosphere of hydrogen and nitrogen (1: 9, v/v) to obtain Ni/Al hydrotalcite2O3A precursor; mixing the obtained Ni/Al2O3The precursor and ammonium hypophosphite are put into a tube furnace according to the initial molar ratio of n (Ni) to n (P) =2:1, and hydrogen and ammonium hypophosphite are put into the tube furnace at the temperature of 450 DEG CReducing for 4 h (flow rate is kept at 50-100 ml/min) under nitrogen (1: 9, v/v) mixed atmosphere, cooling to room temperature, passivating for 1.5h (gas flow rate is kept at 30-70 ml/min) under oxygen and nitrogen (1: 9, v/v) mixed atmosphere, mechanically tabletting and molding (20-40 meshes), and sieving to obtain the supported nickel phosphide catalyst Ni2P/Al2O3。
Example 3
0.00625 mol of Ni (NO)3)2•6H2O、0.0025mol Al(NO3)3•9H2O, 0.05 mol of urea and 0.0225mol of NH4Adding F into 75g of deionized water, stirring uniformly to form a suspension, transferring the suspension into a stainless steel reaction kettle with a polytetrafluoroethylene lining, then placing the suspension into a 150 ℃ oven for static crystallization for 30 h, then statically aging for 10h, cooling to room temperature, carrying out vacuum filtration, washing and precipitating, placing the precipitate into a 105 ℃ oven for drying to constant weight to obtain binary nickel-aluminum hydrotalcite NiAl-LDHs, then placing the obtained binary nickel-aluminum hydrotalcite into a tube furnace, increasing the temperature from room temperature to 700 ℃ at the speed of 2 ℃/min, and reducing for 8h (the flow rate is kept at 50-100 ml/min) under the mixed atmosphere of hydrogen and argon (1: 9, v/v) to obtain Ni/Al hydrotalcite2O3A precursor; mixing the obtained Ni/Al2O3Putting the precursor and ammonium phosphite in a tube furnace according to the initial molar ratio of n (Ni) to n (P) =2:1, reducing for 8h (the flow rate is kept at 50-100 ml/min) under the mixed atmosphere of hydrogen and nitrogen at 550 ℃ (1: 9, v/v), cooling to room temperature, passivating for 2.5h (the gas flow rate is kept at 30-70 ml/min) under the mixed atmosphere of oxygen and nitrogen (1: 9, v/v), mechanically tabletting, molding and sieving (20-40 meshes) to obtain the supported nickel phosphide catalyst Ni catalyst2P/Al2O3。
Example 4
0.005 mol of Ni (NO)3)2•6H2O、0.0025mol Al(NO3)3•9H2O, 0.05 mol of urea and 0.02mol of NH4Adding F into 70g of deionized water, stirring uniformly, transferring the suspension to a stainless steel reaction kettle with a polytetrafluoroethylene lining after forming suspension, and then placing the suspension in the stainless steel reaction kettleStatically crystallizing in an oven at 130 ℃ for 18 h, statically aging for 6h, cooling to room temperature, carrying out vacuum filtration, washing the precipitate, placing the precipitate in an oven at 85 ℃ for drying to constant weight to obtain binary nickel-aluminum hydrotalcite NiAl-LDHs, then placing the obtained binary nickel-aluminum hydrotalcite in a tube furnace, heating from room temperature to 500 ℃ at the speed of 2 ℃/min, and reducing for 4 h (the flow rate is kept at 50-100 ml/min) under the mixed atmosphere of hydrogen and argon (1: 9, v/v) to obtain Ni/Al2O3A precursor; mixing the obtained Ni/Al2O3Putting the precursor and red phosphorus in a tube furnace according to the initial molar ratio of n (Ni) to n (P) =2:1, reducing for 4 h (the flow rate is kept at 50-100 ml/min) under the mixed atmosphere of hydrogen and argon at 450 ℃ (1: 9, v/v), cooling to room temperature, passivating for 2.0h (the gas flow rate is kept at 30-70 ml/min) under the mixed atmosphere of oxygen and argon (1: 9, v/v), mechanically tabletting, molding and sieving (20-40 meshes) to obtain the supported nickel phosphide catalyst Ni catalyst2P/Al2O3。
Example 5
0.005 mol of Ni (NO)3)2•6H2O、0.0025mol Al(NO3)3•9H2O, 0.05 mol of urea and 0.02mol of NH4Adding F into 70g of deionized water, stirring uniformly to form a suspension, transferring the suspension into a stainless steel reaction kettle with a polytetrafluoroethylene lining, then placing the suspension into an oven at 130 ℃ for static crystallization for 30 h, then statically aging for 10h, cooling to room temperature, carrying out vacuum filtration, washing and precipitating, placing the precipitate into an oven at 85 ℃ for drying to constant weight to obtain binary nickel-aluminum hydrotalcite NiAl-LDHs, then placing the obtained binary nickel-aluminum hydrotalcite in a tube furnace, raising the temperature from room temperature to 700 ℃ at the speed of 2 ℃/min, and reducing for 8h (the flow rate is kept at 50-100 ml/min) under the mixed atmosphere of hydrogen and nitrogen (1: 9, v/v) to obtain Ni/Al hydrotalcite2O3A precursor; mixing the obtained Ni/Al2O3Placing the precursor and red phosphorus in a tube furnace according to the initial molar ratio of n (Ni) to n (P) =2:1, reducing at 550 ℃ for 8h in a mixed atmosphere of hydrogen and nitrogen (1: 9, v/v) (the flow rate is kept at 50-100 ml/min), cooling to room temperature, and then in a mixed atmosphere of oxygen and nitrogen (1: 9, v/v)Performing warm passivation for 2.0h (keeping the gas flow rate at 30-70 ml/min), mechanically tabletting, molding, and sieving (20-40 mesh) to obtain the supported nickel phosphide catalyst Ni2P/Al2O3。
Example 6
0.005 mol of Ni (NO)3)2•6H2O、0.0025mol Al(NO3)3•9H2O, 0.05 mol of urea and 0.02mol of NH4Adding F into 70g of deionized water, stirring uniformly to form a suspension, transferring the suspension into a stainless steel reaction kettle with a polytetrafluoroethylene lining, then placing the suspension into an oven at 150 ℃ for static crystallization for 18 h, then statically aging the suspension for 6h, cooling the suspension to room temperature, carrying out vacuum filtration, washing and precipitating, placing the precipitate into an oven at 85 ℃ for drying to constant weight to obtain binary nickel-aluminum hydrotalcite NiAl-LDHs, then placing the obtained binary nickel-aluminum hydrotalcite into a tube furnace, increasing the temperature from the room temperature to 500 ℃ at the speed of 2 ℃/min, and reducing the precipitate for 4 h (the flow rate is kept at 50-100 ml/min) under the mixed atmosphere of hydrogen and argon (1: 9, v/v) to obtain Ni/Al hydrotalcite2O3A precursor; mixing the obtained Ni/Al2O3Putting the precursor and red phosphorus in a tube furnace according to the initial molar ratio of n (Ni) to n (P) =2:1, reducing for 4 h under the mixed atmosphere of hydrogen and argon (1: 9, v/v) at 450 ℃ (the flow rate is kept between 50 ml/min and 100 ml/min), cooling to room temperature, passivating for 2.0h under the mixed atmosphere of oxygen and argon (1: 9, v/v) (the gas flow rate is kept between 30 ml/min and 70 ml/min), mechanically tabletting, forming and sieving to obtain the supported nickel phosphide catalyst Ni2P/Al2O3。
Example 7
0.005 mol of Ni (NO)3)2•6H2O、0.0025mol Al(NO3)3•9H2O, 0.05 mol of urea and 0.02mol of NH4Adding F into 70g of deionized water, stirring uniformly to form a suspension, transferring the suspension into a stainless steel reaction kettle with a polytetrafluoroethylene lining, then placing the suspension into a 150 ℃ oven for static crystallization for 30 h, then statically aging for 10h, cooling to room temperature, carrying out vacuum filtration, washing the precipitate, placing the precipitate into an 85 ℃ oven, and drying to constant weight to obtain the binary nickel-aluminum hydrotalciteNiAl-LDHs, then placing the obtained binary nickel-aluminum hydrotalcite in a tube furnace, heating the temperature from room temperature to 700 ℃ at the speed of 2 ℃/min, reducing for 8h (the flow rate is kept between 50 and 100 ml/min) under the mixed atmosphere of hydrogen and argon (1: 9, v/v) to obtain Ni/Al2O3A precursor; mixing the obtained Ni/Al2O3Putting the precursor and red phosphorus in a tube furnace according to the initial molar ratio of n (Ni) to n (P) =2:1, reducing for 8h under the mixed atmosphere of hydrogen and argon (1: 9, v/v) at 550 ℃ (the flow rate is kept between 50 ml/min and 100 ml/min), cooling to room temperature, passivating for 2.0h under the mixed atmosphere of oxygen and argon (1: 9, v/v) (the gas flow rate is kept between 30 ml/min and 70 ml/min), mechanically tabletting, forming and sieving (20-40 meshes) to obtain the supported nickel phosphide catalyst Ni catalyst2P/Al2O3。
Comparative example 1
In order to examine the influence of different active components of the catalyst on the hydrogenation performance of petroleum resin, the comparative example prepared the Ni/Al nickel-based catalyst by the method described in example 12O3For comparison with example 1.
Comparative example 2
In order to investigate the influence of the loading method on the active components of the catalyst and the hydrogenation effect of the final petroleum resin, the comparative example adopts an incipient wetness impregnation method to prepare Ni2P/γ-Al2O3The preparation method comprises the following steps: 2.34 g (8.05 mmol) of Ni (NO)3)2•6H2O、2.13 g(16.1 mmol) (NH4)2HPO4Adding into 40mL deionized water, adding 2.00g gamma-Al after fully dissolving2O3And (3) continuously stirring the carrier for 6 hours, transferring the suspension into a round-bottom flask, removing water through rotary evaporation, drying the suspension in an oven at 85 ℃ to obtain green powder, calcining the obtained powder in a muffle furnace at 550 ℃ for 6 hours, and reducing the calcined powder in a tubular furnace at 700 ℃ for 6 hours to obtain the supported nickel phosphide catalyst Ni2P/γ-Al2O3。
FIG. 1 is an XRD pattern of NiAl-LDHs hydrotalcite-like compound prepared in example 1. As can be seen from the figure, the peaks at 2 θ =11.13 °, 22.32 °, 34.65 °, 38.65 °, 45.68 °, 60.33 °, 61.49 ° are characteristic diffraction peaks of hydrotalcite, corresponding to the (003), (006), (012), (015), (018), (110) and (113) crystal planes thereof, respectively, which proves that NiAl-LDHs binary hydrotalcite is successfully prepared by urea hydrolysis.
FIG. 2 shows Ni/Al obtained by reducing NiAl-LDHs hydrotalcite-like compound obtained in example 12O3XRD pattern of (a). As can be seen from the figure, the diffraction peaks at 2 θ =44.49 °, 51.84 °, 76.37 ° correspond to the (111), (200), (220) crystal planes of Ni, respectively.
FIG. 3 is a XRD comparison of nickel phosphide catalysts prepared in example 1 and comparative example 2. As can be seen from the figure, Ni prepared in example 12P/Al2O3In (2 θ =40.80 °, 44.60 °, 47.31 °, 54.23 °, 54.94 °, 74.68 °, diffraction peaks are all directed to hexagonal Ni2P, corresponding to their (111), (201), (210), (300), (211), (400) crystal planes, respectively. Ni prepared in comparative example 22P/γ-Al2O3Catalyst having triclinic AlPO at 2 θ =17.55 °, 20.79 °, 21.87 °, 30.81 °, 31.47 ° and 35.23 ° diffraction peaks4The characteristic diffraction peaks of (a) correspond to the (203), (212), (213), (0010), (403) and (260) crystal planes thereof, respectively. Illustrating Ni prepared by the impregnation method2P/γ-Al2O3In the catalyst there is AlPO4Spinel formation and successful preparation of AlPO-free via hydrotalcite-like precursor process4Spinel-forming nickel phosphide target catalyst.
FIGS. 4, 5, and 6 show the NiAl-LDHs hydrotalcite prepared in example 1 and Ni/Al obtained by reducing the NiAl-LDHs hydrotalcite2O3Precursor and Ni2P/Al2O3SEM image of catalyst. As can be seen from the figure, the NiAl-LDHs hydrotalcite is formed by a plurality of curled sheets, the appearance of the NiAl-LDHs hydrotalcite is similar to a sphere, and the NiAl-LDHs hydrotalcite is reduced at high temperature to obtain Ni/Al2O3The precursor still maintains the original shape of NiAl-LDHs, and Ni is obtained after the precursor is reduced by temperature programming and a phosphorus source is introduced2P/Al2O3The catalyst still maintains the original shape of the NiAl-LDHs, which shows that the introduction of a phosphorus source and the secondary high temperature do not damage the NiAl-Original morphology of LDHs. The appearance has high exposure rate of the external surface area, and the contact probability of reaction molecules and active sites can be increased, so that the catalytic hydrogenation activity is improved.
3.0g of the catalyst particles prepared in the above examples and comparative examples are loaded into a stainless steel reaction tube of a 10mL fixed bed reactor, nitrogen is used for purging air in the tube for 30 min, then the catalyst is activated for 1 h at 250 ℃ and 50 mL/min hydrogen flow rate, the prepared 10 wt.% C5/C9 petroleum resin/cyclohexane solution is placed in a raw material tank and is injected into the 10mL fixed bed reactor through a high pressure pump for hydrogenation reaction, and the reaction conditions are as follows: the temperature is 250 ℃, the hydrogen pressure is 5MPa, and the liquid volume space velocity is 2.0h-1And (3) performing gas-liquid separation on the product at a hydrogen-oil ratio of 600:1(V/V), performing reduced pressure distillation on the product to separate out a solid product, and performing physical property analysis. The evaluation results are shown in tables 1 and 2.
TABLE 1 comparison of the Effect of the examples with comparative examples hydrogenated C5 Petroleum resin
TABLE 2 comparison of the Effect of the examples with that of the comparative example hydrogenated C9 Petroleum resin
As can be seen from tables 1 and 2, the catalyst prepared by using nickel phosphide as an active component according to the present invention is more excellent in catalytic hydrogenation activity than the catalyst prepared by using metallic nickel as an active component in comparative example 1. Compared with the catalyst prepared by the traditional impregnation method in the comparative example 2, the Ni synthesized by the hydrotalcite-like precursor method of the invention2P/Al2O3The catalyst is free of AlPO4The spinel is generated, so that the catalyst has more excellent catalytic hydrogenation activity, can effectively reduce the breakage of molecular chains, inhibit the hydrogenation degradation of petroleum resin, and improve the hydrogenation degree of unsaturated hydrocarbon bonds of C5/C9 petroleum resin.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (9)
1. A method for preparing a supported nickel phosphide catalyst for preparing hydrogenated petroleum resin is characterized by comprising the following steps: the method comprises the following steps:
(1) mixing a nickel precursor, an aluminum precursor, ammonium salt and urea according to a certain molar ratio, dissolving in deionized water, and stirring until the mixture is completely dissolved to obtain a mixed suspension;
(2) transferring the mixed suspension prepared in the step (1) into a stainless steel reaction kettle with a polytetrafluoroethylene lining, then placing the stainless steel reaction kettle into a drying oven, statically crystallizing the mixed suspension for 6 to 36 hours at the temperature of 80 to 180 ℃, statically aging the mixed suspension for 6 to 12 hours, cooling the mixed suspension to room temperature, filtering the mixed suspension, washing and precipitating the precipitate, and placing the precipitate in the drying oven to dry the precipitate to constant weight at the temperature of 80 to 100 ℃ to obtain a binary hydrotalcite precursor;
(3) reducing the binary hydrotalcite precursor obtained in the step (2) in a reducing atmosphere to obtain a nickel-based catalyst precursor;
(4) and (3) taking the nickel-based catalyst precursor obtained in the step (3) as a nickel source, placing the nickel-based catalyst precursor and a phosphorus source in a reducing atmosphere according to a certain molar ratio for reduction, passivating the nickel-based catalyst precursor and the phosphorus source in a passivation gas at room temperature for a certain time after the reaction is finished, and preparing the supported nickel phosphide catalyst for preparing the hydrogenated petroleum resin by mechanical tabletting and molding and sieving.
2. The method of preparing a supported nickel phosphide catalyst according to claim 1, characterized in that: the molar ratio of nickel precursor, aluminum precursor, urea and ammonium salt used in the step (1) is n (Ni):n (Al): n (urea) = (1-3):1:20 (6-9).
3. The method for producing a supported nickel phosphide catalyst according to claim 1 or 2, characterized in that: the precursor of the nickel is any one of nickel nitrate, nickel acetate, nickel chloride, nickel oxalate or nickel sulfate;
the precursor of the aluminum is any one of aluminum nitrate, aluminum sulfate, aluminum chloride or aluminum hydroxide;
the ammonium salt is any one of ammonium nitrate, ammonium chloride, ammonium fluoride, ammonium sulfate, ammonium carbonate or ammonium bicarbonate.
4. The method of preparing a supported nickel phosphide catalyst according to claim 1, characterized in that: in the step (3), the reducing atmosphere is a mixed gas of hydrogen and inert gas, wherein the volume concentration of the hydrogen is 10%, and the inert gas is any one of argon or nitrogen; the temperature of the reduction is 450-750 ℃, the time is 2-8h, and the gas flow rate is kept at 50-150 ml/min.
5. The method of preparing a supported nickel phosphide catalyst according to claim 1, characterized in that: the molar ratio of the nickel source to the phosphorus source used in the step (4) is n (Ni): n (P) =1:3-3: 1.
6. The method for producing a supported nickel phosphide catalyst according to claim 1 or 5, characterized in that: the phosphorus source is any one of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, red phosphorus, ammonium hypophosphite and ammonium phosphite.
7. The method of preparing a supported nickel phosphide catalyst according to claim 1, characterized in that: in the step (4), the reducing atmosphere is a mixed gas of hydrogen and inert gas, wherein the volume concentration of the hydrogen is 10%, and the inert gas is any one of argon or nitrogen; the reduction temperature is 450-650 ℃, the time is 2-8h, and the gas flow rate is kept at 50-150 ml/min;
the passivation gas is a mixed gas of oxygen and inert gas, wherein the volume concentration of the oxygen is 0.5%, and the inert gas is any one of argon or nitrogen; the passivation time is 0.5h-2.5h, and the gas flow rate is kept at 30-70 ml/min.
8. A supported nickel phosphide catalyst prepared by the process of claim 1.
9. Use of a supported nickel phosphide catalyst as defined in claim 8 in the hydrogenation of petroleum resins to produce hydrogenated petroleum resins, wherein: the petroleum resin is C5 petroleum resin or C9 petroleum resin.
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