CN113398907A - Hydrogenation catalyst, preparation method thereof and application of hydrogenation catalyst in olefin removal of reformed C5 oil - Google Patents

Hydrogenation catalyst, preparation method thereof and application of hydrogenation catalyst in olefin removal of reformed C5 oil Download PDF

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Publication number
CN113398907A
CN113398907A CN202110763635.7A CN202110763635A CN113398907A CN 113398907 A CN113398907 A CN 113398907A CN 202110763635 A CN202110763635 A CN 202110763635A CN 113398907 A CN113398907 A CN 113398907A
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nickel
catalyst
mass
hydrogenation catalyst
hydrogenation
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CN202110763635.7A
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Chinese (zh)
Inventor
姜海英
王文静
李新
陈春雨
高天宇
赵德明
张凤岐
王耀伟
栾波
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Shandong Chambroad Petrochemicals Co Ltd
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Shandong Chambroad Petrochemicals Co Ltd
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Priority to CN202110763635.7A priority Critical patent/CN113398907A/en
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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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • B01J35/615—
    • B01J35/633—
    • 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
    • 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
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70—Catalyst aspects

Abstract

The invention provides a preparation method of a hydrogenation catalyst. Compared with the prior art, the titanium dioxide precursor is added in the carrier forming process, so that the reduction performance of nickel oxide can be changed, the olefin hydrogenation performance is improved, and the activity of the catalyst is improved; meanwhile, the pore expanding agent is added in the carrier molding process, so that the pore structure of the molecular sieve can be adjusted, the diffusion performance of a reactant product is improved, the catalytic performance of the catalyst is further improved, the molding difficulty of the catalyst can be improved, and the strength of the catalyst carrier is improved; in addition, the auxiliary agent is added in the active metal loading process, so that the higher specific surface area and pore volume of the carrier can be kept, the active center and the auxiliary agent are better combined, and the hydrogenation activity of the catalyst is further improved, so that the hydrogenation catalyst is applied to a fixed fluidized bed evaluation reforming C5 oil olefin removal process, the active component loading is low, the hydrogenation reaction condition is mild, and the stability is higher.

Description

Hydrogenation catalyst, preparation method thereof and application of hydrogenation catalyst in olefin removal of reformed C5 oil
Technical Field
The invention belongs to the technical field of hydrogenation catalysis, and particularly relates to a hydrogenation catalyst, a preparation method thereof and application thereof in removing olefin from reformed C5 oil.
Background
The reformed C5 oil contains n-pentane, isopentane and cyclopentane, and may be used widely as blowing agent, catalyst carrier for polyethylene, etc. However, the olefin hydrocarbon has a certain amount of olefin impurities in the processing process, and the olefin hydrocarbon is active and is easy to generate byproducts in the downstream processing process to influence the product performance.
The reformed C5 oil is removed olefin by two methods (1) non-hydrofining, widely applied clay or molecular sieve adsorption process, low price, easy activation, no regeneration and large environmental protection pressure; (2) a catalytic hydrogenation process. With the severe environmental protection situation, catalytic hydrogenation has become the mainstream process developed at present, and how to solve the problems of low activity, poor olefin selectivity and rapid catalyst deactivation of the present hydrogenation catalyst is the problem which needs to be solved at present.
The patent of the preparation of the hydrogenation catalyst reported at present mainly aims at the hydrogenation of the reformed raffinate oil, the required catalyst needs to saturate olefin and aromatic hydrocarbon simultaneously, the reaction conditions are harsh, and the development of the catalyst only for the hydrogenation of olefin in the reformed C5 oil is rarely reported.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a hydrogenation catalyst with good catalytic selectivity and reaction activity, a preparation method thereof, and an application thereof in olefin removal from reformed C5 oil.
The invention provides a preparation method of a hydrogenation catalyst, which comprises the following steps:
s1) mixing aluminum hydroxide dry glue, a binder, a titanium dioxide precursor and a pore-expanding agent in an acidic aqueous solution, molding, drying and roasting to obtain a catalyst carrier;
s2) dipping the catalyst carrier in a mixed solution containing a nickel source and an auxiliary agent, and then drying and roasting to obtain a hydrogenation catalyst; the auxiliary agent is soluble rare earth salt and/or soluble silicon salt.
Preferably, the mass of the acid in the acidic aqueous solution is 1.3-3.4% of the mass of the aluminum hydroxide dry glue; the mass of the binder is 2-8% of that of the aluminum hydroxide dry glue; the weight of the pore-expanding agent is 8-15% of that of the aluminum hydroxide dry glue; the mass of the titanium dioxide precursor is 5-25% of the mass of the aluminum hydroxide dry glue.
Preferably, the binder is selected from sesbania powder; the titanium dioxide precursor is selected from one or more of titanium sulfate, titanium nitrate and metatitanic acid; the pore-expanding agent is selected from one or more of polyethylene glycol, sodium stearate, phosphoric acid, carboxymethyl cellulose, soluble starch and C5 resin fine powder;
the specific surface area of the catalyst carrier is 160m2/g～240m2(ii)/g; the pore volume of the catalyst carrier is 0.43mL/g to 0.49 mL/g.
Preferably, the mass ratio of the nickel element in the mixed solution to the active element in the auxiliary agent is (5-15): (0.1-2);
the impregnation in the step S2) is equal-volume impregnation;
the mass of the nickel source is 40-70% of the mass of the catalyst carrier.
Preferably, the nickel source is selected from one or more of nickel acetate, nickel nitrate, nickel sulfate and basic nickel carbonate; the rare earth element in the soluble rare earth salt is selected from Ce and/or La.
Preferably, the nickel source is selected from one or more of nickel acetate, nickel nitrate and nickel sulfate and basic nickel carbonate; the mass ratio of one or more of nickel acetate, nickel nitrate and nickel sulfate to basic nickel carbonate is (8-12): (0.4 to 1).
Preferably, the drying temperature in the step S1) is 50-130 ℃; the drying time is 5-9 h; the roasting temperature is 500-560 ℃; roasting for 3-6 h;
the drying temperature in the step S2) is 50-130 ℃; the drying time is 6-10 h; the roasting temperature is 500-560 ℃; the roasting time is 4-8 h.
The invention also provides a hydrogenation catalyst prepared by the preparation method.
Preferably, the hydrogenation catalyst takes alumina loaded with titanium dioxide as a carrier; the carrier is provided with oxides corresponding to the loaded nickel oxide and the auxiliary agent; the mass of the aluminum oxide is 70-80% of that of the hydrogenation catalyst; the mass of the titanium dioxide is 5-25% of that of the hydrogenation catalyst; the mass of the nickel oxide is 5-15% of that of the hydrogenation catalyst; the mass of the oxide corresponding to the auxiliary agent is 0.1-2% of the mass of the hydrogenation catalyst.
The invention also provides a method for removing olefin from the reformate, which adopts the hydrogenation catalyst to carry out catalytic hydrogenation on the reformate.
The invention provides a preparation method of a hydrogenation catalyst, which comprises the following steps: s1) mixing aluminum hydroxide dry glue, a binder, a titanium dioxide precursor and a pore-expanding agent in an acidic aqueous solution, molding, drying and roasting to obtain a catalyst carrier; s2) dipping the catalyst carrier in a mixed solution containing a nickel source and an auxiliary agent, and then drying and roasting to obtain a hydrogenation catalyst; the auxiliary agent is soluble rare earth salt and/or soluble silicon salt. Compared with the prior art, the titanium dioxide precursor is added in the carrier forming process, so that the reduction performance of nickel oxide can be changed, the olefin hydrogenation performance is improved, and the activity of the catalyst is improved; meanwhile, the pore expanding agent is added in the carrier molding process, so that the pore structure of the molecular sieve can be adjusted, the diffusion performance of a reactant product is improved, the catalytic performance of the catalyst is further improved, the molding difficulty of the catalyst can be improved, and the strength of the catalyst carrier is improved; in addition, the auxiliary agent is added in the active metal loading process, so that the higher specific surface area and pore volume of the carrier can be kept, the active center and the auxiliary agent are better combined, and the hydrogenation activity of the catalyst is further improved, so that the hydrogenation catalyst is applied to a fixed fluidized bed evaluation reforming C5 oil olefin removal process, the active component loading is low, the hydrogenation reaction condition is mild, and the stability is higher.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of a hydrogenation catalyst, which comprises the following steps: s1) mixing aluminum hydroxide dry glue, a binder, a titanium dioxide precursor and a pore-expanding agent in an acidic aqueous solution, molding, drying and roasting to obtain a catalyst carrier; s2) dipping the catalyst carrier in a mixed solution containing a nickel source and an auxiliary agent, and then drying and roasting to obtain a hydrogenation catalyst; the auxiliary agent is soluble rare earth salt and/or soluble silicon salt.
In the present invention, the sources of all raw materials are not particularly limited, and they may be commercially available.
Mixing aluminum hydroxide dry glue, a binder, a titanium dioxide precursor and a pore-expanding agent in an acidic aqueous solution; the binder is preferably sesbania powder; the mass of the binder is preferably 2-8%, more preferably 3-7%, and even more preferably 4-5% of the mass of the aluminum hydroxide dry glue; the titanium dioxide precursor is preferably one or more of titanium sulfate, titanium nitrate and metatitanic acid; the mass of the titanium dioxide precursor is preferably 5-25%, more preferably 8-25%, even more preferably 10-25%, even more preferably 15-25%, and most preferably 18-21% of the mass of the aluminum hydroxide dry glue; in the embodiment provided by the invention, the mass of the titanium dioxide precursor is specifically 18%, 20% or 21% of the mass of the aluminum hydroxide dry glue; the pore-expanding agent is preferably one or more of polyethylene glycol, sodium stearate, phosphoric acid, carboxymethyl cellulose, soluble starch and C5 resin fine powder; the mass of the pore-expanding agent is preferably 8-15% of that of the aluminum hydroxide dry glue, and more preferably 8-12%; in the embodiment provided by the invention, the mass of the pore-expanding agent is specifically 10%, 11% or 12% of the mass of the aluminum hydroxide dry glue; the acid in the acidic aqueous solution is preferably nitric acid; the mass concentration of the acid in the acidic aqueous solution is preferably 1 to 5 percent, more preferably 2 to 4 percent, still more preferably 2 to 3.5 percent, and most preferably 2 to 3 percent; in the embodiment provided by the invention, the mass concentration of the acid in the acidic aqueous solution is specifically 2.7%; the mass of the acid in the acidic aqueous solution is preferably 1.3-3.4% of the mass of the aluminum hydroxide dry glue, more preferably 1.5-3%, still more preferably 1.5-2.5%, and most preferably 1.7-2%.
After being mixed evenly, the mixture is formed; in the present invention, the bar is preferably formed by a bar extruder.
Drying and roasting after molding to obtain a catalyst carrier; the drying temperature is preferably 50-130 ℃, more preferably 80-130 ℃, more preferably 100-130 ℃, and most preferably 110-120 ℃; the drying time is preferably 5-9 h, and more preferably 6-8 h; the roasting temperature is preferably 500-560 ℃, more preferably 520-560 ℃, and further preferably 540-560 ℃; the roasting time is preferably 3-6 h, and more preferably 4-5 h; the specific surface area of the resulting catalyst support is preferably 160m2/g～240m2(ii)/g; the pore volume of the catalyst carrier is preferably 0.43mL/g to 0.49 mL/g.
Dipping the catalyst carrier in a mixed solution containing a nickel source and an auxiliary agent; the nickel source is preferably one or more of nickel acetate, nickel nitrate, nickel sulfate and basic nickel carbonate, and more preferably one or more of nickel acetate, nickel nitrate and nickel sulfate and basic nickel carbonate; the mass ratio of one or more of nickel acetate, nickel nitrate and nickel sulfate to the basic nickel carbonate is preferably (8-12): (0.4 to 1), more preferably (0.5 to 12): (0.45-0.7); in the embodiment provided by the invention, the mass ratio of one or more of nickel acetate, nickel nitrate and nickel sulfate to basic nickel carbonate is specifically 10: 0.5, 8.5: 0.45, 11: 0.6 or 12: 0.7; the mass of the nickel source is preferably 40-70%, more preferably 44-65%, and even more preferably 44-63.5% of the mass of the catalyst carrier; in the examples provided by the present invention, the mass of the nickel source is specifically 52.5%, 44.75%, 58% or 63.5% of the mass of the catalyst support; the auxiliary agent is soluble rare earth salt and/or soluble silicon salt; wherein, the rare earth elements in the soluble rare earth salt are preferably Ce and/or La; the soluble rare earth salt is preferably one or more of nitrate, chloride and sulfate thereof; the mixed solution is preferably prepared according to the following method: mixing a nickel source, an auxiliary agent and water, heating and dissolving to obtain a mixed solution; the temperature of the heating solvent is preferably 30-70 ℃, and more preferably 50-60 ℃; the impregnation is preferably an equal volume impregnation.
Then drying and roasting to obtain a hydrogenation catalyst; the drying temperature is preferably 50-130 ℃, more preferably 80-130 ℃, more preferably 100-130 ℃, and most preferably 110-120 ℃; the drying time is preferably 6-10 hours, and more preferably 8-9 hours; the roasting temperature is preferably 500-560 ℃, more preferably 520-560 ℃, and further preferably 540-560 ℃; the roasting time is preferably 4-8 hours, and more preferably 4-5 hours.
The titanium dioxide precursor is added in the carrier forming process, so that the reduction performance of nickel oxide can be changed, the olefin hydrogenation performance is improved, and the activity of the catalyst is improved; meanwhile, the pore expanding agent is added in the carrier molding process, so that the pore structure of the molecular sieve can be adjusted, the diffusion performance of a reactant product is improved, the catalytic performance of the catalyst is further improved, the molding difficulty of the catalyst can be improved, and the strength of the catalyst carrier is improved; in addition, the auxiliary agent is added in the active metal loading process, so that the higher specific surface area and pore volume of the carrier can be maintained, the active center and the auxiliary agent are better combined, the dispersion degree of the active center is improved, and the hydrogenation activity of the catalyst is further improved, so that the hydrogenation catalyst is applied to a fixed fluidized bed evaluation reforming C5 oil olefin removal process, the loading capacity of the active component is low, the hydrogenation reaction condition is mild, and the stability is higher.
The invention also provides a hydrogenation catalyst prepared by the method; the hydrogenation catalyst takes alumina loaded with titanium dioxide as a carrier; the carrier is loaded with oxides corresponding to nickel oxide and an auxiliary agent; the mass of the aluminum oxide is preferably 70 to 80 percent of that of the hydrogenation catalyst; the mass of the titanium dioxide is preferably 5 to 25 percent of that of the hydrogenation catalyst; the mass of the nickel oxide is preferably 5 to 15 percent of that of the hydrogenation catalyst; the mass of the oxide corresponding to the auxiliary agent is preferably 0.1-2% of the mass of the hydrogenation catalyst; wherein the corresponding oxide of the auxiliary agent is preferably one or more of silicon oxide, cerium oxide and lanthanum oxide.
The invention also provides a method for removing olefin from the reformate, which adopts the hydrogenation catalyst to carry out catalytic hydrogenation on the reformate.
Wherein the reformate is preferably a reformate of C3-C5.
The catalytic hydrogenation preferably adopts a liquid phase reaction mode; the hydrogenation catalyst is preferably filled in a dense phase, and the reaction materials flow through the catalyst bed layer from bottom to top.
According to the invention, the hydrogenation catalyst is preferably subjected to a reduction treatment before use; the temperature of the reduction treatment is preferably 180-200 ℃; the reducing gas used for the reduction treatment is preferably hydrogen; the gas-agent ratio (volume ratio) during the reduction treatment is preferably (1200-1800): 1, more preferably (1400 to 1700): 1, and preferably (1500-1600): 1; the time for the reduction treatment is preferably 36-60 h, more preferably 40-55 h, still more preferably 45-50 h, and most preferably 48 h.
After reduction treatment, introducing reformate for catalytic hydrogenation; the temperature of the catalytic hydrogenation is preferably 50-100 ℃, more preferably 60-90 ℃, and further preferably 70-80 ℃; said catalytic hydrogenationThe pressure of (A) is preferably 1.0-1.5 MPa; the volume ratio of hydrogen to oil in the catalytic hydrogenation is preferably (1-30): 1, more preferably (1 to 20): 1, and preferably (1.5-15): 1, most preferably (1.5-10): 1; in the embodiment provided by the invention, the volume ratio of the hydrogen to the oil is specifically 3: 1. 1.5: 1.5:1 or 10: 1; the preferred volume space velocity in catalytic hydrogenation is 1-10 h-1More preferably 2 to 8 hours-1And is preferably 3 to 6 hours-1。
In order to further illustrate the present invention, the following will describe in detail a hydrogenation catalyst, its preparation method and its application in reforming C5 oil to remove olefins, which are provided by the present invention, with reference to the examples.
The reagents used in the following examples are all commercially available; in the examples and the comparative examples, the C5 reformate is hydrogenated to remove olefins; in the embodiment, the mass concentration of the concentrated nitric acid is 65-68%.
Example 1
Adding 2.5g of concentrated nitric acid into 60g of deionized water to prepare a solution, adding 100g of aluminum hydroxide dry glue, 10g of carboxymethyl cellulose, 5g of sesbania powder and 20g of metatitanic acid into the solution, uniformly mixing, extruding and molding by using a clover orifice plate, drying at 120 ℃ for 6h, and roasting at 560 ℃ for 4h to obtain the catalyst carrier.
Dissolving 10g of nickel nitrate, 0.5g of basic nickel carbonate and 0.5g of cerium nitrate in deionized water, heating to 60 ℃ to completely dissolve, adding a proper amount of deionized water to dilute to the required volume for impregnation, and impregnating 20g of catalyst carrier by using the same volume of the impregnation liquid. Drying at 120 deg.C for 8h, and calcining at 540 deg.C for 4h to obtain hydrogenation catalyst.
The hydrogenation catalyst is loaded into a 100ml fixed bed reactor for drying reduction, the reducing gas is hydrogen, the temperature is 200 ℃, the gas-agent ratio is 1500:1, and the time is 48 h. After the reduction is finished, the reaction process conditions are adjusted, the reaction temperature is 70 ℃, the reaction pressure is 1.0MPa, the hydrogen/oil volume ratio is 3:1, and the volume space velocity is 3h-1. After the reaction is stable for 24h, a sample is taken for analysis, and the results are shown in Table 1.
Example 2
Adding 2.5g of concentrated nitric acid into 60g of deionized water to prepare a solution, adding 100g of aluminum hydroxide dry glue, 10g of soluble starch, 5g of sesbania powder and 18g of metatitanic acid into the solution, uniformly mixing, extruding and molding by using a clover orifice plate, drying at 120 ℃ for 6 hours, and roasting at 560 ℃ for 4 hours to obtain the catalyst carrier.
Dissolving 8.5g of nickel nitrate, 0.45g of basic nickel carbonate and 0.5g of cerium nitrate in deionized water, heating to 60 ℃ to completely dissolve, adding a proper amount of deionized water to dilute to the required volume for impregnation, and impregnating 20g of catalyst carrier by using the same volume of the impregnation liquid. Drying at 120 deg.C for 8h, and calcining at 540 deg.C for 4h to obtain hydrogenation catalyst.
The hydrogenation catalyst is loaded into a 100ml fixed bed reactor for drying reduction, the reducing gas is hydrogen, the temperature is 200 ℃, the gas-agent ratio is 1500:1, and the time is 48 h. After the reduction is finished, the reaction process conditions are adjusted, the reaction temperature is 70 ℃, the reaction pressure is 1.0MPa, the hydrogen/oil volume ratio is 1.5:1, and the volume space velocity is 6h-1. After the reaction was stabilized for 24 hours, a sample was taken and analyzed, and the results are shown in Table 1.
Example 3
Adding 2.5g of concentrated nitric acid into 60g of deionized water to prepare a solution, adding 100g of aluminum hydroxide dry glue, 11g of carboxymethyl cellulose, 5g of sesbania powder and 21g of metatitanic acid into the solution, uniformly mixing, extruding and molding by using a clover orifice plate, drying at 120 ℃ for 6h, and roasting at 560 ℃ for 4h to obtain the catalyst carrier.
Dissolving 11g of nickel nitrate, 0.6g of basic nickel carbonate and 0.5g of cerium nitrate in deionized water, heating to 60 ℃ to completely dissolve, adding a proper amount of deionized water to dilute to the required volume for impregnation, and impregnating 20g of catalyst carrier by using the same volume of the impregnation liquid. Drying at 120 deg.C for 8h, and calcining at 540 deg.C for 4h to obtain hydrogenation catalyst.
The hydrogenation catalyst is loaded into a 100ml fixed bed reactor for drying reduction, the reducing gas is hydrogen, the temperature is 200 ℃, the gas-agent ratio is 1500:1, and the time is 48 h. After the reduction is finished, the reaction process conditions are adjusted, the reaction temperature is 90 ℃, the reaction pressure is 1.1MPa, the hydrogen/oil volume ratio is 5:1, and the volume space velocity is 3h-1. After the reaction is stable for 24h, a sample is taken for analysis, and the results are shown in Table 1.
Example 4
Adding 2.5g of concentrated nitric acid into 60g of deionized water to prepare a solution, adding 100g of aluminum hydroxide dry glue, 12g of carboxymethyl cellulose, 5g of sesbania powder and 21g of metatitanic acid into the solution, uniformly mixing, extruding and molding by using a clover orifice plate, drying at 120 ℃ for 6h, and roasting at 560 ℃ for 4h to obtain the catalyst carrier.
Dissolving 12g of nickel nitrate, 0.7g of basic nickel carbonate and 0.5g of cerium nitrate in deionized water, heating to 60 ℃ to completely dissolve, adding a proper amount of deionized water to dilute to the required volume for impregnation, and impregnating 20g of catalyst by using the same volume of the impregnation solution. Drying at 120 deg.C for 8h, and calcining at 540 deg.C for 4h to obtain hydrogenation catalyst.
The hydrogenation catalyst is loaded into a 100ml fixed bed reactor for drying reduction, the reducing gas is hydrogen, the temperature is 200 ℃, the gas-agent ratio is 1500:1, and the time is 48 h. After the reduction is finished, the reaction process conditions are adjusted, the reaction temperature is 100 ℃, the reaction pressure is 1.2MPa, the hydrogen/oil volume ratio is 10:1, and the volume space velocity is 3h-1. After the reaction is stable for 24h, a sample is taken for analysis, and the results are shown in Table 1.
Comparative example 1
Adding 2.5g of concentrated nitric acid into 60g of deionized water to prepare a solution, adding 100g of aluminum hydroxide dry glue, 5g of sesbania powder and 20g of metatitanic acid into the solution, uniformly mixing, adopting a clover orifice plate to extrude and form, drying at 120 ℃ for 6h, and roasting at 560 ℃ for 4h to obtain the catalyst carrier.
Dissolving 10g of nickel nitrate, 0.5g of basic nickel carbonate and 0.5g of cerium nitrate in deionized water, heating to 60 ℃ to completely dissolve, adding a proper amount of deionized water to dilute to the required volume for impregnation, and impregnating 20g of catalyst by using the same volume of the impregnation solution. Drying at 120 deg.C for 8h, and calcining at 540 deg.C for 4h to obtain hydrogenation catalyst.
Loading a hydrogenation catalyst into a 100ml fixed bed reactor for drying reduction, wherein the reducing gas is hydrogen, the temperature is 200 ℃, and the gas-agent ratio is 1500:1, the time is 48 h. Adjusting the reaction process conditions after the reduction is finished, wherein the reaction temperature is 70 ℃, the reaction pressure is 1.0MPa, and the volume ratio of hydrogen to oil is 3:1, volume space velocity of 3h-1. After the reaction is stable for 24h, a sample is taken for analysis, and the results are shown in Table 1.
Comparative example 2
Adding 2.5g of concentrated nitric acid into 60g of deionized water to prepare a solution, adding 100g of aluminum hydroxide dry glue into the solution, uniformly mixing 10g of starch and 5g of sesbania powder, adopting a clover orifice plate to extrude and form, drying at 120 ℃ for 6h, and roasting at 560 ℃ for 4h to obtain the catalyst carrier.
Dissolving 8.5g of nickel nitrate, 0.45g of basic nickel carbonate and 0.5g of cerium nitrate in deionized water, heating to 60 ℃ to completely dissolve, adding a proper amount of deionized water to dilute to the required volume for impregnation, and impregnating 20g of catalyst carrier by using the impregnation solution. Drying at 120 deg.C for 8h, and calcining at 540 deg.C for 4h to obtain hydrogenation catalyst.
The hydrogenation catalyst is loaded into a 100ml fixed bed reactor for drying reduction, the reducing gas is hydrogen, the temperature is 200 ℃, the gas-agent ratio is 1500:1, and the time is 48 h. After the reduction is finished, the reaction process conditions are adjusted, the reaction temperature is 70 ℃, the reaction pressure is 1.0MPa, the hydrogen/oil volume ratio is 1.5:1, and the volume space velocity is 6h-1. After the reaction is stable for 24h, a sample is taken for analysis, and the results are shown in Table 1.
Comparative example 3
Adding 2.5g of concentrated nitric acid into 60g of deionized water to prepare a solution, adding 100g of aluminum hydroxide dry glue, 11g of carboxymethyl cellulose, 5g of sesbania powder and 21g of metatitanic acid into the solution, uniformly mixing, extruding and molding by using a clover orifice plate, drying at 120 ℃ for 6h, and roasting at 560 ℃ for 4h to obtain the catalyst carrier.
Dissolving 11g of nickel nitrate and 0.6g of basic nickel carbonate in deionized water, heating to 60 ℃ to completely dissolve, adding a proper amount of deionized water to dilute to the required volume for impregnation, and impregnating 20g of catalyst carrier by using the impregnation solution. Drying at 120 deg.C for 8h, and calcining at 540 deg.C for 4h to obtain hydrogenation catalyst.
The hydrogenation catalyst is loaded into a 100ml fixed bed reactor for drying reduction, the reducing gas is hydrogen, the temperature is 200 ℃, the gas-agent ratio is 1500:1, and the time is 48 h. After the reduction is finished, the reaction process conditions are adjusted, the reaction temperature is 90 ℃, the reaction pressure is 1.1MPa, the hydrogen/oil volume ratio is 5:1, and the volume space velocity is 3h-1. After the reaction is stable for 24h, a sample is taken for analysis, and the results are shown in Table 1.
Comparative example 4
Adding 2.5g of concentrated nitric acid into 60g of deionized water to prepare a solution, adding 100g of aluminum hydroxide dry glue, 11g of carboxymethyl cellulose, 5g of sesbania powder, 0.5g of cerium nitrate and 21g of metatitanic acid into the solution, uniformly mixing, extruding and molding by using a clover orifice plate, drying at 120 ℃ for 6h, and roasting at 560 ℃ for 4h to obtain the catalyst carrier.
Dissolving 11g of nickel nitrate and 0.6g of basic nickel carbonate in deionized water, heating to 60 ℃ to completely dissolve, adding a proper amount of deionized water to dilute to the required volume for impregnation, and impregnating 20g of catalyst carrier by using the same volume of the impregnation solution. Drying at 120 deg.C for 8h, and calcining at 540 deg.C for 4h to obtain hydrogenation catalyst.
The hydrogenation catalyst is loaded into a 100ml fixed bed reactor for drying reduction, the reducing gas is hydrogen, the temperature is 200 ℃, the gas-agent ratio is 1500:1, and the time is 48 h. After the reduction is finished, the reaction process conditions are adjusted, the reaction temperature is 90 ℃, the reaction pressure is 1.1MPa, the hydrogen/oil volume ratio is 5:1, and the volume space velocity is 3h-1. After the reaction is stable for 24h, a sample is taken for analysis, and the results are shown in Table 1.
TABLE 1 reaction conditions and results for different catalysts
Figure BDA0003149969290000091
The catalyst carriers obtained in examples 1 to 4 and comparative examples 1 to 4 were analyzed by a Quadrasorb evoTM full-automatic specific surface and porosity analyzer of Quantachrome company, usa, using a GB/T21650.2-2008 method, and specific surface areas and pore volumes thereof were obtained as shown in table 2.
TABLE 2 results of specific surface area and pore volume test of catalyst carrier
Figure BDA0003149969290000101

Claims (10)

1. A method for preparing a hydrogenation catalyst, comprising:
s1) mixing aluminum hydroxide dry glue, a binder, a titanium dioxide precursor and a pore-expanding agent in an acidic aqueous solution, molding, drying and roasting to obtain a catalyst carrier;
s2) dipping the catalyst carrier in a mixed solution containing a nickel source and an auxiliary agent, and then drying and roasting to obtain a hydrogenation catalyst; the auxiliary agent is soluble rare earth salt and/or soluble silicon salt.
2. The preparation method according to claim 1, wherein the mass of the acid in the acidic aqueous solution is 1.3-3.4% of the mass of the aluminum hydroxide dry glue; the mass of the binder is 2-8% of that of the aluminum hydroxide dry glue; the weight of the pore-expanding agent is 8-15% of that of the aluminum hydroxide dry glue; the mass of the titanium dioxide precursor is 5-25% of the mass of the aluminum hydroxide dry glue.
3. The method of claim 1, wherein the binder is selected from sesbania powder; the titanium dioxide precursor is selected from one or more of titanium sulfate, titanium nitrate and metatitanic acid; the pore-expanding agent is selected from one or more of polyethylene glycol, sodium stearate, phosphoric acid, carboxymethyl cellulose, soluble starch and C5 resin fine powder;
the specific surface area of the catalyst carrier is 160m2/g～240m2(ii)/g; the pore volume of the catalyst carrier is 0.43mL/g to 0.49 mL/g.
4. The preparation method according to claim 1, wherein the mass ratio of the nickel element in the mixed solution to the active element in the auxiliary agent is (5-15): (0.1-2);
the impregnation in the step S2) is equal-volume impregnation;
the mass of the nickel source is 40-70% of the mass of the catalyst carrier.
5. The preparation method according to claim 1, wherein the nickel source is selected from one or more of nickel acetate, nickel nitrate, nickel sulfate and basic nickel carbonate; the rare earth element in the soluble rare earth salt is selected from Ce and/or La.
6. The method of claim 6, wherein the nickel source is selected from the group consisting of nickel acetate, one or more of nickel nitrate and nickel sulfate, and basic nickel carbonate; the mass ratio of one or more of nickel acetate, nickel nitrate and nickel sulfate to basic nickel carbonate is (8-12): (0.4 to 1).
7. The method according to claim 1, wherein the temperature for drying in the step S1) is 50 ℃ to 130 ℃; the drying time is 5-9 h; the roasting temperature is 500-560 ℃; roasting for 3-6 h;
the drying temperature in the step S2) is 50-130 ℃; the drying time is 6-10 h; the roasting temperature is 500-560 ℃; the roasting time is 4-8 h.
8. A hydrogenation catalyst prepared by the method of any one of claims 1 to 7.
9. The hydrogenation catalyst according to claim 8, wherein the hydrogenation catalyst uses alumina loaded with titania as a carrier; the carrier is provided with oxides corresponding to the loaded nickel oxide and the auxiliary agent; the mass of the aluminum oxide is 70-80% of that of the hydrogenation catalyst; the mass of the titanium dioxide is 5-25% of that of the hydrogenation catalyst; the mass of the nickel oxide is 5-15% of that of the hydrogenation catalyst; the mass of the oxide corresponding to the auxiliary agent is 0.1-2% of the mass of the hydrogenation catalyst.
10. A method for removing olefins from reformate is characterized in that the reformate is subjected to catalytic hydrogenation by using the hydrogenation catalyst prepared by the preparation method of any one of claims 1 to 7 or the hydrogenation catalyst of claim 8 or 9.
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CN114870890A (en) * 2022-03-07 2022-08-09 宁波中金石化有限公司 Catalyst for deeply removing olefin in aromatic hydrocarbon and preparation method thereof

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