CN116060022A - Hydrogenation catalyst and production method thereof - Google Patents

Hydrogenation catalyst and production method thereof Download PDF

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Publication number
CN116060022A
CN116060022A CN202111268705.8A CN202111268705A CN116060022A CN 116060022 A CN116060022 A CN 116060022A CN 202111268705 A CN202111268705 A CN 202111268705A CN 116060022 A CN116060022 A CN 116060022A
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solution
reaction
hydrogenation
reaction kettle
catalyst
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CN202111268705.8A
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Chinese (zh)
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吕振辉
朱慧红
金浩
杨光
时一鸣
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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Priority to CN202111268705.8A priority Critical patent/CN116060022A/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
    • 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
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/883—Molybdenum and nickel
    • B01J35/40—
    • B01J35/615—
    • B01J35/638—
    • B01J35/651—
    • 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
    • C10G45/06—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 nickel or cobalt metal, or compounds thereof
    • C10G45/08—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 nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention discloses a hydrogenation catalyst and a production method thereof. The method comprises the following steps: (1) Adding an organic solvent, a polar metal seed crystal, an acidic solution I and an alkaline solution I into a first reaction kettle in parallel flow for neutralization and gel formation to obtain a generated liquid I; (2) The obtained generated liquid I enters a settling tank for settling separation to obtain an upper layer, namely an organic solvent, and a lower layer, namely sol II; (3) The sol II and the acid solution I or the alkaline solution II flow into a second reaction kettle in parallel to be neutralized and gel to obtain a generated liquid III; (4) The generated liquid III enters an aging kettle, and a polymerization monomer and an initiator are added, and then an aging polymerization reaction is carried out; (5) Drying and roasting the ageing material obtained in the step (4) to obtain the hydrogenation catalyst; wherein the alumina and the hydrogenation active metal are introduced into the hydrogenation catalyst from an acidic solution and/or a basic solution. The hydrogenation catalyst has the characteristics of large particle size, concentrated distribution, high specific surface area, large pore volume, large pore diameter and the like, and can be used as a hydrogenation catalyst for poor raw materials.

Description

Hydrogenation catalyst and production method thereof
Technical Field
The invention relates to the field of hydrogenation catalyst preparation, in particular to a method for continuously producing a macroporous hydrogenation catalyst.
Background
At present, the production mode of pseudo-boehmite mainly comprises an inorganic aluminum salt method and an organic aluminum salt method, and batch kettle reactors are adopted in the production process. Pseudo-boehmite is mainly prepared by a precipitation mechanism, wherein precipitation refers to a process of generating insoluble substances through chemical reaction in a liquid phase and forming a new solid phase to be settled out of the liquid phase. From classical theoretical analysis of precipitation, the precipitate formation process is divided into: (1) nucleation: because of the continuous collision motion of molecules or ions, the molecules in the local area are clustered, the aggregation is not only due to the collision among moving particles in the solution, but also the mutual adhesion of the moving particles through weak acting force (Van der Waals force), chemical bonds are generated through crystals, and the aggregation is solidified; (2) Crystal nucleus growth: cluster molecular particles are contacted with each other and combined to grow; wherein, the colloid is uniform, the particles are tiny, and the method has very strong effect on nucleation and crystal growth.
The coprecipitation method is a typical method for preparing aluminum hydroxide. The method is to prepare aluminum salt from raw materials by taking water as a medium, and then to control certain solution concentration, solution flow rate, temperature and reaction time, and to prepare the aluminum hydroxide by acid/alkali neutralization. However, the initial nuclei Al (OH) in the coprecipitation process 3 The polymer has complex structure, small molecular polarity and extremely small solubility, so that the aggregation rate is far higher than the orientation rate, and amorphous gelatinous precipitation is easy to generate, so that the polymer has low crystallinity, incomplete crystal form and unsatisfactory pore structure. Accordingly, the same problems exist with catalysts prepared by the coprecipitation method.
CN103787390a discloses a preparation method of pseudo-boehmite, comprising the following steps: (1) Performing gel forming reaction on the acidic aluminum salt solution and the alkaline solution, and then aging; the glue forming reaction and aging are carried out under the condition of ultrasonic radiation, ultrasonic waves with different frequencies are adopted in the glue forming reaction process and the aging process, and ultrasonic waves with the frequency of 10-160 kHz are adopted in the glue forming reaction process; the aging process adopts ultrasonic frequency which is 1-50 kHz higher than that of the gel forming reaction process; (2) filtering and washing the aged materials; (3) And (3) drying the material obtained in the step (2) to obtain pseudo-boehmite. The method is to prepare pseudo-boehmite by controlling the grain size by using ultrasonic waves with different frequencies during the gelling and aging.
CN101890379a discloses a bulk catalyst and a process for preparing the same. The bulk phase catalyst is obtained by respectively obtaining inorganic oxide precursor hydroxide gel and active metal hydroxide gel as raw materials, molding and roasting. In the preparation process of the bulk phase catalyst, as the hydroxide gel contains a surfactant and a hydrocarbon component, nano oxide particles formed after the polymerized hydroxide is dehydrated still have a rod-shaped basic structure and are randomly stacked into a framework structure after being molded and baked.
In the prior art, although the grain size is controlled by different methods so as to prepare hydrogenation catalysts with different pore structures and properties, how to prepare macroporous hydrogenation catalysts with high specific surface area is an important subject of continuous and diligent research in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a hydrogenation catalyst and a production method thereof, in particular to a method for continuously producing a macroporous hydrogenation catalyst. The hydrogenation catalyst has the characteristics of large particle size, concentrated distribution, high specific surface area, large pore volume, large pore diameter and the like, and can be used as a poor-quality raw material hydrogenation catalyst.
The first aspect of the present invention provides a method for producing a hydrogenation catalyst, comprising:
(1) Adding an organic solvent, a polar metal seed crystal, an acidic solution I and an alkaline solution I into a first reaction kettle in parallel flow for neutralization and gel formation to obtain a generated liquid I;
(2) The obtained generated liquid I enters a settling tank for settling separation to obtain an upper layer, namely an organic solvent, and a lower layer, namely sol II;
(3) The sol II and the acid solution II or the alkaline solution II flow in parallel and enter a second reaction kettle to be neutralized and gel to obtain a generated liquid III;
(4) The generated liquid III enters an aging kettle, and a polymerization monomer and an initiator are added, and then an aging polymerization reaction is carried out;
(5) Drying and roasting the ageing material obtained in the step (4) to obtain the hydrogenation catalyst;
wherein the components of the acidic solution I and the alkaline solution I introduced into the hydrogenation catalyst comprise aluminum oxide and hydrogenation active metals, namely first aluminum oxide and first hydrogenation active metals, and the components of the acidic solution II or the alkaline solution II introduced into the hydrogenation catalyst comprise aluminum oxide and hydrogenation active metals, namely second aluminum oxide and second hydrogenation active metals.
In the method, the production method of the hydrogenation catalyst is preferably carried out in a continuous mode, wherein a plurality of settling tanks used in the step (2) and a plurality of ageing tanks used in the step (4) can be arranged, and the continuous production is switched.
In the method of the invention, when the hydrogenation catalyst is continuously produced, preferably, the first reaction kettle in the step (1) is operated in a mode of discharging the generated liquid I out of the first reaction kettle in an overflow mode. When the first reaction kettle is started, preferably, an organic solvent and a polar metal seed crystal are firstly added as base solution, and then an acidic solution I and an alkaline solution I are added in parallel flow for neutralization and gel formation until the generated solution I starts to be discharged from the first reaction kettle. Wherein the addition amount of the organic solvent in the base solution is 1/5-1/3 of the actual effective use volume of the first reaction kettle, and before the generated solution I is discharged out of the first reaction kettle, the acid solution I and the alkaline solution I in the first reaction kettle are prepared by using Al 2 O 3 And the addition amount of the polar metal salt seed crystal is 0.1-5.0%, preferably 0.2-2.0% based on the total mass of the hydrogenation active metal oxide.
In the method of the invention, when the hydrogenation catalyst is continuously produced, preferably, the second reaction kettle in the step (3) adopts an overflow type operation mode for discharging the generated liquid III out of the second reaction kettle. When the second reaction kettle is started, preferably, the bottom water is added first, then the sol II and the acidic solution II or the alkaline solution II are added in parallel flow for neutralization and gel formation, and the generated liquid III starts to be discharged from the second reaction kettle. Wherein, the addition amount of the bottom water is 1/7-1/2, preferably 1/6-1/3 of the actual effective use volume of the second reaction kettle.
In the method of the present invention, the organic solvent in the step (1) is an organic substance that is not or slightly soluble in water, and the organic substance may be one or more of alkane, alkene, organic alcohol, organic acid, etc., preferably, the carbon number of the organic substance is 5-12. Wherein the molecular structural formula of alkane is C n H 2n+2 (n is more than or equal to 5, preferably n=5-12), and at least one of pentane, hexane, dodecane and the like can be selected; the molecular structural formula of the olefin is C n H 2n (n is more than or equal to 5, preferably n=5-12), and at least one of pentene, hexene and the like can be selected; the organic alcohol is at least one selected from organic monohydric alcohol and organic polyalcohol, wherein the molecular structural formula of the organic monohydric alcohol is C n H 2n+2 O (n is more than or equal to 6, preferably n=6-12), and at least one of n-hexanol, n-heptanol and the like can be selected; wherein the molecular structural formula of the polyol is C n H 2n+2-x (OH) x (n is more than or equal to 6, preferably n=6-12, and x is more than or equal to 3), and at least one of polyhydric alcohols such as pentaerythritol, glycerol, trimethylolethane, xylitol, sorbitol and the like can be selected; the organic acid may be at least one of aliphatic or aromatic carboxylic acid, such as benzoic acid.
In the method of the invention, the polar metal seed crystal is selected from metal halogen compounds, and at least one of metal sulfides is preferably one or more of AgCl, znS, cuS or HgS.
In the method of the invention, the operation conditions of the first reaction kettle in the step (1) are as follows: the temperature is-15 to 15 ℃, the pressure is 1 to 20MPa, and preferably 4 to 10MPa. The pressure atmosphere can be one or more of air, nitrogen or inert gas. The reaction conditions for neutralizing and gelling in the step (1) are as follows: the pH value is 2 to 6, preferably 2 to 5, and the reaction time is 10 to 180 minutes, preferably 10 to 60 minutes (when continuous production is employed, the reaction time is the residence time of the acidic solution I and the alkaline solution I into the first reaction vessel). The neutralization and gelling reaction is preferably carried out under stirring at a rate of from 100 to 500rad/min, preferably from 150 to 500rad/min.
In the method of the invention, the components of the acid solution I and the alkaline solution I introduced into the hydrogenation catalyst comprise aluminum oxide and hydrogenation active metals, namely first aluminum oxide and first hydrogenation active metals, and the components of the acid solution II or the alkaline solution II introduced into the hydrogenation catalyst comprise aluminum oxide and hydrogenation active metals, namely second aluminum oxide and second hydrogenation active metals. The hydrogenation active metal is at least one of the metals of the VIB group and the VIII group, the metal of the VIB group is preferably at least one of Mo and W, and the metal of the VIII group is preferably at least one of Ni and Co. The first hydrogenation active metal and the second hydrogenation active metal may be the same or different. The mass ratio of the first alumina to the second alumina is 1:5-5:1. The mass ratio of the first hydrogenation active metal to the second hydrogenation active metal in terms of oxide is 1:10-10:1. Preferably, the first hydrogenation active metal is selected from a first group VIB metal and a first group VIII metal, the second hydrogenation active metal is selected from a second group VIB metal and a second group VIII metal, further preferably, the mass ratio of the first group VIB metal to the second group VIB metal in terms of oxide is 1:8 to 8:1, and the mass ratio of the first group VIII metal to the second group VIII metal in terms of oxide is 1:8 to 8:1.
In the process of the present invention, the acidic solution I and the basic solution I in the neutralization gel in the step (1) may be selected according to a conventional coprecipitation method. The acidic solution I and the alkaline solution I may be aqueous solutions. The first alumina source is selected from at least one of an acidic aluminum source and a basic aluminum source, and can be introduced into the hydrogenation catalyst along with the acidic solution or the basic solution according to the acid-base property of the solution. The acidic aluminum source may be selected from AlCl 3 、Al 2 (SO 4 ) 3 Or Al (NO) 3 One or more of them, preferably Al 2 (SO 4 ) 3 、AlCl 3 One or more of them. The alkaline aluminum source may be selected from NaAlO 2 Or KAlO 2 One or both, preferably NaAlO 2 . The first hydrogenation active metal source may be introduced into the hydrogenation catalyst with an acidic or basic solution as determined by the acid base of its solution. The first hydrogenation active metal source is, for example, ammonium molybdate or molybdic acid, sodium tungstate, ammonium metatungstate or tungstic acid is used as the tungsten source, one or more of nickel nitrate, nickel chloride and basic nickel carbonate is used as the nickel source, and one or more of cobalt nitrate, cobalt chloride and basic cobalt carbonate is used as the cobalt source. The concentration of the acidic solution I is 10-100 g/100mL in terms of oxide, and the concentration of the alkaline solution I is 10-100 g/100mL in terms of oxide. For example, the acidic solution I is an acidic aluminum source solution, and the alkaline solution I is an alkaline active metal solution or a mixture of an alkaline active metal solution and an alkaline aluminum source solution; for another example, the acidic solution I is an acidic active metal solution, and the alkaline solution I is an alkaline aluminum source solution or a mixture of an alkaline active metal solution and an alkaline aluminate solution; for another example, the acidic solution I is a mixed solution of an acidic aluminum source solution and an acidic active metal solution, and the basic solution I is a basic active metal solution or a mixed solution of a basic active metal solution and a basic aluminum source solution or a basic aluminum source solution.
In the method of the invention, the organic solvent and the polar metal seed crystal are added into the first reaction kettle in parallel, wherein the adding rate of the organic solvent is the ratio of the adding rate of the acid solution I to the adding rate of the alkaline solution I in terms of volume of the two to be 0.1:1 to 10:1, preferably 0.1:1 to 5:1, the addition rate of the polar metal seed crystal is that the acid solution I and the alkaline solution I are added with Al 2 O 3 And the mass of the hydrogenation active metal oxide is 0.1 to 10%, preferably 0.2 to 5%.
In the method of the invention, the particle size distribution of the sol II obtained in the step (2) is as follows: the proportion of the crystal grains with the grain diameter smaller than 100nm is 0.5-5.0%, the proportion of the crystal grains with the grain diameter of 100-200 nm is 2-5%, and the proportion of the crystal grains with the grain diameter larger than 200nm is 90-95%.
In the method of the present invention, the operating conditions of the settling tank of step (2) are as follows: the temperature is-15 to 15 ℃, the pressure is 1 to 20MPa, and preferably 4 to 10MPa.
In the method, after the sedimentation in the step (2), the organic solvent on the upper layer can be recycled to the first reaction kettle for continuous use.
In the method of the invention, the operation conditions of the second reaction kettle in the step (3) are as follows: the temperature is 100 to 300 ℃, preferably 100 to 200 ℃, and the pressure is 5 to 20MPa, preferably 10 to 20MPa. Preferably, the operating pressure of the second reactor is at least 1MPa, more preferably at least 2MPa, higher than the operating pressure of the first reactor. The reaction conditions for neutralizing and gelling in the step (3) are as follows: the pH value is 7 to 12, preferably 7.5 to 10.0, and the reaction time is 10 to 180 minutes, preferably 10 to 120 minutes (when continuous production is employed, the reaction time is the residence time of the sol II and the acidic solution II or the alkaline solution II into the second reaction vessel). The neutralization and gelling reaction is preferably carried out under stirring at a rate of from 100 to 500rad/min, preferably from 200 to 500rad/min.
In the process of the present invention, the acidic solution II and the alkaline solution II in the neutralization gel in the step (3) may be selected according to a conventional coprecipitation method. The acidic solution II and the alkaline solution II can be aqueous solutions. The second alumina source is at least one selected from an acidic aluminum source and a basic aluminum source, and can be introduced into the hydrogenation catalyst along with the acidic solution or the basic solution according to the acid-base property of the solution. The acidic aluminum source may be selected from AlCl 3 、Al 2 (SO 4 ) 3 Or Al (NO) 3 One or more of them, preferably Al 2 (SO 4 ) 3 、AlCl 3 One or more of them. The alkaline aluminum source may be selected from NaAlO 2 Or KAlO 2 One or both, preferably NaAlO 2 . The second hydrogenation active metal source may be introduced into the hydrogenation catalyst with the acidic or basic solution as determined by the acid base of its solution. The second hydrogenation active metal source is, for example, ammonium molybdate, molybdic acid or molybdenum oxide, the tungsten source is sodium tungstate, ammonium metatungstate or tungstic acid, the nickel source is one or more of nickel nitrate, nickel chloride and basic nickel carbonate, and the cobalt source is one or more of cobalt nitrate, cobalt chloride and basic cobalt carbonate. The concentration of the acid solution II is 10-100 g/100mL in terms of oxide, and the concentration of the alkaline solution II is in terms of oxide Is 10-100 g/100mL. For example, the acidic solution II is an acidic aluminum source solution, and the alkaline solution II is an alkaline active metal solution or a mixture of an alkaline active metal solution and an alkaline aluminum source solution; for another example, the acidic solution II is an acidic active metal solution, and the alkaline solution II is an alkaline aluminum source solution or a mixture of the alkaline active metal solution and the alkaline aluminum source solution; for another example, the acidic solution II is a mixed solution of an acidic aluminum source solution and an acidic active metal solution, and the alkaline solution II is an alkaline active metal solution or a mixed solution of an alkaline active metal solution and an alkaline aluminum source solution or an alkaline aluminum source solution.
In the method of the invention, the polymer monomer in the step (4) is at least one of organic alcohol or organic acid; the organic alcohol is at least one of monohydric alcohol or polyhydric alcohol, and the monohydric alcohol is C 6 ～C 10 The polyhydric alcohol is one or more of ethylene glycol, pentaerythritol, 2-propylene glycol, 1, 4-butanediol, neopentyl glycol, sorbitol, dipropylene glycol, glycerol, xylitol, trimethylolpropane, diethylene glycol and the like; the organic acid is one or more of tartaric acid, oxalic acid, malic acid, citric acid, acetic acid, oxalic acid, succinic acid, ascorbic acid, benzoic acid, salicylic acid, caffeic acid, aspartic acid, glutamic acid, glycine, alanine, valine, leucine, isoleucine, phenylalanine, proline, tryptophan, serine, tyrosine, cysteine, methionine, asparagine, glutamine or threonine and the like.
In the method of the invention, the initiator in the step (4) can be at least one selected from peroxy compound initiator, azo initiator, redox initiator and the like according to the reaction requirement. Wherein the peroxide initiator is selected from one or more of benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyvalerate, methyl ethyl ketone peroxide, cyclohexanone peroxide, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, ammonium persulfate and potassium persulfate; azo initiators are selected from azobisisobutyronitrile and/or azobisisoheptonitrile, preferably azobisisobutyronitrile. The redox initiator is selected from benzoyl peroxide/sucrose, t-butyl hydroperoxide/diabolo, t-butyl hydroperoxide/sodium metabisulfite, benzoyl peroxide/N, N-dimethylaniline, ammonium persulfate/sodium bisulfite, potassium persulfate/sodium bisulfite, hydrogen peroxide/tartaric acid, hydrogen peroxide/sodium metabisulfite, ammonium persulfate/ferrous sulfate, hydrogen peroxide/ferrous sulfate, benzoyl peroxide/N, one of N-diethylaniline, benzoyl peroxide/ferrous pyrophosphate, potassium persulfate/silver nitrate, persulfate/thiol, cumene hydroperoxide/ferrous chloride, potassium persulfate/ferrous chloride, hydrogen peroxide/ferrous chloride, cumene hydroperoxide/tetraethyl imine, etc.; tert-butyl hydroperoxide/sodium metabisulfite is preferred.
In the method of the present invention, the aging polymerization reaction conditions in the step (4) are as follows: the temperature is 200-400 ℃, the pressure is 15-20.0 MPa, and the time is 10-180 min; the reaction is carried out under stirring conditions, preferably at a stirring speed of 500 to 800r/min.
In the process of the present invention, the polymerization degree of the polymer formed by the polymerization in the step (4) is 5 to 100, preferably 5 to 80, and the polymer can be controlled by selecting an initiator and adjusting the reaction conditions.
In the method of the present invention, the product liquid III in the step (4) is obtained by using Al 2 O 3 And a molar ratio of hydrogenation active metal oxide to polymer monomer of 20:1 to 1:1, preferably 15:1 to 1:1. the addition amount of the initiator is 0.01-3.5% of the mass of the polymer monomer.
In the method of the present invention, the aging polymerization reaction conditions of step (4): the temperature is 200-400 ℃, the pressure is 15-20.0 MPa, the aging time is 100-360 min, and the preferable time is 180-350 min; the aging is carried out under stirring conditions, preferably at a stirring speed of 500 to 800r/min.
In the method of the invention, the drying temperature in the step (5) is 100-450 ℃, preferably 150-400 ℃ and the drying time is 1-10 hours, and the drying mode can be flash evaporation drying, cyclone drying, oven drying, spray drying and the like. The roasting temperature is 300-800 ℃, preferably 350-550 ℃, the roasting time is 2-5 hours, preferably 2-4 hours, and the roasting atmosphere is one or more of air, nitrogen, water vapor and the like.
In a second aspect, the present invention provides a hydrogenation catalyst produced by the above process.
The hydrogenation catalyst provided by the invention comprises alumina and hydrogenation active metal, and has the following properties: the pore volume is 1.5-2.0 mL/g; specific surface area of 300-450 m 2 The pore size of the polymer/g may be less than or equal to 150nm, preferably 190 to 300nm.
The particle size distribution of the hydrogenation catalyst provided by the invention is as follows: the proportion of the grains with the grain diameter smaller than 250 mu m is 0.5% -5.0%, the proportion of the grains with the grain diameter of 250-350 mu m is 2.0% -5.0%, and the proportion of the grains with the grain diameter larger than 350 mu m is 90.0% -95.0%.
In the hydrogenation catalyst of the invention, the hydrogenation active metal is at least one metal selected from the group consisting of group VIB and group VIII metals. The group VIB metal is at least one selected from Mo and W. The VIII group metal is selected from at least one of Ni and Co.
In the hydrogenation catalyst of the present invention, the mass content of the hydrogenation active metal in terms of oxide is 10% to 80%, preferably 40% to 70%, and the mass content of alumina is 20% to 90%, preferably 30% to 60%, based on the mass of the catalyst.
In the hydrogenation catalyst of the present invention, preferably, the mass content of the group VIB in terms of oxide is 5% to 70%, preferably 35% to 65%, the mass content of the group VIII metal in terms of oxide is 5% to 50%, preferably 5% to 30%, and the mass content of alumina is 20% to 90%, preferably 30% to 60%, based on the mass of the catalyst.
The third aspect of the invention provides application of the upper hydrogenation catalyst in the hydrogenation of inferior heavy oil.
Compared with the prior art, the invention has the following beneficial effects:
1. in the method for producing the catalyst, firstly, an organic solvent which is not mutually soluble with water is used as a reaction medium, polar metal salt is used as a seed crystal, neutralization reaction is carried out under higher pressure and lower reaction temperature, on one hand, the generated sol-gel particles are wrapped by hydrophilic hydroxyl on the surface, all sol-gel particles in the organic solvent which is not mutually soluble with water can not adhere, under the action of the polar seed crystal, the characteristics of small molecular weight and large orientation rate are utilized, so that crystal form precipitation or colloidal particles with crystal structure are easy to form, on the other hand, under higher pressure and lower temperature, the Brownian movement of sol-gel molecules or ions is reduced, the aggregation into cluster groups due to continuous collision of the particles is reduced, the amorphous particles are dissolved under the lower pH value, namely the acidic condition, the generated complete particles are kept, and then the crystal particles with complete crystal form are suitable and complete under the high temperature, high pressure and high pH value, namely the alkaline condition, the particle size distribution of the obtained sol-gel particles with complete crystal form is easy to form large particle size through acceleration, and the particle size distribution is easy to form large particles with large particle size distribution.
2. In the method for producing the catalyst, the organic solvent can be complexed with the metal particles to form metal chelate in the coprecipitation process, the particles are further enlarged in the polymerization aging process in a polymerization mode, and finally penetrating pore channels with space network structures are formed in the roasting process, so that a large amount of chelated active metals are exposed on the one hand, the metal utilization rate of the chelated active metals is improved, and a wider diffusion channel is provided for macromolecular reaction on the other hand, so that the activity of the catalyst is greatly improved.
3. The hydrogenation catalyst provided by the invention has the characteristics of large surface area, large pore volume, concentrated particle size distribution and the like, and is particularly suitable for being used as a hydrogenation catalyst for hydrotreating heavy inferior raw materials, such as residual oil, wax oil, coal tar, coal liquefaction oil and the like.
Drawings
FIG. 1 is a schematic flow diagram of a continuous production of a hydrogenation catalyst;
wherein, the reference numerals are as follows: i-a first reaction kettle; II. III-a settling tank; IV-a second reaction kettle; v-aging the kettle; a-an acidic solution I; b-alkaline solution I; c-polar metal seed; d-an organic solvent; e-setting tank II control valve; f-setting tank III control valve; g-sol II; h-acidic solution II or alkaline solution II; i-a second reaction kettle drain valve; j-overflow liquid; k-ageing kettle drain valve, L-polymerization monomer and initiator.
Detailed Description
The method for preparing the hydrogenation catalyst of the present invention will be described in more detail by way of specific examples. The examples are merely illustrative of specific embodiments of the method of the invention and do not constitute a limitation on the scope of the invention.
The flow (shown in figure 1) for continuously producing hydrogenation catalyst provided by the invention comprises the following steps:
(1) Adding an organic solvent D, a polar metal seed crystal C, an acidic solution IA and an alkaline solution IB into a first reaction kettle I in parallel flow for neutralization and gel formation to obtain a generated liquid I;
(2) The obtained generated liquid I enters a settling tank II or III for settling, and is separated through a settling tank II control valve E or a settling tank III control valve F to obtain a lower layer, namely sol IIG, and an upper layer, namely organic solvent;
(3) The sol II and the acid solution II or the alkaline solution IIH flow in parallel and enter a second reaction kettle IV to carry out neutralization and gel forming reaction to obtain a generated liquid III;
(4) The generated liquid III passes through a second reaction kettle liquid discharge valve I, overflow liquid J enters an ageing kettle V, and polymer monomers and an initiator are added, and then ageing polymerization reaction is carried out;
(5) The ageing material obtained in the step (4) is discharged through the ageing kettle drain valve K, and then dried and roasted to obtain the hydrogenation catalyst;
Wherein the components of the acidic solution I and the alkaline solution I introduced into the hydrogenation catalyst comprise first alumina and first hydrogenation active metals, and the components of the acidic solution II or the alkaline solution II introduced into the hydrogenation catalyst comprise second alumina and second hydrogenation active metals.
In the present invention, "first", "second", etc. are used to distinguish between two different elements or portions, such as a first reaction vessel and a second reaction vessel, and are not intended to limit the specific location or relative relationship. Alternatively, "first", "second", etc. are introduced to distinguish between two different steps, such as a first alumina and a second alumina, and the first hydrogenation-active metal and the second hydrogenation-active metal are not intended to limit the specific composition thereof. In other words, in some embodiments, the terms "first," "second," etc. may also be interchanged with one another.
In the invention, the specific surface area and the pore volume are measured by adopting a low-temperature liquid nitrogen adsorption method; the particle size distribution was measured using a laser particle size distribution meter.
In the examples and the comparative examples of the present invention, the Mo-Ni acidic active metal solution is a mixed solution of Mo-Ni-and is prepared from molybdenum oxide, basic nickel carbonate and phosphoric acid, wherein MoO 3 And NiO in a mass ratio of 4:1, the concentration of the Mo-Ni acidic active metal solution being MoO 3 And a NiO meter; the Mo-Ni alkaline active metal solution is Mo-Ni-NH 3 Is prepared from ammonium molybdate, nickel nitrate and ammonia water, wherein MoO 3 And NiO in a mass ratio of 4:1, the concentration of the Mo-Ni alkaline active metal solution being MoO 3 And a NiO meter.
Example 1
The flow of the hydrogenation catalyst produced in this example is shown in FIG. 1.
2L of n-hexanol was added as a reaction medium to 10L of the first reaction vessel I, 1.6g of AgCl was added, the pressure of the first reaction vessel I was adjusted to 5MPa, the temperature was 10℃and the atmosphere was air, and the stirring rate was 200rad/min. After being stirred uniformly, an acid liquid feed inlet and an alkali liquid feed inlet at the upper end of the first reaction kettle are opened, and Al is dripped at a flow rate of 20mL/min 2 O 3 A mixed solution of aluminum sulfate having a concentration of 50g/100mL and an acidic active metal solution of Mo-Ni having a concentration of 15g/100mL was prepared, and Al was added dropwise at a flow rate of 15mL/min 2 O 3 Mixing 100g/100mL sodium metaaluminate and 20g/100mL Mo-Ni alkaline active metal, reacting for pH value of 2.5, neutralizing for 15min, opening a lower overflow port control valve to enable the generated liquid I to flow into a settling tank II, simultaneously adding n-hexanol and AgCl into a first reaction kettle I at the rates of 10mL/min and 0.1g/min respectively, switching to a settling tank III after the generated liquid volume in the settling tank II reaches 1/2, and switching the organic in the settling tank II The solvent was separated from sol II, the organic solvent was recycled to the first reactor I, and sol IIA was characterized in Table 1.
2.5L of purified water is added into the second reaction kettle IV, the pressure of the second reaction kettle is regulated to be 10MPa, the temperature is 180 ℃, and the stirring speed is 300rad/min. Opening a sol II feeding hole and an alkali liquor feeding hole at the upper end of the second reaction kettle, and controlling to drop sol II at a flow rate of 25g/min and Al at a flow rate of 15mL/min 2 O 3 And (3) mixing sodium metaaluminate with the concentration of 100g/100mL and Mo-Ni alkaline active metal with the concentration of 20g/100mL, adjusting the pH value of the reaction to 7.5, carrying out neutralization reaction for 60min, and discharging the generated liquid III out of the second reaction kettle.
The resulting solution III was fed into an aging vessel, and 5.9g of methyl ethyl ketone peroxide and 20g of oxalic acid were added, wherein the resulting solution III was prepared as Al 2 O 3 And the molar ratio of the hydrogenated active metal oxide to the polymer monomer is 15:1, the addition amount of the initiator is 2% of the amount of the polymer monomer, the pressure of an aging kettle is regulated to 15MPa, the temperature is 280 ℃, the stirring speed is 500rad/min, the polymerization aging is carried out for 200min, the catalyst A is obtained by filtering, drying for 4h at 150 ℃, and roasting for 3h at 400 ℃ in air atmosphere, wherein the composition and the properties of the catalyst A are shown in Table 2. Wherein after the polymerization reaction, the degree of polymerization of the polymer in the obtained product was 40.
Example 2
The flow of the hydrogenation catalyst produced in this example is shown in FIG. 1.
2.5L of cyclohexane as a reaction medium was added to 10L of the first reaction vessel I, 9g of ZnS was added thereto, the pressure of the first reaction vessel I was adjusted to 4MPa, the temperature was 0℃and the atmosphere was air, and the stirring rate was 300rad/min. After being stirred uniformly, an acid liquid feed inlet and an alkali liquid feed inlet at the upper end of the first reaction kettle are opened, and Al is dripped at a flow rate of 45mL/min 2 O 3 A mixed solution of aluminum sulfate with a concentration of 100g/100mL and a Mo-Ni acidic active metal solution with a concentration of 30g/100mL was prepared, and Al was added dropwise at a flow rate of 30mL/min 2 O 3 The mixed solution of sodium metaaluminate with the concentration of 70g/100mL and Mo-Ni alkaline active metal with the concentration of 33g/100mL is reacted for 30min at the pH value of 3.5, and after neutralization reaction, a lower overflow port control valve is opened to enable the generated liquid I to flow into a sedimentation tank II, and the same is trueWhen cyclohexane and ZnS are added into the first reaction kettle I at the rates of 15mL/min and 0.2g/min respectively, the liquid generated in the sedimentation tank II is switched to the sedimentation tank III after reaching 3/4 of the liquid volume, the organic solvent in the sedimentation tank II is separated from the sol II, the organic solvent can be recycled into the first reaction kettle I, and the properties of the sol IIB are shown in the table 1.
3L of purified water is added into the second reaction kettle IV, the pressure of the second reaction kettle is regulated to 10MPa, the temperature is 180 ℃, and the stirring speed is 300rad/min. Opening a sol II feeding hole and an alkali liquor feeding hole at the upper end of the second reaction kettle, and controlling to drop sol II at a flow rate of 50g/min and Al at a flow rate of 70mL/min 2 O 3 And (3) mixing solution of sodium metaaluminate with the concentration of 85g/100mL and Mo-Ni alkaline active metal with the concentration of 25g/100mL, wherein the pH value is 7.5, and after neutralization reaction for 120min, the generated liquid III is discharged out of the second reaction kettle.
The resultant solution III was fed into an aging vessel, and 5g of methyl ethyl ketone peroxide and 40g of succinic acid were added, wherein the resultant solution III was prepared as Al 2 O 3 The molar ratio of the initiator to the polymer monomer is 13:1, the addition amount of the initiator is 1.1 percent of the amount of the polymer monomer, the pressure of an aging kettle is regulated to 20MPa, the temperature is 250 ℃, the stirring speed is 500rad/min, the polymerization aging is carried out for 180min, the mixture is filtered, dried for 5h at 180 ℃, and baked for 4h at 350 ℃ in an air atmosphere to obtain alumina B, and the composition and the properties of the alumina B are shown in Table 2. Wherein after the polymerization reaction, the degree of polymerization of the polymer in the obtained product was 70.
Example 3
The flow of the hydrogenation catalyst produced in this example is shown in FIG. 1.
5L of benzoic acid is added as a reaction medium to 10L of the first reaction vessel I, 13g of CuS is added, the pressure of the first reaction vessel I is regulated to 8MPa, the temperature is 15 ℃, and the stirring rate is 250rad/min. After being stirred uniformly, an acid liquid feed inlet and an alkali liquid feed inlet at the upper end of the first reaction kettle are opened, and Al is dripped at a flow rate of 50mL/min 2 O 3 A mixed solution of aluminum sulfate having a concentration of 80g/100mL and an acidic active metal solution of Mo-Ni having a concentration of 35g/100mL was prepared, and Al was added dropwise at a flow rate of 40mL/min 2 O 3 Sodium metaaluminate with a concentration of 70g/100mL and Mo-Ni alkaline active metal with a concentration of 40g/100mLAfter neutralization reaction for 60min, opening a lower overflow port control valve to enable the generated liquid I to flow into a settling tank II, simultaneously adding benzoic acid and CuS into a first reaction kettle I at the rates of 20mL/min and 0.5g/min respectively, switching to a settling tank III after the generated liquid volume in the settling tank II reaches 2/3 of the generated liquid volume, separating an organic solvent in the settling tank II from a sol II, and recycling the organic solvent into the first reaction kettle I, wherein the properties of the sol IIC are shown in Table 1.
3L of purified water is added into the second reaction kettle IV, the pressure of the second reaction kettle is regulated to be 12MPa, the temperature is 200 ℃, and the stirring speed is 450rad/min. Opening a sol II feeding hole and an alkali liquor feeding hole at the upper end of the second reaction kettle, and controlling to drop sol II at a flow rate of 50g/min and Al at a flow rate of 70mL/min 2 O 3 And (3) mixing the sodium metaaluminate with the concentration of 60g/100mL and the Mo-Ni alkaline active metal with the concentration of 25g/100mL, adjusting the pH value of the reaction to 9.5, and discharging the generated liquid III out of the second reaction kettle after the neutralization reaction is carried out for 100 min.
Adding the generated liquid III into an aging kettle, and adding 7g of hydrogen peroxide/ferrous chloride and 52g of ethylene glycol, wherein the generated liquid III is prepared by using Al 2 O 3 The molar ratio of the catalyst to the polymer monomer is 10:1, the addition amount of the initiator is 1.2 percent of the amount of the polymer monomer, the pressure of an aging kettle is regulated to 15MPa, the temperature is 300 ℃, the stirring speed is 400rad/min, the aging is carried out for 240min, the catalyst is filtered, dried for 3h at 200 ℃, and baked for 4h at 500 ℃ in an air atmosphere, so that the catalyst C is obtained, and the composition and the properties of the catalyst C are shown in Table 2. Wherein after the polymerization reaction, the degree of polymerization of the polymer in the obtained product was 50.
Example 4
The flow of the hydrogenation catalyst produced in this example is shown in FIG. 1.
4L of styrene is added into 10L of the first reaction kettle I as a reaction medium, 7g of HgS is added, the pressure of the first reaction kettle I is regulated to 9MPa, the reaction temperature is 5 ℃, and the stirring speed is 500rad/min. After being stirred uniformly, an acid liquid feed inlet and an alkali liquid feed inlet at the upper end of the first reaction kettle are opened, and Al is dripped at a flow rate of 100mL/min 2 O 3 Mixing of aluminium sulphate with a concentration of 50g/100mL and Mo-Ni acidic active metal solution with a concentration of 25g/100mLThe solution was simultaneously dropped with Al at a flow rate of 150mL/min 2 O 3 And (3) a mixed solution of sodium metaaluminate with the concentration of 60g/100mL and Mo-Ni alkaline active metal with the concentration of 25g/100mL, wherein the reaction pH value is 4.5, after neutralization reaction is carried out for 45min, a lower overflow port control valve is opened to enable a generated liquid I to flow into a high-pressure sedimentation tank II, meanwhile, styrene and HgS are respectively added into the high-pressure sedimentation tank I at the rates of 30mL/min and 0.5g/min, after the generated liquid volume in the high-pressure sedimentation tank II reaches 4/5, the high-pressure sedimentation tank III is switched, an organic solvent in the high-pressure sedimentation tank II and the sol II are separated, the organic solvent can be recycled into the first reaction tank I, and the properties of the sol IID are shown in table 1.
3L of purified water is added into the second reaction kettle IV, the pressure of the second reaction kettle is regulated to 15MPa, the temperature is 190 ℃, and the stirring speed is 450rad/min. Opening a sol II feeding hole and an alkali liquor feeding hole at the upper end of the second reaction kettle, and controlling to drop sol II at a flow rate of 80mL/min and Al at a flow rate of 100mL/min 2 O 3 And (3) mixing solution of sodium metaaluminate with the concentration of 60g/100mL and Mo-Ni alkaline active metal with the concentration of 15g/100mL, adjusting the pH value of the reaction to 7.5, carrying out neutralization reaction for 80min, and discharging the generated liquid III out of the second reaction kettle.
The resulting solution III was fed into an aging vessel, and 10g of methyl ethyl ketone peroxide and 30g of neopentyl glycol were added, wherein the resulting solution III was prepared as Al 2 O 3 The molar ratio of the catalyst to the polymer monomer is 12:1, the addition amount of the initiator is 3 percent of the amount of the polymer monomer, the pressure of an aging kettle is regulated to be 20MPa, the temperature is 400 ℃, the stirring speed is 500rad/min, the aging is carried out for 210min, the catalyst is filtered, dried for 2h at 180 ℃, and baked for 3h at 400 ℃ in an air atmosphere, so that the catalyst D is obtained, and the composition and the properties of the catalyst D are shown in Table 2. Wherein after the polymerization reaction, the degree of polymerization of the polymer in the obtained product was 50.
Comparative example 1
The flow of the comparative example for producing a hydrogenation catalyst is shown in FIG. 1.
5L of benzoic acid is added as a reaction medium to 10L of the first reaction vessel I, 13g of CuS is added, the pressure of the first reaction vessel I is regulated to be normal, the temperature is 75 ℃, and the stirring speed is 250rad/min. After being stirred uniformly, an acid liquid feed inlet at the upper end of the first reaction kettle is opened And an alkali liquor feeding port, wherein Al is dropwise added at a flow rate of 50mL/min 2 O 3 A mixed solution of aluminum sulfate having a concentration of 80g/100mL and an acidic active metal solution of Mo-Ni having a concentration of 35g/100mL was prepared, and Al was added dropwise at a flow rate of 40mL/min 2 O 3 And (3) a mixed solution of sodium metaaluminate with the concentration of 70g/100mL and Mo-Ni alkaline active metal with the concentration of 40g/100mL, wherein the reaction pH value is 4.5, after neutralization reaction is carried out for 60min, a lower overflow port control valve is opened to enable a generated solution I to flow into a settling tank II, meanwhile, benzoic acid and CuS are respectively added into a first reaction tank I at the rates of 20mL/min and 0.5g/min, after the generated solution volume in the settling tank II reaches 2/3 of that of the generated solution, the generated solution is switched into a settling tank III, an organic solvent in the settling tank II is separated from a sol II, the organic solvent can be recycled into the first reaction tank I, and the properties of the sol IIE are shown in Table 1.
3L of purified water is added into the second reaction kettle IV, the pressure and the normal pressure of the second reaction kettle are regulated, the temperature is 75 ℃, and the stirring speed is 450rad/min. And (3) starting a sol II feeding hole and an alkali liquor feeding hole at the upper end of the second reaction kettle, dropwise adding the sol II at a flow rate of 50mL/min, dropwise adding a mixed solution of sodium metaaluminate with a concentration of 60g/100mL and Mo-Ni alkaline active metal with a concentration of 25g/100mL at a flow rate of 70mL/min, adjusting the pH value of the reaction to 9.5, and discharging the generated solution III out of the second reaction kettle after neutralization reaction for 100 min.
Adding the generated liquid III into an aging kettle, and adding 7g of hydrogen peroxide/ferrous chloride and 52g of ethylene glycol, wherein the generated liquid III is prepared by using Al 2 O 3 The molar ratio of the catalyst to the polymer monomer is 10:1, the addition amount of the initiator is 1.2 percent of the amount of the polymer monomer, the pressure of an aging kettle is regulated to 15MPa, the temperature is 300 ℃, the stirring speed is 400rad/min, the aging is carried out for 240min, the catalyst is dried for 3h at 200 ℃ by filtration, and the catalyst is obtained after roasting for 4h at 500 ℃ in an air atmosphere, wherein the composition and the properties of the catalyst are shown in Table 2. Wherein after the polymerization reaction, the degree of polymerization of the polymer in the obtained product was 50.
Comparative example 2
The flow of the comparative example for producing a hydrogenation catalyst is shown in FIG. 1.
Adding 5L of purified water as a reaction medium into a 10L first reaction kettle I, adding 13g of CuS, and regulating the first reaction kettleI pressure 8MPa, temperature 15 ℃, stirring rate 250rad/min. After being stirred uniformly, an acid liquid feed inlet and an alkali liquid feed inlet at the upper end of the first reaction kettle are opened, and Al is dripped at a flow rate of 50mL/min 2 O 3 A mixed solution of aluminum sulfate having a concentration of 80g/100mL and an acidic active metal solution of Mo-Ni having a concentration of 35g/100mL was prepared, and Al was added dropwise at a flow rate of 40mL/min 2 O 3 And (3) mixing solution of sodium metaaluminate with the concentration of 70g/100mL and Mo-Ni alkaline active metal with the concentration of 40g/100mL, wherein the reaction pH value is 4.5, after neutralization reaction is carried out for 60min, a lower overflow port control valve is opened to enable the generated solution I to flow into a settling tank II, meanwhile, benzoic acid and CuS are respectively added into a first reaction tank I at the rates of 20mL/min and 0.5g/min, after the generated solution volume in the settling tank II reaches 2/3 of the generated solution volume, the generated solution is switched into a settling tank III, the organic solvent in the settling tank II is separated from the sol II, the organic solvent can be recycled into the first reaction tank I, and the properties of the sol IIF are shown in the table 1.
3L of purified water is added into the second reaction kettle IV, the pressure of the second reaction kettle is regulated to be 12MPa, the temperature is 200 ℃, and the stirring speed is 450rad/min. Opening a sol II feeding hole and an alkali liquor feeding hole at the upper end of the second reaction kettle, and controlling to drop sol II at a flow rate of 50mL/min and Al at a flow rate of 70mL/min 2 O 3 And (3) mixing the sodium metaaluminate with the concentration of 60g/100mL and the Mo-Ni alkaline active metal with the concentration of 25g/100mL, adjusting the pH value of the reaction to 9.5, and discharging the generated liquid III out of the second reaction kettle after the neutralization reaction is carried out for 100 min.
Adding the generated liquid III into an aging kettle, wherein the pressure of the aging kettle is 15MPa, the temperature is 300 ℃, the stirring speed is 400rad/min, aging is carried out for 240min, filtering is carried out, drying is carried out for 3h at 200 ℃, and roasting is carried out for 4h at 500 ℃ under the air atmosphere, thus obtaining the catalyst F, and the composition and the properties are shown in Table 2.
Comparative example 3
The flow of the comparative example for producing a hydrogenation catalyst is shown in FIG. 1.
5L of benzoic acid is added into a 10L first reaction kettle I as a reaction medium, the pressure of the first reaction kettle I is regulated to 8MPa, the temperature is 15 ℃, and the stirring speed is 250rad/min. After being stirred uniformly, an acid liquid feed inlet and an alkali liquid feed inlet at the upper end of the first reaction kettle are opened and controlled to50mL/min of Al was added dropwise 2 O 3 A mixed solution of aluminum sulfate having a concentration of 80g/100mL and an acidic active metal solution of Mo-Ni having a concentration of 35g/100mL was prepared, and Al was added dropwise at a flow rate of 40mL/min 2 O 3 And (3) mixing solution of sodium metaaluminate with the concentration of 70g/100mL and Mo-Ni alkaline active metal with the concentration of 40g/100mL, wherein the reaction pH value is 4.5, after neutralization reaction is carried out for 60min, a lower overflow port control valve is opened to enable the generated solution I to flow into a settling tank II, meanwhile, benzoic acid is added into a first reaction kettle I at the rate of 20mL/min, after the generated solution volume in the settling tank II reaches 2/3, the generated solution is switched to a settling tank III, and an organic solvent in the settling tank II is separated from sol II, wherein the organic solvent can be recycled into the first reaction kettle I, and the properties of sol IIG are shown in table 1.
3L of purified water is added into the second reaction kettle IV, the pressure of the second reaction kettle is regulated to be 12MPa, the temperature is 200 ℃, and the stirring speed is 450rad/min. Opening a sol II feeding hole and an alkali liquor feeding hole at the upper end of the second reaction kettle, and controlling to drop sol II at a flow rate of 50mL/min and Al at a flow rate of 70mL/min 2 O 3 And (3) mixing the sodium metaaluminate with the concentration of 60g/100mL and the Mo-Ni alkaline active metal with the concentration of 25g/100mL, adjusting the pH value of the reaction to 9.5, and discharging the generated liquid III out of the second reaction kettle after the neutralization reaction is carried out for 100 min.
Adding the generated liquid III into an aging kettle, and adding 7g of hydrogen peroxide/ferrous chloride and 52g of ethylene glycol, wherein the generated liquid III is prepared by using Al 2 O 3 The molar ratio of the catalyst to the polymer monomer is 10:1, the addition amount of the initiator is 1.2 percent of the amount of the polymer monomer, the pressure of an aging kettle is regulated to 15MPa, the temperature is 300 ℃, the stirring speed is 400rad/min, the aging is carried out for 240min, the catalyst is filtered, dried for 3h at 200 ℃, and baked for 4h at 500 ℃ in an air atmosphere, so that the catalyst G is obtained, and the composition and the properties of the catalyst G are shown in Table 2. Wherein after the polymerization reaction, the degree of polymerization of the polymer in the obtained product was 50.
Comparative example 4
The flow of the comparative example for producing a hydrogenation catalyst is shown in FIG. 1.
5L of benzoic acid is added into a 10L first reaction kettle I as a reaction medium, the pressure of the first reaction kettle I is regulated to 8MPa, the temperature is 15 ℃, and the stirring speed is 250rad/min.After being stirred uniformly, an acid liquid feed inlet and an alkali liquid feed inlet at the upper end of the first reaction kettle are opened, and Al is dripped at a flow rate of 50mL/min 2 O 3 A mixed solution of aluminum sulfate having a concentration of 80g/100mL and an acidic active metal solution of Mo-Ni having a concentration of 35g/100mL was prepared, and Al was added dropwise at a flow rate of 40mL/min 2 O 3 And (3) mixing solution of sodium metaaluminate with the concentration of 70g/100mL and Mo-Ni alkaline active metal with the concentration of 40g/100mL, wherein the reaction pH value is 4.5, after neutralization reaction is carried out for 60min, a lower overflow port control valve is opened to enable the generated solution I to flow into a settling tank II, meanwhile, benzoic acid is added into a first reaction kettle I at the rate of 20mL/min, after the generated solution volume in the settling tank II reaches 2/3, the generated solution is switched to a settling tank III, and an organic solvent in the settling tank II is separated from the sol II, wherein the organic solvent can be recycled into the first reaction kettle I, so that sol II H is obtained.
3L of purified water is added into the second reaction kettle IV, the pressure of the second reaction kettle is regulated to be 12MPa, the temperature is 200 ℃, and the stirring speed is 450rad/min. Opening a sol II feeding hole and an alkali liquor feeding hole at the upper end of the second reaction kettle, and controlling to drop sol II at a flow rate of 50mL/min and Al at a flow rate of 70mL/min 2 O 3 And (3) mixing the sodium metaaluminate with the concentration of 60g/100mL and the Mo-Ni alkaline active metal with the concentration of 25g/100mL, adjusting the pH value of the reaction to 9.5, and discharging the generated liquid III out of the second reaction kettle after the neutralization reaction is carried out for 100 min.
Adding the generated solution III into an aging kettle, wherein the temperature is 300 ℃, the stirring speed is 400rad/min, aging is carried out for 240min, filtering is carried out, drying is carried out for 3h at 200 ℃, and roasting is carried out for 4h at 500 ℃ under the air atmosphere, thus obtaining the catalyst G, and the composition and the properties of the catalyst G are shown in Table 2.
TABLE 1 Properties of Sol II obtained in examples and comparative examples
Sol number II A B C D E F G
Particle size distribution, percent
＜100nm 4.5 3.7 4.9 4.2 15.6 25.3 10.3
100～200nm 3.2 5.0 3.9 4.5 23.9 32.9 32.9
＞200nm 92.3 91.3 91.2 91.3 60.5 41.8 56.8
Table 2 composition and properties of hydrogenation catalysts obtained in examples and comparative examples
Figure BDA0003327896010000141
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Figure BDA0003327896010000151
Evaluation test
This example is a comparative run of the catalysts of examples 1, 2, 3, 4 and comparative examples 1, 2, 3, 4 on a 100mL fixed bed mini-hydrotreater, fed by the following feed. The properties of the raw oil are shown in Table 3; the evaluation conditions are shown in Table 4; the evaluation results of the catalyst are shown in Table 5.
TABLE 3 Properties of raw oil
Raw oil Inferior residuum
Density (20 ℃), g.cm -3 0.98
Carbon residue, wt% 12.99
S，wt％ 4.2
Ni+V，μg·g -1 118.9
Table 4 evaluation of process conditions
Reaction temperature, DEG C 380
Partial pressure of reaction hydrogen, MPa 15.0
Liquid hourly space velocity, h -1 0.5
Hydrogen to oil volume ratio 1000
Table 5 evaluation results of catalysts obtained in examples and comparative examples
Catalyst numbering A B C D E F G H
HDS，％ 97 98 99 96 82 84 91 93
HD(Ni+V)，％ 96 98 97 97 91 88 87 94
HDCCR，％ 79 77 78 76 51 58 60 69
As can be seen from tables 2 and 5, the catalyst provided by the invention has the advantages of large specific surface area, high pore volume, large pore diameter, concentrated grain distribution, higher hydrogenation activity and suitability for hydrotreating catalysts of heavy inferior raw materials.

Claims (20)

1. A method of producing a hydrogenation catalyst comprising:
(1) Adding an organic solvent, a polar metal seed crystal, an acidic solution I and an alkaline solution I into a first reaction kettle in parallel flow for neutralization and gel formation to obtain a generated liquid I;
(2) The obtained generated liquid I enters a settling tank for settling separation to obtain an upper layer, namely an organic solvent, and a lower layer, namely sol II;
(3) The sol II and the acid solution II or the alkaline solution II flow into a second reaction kettle in parallel to be neutralized and gel to obtain a generated liquid III;
(4) The generated liquid III enters an aging kettle, and a polymerization monomer and an initiator are added, and then an aging polymerization reaction is carried out;
(5) Drying and roasting the ageing material obtained in the step (4) to obtain the catalyst;
wherein, the components of the acid solution I and the alkaline solution I introduced into the hydrogenation catalyst comprise alumina and hydrogenation active metals, namely first alumina and first hydrogenation active metals, and the components of the acid solution II or the alkaline solution II introduced into the hydrogenation catalyst comprise alumina and hydrogenation active metals, namely second alumina and second hydrogenation active metals.
2. The production method according to claim 1, wherein the production method is performed in a continuous manner.
3. The production method according to claim 2, wherein a plurality of settling tanks used in the step (2) and aging tanks used in the step (4) are arranged for switching; the first reaction kettle in the step (1) adopts an overflow type operation mode for discharging the generated liquid I out of the first reaction kettle, and the second reaction kettle in the step (3) adopts an overflow type operation mode for discharging the generated liquid III out of the second reaction kettle.
4. The production method according to claim 2, wherein when the hydrogenation catalyst is continuously produced, when the first reaction kettle is started, the organic solvent and the polar metal seed crystal are added as base solution, and then the acidic solution I and the alkaline solution I are added in parallel to neutralize and gel until the generated solution I starts to be discharged out of the first reaction kettle; wherein the addition amount of the organic solvent in the base solution is 1/5-1/3 of the actual effective use volume of the first reaction kettle, when the generated solution I is discharged out of the first reaction kettle, the acidic solution I and the alkaline solution I in the first reaction kettle are prepared by using Al 2 O 3 And the addition amount of the polar metal salt seed crystal is 0.1-5.0%, preferably 0.2-2.0% based on the total mass of the hydrogenation active metal oxide.
5. The production method according to claim 2, wherein when the continuous production of the hydrogenation catalyst is adopted, when the second reaction kettle is started, the bottom water is added first, then the sol II and the acid solution II or the alkaline solution II are added in parallel to neutralize and gel until the generated liquid III starts to be discharged from the second reaction kettle; wherein, the addition amount of the bottom water is 1/7-1/2, preferably 1/6-1/3 of the actual effective use volume of the second reaction kettle.
6. The process according to any one of claims 1 to 5, wherein the organic solvent in step (1) is an organic substance which is not miscible or slightly soluble with water and is selected from one or more of alkanes, alkenes, organic alcohols, organic acids; preferably, the organic matter has a carbon number of 5 to 12.
7. The method according to any one of claims 1 to 5, wherein the polar metal seed is one or more selected from AgCl, znS, cuS and HgS.
8. The process according to any one of claims 1 to 5, wherein the first reaction vessel of step (1) is operated under the following conditions: the temperature is-15 to 15 ℃, the pressure is 1 to 20MPa, and the preferable pressure is 4 to 10MPa; the reaction conditions for neutralizing and gelling in the step (1) are as follows: the pH value is 2-6, preferably 2-5, and the reaction time is 10-180 minutes, preferably 10-60 minutes; the neutralization and gelling reaction is preferably carried out under stirring at a rate of from 100 to 500rad/min, preferably from 150 to 500rad/min.
9. The production method according to any one of claims 1 to 5, wherein the mass ratio of the first alumina to the second alumina is 1:5 to 5:1, and the mass ratio of the first hydrogenation-active metal to the second hydrogenation-active metal in terms of oxide is 1:10 to 10:1.
10. The process according to any one of claims 1 to 5, wherein the organic solvent and the polar metal seed crystal are added to the first reaction vessel in parallel, wherein the addition rate of the organic solvent is such that the ratio of the addition rates of the acidic solution I and the basic solution I in terms of the sum of the two addition rates by volume is 0.1:1 to 10:1, preferably 0.1:1 to 5:1, the addition rate of the polar metal seed crystal is that the acid solution I and the alkaline solution I are added with Al 2 O 3 And hydrogenation of the active metal oxideThe sum of the rates of entry is 0.1% to 10%, preferably 0.2% to 5%.
11. The process according to any one of claims 1 to 5, wherein the sol II obtained in step (2) has a particle size distribution as follows: the proportion of the crystal grains with the grain diameter smaller than 100nm is 0.5-5.0%, the proportion of the crystal grains with the grain diameter of 100-200 nm is 2-5%, and the proportion of the crystal grains with the grain diameter larger than 200nm is 90-95%.
12. The process according to any one of claims 1 to 5, wherein the operating conditions of the settling tank of step (2) are as follows: the temperature is-15 to 15 ℃, the pressure is 1 to 20MPa, and preferably 4 to 10MPa.
13. The process according to any one of claims 1 to 5, wherein the second reaction vessel of step (3) is operated under the following conditions: the temperature is 100-300 ℃, preferably 100-200 ℃, and the pressure is 5-20 MPa, preferably 10-20 MPa; the reaction conditions for neutralizing and gelling in the step (3) are as follows: the pH value is 7-12, preferably 7.5-10.0, and the reaction time is 10-180 minutes, preferably 10-120 minutes; the neutralization and gelling reaction is preferably carried out under stirring at a rate of from 100 to 500rad/min, preferably from 200 to 500rad/min.
14. The production method according to any one of claims 1 to 5, wherein in the step (4), the polymer monomer is at least one of an organic alcohol or an organic acid, and the initiator is at least one selected from a peroxide initiator, an azo initiator, and a redox initiator; preferably, in the step (4), the production liquid III is formed by Al 2 O 3 And a molar ratio of hydrogenation active metal oxide to polymer monomer of 20:1 to 1:1, preferably 15:1 to 1:1, a step of; the addition amount of the initiator is 0.01-3.5% of the mass of the polymer monomer; further preferably, the degree of polymerization of the polymer formed by the polymerization reaction is 5 to 100, preferably 5 to 80.
15. The process according to any one of claims 1 to 5, wherein in step (4), the aging polymerization conditions are: the temperature is 200-400 ℃, the pressure is 15-20.0 MPa, and the aging time is 100-360 min, preferably 180-350 min; the aging is carried out under stirring conditions, preferably at a stirring speed of 500 to 800r/min.
16. The process according to any one of claims 1 to 5, wherein in step (5), the drying temperature is 100 to 450 ℃, preferably 150 to 400 ℃, and the drying time is 1 to 10 hours; the roasting temperature is 300-800 ℃, preferably 350-550 ℃, the roasting time is 2-5 hours, preferably 2-4 hours, and the roasting atmosphere is one or more of air, nitrogen or water vapor.
17. The hydrogenation catalyst produced by the production process according to any one of claims 1 to 16, comprising alumina and a hydrogenation-active metal component, which is characterized by the following properties: the pore volume is 1.5-2.0 mL/g; specific surface area of 300-450 m 2 The pore size of the polymer/g may be less than or equal to 150nm, preferably 190 to 300nm.
18. The catalyst of claim 17, wherein the catalyst has a particle size distribution of: the proportion of the grains with the grain diameter smaller than 250 mu m is 0.5% -5.0%, the proportion of the grains with the grain diameter of 250-350 mu m is 2.0% -5.0%, and the proportion of the grains with the grain diameter larger than 350 mu m is 90.0% -95.0%.
19. The catalyst of claim 17, wherein the hydrogenation-active metal is selected from at least one of group VIB and group VIII metals, the group VIB metal is selected from at least one of Mo, W, and the group VIII metal is selected from at least one of Ni, co.
20. The catalyst according to claim 17, wherein the catalyst comprises 10 to 80% by mass of the hydrogenation-active metal as an oxide, 20 to 90% by mass of the alumina, 5 to 70% by mass of the group VIB metal as an oxide, and 5 to 50% by mass of the group VIII metal as an oxide, based on the mass of the catalyst.
CN202111268705.8A 2021-10-29 2021-10-29 Hydrogenation catalyst and production method thereof Pending CN116060022A (en)

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