CN104399495A - Catalyst for direct coal liquefaction of oil hydrogenation, and preparation method thereof - Google Patents

Catalyst for direct coal liquefaction of oil hydrogenation, and preparation method thereof Download PDF

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CN104399495A
CN104399495A CN201410776991.2A CN201410776991A CN104399495A CN 104399495 A CN104399495 A CN 104399495A CN 201410776991 A CN201410776991 A CN 201410776991A CN 104399495 A CN104399495 A CN 104399495A
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CN104399495B (en
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张尤华
阴奇力
于晓艳
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Liaoning Technical University
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Abstract

The invention provides a catalyst for direct coal liquefaction of oil hydrogenation, and a preparation method thereof, and aims to solve the defects that the catalyst for direct coal liquefaction of oil hydrogenation is low in atom utilization rate and high in possibility of carbon deposition in the prior art. The catalyst is composed of active ingredients of molybdenum sulfide, cobaltous sulfide and a magnetic composite carrier Fe3O4-SiO2-Al2O3. The preparation method comprises the following steps: coating Fe3O4 magnetic nanoparticles with SiO2; curing aluminum hydroxide sol on the surfaces of the Fe3O4 magnetic nanoparticles coated with SiO2; carrying out solution heat treatment, aging and drying in an alkaline medium to obtain a catalyst magnetic composite carrier Fe3O4-SiO2-Al2O3; adopting a catalyst carrier to carry active metal cobalt and molybdenum to obtain a catalyst intermediate; conducting prevulcanization on the catalyst intermediate. The catalyst is a magnetic nano catalyst, and has relatively high catalytic efficiency; an alumina carrier facilitates dispersion of the active ingredients and stability of the active ingredients in the reaction process; meanwhile an active phase in a Co-Mo-S structure is easy to obtain.

Description

A kind of Catalysts and its preparation method for coal direct liquefaction oil hydrogenation
Technical field
The invention belongs to hydrogenation catalyst field, particularly a kind of Catalysts and its preparation method for coal direct liquefaction oil hydrogenation.
Background technology
The rich coal of China, this resources characteristic oil-poor, determines energy development inevitable based on coal.Development of Coal liquefaction technology and relevant chemical industry, realize replace oil with coal, have important practical significance and long-range historic significance, it will be the grand strategy behave solving China's oil shortage of resources, balance energy resource structure, ensure energy security and national economy sustainable and stable development.Wherein, DCL/Direct coal liquefaction liquefaction is paid attention to widely with its higher energy conversion efficiency.
But DCL/Direct coal liquefaction generates that oil is that the content of heteroatoms such as a kind of oxygen, nitrogen, sulphur are high, easily the rich aromatic hydrocarbons long distillate of polymerization coking is oily under high temperature, needs to obtain fuel oil up to specification by hydrofinishing desulfurization, denitrogenation, deoxidation, aromatic saturation.At present, DCL/Direct coal liquefaction generates oily hydrofining technology and has directly used heterogeneous catalyst traditional in petroleum refining process, does not have to study specially for the new catalyst of coal direct liquefaction oil hydrodesulfurization.As the DCL/Direct coal liquefaction generation oil refining catalyst employing in the world head cover maximization DCL/Direct coal liquefaction demonstration project of Shenhua Group construction is conventional multiphase catalyst RCC-l, RGC-1 and RNC-1 that Beijing Research Institute of Petro-Chemical Engineering develops.Wherein the key component of RGC catalyst is NiO-MoO 3, the key component of RNC catalyst is WO 3-NiO-MoO 3.
Conventional multiphase catalyst is used for coal direct liquefaction oil hydrodesulfurization and there is following shortcoming: 1. most of active component is adsorbed on carrier inner surface, limit by factors such as diffusion rate and aperture blockings, the atom utilization of active metal is very low, and therefore catalyst desulfurizing activity is lower; 2. although, the relevant report not about catalyst carbon deposition inactivation and catalyst life test in domestic and foreign literature, DCL/Direct coal liquefaction generates oily aromatic hydrocarbons, colloid, high and containing solid grain contamination the speciality of olefin(e) centent have been doomed catalyst and have easily been caused inactivation by carbon distribution.And conventional multiphase catalyst is owing to being deposited in one piece, easier because mutually accumulating and tackling solid grain contamination and cause carbon distribution.
The innovation developing into catalysis subject of nanometer technology brings an opportunity, catalyst carrier can be decreased to nanoscale and solve its separation problem by magnetic separation technique by magnetic nanoparticle to greatest extent, has successfully carried out " homogeneous phase " of heterogeneous catalyst.
Summary of the invention
Technical problem to be solved by this invention is the low and shortcoming that is easily carbon distribution of the atom utilization of existing DCL/Direct coal liquefaction oil hydrogenation catalysts, provides a kind of Catalysts and its preparation method for coal direct liquefaction oil hydrogenation.This catalyst is magnetic nano-catalyst, has higher catalytic efficiency.
For a catalyst for coal direct liquefaction oil hydrogenation, by active component molybdenum sulfide and cobalt sulfide and magnetic coupling carrier Fe 3o 4-SiO 2-Al 2o 3composition; Wherein, molybdenum atom accounts for the 16-26% of catalyst gross mass, and cobalt atom accounts for the 2-6% of catalyst gross mass; In described magnetic coupling carrier, SiO 2for Fe 3o 4150% ~ 250%, Fe of quality 3o 4for Al 2o 3the 6-10% of quality.
Present invention also offers the preparation method of above-mentioned a kind of catalyst for coal direct liquefaction oil hydrogenation, comprise the following steps:
(1) by Fe 3o 4magnetic nanoparticle ultrasonic disperse is the Na of 1-3mol/L in concentration 2siO 3in solution, then solution is heated to 80 ~ 90 DEG C, under the inert gas shielding such as nitrogen, argon gas, in solution, drips the HCl that concentration is 2-3mol/L, the pH value of solution is adjusted to 5 ~ 6 in 2 ~ 3h; Isolate precipitated product after reaction terminates, obtain Surface coating SiO 2fe 3o 4magnetic-particle;
Wherein, Na 2siO 3adding quality is Fe 3o 4the 305-508% of quality;
(2) be that the aluminum hydroxide sol of 5-15% mixes with the organic amine mixed solution containing hexamethylenetetramine and urea at 0 ~ 15 DEG C by mass concentration, then by appropriate Surface coating SiO 2fe 3o 4magnetic-particle joins in solution, stirs and ultrasonic disperse uniformly aqueous phase sol solution; The colloidal sol microemulsion of uniform water-in-oil type will be formed in the sulfonated kerosene be dispersed under aqueous phase sol solution low whipping speed 60 ~ 80rpm containing 0.5-4.5wt%Span80, subsequently colloidal sol microemulsion is warming up to 85 ~ 90 DEG C, insulation 20 ~ 30min, aluminum hydroxide sol cure is being covered with SiO 2fe 3o 4magnetic-particle surface, product separation is removed surperficial oil slick with the deionized water washing containing a small amount of Tween80, and ageing is dry through solution heat treatment and in alkaline media subsequently, then at 500 ~ 600 DEG C of sintering 3 ~ 6h, obtain spherical gamma-Al 2o 3/ SiO 2/ Fe 3o 4magnetic coupling carrier;
Wherein, aluminum hydroxide sol quality is 10:1g/mL with the ratio of organic amine mixed liquor volume, and in mixed amines solution, urea concentration is 0.167 ~ 0.33mol/L, and the mol ratio of urea and hexamethylenetetramine is 1:2;
It is Surface coating SiO that aluminium hydroxide adds quality 2fe 3o 4fe in magnetic-particle 3o 4the 15.3-25.5 of quality doubly;
(3) by appropriate γ-Al 2o 3/ SiO 2/ Fe 3o 4magnetic coupling support dispersion, in water, adds appropriate (NH 4) 6mo 7o 244H 2after O, under ultrasonic disperse, in solution, drip NaBH 4solution, stops ultrasonic after dropwising, and continues reaction 30 ~ 60min; Appropriate CoCl is added again in solution 26H 2after O, under ultrasonic disperse, be added dropwise to NaBH 4solution, stops ultrasonic after dropwising, and continues reaction 30 ~ 60min; Again precipitated product is separated, obtains catalyst intermediate;
Wherein, NaBH 4addition is 5% of molybdenum or cobalt atom molal quantity;
(NH 4) 6mo 7o 244H 2it is γ-Al that O adds quality 2o 3/ SiO 2/ Fe 3o 4the 0.35-0.65 of magnetic coupling carrier quality doubly; CoCl 26H 2it is γ-Al that O adds quality 2o 3/ SiO 2/ Fe 3o 4the 0.10-0.33 of magnetic coupling carrier quality doubly;
(4) 2%CS is added with virgin kerosene 2for sulfurized oil, by catalyst intermediate at initial hydrogen dividing potential drop pH 25.0 ~ 6.0Mpa, temperature 280 ~ 320 DEG C, LHSV (liquid volume space time velocity)=2.0h -1, hydrogen to oil volume ratio=500 condition under, presulfurization 36 ~ 72h, namely obtains catalyst.
After tested, the desulfurization degree of this magnetic nano-catalyst to coal direct liquefaction oil reaches 98.8%, denitrification percent reaches 81%.
The present invention compared with prior art, it is advantageous that:
1, magnetic nano-catalyst have that catalytic activity group load capacity is strong, imporosity diffusion restriction, can dispersed in the liquid phase, the characteristics and advantages such as magnetic response, make it be applicable to very much DCL/Direct coal liquefaction and generate oily hydrofinishing.
2, in this catalyst, due to SiO 2steric hindrance limit Fe 3o 4the reunion of crystallite and continued growth, make Fe 3o 4core dispersion keeps less crystallite dimension in the product, improves the weatherability of magnetic component while making coated product show superparamagnetism.
3, alumina support have good dispersibility, larger specific area, good mechanical property, good stability and and interaction between active component stronger, be conducive to the stable of active component in the dispersion of active component and course of reaction, be easy to the active phase obtaining Co-Mo-S structure simultaneously.
4, under nanoscale, active metal does not limit by factors such as diffusion rate and aperture blockings, makes the service efficiency of metallic atom high, has higher catalytic efficiency.
Detailed description of the invention
The raw material that the present invention relates to and reagent except specified otherwise all commercially.
Fe 3o 4the preparation method of nano particle is:
Get the FeCl that mass ratio is 2-3:1 36H 2o and FeCl 24H 2o, is dissolved in water, and solution is heated to 85 ~ 90 DEG C, and mixing speed is 60 ~ 100rpm, under the inert gas shieldings such as nitrogen, add the ammonia spirit that mass concentration is 25-28% in solution, and ammoniacal liquor adds volume and FeCl 3the ratio of amount of substance is (4-5:1) L/mol, and react 2 ~ 4 hours, the precipitate and separate then utilizing magnetic field to be obtained by reacting, obtains Fe 3o 4magnetic nanoparticle.
Embodiment 1
1, by the Fe of 5g 3o 4magnetic nanoparticle ultrasonic disperse is the Na of 1mol/L in 125ml concentration 2siO 3be heated to 85 DEG C in solution, low whipping speed is under 50 ~ 100rpm, nitrogen protection, drips the HCl solution of concentration 2mol/L, in 2.5 ~ 3h, the pH value of solution is adjusted to 6 by alkalescence in solution; After reaction terminates, isolate product and fully wash by deionized water and obtain Surface coating and have SiO 2fe 3o 4magnetic-particle;
2, get the aluminum hydroxide sol that 510g mass concentration is 15%, the mixed amines dissolution homogeneity containing 0.333mol/L hexamethylenetetramine and 0.167mol/L urea at 0 ~ 3 DEG C with 50mL mixes; Obtained for step 1 is coated with SiO 2fe 3o 4magnetic-particle joins in above-mentioned mixed solution the also ultrasonic disperse that stirs and forms uniform aqueous phase sol solution; The colloidal sol microemulsion of uniform water-in-oil type will be formed in the sulfonated kerosene be dispersed under aqueous phase sol solution low whipping speed 60 ~ 80rpm containing 0.5wt%Span8, subsequently colloidal sol microemulsion be warming up to 85 DEG C and keep 30min, aluminum hydroxide sol cure is being covered with SiO 2fe 3o 4magnetic-particle surface, is separated product from kerosene, then removes surperficial oil slick with the deionized water washing containing a small amount of Tween80, subsequently under nitrogen protection, in the autoclave that kerosene is housed, adds aluminum hydroxide sol/SiO 2/ Fe 3o 4magnetic-particle product, in still, mixing speed is 5 ~ 30r/min, and solid-liquid volume ratio is 0.5 ~ 1.5, temperature 120 ~ 200 DEG C, processing time 0.5 ~ 5h; Solid is placed in the ammoniacal liquor of pH=10-11, at 70 ~ 90 DEG C, ageing drying 1 ~ 5h ageing in hydrothermal treatment consists alkaline media is dry again; Finally at 580 DEG C of air atmosphere sintering 3h, obtain spherical gamma-Al 2o 3/ SiO 2/ Fe 3o 4magnetic coupling carrier;
3, by 10g γ-Al 2o 3/ SiO 2/ Fe 3o 4magnetic coupling support dispersion, in water, adds (the NH of 3.5g 4) 6mo 7o 244H 2o, drips the NaBH of 0.126mol/L under ultrasonic disperse 4aqueous solution 157mL, stops ultrasonic after dropwising, and continues stirring reaction 30min under rotating speed 40 ~ 60rpm; And then add the CoCl of 1g 26H 2o, drips the NaBH of 0.126mol/L under ultrasonic disperse 4aqueous solution 33mL, stop ultrasonic after solution dropwises, continue stirring reaction 30min under rotating speed 40 ~ 60rpm, then by precipitated product be separated, obtain catalyst intermediate;
4, by catalyst intermediate at initial hydrogen dividing potential drop pH 2=6.0Mpa, temperature t=290 DEG C, LHSV=2.0h -1, hydrogen to oil volume ratio=500 condition under, sulfurized oil is that virgin kerosene adds 2%CS 2, presulfurization 48 hours, namely obtains catalyst.
Catalyst is by active component molybdenum sulfide, cobalt sulfide and magnetic coupling carrier Fe 3o 4-SiO 2-Al 2o 3composition; Wherein, molybdenum atom accounts for 16% of catalyst gross mass, and cobalt atom accounts for 2% of catalyst gross mass; In described carrier, SiO 2for Fe 3o 4150%, Fe of quality 3o 4for Al 2o 310% of quality.
The hydrogenation evaluation experimental of coal direct liquefaction oil is being carry out in the autoclave of 1 liter at volume, and add feedstock oil 60g, reaction temperature 380 DEG C, hydrogen first pressing 6Mp, the addition of catalyst is 6g, and hydrogen-oil ratio is 500,2 hours stabilization time.Record that the desulfurization degree of this magnetic nano-catalyst to coal direct liquefaction oil reaches 98.5%, denitrification percent reaches 81%.
Embodiment 2
1, by the Fe of 5g 3o 4magnetic nanoparticle ultrasonic disperse is the Na of 3mol/L in 70ml concentration 2siO 3be heated to 90 DEG C in solution, low whipping speed is under 50 ~ 100rpm, argon shield, drips the HCl solution of concentration 3mol/L, in 2 ~ 2.5h, the pH value of solution is adjusted to 5 by alkalescence in solution; After reaction terminates, isolate product and fully wash by deionized water and obtain Surface coating and have SiO 2fe 3o 4magnetic-particle;
2, by 1275g mass concentration be 10% the aluminum hydroxide sol mixed amines dissolution homogeneity that contains 0.67mol/L hexamethylenetetramine and 0.33mol/L urea at 10 ~ 15 DEG C with 128mL mix; Obtained for step 1 is coated with SiO 2fe 3o 4magnetic-particle joins in above-mentioned mixed solution the also ultrasonic disperse that stirs and forms uniform aqueous phase sol solution; The colloidal sol microemulsion of uniform water-in-oil type will be formed in the sulfonated kerosene be dispersed under aqueous phase sol solution low whipping speed 60 ~ 80rpm containing 4.5wt%Span8, subsequently colloidal sol microemulsion be warming up to 90 DEG C and keep 20min, aluminum hydroxide sol cure is being covered with SiO 2fe 3o 4magnetic-particle surface, is separated product from kerosene, then removes surperficial oil slick with the deionized water washing containing a small amount of Tween80, subsequently under argon shield, in the autoclave that kerosene is housed, adds aluminum hydroxide sol/SiO 2/ Fe 3o 4magnetic-particle product, in still, mixing speed is 5 ~ 30r/min, and solid-liquid volume ratio is 0.5 ~ 1.5, temperature 120 ~ 200 DEG C, processing time 0.5 ~ 5h; Solid is placed in the ammoniacal liquor of pH=10-11, at 70 ~ 90 DEG C, ageing drying 1 ~ 5h ageing in hydrothermal treatment consists alkaline media is dry again; Finally at 500 DEG C of air atmosphere sintering 6h, obtain spherical gamma-Al 2o 3/ SiO 2/ Fe 3o 4magnetic coupling carrier;
3, by 10g γ-Al 2o 3/ SiO 2/ Fe 3o 4magnetic coupling support dispersion, in water, adds (the NH of 6.5g 4) 6mo 7o 244H 2o, drips the NaBH of 0.25mol/L under ultrasonic disperse 4aqueous solution 147mL, stops ultrasonic after dropwising, and continues stirring reaction 60min under rotating speed 40 ~ 60rpm; And then add the CoCl of 3.3g 26H 2o, drips the NaBH of 0.25mol/L under ultrasonic disperse 4aqueous solution 56mL, stop ultrasonic after solution dropwises, continue stirring reaction 60min under rotating speed 40 ~ 60rpm, then by precipitated product be separated, obtain catalyst intermediate;
4, by catalyst intermediate at initial hydrogen dividing potential drop pH 2=5.0Mpa, temperature t=320 DEG C, LHSV=2.0h -1, hydrogen to oil volume ratio=500 condition under, sulfurized oil is that virgin kerosene adds 2%CS 2, presulfurization 48 hours, namely obtains catalyst.
Catalyst is by active component molybdenum sulfide, cobalt sulfide and magnetic coupling carrier Fe 3o 4-SiO 2-Al 2o 3composition; Wherein, molybdenum atom accounts for 26% of catalyst gross mass, and cobalt atom accounts for 6% of catalyst gross mass; In described carrier, SiO 2for Fe 3o 4250%, Fe of quality 3o 4for Al 2o 36% of quality.
The desulfurization degree of this magnetic nano-catalyst to coal direct liquefaction oil reaches 98.4%, denitrification percent reaches 80.7% to utilize the method for embodiment 1 to record.
Embodiment 3
1, by the Fe of 5g 3o 4magnetic nanoparticle ultrasonic disperse is the Na of 2mol/L in 83ml concentration 2siO 3be heated to 80 DEG C in solution, low whipping speed is under 50 ~ 100rpm, nitrogen protection, drips the HCl solution of concentration 3mol/L, in 2 ~ 2.5h, the pH value of solution is adjusted to 6 by alkalescence in solution; After reaction terminates, isolate product and fully wash by deionized water and obtain Surface coating and have SiO 2fe 3o 4magnetic-particle;
2, by 1910g mass concentration be 5% the aluminum hydroxide sol mixed amines dissolution homogeneity that contains 0.4mol/L hexamethylenetetramine and 0.2mol/L urea at 5 ~ 8 DEG C with 190mL mix; Obtained for step 1 is coated with SiO 2fe 3o 4magnetic-particle joins in above-mentioned mixed solution the also ultrasonic disperse that stirs and forms uniform aqueous phase sol solution; The colloidal sol microemulsion of uniform water-in-oil type will be formed in the sulfonated kerosene be dispersed under aqueous phase sol solution low whipping speed 60 ~ 80rpm containing 2.5wt%Span8, subsequently colloidal sol microemulsion be warming up to 87 DEG C and keep 30min, aluminum hydroxide sol cure is being covered with SiO 2fe 3o 4magnetic-particle surface, is separated product from kerosene, then removes surperficial oil slick with the deionized water washing containing a small amount of Tween80, subsequently under nitrogen protection, in the autoclave that kerosene is housed, adds aluminum hydroxide sol/SiO 2/ Fe 3o 4magnetic-particle product, in still, mixing speed is 5 ~ 30r/min, and solid-liquid volume ratio is 0.5 ~ 1.5, temperature 120 ~ 200 DEG C, processing time 0.5 ~ 5h; Solid is placed in the ammoniacal liquor of pH=10-11, at 70 ~ 90 DEG C, ageing drying 1 ~ 5h ageing in hydrothermal treatment consists alkaline media is dry again; Finally at 600 DEG C of air atmosphere sintering 3h, obtain spherical gamma-Al 2o 3/ SiO 2/ Fe 3o 4magnetic coupling carrier;
3, by 10g γ-Al 2o 3/ SiO 2/ Fe 3o 4magnetic coupling support dispersion, in water, adds (the NH of 5.14g 4) 6mo 7o 244H 2o, drips the NaBH of 0.25mol/L under ultrasonic disperse 4aqueous solution 116mL, stops ultrasonic after dropwising, and continues stirring reaction 60min under rotating speed 40 ~ 60rpm; And then add the CoCl of 2.2g 26H 2o, drips the NaBH of 0.25mol/L under ultrasonic disperse 4aqueous solution 37mL, stop ultrasonic after solution dropwises, continue stirring reaction 60min under rotating speed 40 ~ 60rpm, then by precipitated product be separated, obtain catalyst intermediate;
4, by catalyst intermediate at initial hydrogen dividing potential drop pH 2=5.5Mpa, temperature t=280 DEG C, LHSV=2.0h -1, hydrogen to oil volume ratio=500 condition under, sulfurized oil is that virgin kerosene adds 2%CS 2, presulfurization 72 hours, namely obtains catalyst.
Catalyst is by active component molybdenum sulfide, cobalt sulfide and magnetic coupling carrier Fe 3o 4-SiO 2-Al 2o 3composition; Wherein, molybdenum atom accounts for 21% of catalyst gross mass, and cobalt atom accounts for 4% of catalyst gross mass; In described carrier, SiO 2for Fe 3o 4200%, Fe of quality 3o 4for Al 2o 38% of quality.
The desulfurization degree of this magnetic nano-catalyst to coal direct liquefaction oil reaches 97.1%, denitrification percent reaches 79.8% to utilize the method for embodiment 1 to record.
Embodiment 4
Catalyst is by active component molybdenum sulfide, cobalt sulfide and magnetic coupling carrier Fe 3o 4-SiO 2-Al 2o 3composition; Wherein, molybdenum atom accounts for 22% of catalyst gross mass, and cobalt atom accounts for 4% of catalyst gross mass; In described carrier, SiO 2for Fe 3o 4150%, Fe of quality 3o 4for Al 2o 310% of quality.
Utilize the method for embodiment 1 to record this magnetic nano-catalyst and 98%, 80.2% is respectively to the hydrodesulfurization of coal direct liquefaction oil, nitric efficiency.
Embodiment 5
Catalyst is by active component molybdenum sulfide, cobalt sulfide and magnetic coupling carrier Fe 3o 4-SiO 2-Al 2o 3composition; Wherein, molybdenum atom accounts for 22% of catalyst gross mass, and cobalt atom accounts for 4% of catalyst gross mass; In described carrier, SiO 2for Fe 3o 4200%, Fe of quality 3o 4for Al 2o 310% of quality.
Utilize the method for embodiment 1 to record this magnetic nano-catalyst and 98.5%, 81% is respectively to the hydrodesulfurization of coal direct liquefaction oil, nitric efficiency.
Embodiment 6
Catalyst is by active component molybdenum sulfide, cobalt sulfide and magnetic coupling carrier Fe 3o 4-SiO 2-Al 2o 3composition; Wherein, molybdenum atom accounts for 22% of catalyst gross mass, and cobalt atom accounts for 4% of catalyst gross mass; In described carrier, SiO 2for Fe 3o 4250%, Fe of quality 3o 4for Al 2o 310% of quality.
Utilize the method for embodiment 1 to record this magnetic nano-catalyst and 97.8%, 79.6% is respectively to the hydrodesulfurization of coal direct liquefaction oil, nitric efficiency.
Embodiment 7
Catalyst is by active component molybdenum sulfide, cobalt sulfide and magnetic coupling carrier Fe 3o 4-SiO 2-Al 2o 3composition; Wherein, molybdenum atom accounts for 22% of catalyst gross mass, and cobalt atom accounts for 4% of catalyst gross mass; In described carrier, SiO 2for Fe 3o 4200%, Fe of quality 3o 4for Al 2o 36% of quality.
Utilize the method for embodiment 1 to record this magnetic nano-catalyst and 98.8%, 80.2% is respectively to the hydrodesulfurization of coal direct liquefaction oil, nitric efficiency.
Embodiment 8
Catalyst is by active component molybdenum sulfide, cobalt sulfide and magnetic coupling carrier Fe 3o 4-SiO 2-Al 2o 3composition; Wherein, molybdenum atom accounts for 16% of catalyst gross mass, and cobalt atom accounts for 4% of catalyst gross mass; In described carrier, SiO 2for Fe 3o 4200%, Fe of quality 3o 4for Al 2o 310% of quality.
Utilize the method for embodiment 1 to record this magnetic nano-catalyst and 97.1%, 78.3% is respectively to the hydrodesulfurization of coal direct liquefaction oil, nitric efficiency.
Embodiment 9
Catalyst is by active component molybdenum sulfide, cobalt sulfide and magnetic coupling carrier Fe 3o 4-SiO 2-Al 2o 3composition; Wherein, molybdenum atom accounts for 26% of catalyst gross mass, and cobalt atom accounts for 4% of catalyst gross mass; In described carrier, SiO 2for Fe 3o 4200%, Fe of quality 3o 4for Al 2o 310% of quality.
Utilize the method for embodiment 1 to record this magnetic nano-catalyst and 98.8%, 79.1% is respectively to the hydrodesulfurization of coal direct liquefaction oil, nitric efficiency.
Embodiment 10
Catalyst is by active component molybdenum sulfide, cobalt sulfide and magnetic coupling carrier Fe 3o 4-SiO 2-Al 2o 3composition; Wherein, molybdenum atom accounts for 22% of catalyst gross mass, and cobalt atom accounts for 2% of catalyst gross mass; In described carrier, SiO 2for Fe 3o 4200%, Fe of quality 3o 4for Al 2o 310% of quality.
Utilize the method for embodiment 1 to record this magnetic nano-catalyst and 97.5%, 80% is respectively to the hydrodesulfurization of coal direct liquefaction oil, nitric efficiency.
Embodiment 11
Catalyst is by active component molybdenum sulfide, cobalt sulfide and magnetic coupling carrier Fe 3o 4-SiO 2-Al 2o 3composition; Wherein, molybdenum atom accounts for 22% of catalyst gross mass, and cobalt atom accounts for 6% of catalyst gross mass; In described carrier, SiO 2for Fe 3o 4200%, Fe of quality 3o 4for Al 2o 310% of quality.
Utilize the method for embodiment 1 to record this magnetic nano-catalyst and 97%, 80.5% is respectively to the hydrodesulfurization of coal direct liquefaction oil, nitric efficiency.

Claims (7)

1. for a catalyst for coal direct liquefaction oil hydrogenation, it is characterized in that, by active component molybdenum sulfide and cobalt sulfide and magnetic coupling carrier Fe 3o 4-SiO 2-Al 2o 3composition.
2. a kind of catalyst for coal direct liquefaction oil hydrogenation according to claim 1, it is characterized in that, molybdenum atom accounts for the 16-26% of catalyst gross mass, and cobalt atom accounts for the 2-6% of catalyst gross mass; In described magnetic coupling carrier, SiO 2for Fe 3o 4150% ~ 250%, Fe of quality 3o 4for Al 2o 3the 6-10% of quality.
3. the preparation method of a kind of catalyst for coal direct liquefaction oil hydrogenation according to claim 1, is characterized in that, comprise the following steps:
(1) by Fe 3o 4magnetic nanoparticle ultrasonic disperse is the Na of 1-3mol/L in concentration 2siO 3in solution, then solution is heated to 80 ~ 90 DEG C, under inert gas shielding, in solution, drips the HCl that concentration is 2-3mol/L, the pH value of solution is adjusted to 5 ~ 6 in 2 ~ 3h; Isolate precipitated product after reaction terminates, obtain Surface coating SiO 2fe 3o 4magnetic-particle;
(2) be that the aluminum hydroxide sol of 5-15% mixes with the organic amine mixed solution containing hexamethylenetetramine and urea at 0 ~ 15 DEG C by mass concentration, then by appropriate Surface coating SiO 2fe 3o 4magnetic-particle joins in solution, stirs and ultrasonic disperse uniformly aqueous phase sol solution; The colloidal sol microemulsion of uniform water-in-oil type will be formed in the sulfonated kerosene be dispersed under aqueous phase sol solution low whipping speed 60 ~ 80rpm containing 0.5-4.5wt%Span80, subsequently colloidal sol microemulsion is warming up to 85 ~ 90 DEG C, insulation 20 ~ 30min, aluminum hydroxide sol cure is being covered with SiO 2fe 3o 4magnetic-particle surface, product separation is removed surperficial oil slick with the deionized water washing containing a small amount of Tween80, and ageing is dry through solution heat treatment and in alkaline media subsequently, then at 500 ~ 600 DEG C of sintering 3 ~ 6h, obtain spherical gamma-Al 2o 3/ SiO 2/ Fe 3o 4magnetic coupling carrier;
(3) by appropriate γ-Al 2o 3/ SiO 2/ Fe 3o 4magnetic coupling support dispersion, in water, adds appropriate (NH 4) 6mo 7o 244H 2after O, under ultrasonic disperse, in solution, drip NaBH 4solution, stops ultrasonic after dropwising, and continues reaction 30 ~ 60min; Appropriate CoCl is added again in solution 26H 2after O, under ultrasonic disperse, be added dropwise to NaBH 4solution, stops ultrasonic after dropwising, and continues reaction 30 ~ 60min; Again precipitated product is separated, obtains catalyst intermediate;
(4) 2%CS is added with virgin kerosene 2for sulfurized oil, by catalyst intermediate presulfurization 36 ~ 72h, namely obtain catalyst.
4. the preparation method of a kind of catalyst for coal direct liquefaction oil hydrogenation according to claim 3, is characterized in that, in described step (1), and Na 2siO 3adding quality is Fe 3o 4the 305-508% of quality.
5. the preparation method of a kind of catalyst for coal direct liquefaction oil hydrogenation according to claim 3, is characterized in that, in described step (2), aluminum hydroxide sol quality is 10:1g/mL with the ratio of organic amine mixed liquor volume; In organic amine mixed solution, urea concentration is 0.167 ~ 0.33mol/L; The mol ratio of urea and hexamethylenetetramine is 1:2; It is Surface coating SiO that aluminium hydroxide adds quality 2fe 3o 4fe in magnetic-particle 3o 4the 15.3-25.5 of quality doubly.
6. the preparation method of a kind of catalyst for coal direct liquefaction oil hydrogenation according to claim 3, is characterized in that, in described step (3), and NaBH 4addition is 5% of molybdenum or cobalt atom molal quantity; (NH 4) 6mo 7o 244H 2it is γ-Al that O adds quality 2o 3/ SiO 2/ Fe 3o 4the 0.35-0.65 of magnetic coupling carrier quality doubly; CoCl 26H 2it is γ-Al that O adds quality 2o 3/ SiO 2/ Fe 3o 4the 0.10-0.33 of magnetic coupling carrier quality doubly.
7. the preparation method of a kind of catalyst for coal direct liquefaction oil hydrogenation according to claim 3, is characterized in that, the presulfurization condition described in step (4) is: initial hydrogen dividing potential drop pH 25.0 ~ 6.0Mpa, reaction temperature 280 ~ 320 DEG C, LHSV=2.0h -1, hydrogen to oil volume ratio=500.
CN201410776991.2A 2014-12-15 2014-12-15 A kind of Catalysts and its preparation method for coal direct liquefaction oil hydrogenation Expired - Fee Related CN104399495B (en)

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