CN106311341A - Preparation method of hydrogenation catalyst for slurry bed of heavy oil as well as catalyst and application thereof - Google Patents

Abstract

A preparation method of a heavy oil slurry bed hydrogenation catalyst, the catalyst and its application. The preparation method prepares a molybdenum-containing compound and at least one soluble salt selected from nickel, cobalt, iron, manganese, and copper metal elements into an aqueous solution. , adding an organic acid to generate a sol, and then directly performing a sulfidation reaction to obtain a sulfide state ultrafine solid powder, and emulsifying and dispersing the obtained sulfide state ultrafine solid powder with distillate oil to obtain a heavy oil slurry bed hydrogenation catalyst. The obtained heavy oil slurry bed hydrogenation catalyst is applied to the hydrogenation process of heavy oil raw materials in slurry bed or suspension bed. The catalyst has good dispersion performance and hydrocracking performance in heavy oil, and can effectively reduce the coke formation rate.

Description

Preparation method, catalyst and application of heavy oil slurry bed hydrogenation catalyst

technical field

The invention relates to a preparation method of a slurry-type hydrogenation catalyst used for hydrogenation of heavy oil, the catalyst and an application method of the catalyst.

Background technique

With the increase in oil extraction and processing of heavy oil, especially low-quality heavy oil, how to efficiently and greenly convert heavy oil has become a huge challenge in the energy field. Slurry bed hydroupgrading or hydrocracking is one of the important heavy oil conversion processes. Compared with fixed-bed and ebullated-bed hydrogenation processes, its advantages are: it can significantly strengthen the uniform mixing of catalyst, hydrogen and heavy oil macromolecules, and improve the accessibility of catalyst active centers; it is easy to control the temperature and pressure of the reaction process to achieve a steady state Operation; easy to control reaction depth by adjusting reaction conditions and process.

Catalysts suitable for slurry bed hydrogenation include oil-soluble, water-soluble and solid powder types. Its characteristics are: the active components of hydrocracking are mainly sulfided substances of transition metals of Group VIII and VIB, among which MoS ₂ and WS ₂ have high activities; the catalyst is easy to disperse efficiently and uniformly in heavy oil, and the active center of hydrocracking The accessibility is good, which can effectively eliminate the local overheating caused by the heat release of hydrogenation.

Based on the above considerations, the catalyst precursors are mostly in the form of homogeneous organic solvents, ultrafine droplets or ultrafine powders that are easy to disperse. The commonly used method is: mixing the catalyst precursor with heavy oil, adding a suitable vulcanizing agent for on-line vulcanization, and finally obtaining a highly dispersed metal sulfide catalyst. Alternatively, the catalyst precursor is dispersed in an oily medium, and then hydrosulfurized to obtain a slurry of a sulfurized catalyst with a higher concentration, and then dispersed into the raw material oil according to the concentration of the catalyst used.

The dispersibility of water-soluble catalysts is between that of oil-soluble catalysts and ultra-fine powder catalysts, but the metal content in oil-soluble catalysts is generally low, the amount of use is large, and the cost is high. The dispersibility of ultrafine powder in oil is limited by the particle size, and the dispersibility is poor. In summary, the modification of water-soluble catalysts has good economic and application effects.

CN1321727A and CN1482214A disclose two-component or more-component metal salt water-soluble composite catalysts containing iron, nickel, cobalt and molybdenum salts. The pH value of the aqueous solution is less than 5, and after being emulsified with heavy oil, it will be vulcanized online, and then react directly. The cost of this type of catalyst is reduced. However, the degree of dispersion in heavy oil is limited, and the application effect is poor. In CN 1459490A, a new heavy oil slurry bed hydrocracking process is proposed, which uses a catalyst composed of two or more metal water-soluble salts containing iron, nickel, manganese, molybdenum, cobalt, etc., and the vulcanizing agent is Water-soluble sulfur-containing compounds, the vulcanization of the catalyst is low-temperature vulcanization. The reactor uses a loop reactor, but the raw material oil, catalyst, and vulcanizing agent need multi-stage shear emulsification, and the water is removed through the dehydration tower, and the operation process is relatively long. CN101024186A introduces a reverse-phase micellar nanocatalyst, which has a water-in-oil structure, and first disperses superfine transition metal particles in a sulfide state in the water phase, and the water phase is wrapped with a surfactant, which can be dispersed into the organic phase. Since the nature of the organic phase is similar to that of heavy oil, it is conducive to the uniform dispersion of catalyst particles in heavy oil. A kind of lyosol catalyst is mentioned in CN101011663A, the soluble salt of the transition metal element in VIII group, VIB group and VIIB is made into aqueous solution, then adds monodentate ligand or organic polydentate ligand to form complex, then adds water-soluble Sexual sulfides, including sodium sulfide, potassium sulfide, ammonium sulfide or thiosulfate, etc., react with complexes to form sulfides.

In US 7214309B2, an improved preparation method of heavy oil hydro-upgrading catalyst is disclosed. MoO ₃ is firstly mixed with ammonia water to generate ammonium molybdate aqueous solution in a mixing tank, and then H ₂ S with 7 to 10 times the theoretical amount is introduced to vulcanize at 54 to 82°C for 4h to 6h. After adding catalyst additives, nitrogen and other inert mixed gases are introduced, VGO is added and high-speed shear mixing is performed to obtain a mixed slurry. Then hydrogen gas is introduced at 177°C to 232°C for a reaction time of 1h to 1.5h. After the reaction, the mixed slurry is reacted in a high-pressure separator at a temperature of 150-370° C., and a uniformly dispersed MoS ₂ oil slurry is obtained after removing steam. The VRST technology proposed by Chevron uses the above-mentioned catalysts, and the application effect is good, but the preparation process of the catalyst is complicated, requiring medium temperature, high temperature, medium pressure and high pressure hydrosulfurization treatment, and the removal of water vapor in the high fraction tank, the operation process is complicated .

Contents of the invention

The purpose of the present invention is to provide a method for preparing a heavy oil slurry bed hydrogenation catalyst with simple steps and easy operation.

The preparation method provided by the invention comprises:

(1) A molybdenum-containing compound and at least one soluble salt of a metal element selected from nickel, cobalt, iron, manganese, and copper are dissolved in water to prepare an aqueous solution, based on all metals in the solution, and in terms of elements, molybdenum The molar fraction of the metal is 10% to 70%, and the sum of the molar fractions of the remaining metals is 30% to 90%.

(2) organic acid is added in step (1) gained aqueous solution, generates sol,

(3) Add a vulcanizing agent to the sol obtained in step (2), feed hydrogen-containing gas, and heat vulcanization at the same time to obtain a solution containing superfine solid powder in a vulcanized state. During the vulcanization process, the temperature is 260°C to 400°C, and the pressure is 1.0 ~7.0MPa, the amount of hydrogen used is 1.2~10 times the theoretical amount of complete vulcanization of all metals in the solvent, and the vulcanization time is 1~6h.

(4) After separating and removing water from the solution containing the sulfided ultrafine solid powder obtained in step (3), emulsifying and dispersing the obtained sulfided ultrafine solid powder and distillate oil to obtain a heavy oil slurry bed hydrogenation catalyst.

In the preparation method provided by the present invention, the active metal first generates a colloid in an organic acid and then hydrosulfurizes, and the obtained sulfide precipitate has a small initial particle size and is easy to be uniformly dispersed in a heavy oil system after shearing. The obtained sulfide is superfine solid powder in sulfide state, and its average particle size range is below 20nm.

The invention adopts one-step high-temperature hydrosulfurization, has simple and convenient operation steps, and has high sulfuration degree of metal active components. In addition, the sulfided ultrafine solid powder obtained in the present invention is directly emulsified and dispersed into distillate oil to obtain an oil slurry type hydrogenation catalyst, which reduces the risk of sulfide being oxidized again.

In step (1), taking all the metals in the solution as the benchmark, the molar fraction of molybdenum is 30%-50% in terms of elements, and the sum of the molar fractions of the remaining metals is 50%-70%.

The molybdenum-containing compound is selected from one or more of molybdenum trioxide, ammonium molybdate and sodium molybdate.

The at least one soluble salt of metal elements selected from nickel, cobalt, iron, manganese and copper in the present invention is one or more selected from nitrates, acetates and sulfates of the above metals. Preferably, it is one or more selected from nickel nitrate, nickel acetate, cobalt nitrate, ferric nitrate, ferric sulfate, ferrous sulfate, manganese nitrate, copper nitrate, copper sulfate or copper acetate.

The concentration of the aqueous solution obtained in step (1) is 0.1-0.5 times, preferably 0.3-0.5 times, the concentration of the saturated aqueous solution of the corresponding metal salt.

The organic acid described in step (2) is selected from one or more of acetic acid, acetic anhydride, oxalic acid, citric acid, tartaric acid and 1,4-succinic acid. Preferably, the organic acid is an aqueous organic acid solution, the mass concentration of the organic acid aqueous solution is 1%-50%, preferably 15%-25%.

The molar weight of the organic acid added to the aqueous solution in step (2) is 1.0 to 2.0 times the molar weight of all metal elements in the aqueous solution in step (1).

The temperature of step (1) and step (2) of the present invention is room temperature, and pressure is normal pressure.

The vulcanizing agent in step (3) is selected from one or more of elemental sulfur, H ₂ S, CS ₂ , ammonium sulfide, sodium sulfide, dimethyl disulfide, and dibenzyl disulfide.

The amount of vulcanizing agent used in step (3) is 1.0 to 10.0 times, preferably 1.1 to 1.5 times, the amount required for complete vulcanization of all metal elements in the sol.

The temperature during the vulcanization process in step (3) is 300° C. to 330° C. The pressure during the vulcanization process is 4.0-6.0MPa.

In the hydrogen-containing gas in step (3), the hydrogen content is 80-100% by volume, and the amount of hydrogen used is 2.0-5.0 times of the theoretically calculated amount of complete sulfidation of all metals in the sol.

The distillate oil in step (4) is hydrocarbon oil with a distillation range of 350-500° C., including one or more of atmospheric and vacuum gas oil, coal tar, and catalytic cracking bottom oil.

In step (4), the content of the vulcanized superfine solid powder in the distillate oil is 10% to 50% by volume. The temperature of step (4) is room temperature, and the pressure is normal pressure.

The present invention also includes the heavy oil slurry bed hydrogenation catalyst prepared by the above preparation method.

The present invention also includes the application of the catalyst obtained by the above preparation method. The heavy oil slurry bed hydrogenation catalyst is used in the hydrogenation process of heavy oil feedstock in slurry bed or suspension bed, and the heavy oil feedstock is selected from heavy distillate oil, One or more of residual oil, crude oil, and mixed raw materials for oil-coal co-refining, including:

(1) Heating the heavy oil raw material to 100° C. to 140° C., then adding the heavy oil slurry bed hydrogenation catalyst and mixing uniformly. The amount of the catalyst added is 0.5 to 2.0% of the weight of the heavy oil raw material in terms of molybdenum disulfide;

(2) The mixture obtained in step (1) is started to react under hydrogenation reaction conditions, the reaction temperature is 390-430°C, the reaction pressure is 8.0-15.0MPa, the reaction time is 1-6h, and the hydrogen-oil volume ratio is 500-500°C. 1500;

(3) cooling, separating and fractionating the reaction product obtained in step (2).

The heavy oil raw material described in the present invention is a relatively poor quality raw material, especially refers to the metal content higher than 150ppm, the asphaltene content higher than 5% by weight, and the S and N content higher than 1% by weight, so it is not suitable for fixed bed or ebullating bed Inferior heavy oil raw materials processed by other methods. Secondly, the heavy oil slurry bed hydrogenation catalyst provided by the invention can also be used in the oil-coal co-refining process. The catalyst has good dispersibility and hydrocracking performance in heavy oil, and can effectively reduce coke formation rate under optimized conditions.

Advantages of the present invention include:

(1) The preparation method provided by the invention has simple operation steps and a high degree of vulcanization of the metal active components.

(2) The sulfided active metal powder obtained in the preparation method provided by the present invention is directly emulsified and dispersed into distillate oil to obtain an oil slurry catalyst, which reduces the risk of sulfide being oxidized again.

(3) The sulfided active metal powder obtained in the oil slurry type hydrogenation catalyst obtained in the present invention has a small particle size and good dispersibility in distillate oil. Therefore, during the hydrogenation process of heavy oil, the sulfided active metal powder of this oil slurry hydrogenation catalyst can also maintain good dispersion, which can significantly inhibit coke formation. high.

detailed description

The technical solutions provided by the present invention will be further described below in conjunction with examples, but the present invention is not limited thereby.

Example 1

Weigh 5.73g of molybdenum trioxide in a beaker, add 8.20g of 25% ammonia solution and dissolve under stirring to obtain solution A; add 11.60g of cobalt nitrate hexahydrate in the beaker, add 15ml of deionized water to dissolve to obtain solution B; Add 20.10g oxalic acid, dissolve it with 20ml deionized water to obtain aqueous solution C; add B dropwise to aqueous solution A, and mix well; then add C dropwise to the above mixed solution, and stir until the solution is clear; then transfer the above solution to 500ml high pressure Add 2.00 g of sublimed sulfur powder to the stirred tank, seal the autoclave, and replace it with hydrogen for 3 times; pressurize to 1.0 MPa. Under high-speed stirring, heat the autoclave to 310°C±5°C, keep at this temperature for 30min, and then stop heating. After the autoclave was lowered to room temperature, the pressure was released and the autoclave was opened, the obtained slurry was transferred to a centrifuge tube, centrifuged, and the upper aqueous solution was poured out. Transfer the lower layer to a beaker, add 25g of vacuum wax oil, the wax oil has an initial boiling point of 344°C, a 5% boiling point of 382°C, a 50% boiling point of 434°C, and an aromatic fraction of 60% in the four-component distribution. Emulsify and disperse into oil slurry catalyst 1#.

Example 2

Weigh 4.93g of ammonium molybdate in a beaker, add 25ml of deionized water to dissolve under stirring to obtain solution A; add 8.11g of nickel nitrate to the beaker, add 10ml of deionized water to dissolve to obtain solution B; add 14.50g of oxalic acid to the beaker , dissolved in 15ml deionized water to obtain aqueous solution C; add B dropwise to aqueous solution A, and mix well; then add C dropwise to the above mixed solution, and stir until the solution is clear; transfer the above solution to a 500ml high-pressure stirring tank, and add Sodium sulfide 15.20g, seal the autoclave, replace with hydrogen 3 times; pressurize to 1.5MPa. Under high-speed stirring, heat the autoclave to 310°C±5°C, keep at this temperature for 30min, and then stop heating. After the autoclave was lowered to room temperature, the pressure was released and the autoclave was opened, the obtained slurry was transferred to a centrifuge tube, centrifuged, and the upper aqueous solution was poured out. Transfer the lower layer to a beaker, add 20g of catalytic cracking bottom oil, the initial boiling point of the bottom oil is 311°C, the 5% boiling point is 356°C, the 50% boiling point is 432°C, and the aromatic fraction in the four-component distribution is 80 %, emulsified and dispersed into oil slurry catalyst 2#.

Example 3

Weigh 5.65g of ammonium molybdate in a beaker, add 30ml of deionized water to dissolve under stirring to obtain solution A; add 8.62g of ferric nitrate to the beaker, add 10ml of deionized water to dissolve to obtain solution B; add g oxalic acid to the beaker, Dissolve with deionized water to obtain aqueous solution C; add B dropwise to aqueous solution A, and mix well; then add C dropwise to the above mixed solution, and stir until the solution is clear; transfer the above solution to a 500ml high-pressure stirred tank, and add sublimation Sulfur powder 2.90g, seal the autoclave, replace with hydrogen 3 times; pressurize to 1.5MPa. Under high-speed stirring, heat the autoclave to 310°C±5°C, keep at this temperature for 30min, and then stop heating. After the autoclave was lowered to room temperature, the pressure was released and the autoclave was opened, the obtained slurry was transferred to a centrifuge tube, centrifuged, and the upper aqueous solution was poured out. Transfer the lower layer to a beaker, add 25g of catalytic cracking bottom oil, the initial boiling point of the bottom oil is 311°C, the 5% boiling point is 356°C, the 50% boiling point is 432°C, and the aromatic fraction in the four-component distribution is 80 %, emulsified and dispersed into oil slurry catalyst 3#.

Example 4

Take by weighing 4.97g of ammonium molybdate in a beaker, add 25ml of deionized water to dissolve under stirring to obtain solution A; add 4.09g of cobalt nitrate to the beaker, add 8ml of deionized water to dissolve, then weigh and add 5.05g of manganese nitrate aqueous solution to obtain Solution B; add 16.00g oxalic acid in a beaker, dissolve it with 20ml deionized water to obtain aqueous solution C; add B dropwise into aqueous solution A, and mix well; then add C dropwise into the above mixed solution, and stir until the solution is clear; The solution was transferred to a 500ml high-pressure stirred tank, 8.50 g of 50% ammonium sulfide aqueous solution was added, the autoclave was sealed, and the autoclave was replaced with hydrogen for 3 times; the pressure was charged to 1.5 MPa. Under high-speed stirring, heat the autoclave to 310°C±5°C, keep at this temperature for 30min, and then stop heating. After the autoclave was lowered to room temperature, the pressure was released and the autoclave was opened, the obtained slurry was transferred to a centrifuge tube, centrifuged, and the upper aqueous solution was poured out. Transfer the lower layer to a beaker, add 25g of vacuum wax oil, the wax oil has an initial boiling point of 344°C, a 5% boiling point of 382°C, a 50% boiling point of 434°C, and an aromatic fraction of 60% in the four-component distribution. Emulsify and disperse into oil slurry catalyst 4#.

Example 5

Weigh 4.14g of ammonium molybdate in a beaker, add 25ml of deionized water to dissolve under stirring to obtain solution A; add 8.11g of iron nitrate and 2.83g of copper nitrate to the beaker, add 10ml of deionized water to dissolve to obtain solution B; Add 15.00g oxalic acid to the solution, dissolve it with 20ml deionized water to obtain aqueous solution C; add B dropwise to aqueous solution A, and mix well; then add C dropwise to the above mixed solution, and stir until the solution is clear; transfer the above solution to 500ml high-pressure Add g of sublimated sulfur powder to the stirred tank, seal the autoclave, and replace it with hydrogen for 3 times; pressurize to 1.5 MPa. Under high-speed stirring, heat the autoclave to 310°C±5°C, keep at this temperature for 30min, and then stop heating. After the autoclave was lowered to room temperature, the pressure was released and the autoclave was opened, the obtained slurry was transferred to a centrifuge tube, centrifuged, and the upper aqueous solution was poured out. Transfer the lower layer to a beaker, add 25g of vacuum wax oil, the wax oil has an initial boiling point of 344°C, a 5% boiling point of 382°C, a 50% boiling point of 434°C, and an aromatic fraction of 60% in the four-component distribution. Emulsify and disperse into oil slurry catalyst 5#.

Comparative example 1

Weigh 4.93g of ammonium molybdate tetrahydrate into a beaker, add 30ml of deionized water to dissolve under stirring to obtain solution A; add 8.11g of nickel nitrate hexahydrate to the beaker, add 20ml of deionized water to dissolve to obtain solution B; drop B Add it to the aqueous solution A and mix evenly; transfer the above solution to a 500ml high-pressure stirred tank, add 2.80 g of sublimed sulfur powder, seal the autoclave, and replace it with hydrogen for 3 times; pressurize to 2.0 MPa. Under high-speed stirring, heat the autoclave to 310°C±5°C, keep at this temperature for 30min, and then stop heating. After the autoclave was lowered to room temperature, the pressure was released and the autoclave was opened, the obtained slurry was transferred to a centrifuge tube, centrifuged, and the upper aqueous solution was poured out. Transfer the lower layer to a beaker, add 20g of catalytic cracking bottom oil, the initial boiling point of the bottom oil is 311°C, the 5% boiling point is 356°C, the 50% boiling point is 432°C, and the aromatic fraction in the four-component distribution is 80 %, emulsified and dispersed into oil slurry catalyst comparison 1#.

Comparative example 2

Take by weighing ammonium molybdate 4.97g in a beaker, add deionized water 25ml and dissolve under stirring to obtain solution A; add cobalt nitrate 4.09g in the beaker, add deionized water 8ml to dissolve, then weigh and add 5.05g manganese nitrate aqueous solution (nitric acid The mass fraction of manganese is 50%), to obtain solution B; B is added dropwise in the aqueous solution A, mixes uniformly; Said solution is transferred in the 500ml high-pressure stirred tank, adds sublimated sulfur powder 2.90g, seals the autoclave, replaces with hydrogen for 3 Times; pressurize to 1.5MPa. Under high-speed stirring, heat the autoclave to 310°C±5°C, keep at this temperature for 30min, and then stop heating. After the autoclave was lowered to room temperature, the pressure was released and the autoclave was opened, the obtained slurry was transferred to a centrifuge tube, centrifuged, and the upper aqueous solution was poured out. Transfer the lower layer to a beaker, add 25g of vacuum wax oil, the wax oil has an initial boiling point of 344°C, a 5% boiling point of 382°C, a 50% boiling point of 434°C, and an aromatic fraction of 60% in the four-component distribution. Emulsification and dispersion into oil slurry catalyst comparison 2#.

Embodiment 6～10 and comparative example 3～4

A high-pressure stirred tank device was used to carry out the application experiment of the above-mentioned heavy oil hydrogenation catalyst. The raw material oil 1 used in Examples 6-7 and Comparative Example 3 was a residue oil with higher asphaltene and metal content, and Examples 8-10 and The raw material oil 2 that comparative example 4 adopts is a kind of inferior residual oil with higher aromatic content, and its properties are as shown in Table 1:

Table 1 Properties of raw oil

Raw oil 1 Raw oil 2 Density(20℃)/(g.cm ^-3 ) 0.9914 1.033 Carbon residue, wt% 16.6 23.5 Saturated hydrocarbon,% 30.8 8.3 Aromatics,% 36.2 52.4 Colloid, wt% 22.1 29.0 Asphaltenes, % by weight 10.9 10.3 S,wt% 2.11 5.0 N,wt% 0.50 0.39 Ni/(μg.g ^-1 ) 35.9 39 V/(μg.g ^-1 ) 201 124 Fe/(μg.g ^-1 ) 15.0 7.0

The steps are as follows: Rinse and dry a 500ml autoclave, heat the raw material oil to 120°C in a beaker, then add 100g raw material oil to the high-pressure stirred tank while it is hot, and then add a slurry-type catalyst while it is hot. The amount of catalyst added is based on disulfide Molybdenum is calculated as 1.0% of the mass of the raw oil. Tighten the screws of the autoclave, fill with nitrogen gas of about 3 MPa to check the air tightness, and release the pressure after passing the test. Then hydrogen was introduced to replace the nitrogen in the autoclave three times, and hydrogen was charged until the gauge pressure in the autoclave was 5.0 MPa. Stir and heat the autoclave to 420°C, and the heating rate is not higher than 20°C/min. When the temperature reached 407°C, the reaction timing was started, and the reaction time was 50 minutes. After the reaction, the heating mantle of the autoclave was disassembled, and the reaction temperature was reduced to 350° C. within 5 minutes by blowing with a fan, and then cooled down to room temperature naturally. After opening the autoclave, take out the product, weigh the total weight, centrifuge to separate the solid and liquid phases, conduct simulated distillation on the liquid phase, wash the solid phase with toluene and suction filter, and weigh the filtrate after drying at 120°C.

The catalytic effect was comprehensively evaluated by coke formation rate, conversion rate and liquid yield. The meaning of each parameter is as follows:

Residual oil conversion rate = [mass of components below 524°C (including gas)/mass of raw oil] × 100%

Coke formation rate = [toluene insoluble matter (TI) mass / raw material oil mass] × 100%

Liquid yield = [liquid product quality / raw material oil quality] × 100%

The results are shown in Table 2:

Table 2

It can be seen that compared with the catalyst prepared by direct aqueous solution hydrosulfurization, the catalyst prepared by the method provided by the present invention has a better application effect in the heavy oil hydrocracking process, and the conversion rate can reach 83%, while the corresponding The coke rate is lower than 2%. This is because, in the preparation method provided by the present invention, when organic acid is added, complexes will be formed with metal ions, and the metal ions will be evenly dispersed, so that the particle size of the composite sulfide obtained after vulcanization is small and the distribution is more uniform , the average particle size of the primary particles is less than 20nm, that is, the average particle size of the vulcanized ultrafine solid powder is less than 20nm. In the comparative example, hydrosulfurization is directly performed in an aqueous solution, and the obtained sulfide precipitates have a large particle size and poor uniformity, and the average particle size of the primary particles is in the range of 20nm to 100nm. Therefore, when added to heavy oil to catalyze the hydrocracking reaction of heavy oil, the catalyst obtained in the present invention can be better dispersed in heavy oil, so that the active center of the catalyst is more likely to approach the heavy oil evenly, and the hydrogenation effect is better.

Claims (16)

1. a preparation method for heavy-oil slurry hydrogenation catalyst, including:

(1) by molybdate compound with at least one selected from nickel, cobalt, ferrum, manganese, copper metallic element Soluble-salt, soluble in water, it is prepared as aqueous solution, in solution on the basis of all of metal, with unit Element meter, the molar fraction of molybdenum is 10%～70%, the molar fraction summation of residual metallic be 30%～ 90%,

(2) organic acid is added in step (1) obtained aqueous solution, generates colloidal sol,

(3) in step (2) gained colloidal sol, add vulcanizing agent, be passed through hydrogen-containing gas, heat simultaneously Sulfuration, obtain the solution containing sulphided state ultrafine solids powder, in sulfidation temperature be 260 DEG C～ 400 DEG C, pressure is 1.0～7.0MPa, and hydrogen consumption is that in colloidal sol, all of metal complete cure theory is used 1.2 times～10 times of amount, cure time is 1～6h,

(4) carry out the solution that step (3) gained contains sulphided state ultrafine solids powder separating except water After, the sulphided state ultrafine solids powder of gained and distillate are carried out emulsion dispersion, obtains heavy oil slurry Bed hydrogenation catalyst.

The most in accordance with the method for claim 1, it is characterised in that with in solution in step (1) On the basis of all of metal, in terms of element, the molar fraction of molybdenum is 30%～50%, residual metallic Molar fraction summation is 50%～70%.

The most in accordance with the method for claim 1, it is characterised in that described molybdate compound is selected from One or more in molybdenum trioxide, molybdenum acid ammonia, sodium molybdate.

The most in accordance with the method for claim 1, it is characterised in that at least one selected from nickel, cobalt, Ferrum, manganese, the soluble-salt of copper metallic element are the nitrate selected from above-mentioned metal, acetate, sulphuric acid One or more in salt.

The most in accordance with the method for claim 1, it is characterised in that step (1) obtained aqueous solution Concentration is 0.1～0.5 times of the saturated aqueous solution concentration of corresponding slaine, preferably 0.3～0.5 times.

The most in accordance with the method for claim 1, it is characterised in that organic described in step (2) Acid is selected from acetic acid, acetic anhydride, oxalic acid, citric acid, tartaric acid, the one of 1, 4-succinic acid or several Kind.

The most in accordance with the method for claim 1, it is characterised in that step (2) adds water-soluble The mole of organic acid all of metallic element mole in being step (1) described aqueous solution in liquid 1.0～2.0 times.

The most in accordance with the method for claim 1, it is characterised in that step (3) described vulcanizing agent Selected from elemental sulfur, H₂S、CS₂, ammonium sulfide, sodium sulfide, Methyl disulfide compound, dibenzyl two One or more in sulphur compound.

The most in accordance with the method for claim 1, it is characterised in that step (3) vulcanizing agent consumption For the desired amount of 1.0 times～10.0 times of metallic element complete cure all of in colloidal sol, preferably 1.1 times～ 1.5 again.

The most in accordance with the method for claim 1, it is characterised in that step vulcanized in (3) In journey, temperature is 300 DEG C～330 DEG C.

11. in accordance with the method for claim 1, it is characterised in that step vulcanized in (3) In journey, pressure is 4.0～6.0MPa.

12. in accordance with the method for claim 1, it is characterised in that step (3) hydrogen-containing gas In, hydrogen content is 80～100 volume %, and hydrogen usage is all of metal complete cure in colloidal sol 2.0～5.0 times of theoretical amount.

13. in accordance with the method for claim 1, it is characterised in that step evaporates described in (4) Dividing oil is boiling range scope hydrocarbon ils between 350～500 DEG C, including Atmospheric vacuum wax oil, coal tar, urges Change one or more in cracking chamber base oil.

14. in accordance with the method for claim 1, it is characterised in that in step (4), with body Long-pending meter, sulphided state pressed powder content in distillate is 10%～50%.

The heavy-oil slurry hydrogenation catalyst of 15. 1 kinds of any one method gained of claim 1-14.

The application of 16. 1 kinds of any one method gained catalyst of claim 1-14, described heavy oil slurry State bed hydrogenation catalyst is applied in the heavy oil feedstock hydrogenation process of slurry bed system or suspension bed, described weight Oil raw material one in the mixing raw material that heavy distillate, residual oil, crude oil, oil-coal refine altogether or Several, including:

(1) heavy oil feedstock is heated to 100 DEG C～140 DEG C, is subsequently adding described heavy-oil slurry hydrogenation Catalyst mix homogeneously, in terms of molybdenum bisuphide, catalyst charge is heavy oil raw materials quality 0.5～2.0%；

(2) mixture of step (1) gained is started under hydrogenation conditions reaction, reaction temperature Degree is 390～430 DEG C, and reaction pressure is 8.0～15.0MPa, and the response time is 1～6h, hydrogen oil volume Ratio is 500～1500；

(3) carry out cooling down, separating and fractional distillation by step (2) gained reaction product.