Mo-Co bimetal supported catalyst and method thereof
阅读说明：本技术 一种Mo-Co双金属负载型催化剂及其方法 (Mo-Co bimetal supported catalyst and method thereof ) 是由 杨涛 扈广法 戴鑫 张生娟 黄传峰 杨天华 杨程 朱永红 刘树伟 程秋香 陈茂森 于 2020-12-27 设计创作，主要内容包括：一种Mo-Co双金属负载型催化剂及其方法,所述Mo-Co双金属负载型催化剂包括碳质颗粒载体和过渡金属Mo、Co活性组分,所述碳质颗粒载体比表面为300～1500m2/g。本发明解决现有重油加氢过渡金属催化剂存在的制备工艺复杂、制备成本高、加氢活性低的问题。(The Mo-Co bimetal supported catalyst comprises a carbonaceous particle carrier and active components of transition metals Mo and Co, wherein the specific surface of the carbonaceous particle carrier is 300-1500 m 2/g. The invention solves the problems of complex preparation process, high preparation cost and low hydrogenation activity of the existing heavy oil hydrogenation transition metal catalyst.)
1. The Mo-Co bimetal supported catalyst is characterized by comprising a carbonaceous particle carrier and active components of transition metals Mo and Co, wherein the specific surface of the carbonaceous particle carrier is 300-1500 m2/g, and a synthetic raw material contains alcohols.
2. The Mo-Co bimetallic supported catalyst of claim 1, wherein the raw materials for the synthesis of the Mo/Co bimetallic supported catalyst mainly comprise molybdenum salt, cobalt salt, carbonaceous particles, sulfur source and acid solution.
3. The synthesis method of the Mo-Co bimetal supported catalyst based on claim 1, which is characterized by comprising the following steps;
(1) dissolving molybdenum salt, a sulfur source and alcohols in water, and placing the solution in a reaction generating device for reaction for a certain time;
(2) adding the carbonaceous particles into a reaction generating device for fully mixing for a certain time;
(3) adding the acid solution and the cobalt salt into a reaction generating device together, and carrying out precipitation loading for a certain time under a certain pH environment to obtain the Mo/Co bimetallic supported catalyst.
4. The method for synthesizing the Mo-Co bimetallic supported catalyst as claimed in claim 3, wherein the reaction time of the step (1) is 10-40min, the mixing time of the step (2) is 10-40min, and the precipitation loading time of the step (3) is 20-80 min.
5. The method for synthesizing the Mo-Co bimetal supported catalyst according to claim 3, wherein the molybdenum salt is any one or combination of ammonium molybdate, potassium molybdate and sodium molybdate, and the addition amount of the molybdenum salt is 0.1-3: 100 of the mass ratio of metal molybdenum to carbonaceous particles.
6. The method for synthesizing the Mo-Co bimetallic supported catalyst according to claim 3, wherein the sulfur source is any one or combination of sodium sulfide and hydrogen sulfide, and the molar ratio of elemental sulfur in the sulfur source to metal molybdenum in the molybdenum salt is 3-6: 1.
7. The method for synthesizing the Mo-Co bimetallic supported catalyst as in claim 3, wherein the alcohol comprises any one or more of polyethylene glycol, ethylene glycol, propanol and ethanol; the adding amount of the alcohols is 0.1-1% of the mass of the water.
8. The method for synthesizing the Mo-Co bimetal supported catalyst according to claim 3, wherein the step (1), the step (2) and the step (3) all need stirring and have heat tracing at 25-85 ℃.
9. The method for synthesizing the Mo-Co bimetallic supported catalyst according to claim 3, wherein the acid solution is any one or more of hydrochloric acid, nitric acid and sulfuric acid solution; the pH environment is pH value of 1-4.
10. The method for synthesizing the Mo-Co bimetallic supported catalyst as recited in claim 3, wherein the amount of the cobalt salt added is measured according to the molar ratio of the metal cobalt contained in the cobalt salt to the metal molybdenum in the molybdenum salt being 1:9-1: 2.
Technical Field
The invention relates to the technical field of heavy oil hydrogenation, in particular to a Mo-Co bimetal supported catalyst and a method thereof.
Background
With the global trend of increasing the weight and deterioration of crude oil and the increasing dependence of domestic crude oil import, the development of hydrogenation technology for petroleum-based heavy oil and coal-based oil becomes a development trend in the refining and chemical field.
Most of the prior dispersed catalysts need to be additionally added with a vulcanizing agent for vulcanization to form an activated state, and the vulcanizing agent usually adopts hydrogen sulfide, industrial sulfur powder or DMDS, and the vulcanizing agents respectively have the defects of high toxicity, difficult dissolution, high cost and the like. In addition, the heavy oil suspension bed hydrogenation catalyst has the contradiction that the cost is low and the activity is high, in general, the Fe system dispersion type catalyst has low cost but low hydrogenation activity, and the transition metal oil-soluble catalysts such as Mo, Ni and Co have high reinforced activity but high cost due to the existence of organic ligands. The patent with application number 201310317514.5 discloses an oil-soluble auto-molybdenum sulfide catalyst, which comprises the steps of (1) putting a molybdenum source, water, sodium sulfide, a solvent and an inorganic acid in a container in sequence under the protection of nitrogen, uniformly mixing and stirring, cooling at 5-50 ℃, and reacting for 10-150 min; (2) adding alkylamine and carbon disulfide, stirring uniformly, heating to 60-200 ℃ and reacting for 3-10 h; (3) after the reaction is finished, fully cooling and filtering the product, fully washing the product with methanol, and drying the product to obtain the oil-soluble molybdenum sulfide catalyst; the hydrogenation activity of the catalyst is enhanced to a certain extent, but the defects of complex synthesis process and high cost still exist.
In general, the existing heavy oil hydrogenation catalyst has the conditions of complex preparation process, high preparation cost or low hydrogenation activity, so that the hydrogenation technology has the conditions of high device investment and operation cost, harsh reaction working conditions, high device operation difficulty and the like.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a Mo-Co bimetal supported catalyst and a method thereof, and solves the problems of complex preparation process, high preparation cost and low hydrogenation activity of the conventional suspended bed transition metal catalyst.
In order to achieve the purpose, the invention adopts the technical scheme that:
the Mo/Co bimetal supported catalyst comprises a carbonaceous particle carrier and active components of transition metals Mo and Co, wherein the specific surface of the carbonaceous particle carrier is 300-1500 m2/g, and a synthetic raw material contains alcohols.
The synthetic raw materials of the Mo/Co bimetallic supported catalyst mainly comprise molybdenum salt, cobalt salt, carbonaceous particles, a sulfur source and an acid solution.
A synthetic method of a Mo-Co bimetal supported catalyst comprises the following steps;
(1) dissolving molybdenum salt, a sulfur source and alcohols in water, and placing the solution in a reaction generating device for reaction for a certain time;
(2) adding the carbonaceous particles into a reaction generating device for fully mixing for a certain time;
(3) adding the acid solution and the cobalt salt into a reaction generating device together, and carrying out precipitation loading for a certain time under a certain pH environment to obtain the Mo/Co bimetallic supported catalyst.
The reaction time of the step (1) is 10-40min, the mixing time of the step (2) is 10-40min, and the precipitation load time of the step (3) is 20-80 min.
The molybdenum salt is any one or combination of more of ammonium molybdate, potassium molybdate and sodium molybdate, and the adding amount of the molybdenum salt is calculated according to the mass ratio of metal molybdenum to carbonaceous particles of 0.1-3: 100.
The sulfur source is any one or combination of sodium sulfide and hydrogen sulfide, and the molar ratio of elemental sulfur in the sulfur source to metal molybdenum in the molybdenum salt is 3-6: 1.
The alcohol comprises any one or more of polyethylene glycol, ethylene glycol, propanol and ethanol.
The adding amount of the alcohols is 0.1-1% of the mass of the water.
The step (1), the step (2) and the step (3) all need stirring and have heat tracing at 25-85 ℃.
The acid solution is any one or more of hydrochloric acid, nitric acid and sulfuric acid solution.
The pH environment is pH value of 1-4.
The adding amount of the cobalt salt is measured according to the molar ratio of the metal cobalt contained in the cobalt salt to the metal molybdenum in the molybdenum salt of 1:9-1: 2.
The invention has the beneficial effects that:
(1) the transition metal catalyst which is simple and convenient in synthesis method in the heavy oil hydrogenation field is provided, and the cost is relatively low;
(2) according to the characteristic that heavy oil hydrogenation is influenced by diffusion and mass transfer, a transition metal catalyst loaded on the outer surface is designed, and active carbon with large specific surface is adopted, so that the activity is high, the internal diffusion process is omitted, the reaction efficiency is improved, and the coke adsorption capacity is enhanced;
(3) the design of the bimetallic catalyst effectively improves the desulfurization level of the catalyst;
(4) provides favorable conditions for reducing the severity of heavy oil hydrogenation reaction.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
Adding 0.0185g of ammonium molybdate and 0.075g of sodium sulfide into a reaction device filled with 200g of deionized water, adding 0.2g of polyethylene glycol, starting stirring, heating to 25 ℃, and reacting for 10 min; the specific surface area is 300m2Adding 10 g/g of carbonaceous particles into a reaction device for fully mixing, and keeping the stirring operation and the reaction temperature at 25 ℃; after mixing well for 10min, the hydrochloric acid solution and 0.275g of cobalt nitrate were added to the reaction apparatus, and the pH was adjusted to 1, and the precipitation load was 80 min.
Example 2:
adding 0.745g of potassium molybdate and 0.638g of hydrogen sulfide into a reaction device filled with 200g of deionized water, adding 2g of ethylene glycol, starting stirring, heating to 85 ℃, and reacting for 40 min; the specific surface area is 1500m2Adding 10 g/g of carbonaceous particles into a reaction device for fully mixing, and keeping stirring operation and reaction temperature at 85 ℃; after mixing well for 40min, the sulfuric acid solution and 1.821g of cobalt nitrate were added to the reaction apparatus, the pH was adjusted to 3, and the precipitation load was 20 min.
Example 3:
adding 0.504g of sodium molybdate and 2.003g of sodium sulfide into a reaction device filled with 200g of deionized water, adding 1g of ethanol, starting stirring, heating to 40 ℃, and reacting for 30 min; the specific surface area is 600m2Adding 10 g/g of carbonaceous particles into a reaction device for fully mixing, and keeping stirring operation and reaction temperature at 40 ℃; after mixing well for 20min, the nitric acid solution and 3.637g were added to the reaction apparatus and the pH was adjusted to 4 and the precipitate was loaded for 60 min.
Example 4:
adding 0.185g of ammonium molybdate and 1.258g of sodium sulfide into a reaction device filled with 200g of deionized water, adding 1g of propanol, starting stirring, heating to 60 ℃, and reacting for 35 min; the specific surface area is 800m2Adding 10 g/g of carbonaceous particles into a reaction device for fully mixing, and keeping stirring operation and reaction temperature at 60 ℃; after mixing well for 25min, the nitric acid solution and 1.220g of cobalt nitrate were added to the reaction apparatus, the pH was adjusted to 1, and the precipitation load was 50 min.
Example 5
The catalysts prepared in examples 1 to 4 were used in a metal concentration of 200. mu.g.g-1The reaction mixture was added to Toledo vacuum residue, and after autoclave reaction was carried out at a reaction temperature of 450 ℃ and an initial hydrogen pressure of 9MPa for 60 minutes, the results are shown in Table 2.
TABLE 1 Toledo vacuum residua Properties and compositions
TABLE 2 distribution of the autoclave reaction products
The above description is only exemplary of the present invention and should not be taken as limiting the invention, as any modifications, equivalents, improvements and the like within the general concept of the present invention are intended to be included within the scope of the present invention.