阅读说明：本技术 浆态床加氢催化剂的制备方法及应用 (Preparation method and application of slurry bed hydrogenation catalyst ) 是由 王卫平 王蕴 吴治国 王鹏飞 崔龙鹏 邹亮 于 2018-08-13 设计创作，主要内容包括：本发明涉及催化剂领域,公开了一种浆态床加氢催化剂的制备方法及应用。所述浆态床加氢催化剂的制备方法包括：1)将含金属活性元素的化合物的溶液与含尘气流接触；2)将步骤1)所得接触产物进行气固分离,得到被所述溶液润湿的固体物流和除尘后气流；3)将所述固体物流干燥,得到浆态床加氢催化剂。本发明提供的方法具有催化剂制备工艺简单、能提高活性组分分散程度的特点,且该方法能同时实现对含尘气体的净化。所制备的浆态床加氢催化剂应用到重质油的加氢反应中具有馏分油收率、脱金属率显著等优势,同时能降低生焦率。(The invention relates to the field of catalysts, and discloses a preparation method and application of a slurry bed hydrogenation catalyst. The preparation method of the slurry bed hydrogenation catalyst comprises the following steps: 1) contacting a solution of a metal-active element-containing compound with a dusty gas stream; 2) carrying out gas-solid separation on the contact product obtained in the step 1) to obtain a solid material flow wetted by the solution and a dedusted gas flow; 3) and drying the solid matter flow to obtain the slurry bed hydrogenation catalyst. The method provided by the invention has the characteristics of simple catalyst preparation process and capability of improving the dispersion degree of the active components, and can simultaneously realize the purification of the dust-containing gas. The prepared slurry bed hydrogenation catalyst has the advantages of remarkable distillate yield and demetalization rate and the like when being applied to the hydrogenation reaction of heavy oil, and can reduce the coking rate.)

1. A method for preparing a slurry bed hydrogenation catalyst, which comprises the following steps:

1) contacting a solution of a metal-active element-containing compound with a dusty gas stream,

wherein dust particles in the dust-containing gas flow are carbon materials or materials containing silicon oxide and/or aluminum oxide;

2) carrying out gas-solid separation on the contact product obtained in the step 1) to obtain a solid material flow wetted by the solution and a dedusted gas flow;

3) and drying the solid matter flow to obtain the slurry bed hydrogenation catalyst.

2. The process according to claim 1, wherein the dusty gas stream is a coke powder-containing gas stream from coal gasification or a coke powder-containing gas stream from coal combustion, or a gas stream containing silicon and/or aluminium ore fines from ore calcination.

3. The process according to claim 1 or 2, wherein the dusty gas stream has a dust particle content of from 10 to 100000g/m³Preferably 100 to 50000g/m³More preferably 1000 to 10000g/m³；

Preferably, the average particle size of the dust particles is 1 to 150 μm, and more preferably 20 to 100 μm.

4. The production method according to claim 1, wherein the metal active element is selected from at least one of iron, zinc, nickel, cobalt, molybdenum, and tungsten, preferably at least one of iron, zinc, and nickel;

preferably, the content of the metal active element in the solution is 0.01-20 wt%.

5. The process according to claim 1, wherein in step 1) the solution is contacted with the dusty gas stream in the form of a spray in droplets;

preferably, the average particle size of the droplets is not more than 500 μm, more preferably 5 to 200 μm.

6. The preparation method according to claim 1, wherein in the step 1), the liquid-gas ratio of the solution of the metal active element-containing compound to the dust-containing gas stream is 0.01-20 kg/m³。

7. The production method according to claim 1 or 5, wherein the contacting temperature in step 1) is 100 to 600 ℃, preferably 200 to 500 ℃.

8. The preparation method according to claim 1, wherein in the step 2), the gas-solid separation is performed by cyclone separation or gravity settling separation.

9. The method according to claim 1, wherein the drying temperature in step 3) is 100 to 500 ℃, preferably 150 to 300 ℃.

10. The production method according to any one of claims 1 to 7 and 9, wherein the production method is performed in a cyclone separator or a gravity separator;

the upper section of the cyclone separator is a cylindrical barrel, the lower section of the cyclone separator is an inverted conical barrel, the top of the cylindrical barrel is provided with a dedusted airflow outlet, the middle of the cylindrical barrel is provided with a dust-containing airflow inlet, and the upper part in the barrel is provided with a nozzle for atomizing the solution into liquid drops; the gravity settling separator is a cylindrical barrel, the top of the gravity settling separator is provided with a dust-removed airflow outlet, the middle of the gravity settling separator is provided with a dust-containing airflow inlet, and the upper part in the barrel is provided with a nozzle for atomizing the solution into liquid drops.

11. Use of the slurry bed hydrogenation catalyst prepared by the preparation method of any one of claims 1 to 10 in heavy oil hydrocracking reaction.

12. The use according to claim 11, wherein the content of the metal active element is 0.1-30 wt% based on the total weight of the slurry bed hydrogenation catalyst;

preferably, the average particle size of the slurry bed hydrogenation catalyst is 5-150 μm, and more preferably 10-100 μm.

Technical Field

The invention relates to the field of catalysts, in particular to a preparation method and application of a slurry bed hydrogenation catalyst.

Background

The increasing weight and deterioration problems of world petroleum resources and the rapid increase of economy are contradictory to the increasing demand of petroleum products, so that heavy oil lightening technology is more and more concerned by various refineries. Among the existing heavy oil lightening technologies, the slurry bed hydrogenation technology has strong competitiveness and good development prospect because of being capable of processing poor-quality raw materials with high carbon residue and high metal content. The catalyst is one of the core technologies of slurry bed hydrogenation process, and has very important functions of reducing reaction severity, improving reaction efficiency and light oil yield, reducing coke yield and heavy oil processing cost and the like.

The slurry bed hydrogenation catalyst is classified into a supported type, an oil-soluble type, a water-soluble type and the like. The oil-soluble catalyst has better dispersing capacity and catalytic activity, can effectively improve the yield of light oil, but is usually toxic, and the metal active component content in the organic metal compound is low, so the usage amount is large when the metal is used for metering, and the cost is high. Water-soluble metal catalysts generally require dispersing an active metal-containing compound in an alcohol or alcohol/water mixture solution for uniform dispersion in the oil, but such catalysts require removal of water prior to processing of the heavy oil to reduce the total reaction pressure or reduce corrosion of the reaction apparatus by water.

The supported catalyst is a heavy oil slurry bed hydrogenation catalyst with more applications, and the main preparation methods of the supported catalyst comprise an impregnation method, a precipitation method, a solid phase method, hydrothermal/solvothermal synthesis and the like. The solid phase method is difficult to form nano-scale grains; the hydrothermal/solvothermal synthesis method needs to be carried out in a closed container under the conditions of relatively high temperature and high pressure (generally 200 ℃, the pressure is generated by heating the solution), and a large amount of solvent is needed, so that the production cost is high; the precipitation method needs an alkaline precipitator, the preparation process is relatively complex, and the water consumption is large; impregnation methods are relatively simple, but it is often difficult to achieve high dispersion of the active metal at the surface, resulting in a catalyst that is not highly active.

Therefore, there is a need for a new method for preparing a slurry bed hydrogenation catalyst with simple preparation process and uniformly dispersed active components.

Disclosure of Invention

Aiming at the problems in the prior art, the invention provides a preparation method and application of a slurry bed hydrogenation catalyst. The method realizes the coupling of the catalyst preparation and the dust-containing gas de-solidification purification technology, improves the dispersion degree of active components in the prepared catalyst in a carrier (namely dust particles), simplifies the preparation process, and simultaneously realizes the purification of dust-containing gas flow.

According to a first aspect of the present invention, there is provided a process for the preparation of a slurry bed hydrogenation catalyst, the process comprising:

1) contacting a solution of a metal-active element-containing compound with a dusty gas stream,

wherein dust particles in the dust-containing gas flow are carbon materials or materials containing silicon oxide and/or aluminum oxide;

2) carrying out gas-solid separation on the contact product obtained in the step 1) to obtain a solid material flow wetted by the solution and a dedusted gas flow;

3) and drying the solid matter flow to obtain the slurry bed hydrogenation catalyst.

According to a second aspect of the invention, the invention provides the application of the slurry bed hydrogenation catalyst prepared by the preparation method of the first aspect of the invention in heavy oil hydrocracking reaction.

Compared with the prior art, the method provided by the invention has the characteristics of simple catalyst preparation process and capability of improving the dispersion degree of the active components in the catalyst, and can realize the purification of the dust-containing gas. In addition, the slurry bed hydrogenation catalyst prepared by the invention has higher catalytic activity when being applied to the hydrocracking reaction of heavy oil, can improve the yield of distillate oil and the demetalization rate, and simultaneously reduces the coking rate.

Detailed Description

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

According to a first aspect of the present invention, there is provided a process for the preparation of a slurry bed hydrogenation catalyst, the process comprising:

1) contacting a solution of a metal-active element-containing compound with a dusty gas stream;

2) carrying out gas-solid separation on the contact product obtained in the step 1) to obtain a solid material flow wetted by the solution and a dedusted gas flow;

3) and drying the solid matter flow to obtain the slurry bed hydrogenation catalyst.

According to the method of the invention, the dust particles in the dust-containing gas flow are carbon materials or materials containing silicon oxide and/or aluminum oxide, and the dust particles are carriers of the slurry bed hydrogenation catalyst.

The carbonaceous material is, for example, at least one of coke powder, carbon powder, and pulverized coal.

The material containing silica and/or alumina is, for example, at least one of alumina fine particles, silica fine particles, and ore powder (e.g., kaolin powder) containing both alumina and silica.

According to the method of the invention, the dust-containing gas stream may in particular be a coke powder-containing gas stream resulting from coal gasification (e.g. a coke powder-containing gas stream resulting from fluidized-bed gasification of coal), a coke powder-containing gas stream resulting from coal combustion (e.g. a coke powder-containing gas stream resulting from coal combustion in a power plant), or a gas stream containing silicon and/or aluminium ore fines resulting from ore calcination. Preferably, the dusty gas stream is selected from the group consisting of a coke powder-containing gas stream produced by coal gasification or a coke powder-containing gas stream produced by combustion of power plant coal. More preferably, the dusty gas stream is a dusty gas stream produced by the gasification section of a coal circulating fluidized bed pyrolysis gasification unit.

According to the method of the invention, the content of dust particles in the dusty gas stream may be 10-100000 g/m³Preferably 100 to 50000g/m³More preferably 1000 to 10000g/m³. The average particle diameter of the dust particles may be 1 to 150 μm, preferably 5 to 100 μm.

According to the process of the present invention, the metal active element is a conventional choice in the preparation of slurry bed hydrogenation catalysts. Generally, the metal active element may be selected from at least one of iron, zinc, nickel, cobalt, molybdenum, and tungsten. Preferably, the metal active element is selected from at least one of iron, zinc and nickel, and is further preferably iron, so that the catalyst performance is ensured and the raw material cost is further reduced.

The kind of the metal active element-containing compound is not particularly limited in the present invention as long as it can be dissolved in water. Wherein the iron-containing compound may be selected from at least one of ferric sulfate, ferrous sulfate, ferric acetate, ferric oxalate, ferric nitrate, ferric citrate, ferric phosphate and ferric chloride, and preferably selected from at least one of ferric sulfate, ferrous sulfate, ferric acetate and ferric oxalate. The zinc-containing compound may be selected from at least one of zinc sulfate, zinc chloride and zinc nitrate, preferably zinc sulfate. The nickel-containing compound may be selected from at least one of nickel sulfate, nickel chloride and nickel nitrate, preferably nickel sulfate.

According to the method of the present invention, the content of the metal active element in the solution of the metal active element-containing compound may be 0.01 to 20 wt%, preferably 0.1 to 15 wt%.

According to the method of the invention, in step 1), in order to further uniformly disperse the metal active component on the dust particles, the solution is preferably contacted with the dust-containing gas stream in the form of spray-applied droplets. The droplets typically have a particle size of no more than 500 μm. Further preferably, the particle size of the liquid drops is 5-200 μm, so that the catalytic performance of the prepared catalyst can be further improved.

In the step 1), the liquid-gas ratio of the solution of the metal active element-containing compound to the dust-containing gas flow can be 0.01-20 kg/m³. Preferably, the liquid-gas ratio of the solution of the metal active element-containing compound to the dust-containing gas flow is 0.1-10 kg/m³Therefore, the catalytic performance of the catalyst is favorably improved, higher dust removal rate can be obtained, and the liquid-gas ratio is more preferably 0.5-5 kg/m³. In this context, the unit of liquid-to-gas ratio "kg/m³"indicates the required kilograms of solution per cubic meter of dusty gas stream.

In the step 1), the contact temperature may be 100-600 ℃, and preferably 200-500 ℃.

According to the method of the invention, in step 2), the purpose of the gas-solid separation is to separate the solid matter stream wetted by the solution from the contact product and obtain purified gas (i.e. post-dedusting gas stream). The gas-solid separation can be implemented by cyclone separation or gravity settling separation, and preferably cyclone separation is adopted.

According to the method of the invention, in step 3), the slurry bed hydrogenation catalyst is obtained by drying the solid stream. For the invention, the drying temperature can be 100-500 ℃, and preferably 150-300 ℃.

According to one embodiment, the process of the invention (i.e. steps 1) to 3)) is carried out in a cyclone separator, the upper section of which is a cylindrical drum and the lower section of which is an inverted conical drum; the top of the cylindrical barrel is provided with a dust-removed airflow outlet, the middle of the cylindrical barrel is provided with a dust-containing airflow inlet, and the upper part of the cylindrical barrel is provided with a nozzle for atomizing the solution into liquid drops.

The process for preparing the slurry bed hydrogenation catalyst by adopting the cyclone separator comprises the following steps: and atomizing the solution into liquid drops through the nozzle, carrying out countercurrent contact on the liquid drops and a dedusting airflow entering from the dust-containing airflow inlet at an upper section, then carrying out cyclone separation, enabling the wetted solid material flow to enter a lower section for drying to obtain the slurry bed hydrogenation catalyst, and discharging the airflow from the top after dedusting.

According to another embodiment, the process of the invention is carried out in a gravity separator (e.g. a settler), which is a cylindrical drum provided with a dedusted gas stream outlet at the top, a dust-laden gas stream inlet in the middle and a nozzle in the upper part of the drum for atomizing the solution into droplets.

The flow when the gravity settling separator is adopted to prepare the slurry bed hydrogenation catalyst comprises the following steps: and atomizing the solution into liquid drops through the nozzle, carrying out countercurrent contact on the liquid drops and a dedusting airflow entering from the dust-containing airflow inlet at an upper section, then carrying out gravity settling separation, enabling the wetted solid material flow to enter a lower section for drying to obtain the slurry bed hydrogenation catalyst, and discharging the airflow from the top after dedusting.

In addition, the cyclone and gravity separator and the operation are as described above in the following examples.

The preparation method of the invention has the following advantages:

(1) the preparation of the catalyst is coupled with the dust-containing gas solid removal purification technology, and the preparation of the catalyst and the dust removal process of the dust-containing gas are carried out simultaneously, so that the preparation process of the catalyst is simplified, the cost of the catalyst is reduced due to reasonable utilization of the solid in the dust-containing gas, the problem of resource utilization of the solid in the dust-containing gas is solved, and three purposes are achieved at one stroke;

(2) in a preferred embodiment, the solution is sprayed and atomized into liquid drops to be contacted with the dust-containing gas flow, on one hand, the dispersion degree of active components in the catalyst is improved, and on the other hand, for gas dust removal, the liquid drops of the solution replace spray water commonly used in the prior art, the water consumption required by subsequent gas dust removal and purification is reduced, and the method is particularly suitable for areas with short water resources.

According to a second aspect of the invention, the invention provides the use of a slurry bed hydrogenation catalyst prepared by the process of the invention in heavy oil hydrocracking reactions.

The slurry bed hydrogenation catalyst prepared by the method belongs to a supported slurry bed hydrogenation catalyst, and comprises dust particles serving as a carrier and an active component formed by a compound of the metal active element and supported on the dust particles. Preferably, the content of the active component is 0.1-30 wt% calculated by metal element based on the total weight of the slurry bed hydrogenation catalyst. In addition, the slurry bed hydrogenation catalyst can also contain 0.5-5 wt% of water.

According to one embodiment, the slurry bed hydrogenation catalyst has an average particle size of 5 to 150 μm, preferably 10 to 100 μm. The size of the active component containing the metal active element is less than 200nm, preferably less than 100nm, more preferably less than 80 nm.

In the present invention, the average particle size of the slurry bed hydrogenation catalyst and the dust particles refers to the median particle diameter (D)₅₀) The particle size is determined by a laser particle sizer, and the size of the active ingredient is determined by Scanning Electron Microscopy (SEM).

The heavy oil is not particularly limited in the present invention, and may be, for example, various heavy oils of refineries, residual oils, tail oils, oil slurries, coal tar, or the like.

The hydrocracking conditions, according to the application of the present invention, can be carried out with reference to the prior art. Specifically, the temperature of the hydro-conversion reaction can be 300-480 ℃, and is preferably 360-470 ℃; the pressure is 5-20 MPa, preferably 8-18 MPa; the reaction time is 0.2-10 h, and the preferable time is 0.5-6 h; the volume ratio of the hydrogen to the oil can be 200-5000, preferably 500-2000; the amount of the slurry bed hydrogenation catalyst is 0.1 to 10 wt%, preferably 0.1 to 5 wt%, calculated as element, relative to the weight of the heavy oil.

According to the use of the present invention, the slurry bed hydrogenation catalyst may be sulfided prior to use to convert the metal oxide in the active component to a metal sulfide, the sulfiding process being well known in the art. Generally, the vulcanization is carried out under hydrogen, the adopted vulcanizing agent can be sulfur, and the vulcanization temperature can be 300-400 ℃.

The slurry bed hydrogenation catalyst is suitable for the hydrocracking reaction of heavy oil, has higher catalytic performance, can improve the yield of distillate oil and the demetalization rate, and simultaneously reduces the coke rate. The reason for this is that the molecules of heavy hydrocarbons are relatively large and difficult to enter the micro channels of the catalyst, the main reaction sites are the outer surface and the large channels, and the active components of the hydrogenation catalyst are mainly distributed on the outer surface and the large channels of the carrier. Compared with the hydrogenation catalyst with the same loading amount in the prior art, the catalyst has the characteristics of more active sites on the outer surface and the large pore channel, namely, the catalyst with the same activity has the characteristic of less consumption of metal active components, so the catalyst is low in cost.

The present invention will be described in detail below by way of examples.

In the following examples and comparative examples, the iron contents of the solvents and catalysts are calculated based on the iron element.

The following examples 1-7 are provided to illustrate the preparation of slurry bed hydrogenation catalysts according to the present invention.