CN111014247B - High-value utilization process of heavy oil suspension bed hydrogenation solid waste - Google Patents

High-value utilization process of heavy oil suspension bed hydrogenation solid waste Download PDF

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CN111014247B
CN111014247B CN201911350227.8A CN201911350227A CN111014247B CN 111014247 B CN111014247 B CN 111014247B CN 201911350227 A CN201911350227 A CN 201911350227A CN 111014247 B CN111014247 B CN 111014247B
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solid waste
heavy oil
bed hydrogenation
washing
value utilization
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CN111014247A (en
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杜辉
张丽华
陈照军
段雅静
姜鹏
付慧
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Qingdao University
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Abstract

The invention discloses a high-value utilization process of heavy oil suspension bed hydrogenation solid waste, aiming at the solid waste of which coke is wrapped with dispersed catalyst particles, the invention designs and adopts carbonization and structure activation treatment processes to prepare a transition metal sulfide/activated carbon composite material with high added value. The specific process comprises the following steps: first washing the solid waste with toluene or solvent oilCleaning, drying, pulverizing, grinding, mixing with alkali metal hydroxide, and reacting in the presence of hydrogen peroxide2And under the mixed atmosphere of the/He, heating to 750-1200 ℃ at a certain speed for structural activation, cooling, washing and drying to obtain the transition metal sulfide/activated carbon composite material, and the preparation method has the advantages of simple process, wide and easily obtained raw materials, low cost, high added value of products, wide application and the like.

Description

High-value utilization process of heavy oil suspension bed hydrogenation solid waste
Technical Field
The invention belongs to the field of petrochemical industry, and particularly relates to a high-valued utilization process of heavy oil suspension bed hydrogenation solid waste.
Background
The heavy oil suspension bed hydrogenation process, also known as slurry bed hydrogenation process and slurry bed hydrogenation process, is especially suitable for processing inferior heavy oil/residual oil. The heavy oil suspension bed hydrogenation process adopts non-supported dispersed catalyst, the solid powder catalyst or water/oil soluble catalyst is uniformly dispersed in the heavy oil raw material, no catalyst bed layer is arranged in the empty barrel reactor, and the dispersed catalyst is enriched in a large amount in the solid product after passing through the reactor along with the raw material, and is not separated and collected. At present, transition metal sulfides are generally adopted as the dispersed catalyst, and with the increasing treatment capacity of the suspension bed hydrogenation process, a large amount of consumed dispersed catalyst has higher economic value, and can cause serious resource waste and environmental pollution along with the treatment of solid products as wastes. The heavy oil suspension bed hydrogenation solid waste is composed of dispersed catalyst particles wrapped by coke, and the two cannot be separated, so that the high-value utilization of the heavy oil suspension bed hydrogenation solid waste is very difficult. At present, no report on high-value utilization of the hydrogenated solid waste of the heavy oil suspension bed is available.
Disclosure of Invention
The invention aims to make up the blank of the prior art and provide a high-value utilization process of heavy oil suspension bed hydrogenation solid waste, aiming at the solid waste of which coke is wrapped with dispersed catalyst particles, a carbonization and structure activation treatment process is designed to prepare the transition metal sulfide/activated carbon composite material with high added value, and the product can be widely applied to the fields of energy storage, catalysis, environmental protection and the like.
The invention is realized by adopting the following technical scheme:
a high-value utilization process of heavy oil suspension bed hydrogenation solid waste comprises the following steps:
(1) pretreating solid waste;
(2) mixing with alkali metal hydroxide uniformly in the presence of H2Heating to activate the structure in the mixed atmosphere of/He;
(3) and cooling, washing and drying to obtain the transition metal sulfide/activated carbon composite material.
Further, the solid waste is a product obtained by subjecting heavy raw oil to a suspension bed hydrogenation process, wherein the heavy raw oil comprises heavy crude oil, atmospheric residue, vacuum residue, coal tar and pitch;
the suspension bed hydrogenation process adopts a dispersed nano catalyst which is a transition metal sulfide and is selected from one or more of a nickel sulfide nano catalyst, a molybdenum disulfide nano catalyst and a tungsten disulfide nano catalyst.
Further, the solid waste is dispersed catalyst particles wrapped by coke, and the dispersed catalyst particles are dispersed in the coke in a size of less than 20 nanometers.
Further, the pretreatment process in the step (1) is as follows: washing the solid waste with toluene or solvent oil, extracting with furfural, washing, drying, crushing, and grinding to 50-400 meshes; preferably, grinding to 50-300 meshes; the extraction conditions are as follows: the temperature is 70 ℃, the mass ratio of the furfural to the solid waste is 1.0, and the extraction time is 40 min.
Further, the mass ratio of the solid waste pretreated in the step (2) to the alkali metal hydroxide is 1: 0.5 to 15; preferably, the mass ratio is 1: 2-12;
the alkali metal hydroxide is potassium hydroxide or sodium hydroxide;
the above-mentionedH2Volume ratio to He is 1: 9;
in the structure activation process, the heating rate is 1-20 ℃/min, the activation temperature is 750-1200 ℃, and the treatment time is 0.5-10 hours; preferably, the heating rate is 2-15 ℃/min, the activation temperature is 900-1200 ℃, and the treatment time is 0.5-8 hours.
Further, the washing process in the step (3) comprises three steps of washing with distilled water, pickling with dilute hydrochloric acid solution and washing with distilled water in sequence.
Further, the specific surface area of the composite material is 2500-3300 m2The content of transition metal sulfide in the composite material is 8-50 wt%.
The invention also aims to provide a transition metal sulfide/activated carbon composite material which is prepared by adopting the high-value utilization process of the heavy oil suspended bed hydrogenation solid waste.
The invention also provides the application of the transition metal sulfide/activated carbon composite material in the fields of lithium ion battery cathode materials, supercapacitor electrode materials, water electrolysis hydrogen production catalysis materials and mercury adsorption materials.
The invention adopts a complex system which is low in added value and extremely difficult to treat and is the heavy oil suspension bed hydrogenation solid waste with dispersed catalyst particles wrapped by coke as a raw material, firstly, residual petroleum hydrocarbon molecules in the solid waste are removed by pretreatment, washing and cleaning, then removing strong polar components by furfural extraction, carbonizing and structurally activating the crushed components by adopting alkali metal hydroxide at high temperature in mixed atmosphere, wherein in the treatment process, coke molecules with low condensation degree can partially undergo hydrocracking reaction under the action of a dispersed nano catalyst and hydrogen, and generated micromolecular hydrocarbon substances escape from a reaction system to form pores inside solid waste particles, so that the alkali metal hydroxide can enter the solid waste particles through the pores to perform an activation reaction, and finally the transition metal sulfide/activated carbon composite material with high specific surface area is prepared.
Compared with the prior art, the technical scheme of the invention has the following advantages and progresses:
the high-valued utilization process of the heavy oil suspended bed hydrogenation solid waste provided by the invention has the advantages of simple process, wide and easily available raw materials, low cost, high added value of products, wide application of products and the like.
Drawings
FIG. 1 is a transmission electron micrograph of a nickel sulfide/activated carbon composite prepared in example 1.
FIG. 2 is a transmission electron micrograph of the molybdenum disulfide/activated carbon composite prepared in example 2.
Figure 3 is a transmission electron micrograph of the tungsten disulfide/activated carbon composite prepared in example 3.
FIG. 4 is a transmission electron micrograph of the nickel sulfide/activated carbon composite prepared in comparative example 1.
FIG. 5 is a transmission electron micrograph of the molybdenum disulfide/activated carbon composite prepared in comparative example 2.
Detailed Description
The embodiments of the present invention will be described in detail with reference to the accompanying drawings, wherein the examples do not indicate specific conditions, and are performed according to conventional conditions or conditions recommended by the manufacturers. The reagents or instruments used are conventional products which are commercially available.
Example 1
Taking solid waste obtained by a suspension bed hydrogenation reaction process of venezuela super-thick oil under the action of a dispersive nickel sulfide nano catalyst as a raw material, firstly washing the solid waste by using toluene to remove residual petroleum hydrocarbon molecules, extracting by using furfural under the conditions that the temperature is 70 ℃, the mass ratio of the furfural to the solid waste is 1.0, and the extraction time is 40min, drying, crushing and grinding to 50-200 meshes, and then mixing the dried solid waste with potassium hydroxide according to the mass ratio of 1: 12 are mixed uniformly in H2Heating to 900 ℃ at the speed of 2 ℃/min under the mixed atmosphere of/He (volume ratio of 1:9) for structural activation, wherein the activation time is 6 hours, cooling, washing with distilled water, washing with dilute hydrochloric acid solution, washing with distilled water, and finally drying to obtain the nickel sulfide/activated carbon composite material, wherein the specific surface area of the composite material is 2955m2Per g, nickel sulphide content in the composite materialAt 23 wt%, nickel sulfide is uniformly dispersed in the composite material as particles having a particle size of less than 20 nm.
Example 2
Taking solid waste obtained by the Crayar atmospheric residue through a suspension bed hydrogenation reaction process under the action of a dispersed molybdenum disulfide nano catalyst as a raw material, firstly washing the solid waste by using 100# solvent oil to remove residual petroleum hydrocarbon molecules, extracting by using furfural under the conditions that the temperature is 70 ℃, the mass ratio of the furfural to the solid waste is 1.0, and the extraction time is 40min, drying, crushing and grinding to 100-250 meshes, and then mixing the dried solid waste with potassium hydroxide according to the mass ratio of 1: 2 mixing them uniformly in H2Heating to 1100 ℃ at the speed of 10 ℃/min under the mixed atmosphere of/He (volume ratio of 1:9) for structural activation, wherein the activation time is 8 hours, cooling, washing with distilled water, washing with dilute hydrochloric acid solution, washing with distilled water, and finally drying to obtain the molybdenum disulfide/activated carbon composite material, wherein the specific surface area of the composite material is 2718m2And the content of molybdenum disulfide in the composite material is 11 wt%, and the molybdenum disulfide is uniformly dispersed in the composite material in a monolithic layer structure.
Example 3
Taking solid waste obtained by subjecting asphalt to a suspension bed hydrogenation reaction process under the action of a dispersed tungsten disulfide nano catalyst as a raw material, firstly washing the solid waste by using 120# solvent oil to remove residual petroleum hydrocarbon molecules, extracting by using furfural under the conditions that the temperature is 70 ℃, the mass ratio of the furfural to the solid waste is 1.0 and the extraction time is 40min, drying, crushing and grinding to 100-300 meshes, and then mixing the dried solid waste with sodium hydroxide according to the mass ratio of 1: 8 mixing them uniformly in H2Heating to 1200 ℃ at the speed of 15 ℃/min under the mixed atmosphere of/He (volume ratio of 1:9) for structural activation, wherein the activation time is 0.5 hour, cooling, washing with distilled water, acid washing with dilute hydrochloric acid solution, washing with distilled water, and finally drying to obtain the tungsten disulfide/activated carbon composite material, wherein the specific surface area of the composite material is 3286m2And/g, the content of tungsten disulfide in the composite material is 47 wt%, and the tungsten disulfide is uniformly dispersed in the composite material in a monolithic layer structure.
Comparative example 1
Taking solid waste obtained by a suspension bed hydrogenation reaction process of venezuela super-thick oil under the action of an oil-soluble nickel catalyst as a raw material, firstly washing the solid waste by using toluene to remove residual petroleum hydrocarbon molecules, extracting by using furfural under the conditions that the temperature is 70 ℃, the mass ratio of the furfural to the solid waste is 1.0, and the extraction time is 40min, drying, crushing and grinding to 50-200 meshes, and then mixing the dried product with potassium hydroxide according to the mass ratio of 1: 12 are mixed uniformly in H2Heating to 900 ℃ at the speed of 2 ℃/min under the mixed atmosphere of/He (volume ratio of 1:9) for structural activation, wherein the activation time is 6 hours, cooling, washing with distilled water, acid washing with dilute hydrochloric acid solution, washing with distilled water, and finally drying to obtain the nickel sulfide/activated carbon composite material, wherein the specific surface area of the composite material is 378m2The content of nickel sulfide in the composite material is 2.3 wt%, and the particle size of the dispersed nickel sulfide is larger than 100 nanometers.
Comparative example 2
Taking solid waste obtained by the Crayar atmospheric residue through a suspension bed hydrogenation reaction process under the action of a dispersed molybdenum disulfide nano catalyst as a raw material, firstly washing the solid waste by using 100# solvent oil to remove residual petroleum hydrocarbon molecules, drying, crushing, grinding to 100-250 meshes, and then mixing the solid waste with potassium hydroxide according to a mass ratio of 1: 2, uniformly mixing, heating to 1100 ℃ at a speed of 10 ℃/min under the atmosphere of He gas for structural activation, wherein the activation time is 8 hours, cooling, washing with distilled water, washing with dilute hydrochloric acid solution, washing with distilled water, and finally drying to obtain the molybdenum disulfide/activated carbon composite material, wherein the specific surface area of the composite material is 852m2The content of molybdenum disulfide in the composite material is 5.6 wt%, and the particle size of dispersed molybdenum disulfide is more than 60 nanometers.
Comparative example 3
Taking solid waste obtained by the Craya atmospheric residue oil through a suspension bed hydrogenation reaction process under the action of a dispersed molybdenum disulfide nano catalyst as a raw material, firstly washing the solid waste by using 100# solvent oil to remove residual petroleum hydrocarbon molecules, drying, crushing, grinding to 100-250 meshes, and then mixing the solid waste with potassium hydroxide according to a mass ratio1: 2 mixing them uniformly in H2Heating to 1100 ℃ at the speed of 10 ℃/min under the mixed atmosphere of/He (volume ratio of 1:9) for structural activation, wherein the activation time is 8 hours, cooling, washing with distilled water, washing with dilute hydrochloric acid solution, washing with distilled water, and finally drying to obtain the molybdenum disulfide/molybdenum oxide/activated carbon composite material, wherein the specific surface area of the composite material is 755m2The content of molybdenum disulfide in the composite material is 3.9 wt%, the content of molybdenum oxide in the composite material is 1.3 wt%, and the particle size of dispersed molybdenum disulfide and molybdenum oxide is larger than 60 nanometers.
Comparative example 4
Using asphalt as a raw material, firstly washing the asphalt by using No. 120 solvent oil to remove soluble petroleum hydrocarbon molecules in the asphalt, drying the rest part, crushing, grinding to 100-300 meshes, and then mixing the rest part with sodium hydroxide according to a mass ratio of 1: 8 mixing them uniformly in H2Heating to 1200 ℃ at a speed of 15 ℃/min under a mixed atmosphere of/He (volume ratio of 1:9) for structure activation, wherein the activation time is 0.5 hour, cooling, washing with distilled water, washing with dilute hydrochloric acid solution, washing with distilled water, and finally drying to obtain the activated carbon, wherein the specific surface area of the activated carbon is 659m2(ii)/g, no other transition metal sulfide.

Claims (13)

1. A high-value utilization process of heavy oil suspension bed hydrogenation solid waste is characterized by comprising the following steps:
(1) pretreating solid waste;
(2) mixing with alkali metal hydroxide uniformly in the presence of H2Heating to activate the structure in the mixed atmosphere of/He;
(3) cooling, washing and drying to obtain the transition metal sulfide/activated carbon composite material;
the solid waste is a product obtained by subjecting heavy raw oil to a suspension bed hydrogenation process;
the suspension bed hydrogenation process adopts a dispersed nano catalyst which is a transition metal sulfide.
2. The process for high-value utilization of the solid waste from the hydrogenation of the heavy oil suspended bed according to claim 1, wherein the heavy raw oil comprises heavy crude oil, atmospheric residue, vacuum residue, coal tar and pitch.
3. The high-value utilization process of the heavy oil suspended bed hydrogenation solid waste according to claim 1, wherein the transition metal sulfide is selected from one or more of nickel sulfide nano-catalyst, molybdenum disulfide nano-catalyst and tungsten disulfide nano-catalyst.
4. The process for high-value utilization of the solid waste from the hydrogenation of the heavy oil suspended bed according to claim 1, wherein the pretreatment process in the step (1) is as follows: washing the solid waste with toluene or solvent oil, extracting with furfural, washing, drying, crushing, and grinding to 50-400 meshes; the extraction conditions are as follows: the temperature is 70 ℃, the mass ratio of the furfural to the solid waste is 1.0, and the extraction time is 40 min.
5. The high-value utilization process of the heavy oil suspended bed hydrogenation solid waste as claimed in claim 4, wherein the heavy oil suspended bed hydrogenation solid waste is crushed and ground into 50-300 meshes.
6. The process for high-value utilization of the heavy oil suspended bed hydrogenation solid waste as claimed in claim 1, wherein the mass ratio of the solid waste pretreated in the step (2) to the alkali metal hydroxide is 1: 0.5 to 15;
the alkali metal hydroxide is potassium hydroxide or sodium hydroxide.
7. The high-value utilization process of the heavy oil suspended bed hydrogenation solid waste according to claim 6, characterized in that the mass ratio of 1: 2 to 12.
8. The process for high-value utilization of the heavy oil suspended bed hydrogenation solid waste as claimed in claim 1, wherein the H is2Volume ratio to He is 1: 9;
in the structure activation process, the heating rate is 1-20 ℃/min, the activation temperature is 750-1200 ℃, and the treatment time is 0.5-10 hours.
9. The high-value utilization process of the heavy oil suspended bed hydrogenation solid waste according to claim 8, wherein the heating rate is 2-15 ℃/min, the activation temperature is 900-1200 ℃, and the treatment time is 0.5-8 hours.
10. The process for utilizing the solid waste from the hydrogenation of the heavy oil suspended bed as claimed in claim 1, wherein the washing step in step (3) comprises three steps of washing with distilled water, acid washing with dilute hydrochloric acid solution and washing with distilled water in sequence.
11. The high-value utilization process of the heavy oil suspended bed hydrogenation solid waste as claimed in claim 1, wherein the specific surface area of the composite material is 2500-3300 m2The content of transition metal sulfide in the composite material is 8-50 wt%.
12. A transition metal sulfide/activated carbon composite material, which is prepared by the high-value utilization process of the heavy oil suspended bed hydrogenation solid waste of any one of claims 1 to 11.
13. The transition metal sulfide/activated carbon composite material of claim 12 is applied to the fields of lithium ion battery negative electrode materials, supercapacitor electrode materials, water electrolysis hydrogen production catalysis materials and mercury adsorption materials.
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CN103080277A (en) * 2010-07-06 2013-05-01 道达尔炼油与销售部 Slurry catalyst and slurry flakes valorization
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US8177963B2 (en) * 2007-12-20 2012-05-15 Exxonmobil Research And Engineering Company Partial electro-hydrogenation of sulfur containing feedstreams followed by sulfur removal
CN102134643A (en) * 2010-01-21 2011-07-27 英特卫普公司 Metal recovery from hydroconverted heavy effluent
CN102971439A (en) * 2010-03-04 2013-03-13 英特卫普公司 Method of metals recovery from refinery residues
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