CN104789252B - A general-purpose method and device for catalytic slurry hydrogenation and lightening of heavy raw materials - Google Patents

Abstract

The invention relates to a general method for hydrogenation and lightening of heavy raw material catalytic slurry, a device for implementing the method, a catalytic fluid applicable to the method and the heavy raw material catalytic slurry prepared by the method. The heavy raw material can be oil-based, coal-based, bio-based and mixed-basis heavy raw materials.

Description

A general-purpose method and device for catalytic slurry hydrogenation and lightening of heavy raw materials

field of invention

The invention relates to a general-purpose method for hydrogenation and lightening of heavy raw material catalytic slurry and a device for implementing the method, and also relates to a catalytic fluid and the heavy raw material catalytic slurry prepared therefrom. The heavy raw materials can be oil-based, coal-based, bio-based and mixed-based heavy raw materials.

Background technique

Heavy raw materials are divided into oil-based or petroleum-based based on conventional fossil energy classification, that is, heavy oil products with an API gravity ≤ 25°, usually with a hydrogen content ≤ 11.0%; coal-based, that is, sapropelic sludge with a maturity R° ≤ 0.75 Humic coal with coal and vitrinite content ≥ 50%, such as ≥ 60%, and the organic phase (daf) in the coal-based heavy raw material is ≥ -30° according to the gravity of petroleum API, and the hydrogen content in the organic phase is usually 4.3- 7.0%; bio-based, that is, the parent material precursor of fossil energy (R°≈0), such as bio-oil, blue-green algae, pine needles, etc., which usually have an oxygen content of 5wt%-30wt% and a hydrogen content of ≥6.5wt% high burn-up components; and also heavy feedstocks for their mixed bases.

Existing heavy raw material lightening projects are usually divided into heavy oil decarbonization or hydrogenation process, coal direct liquefaction process, biomass hydrogenation liquefaction process, and their mixed base hydrogenation co-refining process according to the type of raw material .

China is a country dominated by continental sedimentary basins. Coal accounts for 99% of the total fossil energy resources, and conventional oil and gas resources only account for about 1% of the total fossil energy resources. This also means that heavy raw materials (fuels) and unconventional Oil and gas resources (coal rock oil, shale gas, and coalbed methane) are abundant. Therefore, the characteristics of China's fossil energy resources determine the important position of lightening and cleaning heavy raw materials in China's energy industry.

At present, there are two main ways to process heavy oil: decarburization or hydrogenation. Delayed coking is a typical decarbonization process, which can process various low-quality heavy oils and residual oils, but its liquid products have low yield and poor quality, and their application in petroleum coke is also limited. Therefore, in order to increase the yield of light distillate oil in refineries, hydrogenation technology is generally used to treat residual oil or heavy oil. This hydrogenation technology mainly includes fixed bed, moving bed, ebullating bed (slurry bed) and suspension bed hydrogenation technology. Among them, the disadvantage of heavy oil fixed bed hydrogenation technology is that the operation cycle is too short when processing low-quality heavy oil with high metal and high asphaltene content. Moving bed and ebullating bed heavy oil hydrogenation technology can process relatively inferior raw materials, but the technology is complicated and the operation cost is high.

The coal coking process is a carbon fixation and dehydration process for coal processing in the coal industry. As a by-product in the process, coal tar is a very inferior liquid hydrocarbon-containing product, which is widely used as primary chemical raw material or fuel.

The direct liquefaction process of coal and biomass is to react the mixture of coal or biomass, solvent and catalyst with hydrogen under the conditions of temperature (400-500°C) and pressure (15-30MPa) to generate liquid products. The catalyst used is cobalt , molybdenum, tungsten, tin, iron and lead oxides or halides. The direct coal liquefaction technology mainly includes the H-coal process in the United States, the NEDOL process in Japan, the IGOR process in Germany, and the Shenhua process in my country. Industrialization of the process.

Canadian patent CA1073389 and US patent US4214977 proposed the method of adding coal or coal-based additives in heavy oil processing to reduce the amount of coke settlement in heavy oil hydrocracking process. However, in this technology, the solid powder will remain in the unconverted residue after the conversion of the raw material oil, which is difficult to separate, reduces the use of the unconverted residue, and also brings environmental problems.

In the 1940s, Canada began the research on the production of liquid products from tar pitch and sub-bituminous coal by hydrogenation. Canadian patent CA1160586 proposed the Canmet process of coal-tar pitch co-refining, and the American hydrocarbon company in H-Coal and H- On the basis of the Oil process, the HRI process of kerosene co-refining was proposed, and Japanese patents 8045703 and 8023407 proposed the solvent decomposition process. In the mid-1980s and 1990s, China's Liaohe Oilfield and Shanxi Coal Chemical Institute cooperated with Canadian and American HRT companies to introduce industrial test technology for kerosene co-refining of heavy oil, super heavy oil, and vacuum residue, but none of them were realized. Operation of industrial plants.

In the late 1980s, major oil companies in the world competed to research and develop homogeneous catalysts. Representative technologies include Canada's (HC)3 technology (using oil-soluble organometallic catalysts), and water-soluble homogeneous catalysts include Exxon's phosphomolybdic acid catalyst and Chevron's ammonium molybdate catalyst. Homogeneous catalysts exist in the form of metal particles and their sulfides during the reaction process, so they have high activity, less addition, and less wear on the reaction system, but they are expensive and the catalyst recovery method is complicated.

CN1778871A proposes that the catalyst of γ-FeOOH supported by coal particles is used for the direct hydrogenation liquefaction of coal, US Patent No. 4338183 proposes a kerosene co-refining process using organometallic complexes as catalysts, and CN101020834A proposes using iron pentacarbonyl as a catalyst The coal direct hydrogenation liquefaction method, CN1089037C proposes to use the heteropoly acid salt catalyst for the heat treatment of super heavy oil, CN102041017A, CN102233279A proposes the lignin sulfonic acid metal complex catalyst and the humic acid complex and the dispersed metal catalyst Used for hydrogenation and lightening of coal and vacuum residue.

In U.S. Patents US2848530, US3238118, and US4090947, a method for partially hydrogenating aromatic naphthenic diluents to treat hydrogen-poor petroleum to produce liquid hydrocarbons is proposed. Thermal tar, gas oil, high-grade coking gas oil, coal-derived liquids, and catalytic cycle oil are preferred hydrogen Donor Diluent Precursor. US Patent US6702936 uses the partial oxidation of asphaltene products to produce hydrogen donor diluent cracking method, and CN1032669A proposes a complete ionic liquid solvent process.

CN102041015A proposes a method for producing liquid fuel from coal rock oil and gas reservoirs. In this method, coal powder and heavy oil are mixed, aged, thermally dissolved and dispersed, and then a stable coal sol phase slurry is produced by phase separation. The coal sol phase slurry greatly improves the stability and transport properties of the fluid, thereby facilitating the operation of the heavy oil cracking and hydrogenation unit to produce light oil.

In the existing heavy oil fluidized bed hydrogenation conversion process technology, coal hydrogenation direct liquefaction process technology, etc., the reaction materials are all three-phase mass transfer processes, which requires the use of high-temperature and high-pressure multi-phase circulating pumps for material transportation. In addition, the circulation of the reaction materials causes problems such as large wall thickness, heavy tonnage, high manufacturing difficulty, and high manufacturing cost of processing equipment, especially large-scale high-temperature and high-pressure reactors, which seriously restricts the lightening and cleaning of heavy raw materials. process.

In the existing heavy oil suspension bed hydroconversion technology and coal hydrogenation direct liquefaction technology, the amount of catalyst used per ton of oil for light distillate products is huge, and the water consumption in the process of preparing or recovering the catalyst occupies the main part of the hydroconversion process. Water consumption increases the environmental cost of the lightening and cleaning process of heavy raw materials.

Summary of the invention

The task of the present invention is to overcome the following defects in the prior art to oil-based, coal-based, bio-based heavy raw materials and their arbitrary mixtures in the hydroconversion process: (1) the existing hydrogenation light process The raw material is single; (2) solvents in the prior art have low dissolving and dispersibility capabilities to heavy raw material solutes and a narrow range of applicable heavy raw materials; (3) rheology and thixotropy of the slurry are poor; (4) catalyst The preparation and recovery process is complicated and the water consumption is high; (5) Traditional catalysts have narrow catalytic adaptability to the composition of hydrogenation raw materials, low conversion rate of distillate oil, poor quality and other technical problems. At the same time, for the corresponding process engineering, the task of the present invention is to overcome the complexity of the system flow and low utilization rate in the prior art. Most of the reaction devices are high-temperature and high-pressure multi-phase cycle reaction systems. The reaction system devices and equipment are difficult to manufacture and the device control is difficult. A series of problems such as poor security.

Surprisingly, it is found that the method for hydrogenation and lightening of a general-purpose heavy raw material catalytic slurry provided by the present invention, the catalytic fluid and the heavy raw material catalytic slurry can well complete the basis of the present invention. , tasks as described above.

Therefore, the present invention relates to a general-purpose method for catalytic slurry hydrogenation and lightening of heavy raw materials, the method comprising: dissolving, dispersing and/or diluting heavy raw materials with a catalytic fluid having a catalytic function, and then treating Finally, a heavy raw material catalytic slurry is prepared, and then the heavy raw material catalytic slurry is catalyzed and supplied with hydrogen under hydrogenation reaction conditions, thereby producing light distillate oil and cracked gas.

Among them, the Fann's viscosity of the treated heavy raw material catalytic slurry is ≤2000MPa·s (80°C), the static shear stress is ≤35MPa·m ^-2 (80°C), and the industrial stability ratio is ≥0.80.

In another aspect, the present invention relates to a catalytic fluid with catalytic function, which comprises or consists of the following components: a multi-component starting and/or circulating solvent, a multi-element metal containing two or more metal elements Compound, complexing agent and optional complexing aid, wherein the total content of the metal element in the catalytic fluid is 0.05wt%-5.0wt% of the catalytic fluid and the multi-element metal compound forms with the complexing agent complexes or chelates. The catalytic fluid can be particularly used in the above-mentioned general-purpose method for catalytic slurry hydrogenation and lightening of heavy raw materials.

In yet another aspect, the present invention relates to a heavy raw material catalytic slurry, which is characterized in that it is prepared by dissolving, dispersing and/or diluting the heavy raw material with the above-mentioned catalytic fluid, and then treating it. Viscosity≤2000MPa·s (80℃), static shear stress≤35MPa·m ^-2 (80℃) and industrial stability ratio≥0.80.

Finally, the invention also relates to a device for carrying out the method described above.

Detailed description of the invention

Within the scope of this patent, the catalytic slurry prepared by mixing different types of heavy raw materials such as oil-based, coal-based, bio-based and mixed-based with catalytic fluid is subjected to the process of hydrogenation and lightening under hydrogenation reaction conditions. The hydrogenation and lightening process called heavy feedstock is not limited to the type and structure of the reactor, whether there are fillers or internals in the reactor, etc.

Within the scope of the present invention, heavy raw materials suitable for the hydrogenation lightening method of the present invention are oil-based, coal-based, bio-based heavy raw materials and any mixture thereof (also called mixed-based heavy raw materials), wherein Oil-based heavy raw materials are fluid fuels such as heavy crude oil, processed heavy oil, coal tar, biological waste oil, etc. Coal-based heavy raw materials are low-to-medium The base heavy raw materials are, for example, high calorific value components such as algae, biological lipids, bark bodies, and lignin in fossil fuel precursor biomass.

The oil-based raw materials in the heavy raw materials can be heavy crude oil with API°≤25, processed heavy oil, coal tar, biological waste oil, etc., and their mixed oil products. Generally speaking, the content of fractions with a boiling point >350°C in the oil-based raw material is >90wt%, for example >95wt%. Preferably, the selected oil-based raw material is super-heavy oil, super-heavy oil, vacuum residue, coal tar, biological waste oil, etc. or their mixed oils with API°≤15.0; the boiling point of the oil-based raw material is >350°C distillate content 100wt%, water content ≤0.2wt%, solid residue ≤0.2wt%.

In addition, the coal-based raw materials suitable for the heavy raw materials of the present invention can be, for example, sapropelite with maturity R°≤0.85, such as sapropelite with R°≤0.75 and humic coal with vitrinite content≥50wt%, and their differences A blend of coals. The powder particle size of coal-based raw materials is suitably 80-400 mesh, such as 80-200 mesh, and the moisture content of coal powder is suitably ≤15.0wt% (such as <10.0wt%) and ash content ≤15wt% (such as ≤10wt%) . Advantageously, the selected coal-based raw materials can be sapropelite with maturity R°≤0.70, humic coal with vitrinite content≥65wt%, and their mixed coals of different types and qualities.

In addition, the bio-based raw material suitable for the heavy raw material of the present invention can be, for example, high calorific value organic biomass with a hydrogen content ≥ 6.5 wt% and an oxygen content ≤ 30%. The particle size of the powder of the bio-based raw material can be 80-400 mesh (such as 80-200 mesh), and the moisture content of the powder of the bio-based raw material can be, for example, ≤15.0% and/or the ash content ≤5%. Preferably, the selected bio-based raw material is lignin and suberinite biomass with hydrogen content≥7.0wt% and oxygen content≤26wt%.

In the method of the present invention, the mixed-based raw materials in the heavy raw materials can be, for example, any mixture of the above three types of heavy raw materials among oil-based, coal-based and bio-based. Similarly, the powder particle size of the solid raw material in the mixed base heavy raw material can be 80-400 mesh, the ash content in the powder body is ≤10% and the water content is ≤15.0wt%.

On the one hand, the subject of the present invention is a general-purpose method for catalytic slurry hydrogenation and lightening of heavy raw materials, the method comprising: using a catalytic fluid with catalytic function to dissolve, disperse and/or dilute the heavy raw materials, After being treated again, the heavy raw material catalytic slurry is prepared, and then the heavy raw material catalytic slurry is catalyzed and supplied with hydrogen under hydrogenation reaction conditions, thereby producing light distillate oil and cracked gas, wherein the The Van's viscosity of the treated heavy raw material catalytic slurry is ≤2000MPa·s (80°C), the static shear stress is ≤35MPa·m ^-2 (80°C), and the industrial stability ratio is ≥0.80, more preferably ≥0.90 or ≥0.93.

In a preferred embodiment, the catalytic slurry for different types of heavy raw materials is required to have the following preferred ranges:

1. The Fann's viscosity of the oil-based heavy raw material catalytic slurry is ≤200MPa·s (80°C), the static shear stress is ≤5MPa·m ^-2 (80°C), and the industrial stability ratio is ≥0.95, more preferably ≥0.98 or 1.0.

2. The Fann's viscosity of the coal-based heavy raw material catalytic slurry is ≤1200MPa·s (80°C), the static shear stress is ≤20MPa·m ^-2 (80°C), preferably ≤10MPa·m ^-2 (80°C) and industrial The stability ratio is > 0.93, more preferably > 0.95 or > 0.98.

3. The Fann’s viscosity of the kerosene-based heavy raw material catalytic slurry is ≤500MPa·s (80°C), the static shear stress is ≤10MPa·m ^-2 (80°C), preferably ≤5MPa·m ^-2 (80°C) and Industrial stability ratio > 0.93, more preferably > 0.95 or > 0.98.

On the other hand, correspondingly, the present invention relates to a device for implementing the above method, which device includes at least the following three process units in sequence: a catalytic fluid preparation unit, a catalytic slurry preparation unit and a hydrogenation and lightening reaction unit . In particular, in the catalytic slurry preparation unit and the hydrogenation lightening reaction unit, the steps of dissolving, dispersing and/or diluting the heavy raw material with catalytic fluid and then processing to prepare the heavy raw material catalytic slurry and The step of catalyzing and supplying hydrogen to the heavy raw material catalytic slurry under hydrogenation reaction conditions.

In particular, as a relatively complete implementation, the method and device may sequentially include at least five process units, namely heavy raw material pre-treatment unit, catalytic fluid preparation unit, catalytic slurry preparation unit, hydrogenation and lightening The reaction unit and product post-processing unit can produce, for example, light distillate oil and cracked gas at ≤350°C.

The method of the present invention is based on the theory of depositional distribution of biological communities and fossil energy resources in nature, as well as the development and inheritance relationship between biomass and different types of fossil resources, and the multi-component distribution characteristics of heavy raw materials, and is based on multi-component raw materials Process theoretical basis for catalytic hydrogenation reactions and reaction kinetics. A notable feature of this method is to use the industrially stable multi-component catalytic dispersion slurry as the working fluid, which can provide a reaction engineering system for hydrogenation and lightening by homogeneous pumping in industrial reaction devices, thereby greatly Simplify the operating conditions of hydrogenation lightening and bring higher safety and reliability.

Due to these advantages, the method of the present invention is in the catalytic slurry preparation unit and the hydrolightening reaction unit, preferably in the dehydration or anhydrous environment, more preferably the method is completed in a dehydrated or anhydrous environment throughout.

The present invention will be further described in detail according to the above-mentioned relatively complete process flow below.

Heavy raw material pre-processing unit

In the hydrogenation lightening method of the present invention, the process flow of the heavy raw material pre-processing unit is the sum of the raw material treatment process flow before the raw material enters the raw material inlet of the catalytic slurry unit, that is, the storage and transportation of the heavy raw material, Milling, dehydration, deashing and other purification treatment, as well as raw material mixing and storage, etc.

The heavy raw material pre-processing unit device refers to the sum of all equipment flowing through the route in the raw material treatment process before the raw material enters the catalytic slurry preparation unit, such as the combined purification system device for oil-based heavy raw materials, coal-based, Crushing, milling, sorting, dehydration, gas separators, powder storage system devices for bio-based heavy raw materials, and related control equipment and safety systems, etc.

In a specific embodiment of the present invention, the heavy raw material pre-processing unit is divided into fluid storage and powder storage according to the material type and state of the heavy raw material. Among them, for the fluid storage system of oil-based heavy raw materials, the heavy oil storage and transportation equipment and technology of the national standard of the petroleum industry can be selected. For the solid powder storage system of coal-based, bio-based and mixed-based raw materials, you can choose the coal powder storage and transportation device and process of the national standard in the cement and electric power industry. The requirements for these materials are, for example, the powder particle size is 80 mesh- 200 mesh, material moisture content ≤ 10.0wt%, inorganic matter content ≤ 10.0wt%. The powder storage tank needs nitrogen protection, and the powder is conveyed by nitrogen air exhaust or by screw conveyor under nitrogen protection.

Catalytic Fluid Preparation Unit

In the hydrogenation and lightening method of the present invention, the catalytic fluid is prepared in the catalytic fluid preparation unit.

In the present invention, the catalytic fluid suitable for the method of the present invention can in principle be any conventional catalytic fluid used in the direct hydroliquefaction process of heavy feedstock, especially coal-based heavy feedstock, in the prior art, for example A catalytic fluid comprising a γ-FeOOH catalyst supported by coal particles and a dispersion solvent.

However, a new type of catalytic fluid is proposed in the present invention, which is more suitable for the process of the present invention. The catalytic fluid comprises and preferably consists of the following components: a multi-component solvent, a multi-element metal compound containing two or more metal elements, a complexing agent and an optional complexing aid, wherein The total content of the metal element in the catalytic fluid is 0.05wt%-5.0wt%, such as 0.05wt%-4.0wt% or 0.07wt%-3.0wt% of the catalytic fluid, and the multi-element metal compound is complexed with Agents form complexes or chelates.

As a preferred embodiment, although it is desirable to complex as much as possible, generally speaking, the degree of complexation of polynary metal compounds is ≥ 40%, preferably ≥ 50%, more preferably ≥ 60% or 70%, so in the The multi-element metal elements in the catalytic fluid will be dissolved or dispersed in the solvent in the state of ions, molecules, complexes and/or polymolecules.

The catalytic fluid of the present invention is a fluid with catalytic performance composed of a multi-component solvent and multi-element organometallic compounds complexed and dissolved or dispersed in the solvent. Although in the process according to the present invention, the slurry formed by those traditional catalysts and solvents in the prior art can also realize the improvement of the process and the promotion of performance, but by adopting the catalytic fluid selected according to the present invention, in the process with heavy raw materials After mixing, it can be more helpful to prepare a homogeneous and stable catalytic slurry on the colloidal scale. Especially for coal-based raw materials, compared with the traditional coal direct liquefaction technology, it avoids the multi-phase transmission process that is unstable and prone to sedimentation and separation, and overcomes the deposition and serious Wear, coking, clogging and other problems. In addition, since the catalyst containing ionic liquid is used in the present invention to form a catalytic fluid, the liquefaction effect is enhanced, and the complex process and huge water and electricity consumption in the conventional liquefaction technology such as the preparation of solid γ-FeOOH catalyst supported by coal particles are avoided quantity.

In the catalytic fluid of the present invention, the solvent may preferably be the initial and/or circulating solvent of the system, which is a solvent (such as a fraction ≥ 300°C) or The circulating solvent or the mixture of the two operating in the system constitutes, and the composition of the two can be the same or different. The circulating solvent can be, for example, the tower bottom oil in the deslagging hydrogenation slurry fraction section of the present invention with a temperature of 320°C-550°C. According to the difference in the type of heavy raw materials for hydrogenation, an appropriate amount of heterocyclic compounds and/or solubilizers should be supplemented 0-5.0wt%. The described solvent has multi-component distribution characteristics rather than a relatively single component solvent as used in the prior art. It must have the fluid functions of dissolving, dispersing, and diluting heavy raw materials, and has the functions of adding Under hydrogen reaction conditions, it has the reaction functions of dissolving hydrogen storage, activating, and transferring hydrogen supply. Therefore, in the catalytic fluid of the present invention, it is practically unnecessary to add a prehydrogenation solvent as commonly used in conventional techniques.

Specifically, the solvent used in the catalytic fluid of the present invention includes neutral components, acidic components, basic components and ionic liquids. In the multi-component composition of solvents, generally as the content of heteroatoms (such as N, O, S) in heavy raw materials decreases, the polar components decrease, but in the solvent, neutral components and ionic liquids must form the basic components.

In an advantageous embodiment, the solvent comprises >40% by weight, preferably >45% by weight, more preferably >50% by weight of neutral components, 3% to 25% by weight, preferably 5% to 22% by weight % by weight of acidic components, 3 to 25% by weight, preferably 5 to 20% by weight of basic components and 3 to 15% by weight, preferably 3 to 10% by weight, of ionic liquids.

As a neutral component, it can be considered to be selected from heavy aromatic oils, polycyclic aromatic hydrocarbons, partially or fully hydrogenated polycyclic aromatic hydrocarbon oils, etc. One or more, preferably two or more.

As the acidic component, one or more, preferably two or more, selected from phenol, C3-C4 alkylphenol, naphthol and indenol, high phenolic oil, etc. can be considered.

As the basic component, one or more, preferably two or more, selected from nitrogen heterocyclic compounds such as anilines, quinolines, indole, pyridine, and acridine, etc. can be considered.

As the ionic liquid, one or more selected from imidazolium salts, pyridinium salts, quaternary ammonium salts, and quaternary phosphonium salts, etc., may be considered, preferably two or more.

In addition, it is also possible to directly use distillate oils from 330°C to 541°C in the distillate section of coker wax oil or hydrogenated slurry, which are complex in composition but contain one or more of the above four components. mixture of species.

In a preferred embodiment of the present invention, from improving the suspension of the solvent to the dispersed solids, improving the transportability of the prepared catalytic slurry, satisfying the hydrogen transfer characteristics in the hydrogenation lightening reaction and improving the heavy Considering the solubility of raw materials, it is required that the density of the solvent is ≥0.95, preferably 0.95-1.02g/cm ³ , especially 0.96-0.99g/cm ³ , and the Fann’s viscosity is ≥5MPa·s, preferably 15-35MPa·s , such as 15-28MPa·s (50°C), and the average aromatization rate fa is ≥0.60, preferably 0.65-0.72, especially 0.67-0.70, wherein the total content of organic heteroatoms N, S, O in the solvent is ≤ 8.0, preferably 3.0-8.0wt%, especially such as 4.0-6.5wt%.

For the formulation of solvents, the ratio of polar components in said solvents is generally increased according to the type of heavy raw materials and the proportion of polar components in the group components.

As a preferred embodiment, the solvent contains heavy aromatic oil, preferably heavy aromatic oil accounting for 70wt%-90wt% of the total amount of solvent, as the base solvent oil of the solvent.

Preferably, in said solvent of the present invention, the solubility characteristic parameter distribution of the solvent is directly related to the solubility characteristic parameter distribution of the type and group components of the heavy feedstock. Generally speaking, in the present invention, the difference between the median solubility characteristic parameter of the solvent and the median solubility characteristic parameter of the heavy raw material is Δδ ^1/2 ≤ 5, preferably Δδ ^1/2 ≤ 3.

In the present invention, the solvent can be prepared by those skilled in the art through known methods, such as compounding. In a preferred embodiment, for example, heavy aromatic base solvent oil, auxiliary solvent oil of polycyclic aromatic hydrocarbons, partially or fully hydrogenated polycyclic aromatic hydrocarbons, heterocyclic compounds or solubilizers, etc., are mixed at a temperature of 50°C-80°C Next, stir and mix sequentially to prepare multi-component non-aqueous starting solvents.

In the present invention, the metal element is selected from two or more of Group IA to Group VA, Group IB to Group VIIB and Group VIII of the periodic table of elements, and lanthanide rare earth elements. Preferably, the metal element is selected from iron, nickel, molybdenum, copper, zinc, tin, aluminum, tungsten, manganese, titanium, vanadium, chromium, cobalt, gold, cadmium, mercury, cerium and lanthanide rare earth elements, more preferably It is selected from iron, nickel, molybdenum, tungsten, titanium, zinc, aluminum and lanthanide rare earth elements, especially selected from iron, nickel, aluminum, titanium and lanthanide rare earth elements.

As a very favorable embodiment, the content of iron, aluminum and/or titanium (preferably iron) is >50wt%, preferably >65wt%, especially >70wt% and For example, 70wt-80wt%, and the content of lanthanide rare earth elements is 0-5wt% based on the weight of all metal elements, preferably 0.1-3wt%, more preferably 0.1-1wt% and especially 0.2-0.5wt%.

In addition, in a preferred embodiment, the total content of the metal element in the catalytic fluid is 0.05wt%-3.0wt%, preferably 0.05wt%-2.0wt% of the catalytic fluid.

There is no particular limitation on the multi-element metal compound, which should be compatible with the solvent and be able to form a complex or chelate compound dissolved or dispersed in the solvent with the added complexing agent in the subsequent reaction. Those skilled in the art can select suitable multi-element metal compounds accordingly. Suitable polynary metal compounds are, for example, inorganic and/or organic salts, preferably hydrochlorides, sulfates, nitrates, carbonates, carboxylates, C ₁ -C ₁₈ aliphatic acid salts and/or C ₆ - Aromatic acid salts of _C20 , etc.

Here, further complexing agent components are required for the formation of complexes or chelates with the metal ions in the solvent. In principle, all complexing agents that can form stable complexes or chelated states with the above metal ions are applicable, and those skilled in the art can reasonably select suitable complexing agents according to their own production practice common sense.

In a specific embodiment, heterocyclic compounds (for example with 6-40 or 6-30 carbon atoms) containing heteroatoms such as N, O or S come into consideration as complexing agents and which may be optionally substituted (such as hydroxyl or mercapto), C ₁ -C ₁₈ aliphatic alcohols, aliphatic amines, aliphatic carboxylic acids and aliphatic sulfonic acids each of which may be substituted by one or more hydroxyl, carboxyl or mercapto groups, and for example thiourea or thiourea derivatives. Examples include the following: 1,10-phenanthroline, EDTA, dimercaptopropanol, sodium dimercaptopropanesulfonate, mercaptoethylamine, thioglycolic acid, thiourea, 8-hydroxyquinoline and the like. The complexing agents can be used alone or in combination in multiple forms.

According to the selected complexing agent and multi-metal compound, you can optionally add complexing aids, such as cyanide, citric acid, tartaric acid, oxalic acid, sulfosalicylic acid, triethanolamine and sodium alkoxide, methyl silicon One or more of sodium alkoxide, NaOH, KOH, etc.

In order to prepare the catalytic fluid of the present invention, the solvent is pre-prepared as described above, and then the complexing agent and optional complexing aids and polynary metal compounds are added thereto, after fully reacting and discharging the non-condensable The gas and water then give the desired catalytic fluid.

For example, in a specific embodiment, in order to prepare the catalytic fluid, the prepared and adjusted solvent is provided in advance, and the solvent is adjusted by a complexing aid at a temperature of 20-100°C, preferably 30°C-80°C After the pH range of 7.0-11.0, preferably 8.0-10.0, add the complexing agent in proportion and sequentially add the above-mentioned multiple metal compounds (such as Fe ₂₊ ^, Ni ²⁺ , Al ³⁺ and a small amount of lanthanide rare earth Elemental multi-element metal salt) mixture, heat up to 120°C-150°C, under stirring (such as stirring for 30-120 minutes), after separating non-condensable gas and water, heat up to 180°C-250°C, continue to stir the reaction (such as stirring for another 30-180 minutes), thus preparing a catalytic fluid containing a multi-element metal compound.

Catalytic slurry preparation unit

In the catalytic slurry preparation unit of the hydrogenation lightening method of the present invention, the catalytic fluid is used to dissolve, swell, disperse and/or dilute the heavy raw material (for example, it can be realized by simply mixing), and then A heavy feedstock catalytic slurry with improved fluid properties is produced.

Advantageously, the present invention requires that the fluid property parameters of the catalytic slurry prepared according to these two methods are: the Fann's viscosity of the slurry fluid≤2000MPa.s (80°C), the static shear stress≤35MPa×m ^-2 (80°C ), the industrial stability ratio ≥ 0.90; preferably, the fluid Vane viscosity ≤ 2000MPa.s (80°C), the static shear stress ≤ 30MPa·m-2 (80°C) and the industrial stability ratio ≥ 0.95. In addition, it is also advantageous that the solid content in the catalytic slurry fluid is 0-65wt%, preferably 0-55wt%, more preferably 0-42wt%. The catalytic slurry fluid thus produced achieves excellent processability and is therefore particularly suitable for subsequent hydrolightening steps.

The industrial stability ratio of the catalytic slurry is obtained through experiments and calculations. The experimental method is as follows: Pour fully stirred catalytic slurry into a 1000mm static liquid pipe, and then lead out the fluid from the middle of the static liquid pipe after flowing for 10 minutes, and measure the fluid density D ₀ ; Get ^{the upper part of} the average density D (24h); derive the fluid from the lower part 100mm, measure ^{the lower part of} the average density D (24h), and calculate the industrial stability ratio by the following formula:

In order to achieve the above-mentioned desired Vann's viscosity, static shear stress and industrial stability ratio, the treatment process advantageously includes the following two key steps, that is, mixing the oil-based heavy feedstock with the catalytic fluid prepared according to the present invention and mixing Coal-based, bio-based and mixed-based heavy raw materials containing solids are subjected to slaking treatment. Those skilled in the art can understand that the slaking treatment refers to the process of subjecting heavy raw materials to pressure and temperature for a certain period of time in a slaking vessel (such as a tubular reactor), thereby adjusting the maturity of the heavy raw materials and wherein Contains organic components, etc. In the method of the present invention, the aging is advantageously carried out at a working pressure of 0.1-5.0 MPa and a temperature of 120°C-300°C, and the aging treatment time can be kept at, for example, more than 0.5 hours, preferably more than 1 hour or 2 hours, The length of the curing treatment time can be adjusted according to the desired performance, such as the measured industrial stability ratio.

Therefore, described catalytic slurry preparation method can be divided into oil-based heavy raw material catalytic slurry technology that Newtonian fluid is obtained by mixing oil-based heavy raw material in proportion with catalytic fluid according to the type of heavy raw material, and solid-containing The two-step preparation method of the coal-based, bio-based and mixed-based heavy raw materials in proportion to the catalytic fluid, the latter method can prepare the non-Newtonian fluid coal-based, bio-based and mixed-based heavy raw material catalytic slurry. For example, the method for preparing the catalytic slurry can be divided into a method for preparing the catalytic slurry of the dissolved oil-based raw material and a method for preparing the catalytic slurry of the dispersed mixed-based, coal-based, or bio-based powder raw material.

In the catalytic slurry preparation unit, the catalytic slurry is composed of catalytic fluid mixed with different types of heavy raw materials in proportion, and the oil-based catalytic slurry mainly in the dissolved state can be prepared according to the fluid mixing and mutual solubility method. The kerosene mixed-based co-refinery catalytic slurry with low dispersion phase state, the coal-based catalytic slurry with high dispersion phase colloidal state, and the bio-based catalytic slurry with high dispersion phase suspension state were prepared by volume dispersion mixing method.

For the two-step preparation method of solid coal-based, bio-based and mixed-based heavy raw materials in proportion to catalytic fluid, firstly, the heavy raw material and catalytic fluid are simply mixed in proportion to prepare the initial catalytic slurry, and then the initial slurry is made The material is at a working pressure of 0.1-5.0MPa and a temperature of 120°C-300°C, preferably a working pressure of 1.0-3.5MPa and a temperature of 180°C-280°C, more preferably a working pressure of 1.0 (eg 1.1)-3.0MPa and a temperature of 210°C-280°C After aging and an optional homogenization step, coal-based, bio-based and mixed-based non-Newtonian fluid catalytic slurry with stable working performance is prepared. Wherein the content of the solid phase heavy raw material in the catalytic slurry is advantageously ≤65wt%, preferably ≤55wt%, more preferably ≤42wt%.

Generally speaking, in order to prepare the catalytic slurry of the heavy raw material, the heavy raw material is fully mixed with the catalytic fluid, and then degassed, dehydrated, matured and/or homogenized according to the situation, wherein further Advantageously, the total content of S element in the catalytic slurry can be ≤2.0wt%, the solid content can be 0-65wt%, and the water content can be ≤0.2wt%. In the catalytic slurry, the mixing ratio of the heavy raw material is 10-65wt%, such as 20-55wt% or 30-45wt%.

As mentioned above, preferably and critically, the treatment includes a maturation step of the mixture of the produced catalytic fluid and heavy feedstock (particularly coal-based, bio-based and mixed-based heavy feedstock containing solids), and more preferably Optionally a homogenization step is also performed. The mixture undergoes degassing and dehydration processes during the maturation step (although the possibility of additional degassing and dehydration treatments is not excluded), thereby removing, for example, free water from coal-based feedstocks and reducing low-maturity coal-based The oxygen content of the organic phase in the raw material should appropriately increase the average maturity R° of the coal-based raw material, especially reduce the dispersion of maturity, thereby increasing the content of (C+H) effective elements in the organic phase of the heavy coal-based raw material. This process is especially effective for lignite and sub-bituminous coal with R°≤0.55. It was also found that after such an aging step, the fluidity of the slurry can be greatly improved, making it possible to simplify subsequent operations.

In the prior art, heavy raw materials such as coal-based raw materials are usually directly pulverized, dried and dehydrated, and the dehydrated coal powder is fully mixed and homogenized, and then mixed with a catalyst and a solvent to prepare a slurry; In the homogenization process of raw materials, although the moisture content of coal-based powder raw materials is reduced by drying, at the same time, safety problems such as coal powder spontaneous combustion are increased, so complex safety auxiliary measures are required and the requirements for raw materials are high. Compared with the prior art, the process of the present invention particularly requires the slurry to be matured, thus eliminating the drying step and avoiding the risk of spontaneous combustion, while expanding the scope of engineering application of coal-based raw materials.

In a preferred embodiment, the mixture of the catalytic fluid and the heavy raw material is further homogenized for more than 1 hour, preferably more than 2 hours, such as 12-48 hours or 12-24 hours. In particular, such homogenization time depends on the type of heavy raw materials and the degree of homogenization. For example, the homogenization step can be omitted for some oil-based heavy raw materials with a relatively good degree of homogenization. In an advantageous embodiment, homogenization is preferred for oil-based heavy feedstocks for 2-4 hours, and for solids or heavy feedstocks containing solids such as coal-based, bio-based or mixed-based heavy feedstocks, homogenization is preferred > 24 hours, eg > 48 hours.

In the catalytic slurry preparation unit, when preparing the oil-based heavy raw material catalytic slurry, it is only necessary to mix the catalytic fluid with the oil-based heavy raw material, such as heavy crude oil with an API≤25° The case is optionally homogenized. In the present invention, according to the restrictions on the properties of the catalytic slurry fluid, the mixing ratio of the oil-based heavy raw material in the catalytic slurry is 40wt%-70wt%, and this type of catalytic slurry fluid is Newtonian at a temperature of ≥30°C. fluid.

In addition, in the catalytic slurry preparation unit, it is possible to prepare a highly dispersed phase-soluble colloidal coal-based heavy raw material catalytic slurry, wherein the heavy raw material is a coal-based 80-200 mesh powder raw material, and the stable component in the pulverized coal , The vitrinite component has excellent solubility, swelling, peptization and dispersibility in solvents. The coal-based catalytic slurry fluid has a large difference with the particle size distribution of coal powder, and the non-Newtonian property increases with the increase of the concentration. In the present invention, the mixing ratio of the coal-based raw material in the coal-based catalytic slurry is 30wt%-55wt%.

In addition, in the said catalytic slurry preparation unit, the catalytic slurry of bio-based heavy raw material in high dispersion phase suspension state can be prepared, wherein the heavy raw material is 80-200 mesh powder of dehydrated biomass, which is in the catalytic fluid Only good suspension dispersibility, this kind of catalytic slurry fluid is a non-Newtonian plastic fluid, and with the increase of the concentration of dehydrated biomass powder, the thixotropy of the fluid increases rapidly. In the present invention, the mixing ratio of the bio-based raw material in the bio-based catalytic slurry is 30wt%-50wt%.

More specifically, in order to prepare the catalytic slurry of oil-based heavy feedstock according to the method of the present invention, an exemplary method is: under normal pressure conditions, in proportion (such as the compounding ratio of oil-based heavy feedstock and catalytic fluid 40wt%-70wt%: 60wt%-30wt%) at a temperature in the range of 50°C-250°C, preferably 50°C-100°C, mix the heavy oil with the catalytic fluid (for example in a static mixer), and then add 0.5wt- 2.0wt%, preferably 0.5wt-1.0wt% co-catalyst such as liquid sulfur or sulfur powder (>100 mesh), CS2, at a temperature of 50°C-250°C, pre-sulfurized for 2-5 hours, preferably 2-4 hours, A Newtonian fluid catalytic slurry with a good flow state is prepared, which is transported into the output buffer tank of the catalytic slurry.

In order to prepare coal-based and bio-based powder raw material catalytic slurry in the catalytic slurry preparation unit according to the present invention, an exemplary method is: under normal pressure conditions, coal powder or biomass powder The raw material is blown into the catalytic fluid in the temperature range of 120°C-250°C (for example, at a temperature from 150°C to 250°C) in proportion (for example, powder raw material: catalytic fluid = 30wt%-55wt%: 70wt%-45wt%) In, and continue to stir and disperse for 10-60 minutes. Then pump the material into the aging reactor, and react for 2-4 hours at a temperature of 230°C-280°C and a pressure of 2.2-3.5MPa. After degassing and moisture (such as flash evaporation and condenser), the material is matured and Add a slurry amount of 0.5wt-2.0wt%, preferably 0.5wt%-2.0wt% cocatalyst such as liquid sulfur or sulfur powder (>100 mesh) or CS2, and then pump it into the homogenization, aging, and pre-curing tank Circulation, at a temperature of 150°C-250°C and a pressure of 0.1MPa, homogenize and age according to the homogeneity of the raw materials for ≥12 hours, preferably ≥24 hours, more preferably ≥48 hours, and prepare a product at 50°C- The non-Newtonian fluid catalytic slurry with the industrial stability ratio of the fluid within the working range of 250°C ≥ 0.90 is sent to the catalytic slurry output buffer tank.

In addition, the specific exemplary method of preparing the catalytic slurry of mixed-based raw materials may be a simple combination of the above two methods, and may be adjusted accordingly by those skilled in the art according to production practice.

For example, in the described catalytic slurry preparation unit, low-dispersion kerosene mixed-base co-refining catalytic slurry can be prepared, wherein the heavy raw material is a mixed-based raw material in which heavy oil and pulverized coal can be mixed in any proportion. The catalytic slurry-like fluid is a non-Newtonian fluid at normal temperature, and a Newtonian fluid after heating up. In the present invention, the weight ratio of heavy oil in the mixed-based raw material: pulverized coal can be 65-75:25-35 or 25-35:65-75, and the ratio of oil-coal mixed-based raw material in the catalytic slurry can be 30wt%-60wt %.

According to the kerosene mixed-base co-refinery hydro-upgrading process of the present invention, preferably, the mixing ratio of heavy raw materials is heavy oil: pulverized coal = 68wt%-75wt%: 25wt%-32wt% or 25wt%-32wt%: 68wt %-75wt%; In addition, preferably, the mixing ratio of mixed heavy raw material and catalytic fluid is =40wt%-70wt%: 60wt%-30wt%, and the amount of slurry added to the material is 0.5wt%-2.0wt % of co-catalyst sulfur powder (>100 mesh) or liquid sulfur, CS2, into the catalytic slurry homogenization tank for repeated mixing and homogenization, aging for 12-24 hours, and then the material is input into the catalytic slurry tank.

In a preferred embodiment, in the coal-based heavy raw material catalytic slurry, especially when the coal-based heavy raw material content is ≤60wt%, the working reaction temperature of the slurry is in the range of 120°C-250°C, and the slurry The industrial stability ratio of feed fluid is ≥0.93 and the flow state is low thixotropic (static shear stress ≤20MPa·m ^-2 (80°C)) non-Newtonian fluid; in bio-based heavy raw material catalytic slurry, especially in bio-based When the heavy raw material content is ≤50wt%, the working reaction temperature of the slurry is in the range of 120°C-250°C, the industrial stability ratio of the slurry fluid is ≥0.90 and the flow state is medium thixotropic (static shear stress 10-30MPa· m ^-2 (80°C)) non-Newtonian fluid; in the mixed-based heavy raw material catalytic slurry, especially when the content of coal-based heavy raw material in the mixed-based heavy raw material is ≤ 30wt%, the working reaction of the slurry Within the temperature range of 120°C-250°C, the industrial stability ratio of slurry fluid is ≥0.95 and the flow state is Newtonian fluid or low thixotropic (static shear stress ≤10MPa·m ^-2 (80°C)) non-Newtonian fluid.

In the heavy raw material catalytic slurry preparation unit, the mixing, maturing and homogenizing processes can be carried out in any suitable reactor, mixer or maturing device, and these devices are understood and well known to those skilled in the art. In particular, these processes can be carried out in tubular reactors suitable for fluid handling.

Hydrogenation Lightening Reaction Unit

The heavy raw material catalytic slurry hydrogenation lightening reaction unit according to the present invention is composed of catalytic slurry pumping, hydrogen charging and mixing, heating process and hydrogenation lightening reaction process.

The process consisting of the catalytic slurry pumping, hydrogen charging mixing and heating process is the sum of the process flow before the hydrogen charging catalytic slurry enters the reactor, including the collection and transportation of catalytic slurry, high-pressure pumping and mixing compressed hydrogen , The heating furnace is heated up to the working temperature, etc. In addition, the hydrogenation working conditions in the hydrogenation and lightening reaction unit are generally: reaction pressure 5MPa-30MPa and reaction temperature 380°C-520°C. The volumetric space velocity of the heavy raw material catalytic slurry in the reactor is from 0.1h ^-1 to 10h ^-1 , while hydrogen or high hydrogen-containing mixed gas and heavy raw material catalytic slurry (hereinafter also referred to as hydrogen slurry) Ratio) The volume ratio is 100Nm ³ /m ³ -10000Nm ³ /m ³ .

Therefore, for example, in the above-mentioned catalytic slurry pumping, hydrogen charging mixing and heating process, the working temperature of the catalytic slurry pumped from the storage tank through the heavy oil pump can be 25°C-250°C, and the pump pressure after the pump The working pressure for the hydrogenation reaction is 10.0-20.0 MPa, preferably 12.0-20.0 MPa. After the high-pressure hydrogen gas is charged in proportion, the temperature is raised to the hydrogenation working temperature of 420°C-465°C, preferably 430°C-465°C through the heating furnace.

Correspondingly, the device of the process consisting of the catalytic slurry pumping, hydrogen charging mixing and heating process is the sum of all devices and equipment on the material flow route before the hydrogen charging catalytic slurry enters the reactor, such as the catalytic slurry Gathering devices and tanks, high-pressure heavy oil pumps, hydrogen compressors, hydrogen mixers, heating furnaces, control systems and related safety equipment, etc.

The process flow of the hydrogenation lightening reaction is as follows: the mixed hydrogen catalytic slurry enters the hydrogenation lightening working condition through the pumping, hydrogenation mixing and heating process, enters the reactor through the reactor inlet control valve, The heavy raw material in the material fluid undergoes cracking and hydrogenation reactions in the suspended state of laminar flow or turbulent flow in the reactor. According to the requirements of the target product, after the required reaction time is completed, the product is discharged through the reactor outlet control valve, thereby preparing a lightweight slurry.

In the hydrogenation reaction lightening process, the main engineering device is the hydrogenation reactor, and the reaction tooling system selects the high temperature and high pressure hydrogenation safety control standard. The type of the reactor can be a tubular reactor, a vacuum reactor, a full back-mixed loop reactor, a trickle bed reactor, a reverse counterflow reactor, a slurry bed reactor, a suspended bed reactor and a downhole reactor. one or more of.

Therefore, in an exemplary embodiment, the process flow of the hydrogenation and lightening reaction is as follows: under the condition of hydrogenation, the high-pressure catalytic slurry heated by mixing hydrogen passes through the inner pipe valve in the ground control valve group Enter the downhole reactor for hydrogenation reaction, and then enter the next reactor or process unit.

Further, in the hydrogenation reaction lightening process, for the hydrogenation lightening of oil-based catalytic slurry, the selected operating conditions can be, for example: reaction pressure=8.0-18.0MPa (preferably 10.0-18.0MPa, More preferably 12.0-18.0MPa), reaction temperature = 380°C-470°C (preferably 420°C-465°C, more preferably 440°C-455°C); hydrogen slurry ratio = 500Nm ³ /m ³ -1200Nm ³ /m ³ ( Preferably 600Nm ³ /m ³ -950Nm ³ /m ³ ), the volumetric space velocity of the catalytic slurry is from 0.5h ^-1 to 5h ^-1 (preferably from 0.5h ^-1 to 2.0h ^-1 , more preferably from 0.8h ^-1 to 1.2h ^-1 ).

In addition, in the hydrogenation reaction lightening process, for the hydrogenation lightening of coal-based catalytic slurry, the selected operating conditions can be, for example: reaction pressure = 12.0-18.0MPa (preferably 15.0-18.0MPa), Reaction temperature = 400°C-470°C (preferably 420°C-455°C, more preferably 440°C-455°C); hydrogen slurry ratio = 1000Nm ³ /m ³ -2500Nm ³ /m ³ (preferably 1200Nm ³ /m ³ -1700Nm ³ /m ³ , more preferably 1300Nm ³ /m ³ -1700Nm ³ /m ³ ), the volume space velocity of the catalytic slurry is from 0.5h ^-1 to 5h ^-1 (preferably from 0.5h ^-1 to 2.0h ^-1 , more Preferably from 0.8h ⁻¹ to 1.5h ⁻¹ ).

In addition, in the hydrogenation reaction lightening process, for the hydrogenation lightening of bio-based catalytic slurry, the selected working conditions can be, for example: reaction pressure=8.0-16.0MPa (preferably 12.0-18.0MPa, preferably 12.0-16.0MPa), reaction temperature = 350°C-470°C (preferably 420°C-445°C, more preferably 420°C-435°C); hydrogen slurry ratio = 1200Nm ³ /m ³ -3000Nm ³ /m ³ (preferably 1500Nm ³ /m ³ -2000Nm ³ /m ³ , more preferably 1500Nm ³ /m ³ -1800Nm ³ /m ³ ), the volumetric space velocity of the catalytic slurry is from 0.5h ^-1 to 5h ^-1 (preferably from 0.5h ^-1 to 2.0 h ⁻¹ , more preferably from 1.0 h ⁻¹ to 2.0 h ⁻¹ ).

In this hydrogenation reaction lightening process, the kerosene-based catalytic slurry can also be hydrogenated and lightened. In this case, the working conditions can be, for example: working pressure = 12.0-18.0MPa, reaction temperature = 400°C-460°C (preferably 420°C-460°C, more preferably 440°C-460°C); hydrogen slurry ratio = 700Nm ³ /m ³ -2000Nm ³ /m ³ (preferably 900Nm ³ /m ³ -1500Nm ³ /m ³ ), the volume space velocity of the catalytic slurry is from 0.5h ^-1 to 5h ^-1 (preferably from 0.5h ^-1 to 2.0h ^-1 , more preferably from 1.0h ^-1 to 1.5h ^-1 ).

Under the working conditions of the hydrogenation lightening process, the lightening rate and light oil rate of heavy raw materials and the residual solid content in the hydrogenation slurry are calculated according to the following formula:

Product post-processing unit

The process flow in the hydrogenation product post-processing unit according to the present invention is the sum of the product flow through the treatment process flow after the product outlet of the hydrogenation and lightening reaction unit, that is, for example, the following procedures that the reaction product flows through : Gas-liquid separation, solid-liquid separation of degassed hydrogenation slurry, light distillate oil/gas (distillation section ≤ 350°C) of the target product in deslagging hydrogenation slurry and ≥ 330°C as the base of circulating solvent and auxiliary oil ( Such as 350°C-550°C) fraction oil separation and recovery, and/or processes such as enrichment of unreacted hydrogen and pressurized recycling.

In the hydrogenation product post-processing unit, the reaction cracked gas separated from the hydrogenation product enters the storage tank, is transported outside or used as fuel gas, the residue is separated and enters the residue tank as fuel, and the untreated The reacted hydrogen is enriched and pressurized for recycling. At the same time, the distillate oil at ≥330°C (such as 350°C-550°C) is pumped to the circulating solvent raw material tank, and the light oil is pumped to the light oil tank, and then exported or entered into the oil hydrorefining unit.

After the process device in the hydrogenation product post-processing unit according to the present invention is the product outlet of the hydrogenation and lightening reaction unit, the sum of all equipment on the route that the product flows through, such as gas separator, stripping tower , solid-liquid centrifugal separator, fractionation tower, heat exchanger, solvent deslagging tower, related control system and safety equipment, etc.

All the process parameters and performance parameters mentioned above can be determined by those skilled in the art according to the petroleum development and refining API engineering standard methods or national standards, except for the measurement and calculation methods.

In addition, the content of each substance in the composition in this application is in weight percentage, unless otherwise specified; the temperature in brackets after each parameter data indicates that it is measured at this temperature.

Description of drawings

Fig. 1 is a schematic diagram of the device process for implementing the general-purpose method for catalytic slurry hydrogenation and lightening of heavy raw materials according to the present invention.

The complete process shows the sequence of heavy raw material pre-processing unit, catalytic fluid preparation unit, catalytic slurry preparation unit, hydrogenation lightening reaction unit and product post-processing unit. Wherein, the circulating solvent in the system can be recycled into the catalytic fluid preparation unit for preparing catalytic fluid.

Example

The present invention will be further described with reference to the following examples, but these examples should not be construed as limiting the present invention.

Example 1

1. The raw materials used and the preparation of catalytic fluid

In an embodiment according to the present invention, a 1.5t/d industrial test system device is selected. The process device system consists of a heavy raw material pre-treatment unit, a catalytic fluid preparation unit, a catalytic slurry preparation unit, and a hydrogenation lightening reaction. Unit and product post-processing unit, in which the high-temperature and high-pressure process device of the industrial test system device is a horizontal loop heating furnace, a 1.5t/d heat-insulated and empty suspension bed reactor, and a downhole heat-insulation and empty suspension bed reactor .

The following heavy raw materials selected for processing are processed in the heavy raw material pre-treatment unit:

The oil-based heavy raw material is vacuum residue from Yumen Refinery.

The coal-based heavy raw material is the dehydrated coal powder (≥120 mesh) of 2# power coal in Xinjiang Tuha Naomaohu Mine.

The heavy raw material of the mixed base is Yumen slag reduction and 2# coal dehydrated coal powder (≥120 mesh) according to the mixing ratio Yumen slag reduction: 2# coal dehydrated coal powder=72.7wt%:27.3wt% mixed oil coal See raw materials 1-3 in Table 1 for properties of pulp and heavy raw materials.

The starting solvent in the catalytic fluid is coker wax oil, high phenolic oil, organic nitrogen-containing heterocyclic compound and imidazolium salt and pyridinium salt compound at a temperature of 20 It is prepared by stirring and mixing at ℃-50℃. The H/C atomic ratio of the starting solvent is 1.36, and the content of oxygen-containing and nitrogen-containing compounds in the starting solvent (based on the content of oxygen and nitrogen elements) is 2.26wt% and 2.37wt%, respectively.

For the circulating solvent in the catalytic fluid, choose the distillate oil in the distillate section of the hydrogenation slurry at 330°C-541°C, the H/C atomic ratio of the circulating solvent is 1.39, and the content of oxygen-containing and nitrogen-containing compounds in the circulating solvent (in terms of oxygen and Nitrogen content) were 2.51wt% and 2.42wt%.

In order to prepare the catalytic fluid, select the compounds of ferrous sulfate, nickel nitrate, molybdenum nitrate, titanium sulfate, aluminum sulfate and lanthanide metal oxalate to prepare Fe and Ni, Mo, Ti, Al metals according to the ratio as follows A mixed solution of ions and a small amount of lanthanide rare earth element compounds is used as a multi-element metal compound component, wherein the mixed metal elements are mainly Fe ²⁺ and the content of the iron element is 73.2wt%, and the total amount of elements such as Al, Ti, Ni, Mo, etc. The content is about 26.6wt%, and the content of lanthanide rare earth elements is about 0.2wt%; in addition, the 1,10-o-phenanthroline, dimercaptopropanol complexing agent and a small amount of sodium methyl siliconate additives, with a concentration of 10wt % multi-element metal group mixed solution (total metal element concentration 21.7wt%) was sequentially added to 100wt% starting or circulating solvent to form a mixed fluid.

The mixed fluid is heated up to 120°C-150°C under stirring, after dehydration and degassing, the temperature is raised to 210°C, and then the stirring reaction is continued for 30-60 minutes to receive 104.7wt% of the total amount of metal elements in terms of catalytic slurry~ 0.83wt% multi-element metal compound catalytic fluid is pumped into the catalytic fluid storage tank. See Feedstock 4-5 in Table 1 for the feedstock properties of the heavy feedstock and the starting catalytic fluid.

Table 1 Properties of heavy feedstock and catalytic fluid

2. Preparation of catalytic slurry for heavy raw materials

To prepare the catalytic slurry of the oil-based heavy feedstock shown in Table 2, mix the oil-based heavy feedstock with the "Catalytic Fluid 2" described in Part 1 as "Slurry 1" at a temperature of 80 °C. The ratios shown in the columns were mixed to obtain a catalytic slurry with an oil-based heavy stock content of 51.1 wt%.

In order to prepare the catalytic slurry of the kerosene mixed-based heavy raw material shown in Table 2, firstly mix 34.1 parts of coal-based heavy raw material powder with 120 meshes and 75.9 parts of oil-based heavy raw material under the condition of catalytic fluid temperature of 80°C And 100 parts of "catalytic fluid 2" described in Part 1, mix and prepare 210 parts of initial catalytic slurry of kerosene mixed base heavy feedstock at 80°C, then raise the temperature to 210°C and pressure 1.2MPa conditions React at low temperature for 90 minutes, after ripening, degassing and dehydration, further add 0.5wt% co-catalyst sulfur powder (>100 mesh), then homogenize, age and pre-cure for 24 hours at a pressure of 0.1MPa and a temperature of 150°C. 205 parts of catalytic slurry with an average content of 51.2wt% of kerosene-based heavy feedstock were prepared.

In order to prepare the catalytic slurry of the coal-based heavy raw material shown in Table 2, firstly mix 103 parts of coal-based heavy raw material powder of 120 meshes with 100 parts of the The above-mentioned "catalytic fluid 2" was mixed at a temperature of 150°C to prepare 203 parts of initial catalytic slurry of coal-based heavy raw materials, and then heated to 250°C and reacted at a pressure of 2.5MPa for 150min, after aging, degassing and dehydration , further adding 0.8wt% co-catalyst sulfur powder (>100 mesh), followed by homogenization, aging and pre-sulfurization at a pressure of 0.1MPa and a temperature of 170°C for 48 hours to prepare 187.6 parts of coal-based heavy raw materials with an average content of It is 46.7wt% catalytic slurry.

Table 2 Properties and flow pattern of heavy feedstock catalytic slurry

3. Hydrogenation and lightening of catalytic slurry

The hydrogenation and lightening process unit in the embodiment of the present invention is composed of 1.5t/d tubular reactor and downhole reactor industrial test device, in which each catalytic slurry obtained from the second part is hydrogenated and lightened deal with. See the hydrogenation examples 1-3 in Table 3 for the parameters and test results of the hydrogenation light chemical process of the oil-based, coal-based, and mixed-based heavy feedstocks obtained from Part 2.

Table 31. Parameters and results of hydrogenation and lightening process of 5t/d tubular reactor and downhole reactor

4. Post-processing of products

In this embodiment, the product post-processing unit according to the present invention is operated through a 1.5t/d industrial test device post-processing device, and oil-based, coal-based, and mixed-based heavy raw materials are obtained from the third part. Distillate oil, wherein the basic properties of light distillate oil are shown in light products 1-3 in Table 4.

Table 41. 5t/d industrial test plant hydrogenation lightening results and basic properties of light distillates

In an embodiment according to the present invention, the oil-based, coal-based, and mixed-based heavy raw materials hydrogenated light Distillate oil can be used as raw material for hydrorefining or hydroreforming units in refineries to produce qualified gasoline, kerosene, diesel and other commercial oils.

In order to further demonstrate the superiority of the present invention, the process according to the present invention will be compared with the traditional process of the prior art below.

Comparative example 1

Comparison of the Heavy Raw Material Hydrogenation and Lightening Process of the Present Invention with the Conventional Hydrogenation Process

The coal-based heavy raw material in this comparative example is the same coal powder (≥120 mesh) (raw material 6) and The properties of the nitrogen-dried dehydrated coal powder (≥120 mesh) (raw material 7) used in the conventional hydrogenation liquefaction raw material of Scheme 1 below are shown in Table 5.

Table 52# thermal coal pulverized coal and dry base pulverized coal properties

In schemes 1 and 2, the γ-FeOOH/coal-supported catalyst prepared by FeSO ₄ 7H ₂ O, ammonia water, and 2# thermal coal powder in aqueous solution was used as the catalyst, and the solvent was reformed oil slurry of Yumen Refinery Conventional prehydrogenation solvent for direct liquefaction of coal prepared with coker wax oil (1:1) at temperature 430℃, pressure 12.0MPa and space velocity 1.0h ^-1 . In Scheme 3, the "catalytic fluid 2" prepared according to Example 1 is used.

In addition, option 1 selects the conventional coal direct liquefaction process and the conventional raw material slurry preparation process, in which the coal direct liquefaction conventional prehydrogenation solvent containing the above-mentioned γ-FeOOH/coal-supported catalyst is combined with the coal-based raw material Mixing; Schemes 2 and 3 include the preparation step of the mature coal-based heavy raw material slurry according to the process of the present invention, and the preparation process is the same as that in Example 1 except for the curing conditions and homogenization conditions described in Table 6 below . The conventional pre-hydrogenated solvent is typically a mixture of coker gas oil and aromatics catalytic oil slurry and is pre-hydrotreated. The results of the comparison are shown in Table 6.

Table 6 Coal-based heavy raw material slurry preparation and slurry properties

Subsequently, the coal-based heavy raw material slurry prepared in schemes 1-3 was subjected to hydrogenation and lightening (liquefaction), and the results are listed in Table 7.

Table 7 Hydrogenation results of different coal-based heavy feedstock slurries

It can be seen from the above table that under the same hydrogenation conditions, although the conversion rate (daf)/% of coal-based heavy raw materials is basically the same, there is a big difference between the light rate and light oil rate, especially the liquefaction There are obvious differences in the properties of the oil. The oxygen content in the liquefied oil prepared according to the conventional direct coal liquefaction process reaches 4.66wt%, which is equivalent to the properties of the liquefied oil of the Shenhua demonstration project. The basic properties of liquefied oil produced by different processes are shown in Table 8.

Table 8 Basic properties of liquefied oil products of coal-based heavy raw material slurry in different processes

Comparative example 2

Effect of Different Components of Catalytic Fluids of the Invention on Heavy Feedstock Catalytic Slurries

Schemes 4 and 5 are to repeat the preparation process of slurry 3 in Parts 1 and 2 of Example 1 to prepare catalytic slurry for coal-based heavy raw materials, but different compositions of catalytic fluids are used respectively.

The catalytic fluid used in scheme 4 is mainly composed of gamma-FeOOH/loaded coal in scheme 1 of comparative example 1 and the initial solvent prepared according to the first part of embodiment 1 as a solvent mixture, and used in scheme 5 The catalytic fluid 3 is the same as the catalytic fluid 1 prepared according to the first part of Example 1, but wherein the amount of the starting solvent is adjusted so that the Fe element content in the scheme 4 and the total metal content in the scheme 5 are 1.8wt %.

The results of commercially stable ratios of the catalytic fluids of different compositions and their resulting coal-based heavy feedstocks under the same operation are shown in Table 9 below.

Table 9 Different catalytic fluid compositions and the resulting different industrial stability ratios

Claims (70)

1. A general-purpose heavy raw material catalytic slurry hydrogenation lightening method, the method comprising: using a catalytic fluid to dissolve, disperse and/or dilute the heavy raw material, and then obtain a heavy raw material catalytic slurry, and then catalyze and supply hydrogen to the heavy raw material catalytic slurry under hydrogenation reaction conditions, thereby producing light distillate oil and cracked gas, Among them, the Fann's viscosity at 80°C of the treated heavy raw material catalytic slurry is ≤2000MPa·s, the static shear stress at 80°C is ≤35MPa·m ^-2 , and the industrial stability ratio is ≥0.80; The catalytic fluid described therein comprises: multi-component solvents, multi-metal compounds containing two or more metal elements, complexing agents and optional complexing aids, wherein the metal elements are selected from iron, The total content of nickel, molybdenum, copper, zinc, tin, aluminum, tungsten, manganese, titanium, vanadium, chromium, cobalt, gold, cadmium, mercury and lanthanide rare earth elements in the catalytic fluid is 0.05wt of the catalytic fluid %-5.0wt% and the multi-element metal compound forms a complex or chelate with a complexing agent; Wherein the multinary metal compound is dissolved or dispersed in the solvent in an ion state, a molecular state, a complex state, or a polymolecular polymerization state; and Wherein said industrial stability ratio is obtained by following experiments and calculations: pour fully stirred catalytic slurry into a 1000mm hydrostatic pipe, flow and stand still for 10 minutes and then lead fluid from the middle of the hydrostatic pipe to measure the fluid density D ₀ ; static settlement After 24h, the fluid is derived from the upper 100mm, and the average density D ^{upper part} (24h) is measured; the fluid is derived from the lower 100mm, and the average density D ^{lower part} (24h) is measured, and the industrial stability ratio is calculated by the following formula: 2. The method according to claim 1, characterized in that said metal element is selected from cerium. 3. The method according to claim 1, characterized in that said treatment comprises the step of maturing and optionally homogenizing the mixture of catalytic fluid and heavy feedstock. 4. The method according to claim 1 or 2, wherein the total content of S in the catalytic slurry is ≤2.0wt%, the solid content is 0-65wt%, and the water content is ≤0.2wt%. 5. The method according to claim 1 or 2, characterized in that, for solid-containing coal-based, bio-based and any mixture thereof, first heavy raw materials are mixed with catalytic fluid to prepare initial catalytic slurry, and then the initial catalytic The slurry undergoes an aging step for more than 0.5 hours at a pressure of 0.1-5.0 MPa and a temperature of 120° C.-300° C.; or for oil-based heavy feedstock, the oil-base heavy feedstock is mixed with a catalytic fluid. 6. The method according to claim 5, characterized in that said pressure is 1.0-3.5 MPa. 7. The method according to claim 5, characterized in that said temperature is 180-280°C. 8. A method according to claim 5, characterized in that the initial catalytic slurry is also subjected to a degassing and/or dehydrating step. 9. The method according to claim 1 or 2, characterized in that the mixture of catalytic fluid and heavy feedstock is homogenized for more than 1 hour. 10. The method according to claim 9, characterized in that, the homogenization treatment for oil-based heavy raw materials takes 2-4 hours. 11. The method according to claim 9, characterized in that, for coal-based, bio-based or any mixture thereof, the homogenization treatment is ≥ 24 hours. 12. The method according to claim 11, characterized in that, for coal-based, bio-based or any mixture thereof, the homogenization treatment is ≥ 48 hours. 13. The method according to claim 1 or 2, characterized in that, in the catalytic slurry, the mixing ratio of the heavy raw material is 10-80wt%. 14. The method according to claim 13, characterized in that the mixing ratio of the heavy raw material is 20-70 wt%. 15. The method according to claim 13, characterized in that the mixing ratio of the heavy raw material is 30-70 wt%. 16. The method according to claim 1 or 2, characterized in that, in the catalytic slurry, the mixing ratio of oil-based heavy feedstock and catalytic fluid is 40-70wt%: 60-30wt%. 17. The method according to claim 1 or 2, characterized in that, in the catalytic slurry, the mixing ratio of powdered coal-based or bio-based heavy raw material and catalytic fluid is 30-55wt%: 70-45wt% . 18. The method according to claim 1 or 2, characterized in that, in the catalytic slurry, the mixing ratio of any mixture of oil-based, coal-based and bio-based heavy raw materials and catalytic fluid is 40-70wt%: 60-30wt%. 19. The method according to claim 1 or 2, characterized in that, in the coal-based heavy raw material catalytic slurry, the operating temperature of the slurry is in the range of 120°C-250°C, and the industrial stability ratio of the slurry is ≥0.93 And the flow state is a low thixotropic non-Newtonian fluid with static shear stress ≤ 20MPa·m ^-2 at 80°C. 20. The method according to claim 1 or 2, characterized in that, in the bio-based heavy raw material catalytic slurry, the operating temperature of the slurry is in the range of 120°C-250°C, and the industrial stability ratio of the slurry is ≥0.90 And the fluid state is a medium-thixotropic non-Newtonian fluid with a static shear stress of 10-30MPa·m ^-2 at 80°C. 21. The method according to claim 1 or 2, characterized in that, in the catalytic slurry of any mixture of oil-based, coal-based and bio-based heavy feedstock, the operating temperature of the slurry is in the range of 120°C-250°C Inside, the industrial stability ratio of the slurry is ≥0.95 and the flow state is Newtonian fluid or low thixotropic non-Newtonian fluid with static shear stress ≤10MPa·m ^-2 at 80°C. 22. The method according to claim 1 or 2, characterized in that, the method sequentially comprises at least the following three process units, namely a catalytic fluid preparation unit, a catalytic slurry preparation unit and a hydrolightening reaction unit. 23. The method according to claim 1 or 2, characterized in that the method further comprises a heavy raw material pre-processing unit and a product post-processing unit. 24. The method according to claim 1 or 2, characterized in that the method is carried out in a dehydration or anhydrous environment in the catalytic slurry preparation unit and the hydrolightening reaction unit. 25. The method according to claim 24, characterized in that the method is carried out in a dehydration or anhydrous environment in the catalytic fluid preparation unit, the catalytic slurry preparation unit and the hydrolightening reaction unit. 26. The method according to claim 24, characterized in that the whole process is carried out in a dehydrated or anhydrous environment. 27. The method according to claim 1 or 2, characterized in that, said catalytic fluid consists of said multi-component solvent, said multi-element metal compound containing two or more metal elements, said The complexing agent and the optional complexing aid composition. 28. The method according to claim 1 or 2, wherein the metal element is selected from iron, nickel, molybdenum, tungsten, titanium, zinc, aluminum and lanthanide rare earth elements. 29. The method according to claim 1 or 2, characterized in that the metal element is selected from iron, nickel, aluminum, titanium and lanthanide rare earth elements. 30. The method according to claim 1 or 2, characterized in that, based on the weight of all metal elements of the multinary metal compound, the content of iron, aluminum and/or titanium elements is >50wt%, and the content of lanthanide rare earth elements is based on The weight of all metal elements is 0-5wt%. 31. The method according to claim 30, characterized in that the elemental iron content is >50 wt%. 32. The method according to claim 30, characterized in that the iron, aluminum and/or titanium element content is >65 wt%. 33. The method according to claim 30, characterized in that the iron, aluminum and/or titanium element content is >70 wt%. 34. The method according to claim 30, characterized in that the content of iron, aluminum and/or titanium elements is 70wt-80wt%. 35. The method according to claim 30, characterized in that the content of lanthanide rare earth elements is 0.1-3 wt% based on the weight of all metal elements. 36. The method according to claim 30, characterized in that the content of lanthanide rare earth elements is 0.1-1 wt% based on the weight of all metal elements. 37. The method according to claim 30, characterized in that the content of lanthanide rare earth elements is 0.2-0.5 wt% based on the weight of all metal elements. 38. The method according to claim 1 or 2, characterized in that the polynary metal compound is an inorganic salt and/or an organic salt. 39. The method according to claim 38, characterized in that the polynary metal compound is a hydrochloride, sulfate, nitrate, carbonate and/or carboxylate. 40. The method according to claim 38, characterized in that the multi-element metal compound is an aliphatic acid salt of C ₁ -C ₁₈ and/or an aromatic acid acid salt of C ₆ -C ₂₀ . 41. The method according to claim 1 or 2, characterized in that, the solvent has an average aromatization rate fa≥0.60, a density ≥0.95g/cm ³ and a Van's viscosity at 50°C ≥5MPa·s, wherein the solvent The total content of organic heteroatoms N, S, and O in the compound is ≤8.0wt%. 42. The method according to claim 1 or 2, characterized in that the solvent comprises >40% by weight of neutral components, 5% to 25% by weight of acidic components, 5% to 25% by weight of bases Active components and 5% to 15% by weight of ionic liquid. 43. The method according to claim 42, wherein the acidic component is one or more selected from phenol, C3-C4 alkylphenol, naphthol and indenol, and high phenolic oil. 44. The method according to claim 42, wherein the acidic component is two or more selected from phenol, C3-C4 alkylphenol, naphthol and indenol, and high phenolic oil. 45. The method according to claim 42, characterized in that, the basic component is one or more selected from the nitrogen heterocyclic compounds of anilines, quinolines, indole, pyridine, acridine . 46. The method according to claim 42, characterized in that, the basic component is selected from two or more nitrogen heterocyclic compounds of anilines, quinolines, indole, pyridine, acridine kind. 47. The method according to claim 42, wherein the ionic liquid is one or more selected from imidazolium salts, pyridinium salts, quaternary ammonium salts and quaternary phosphonium salts. 48. The method according to claim 42, wherein the ionic liquid is two or more selected from imidazolium salts, pyridinium salts, quaternary ammonium salts and quaternary phosphonium salts. 49. The method according to claim 42, wherein the neutral component is selected from heavy aromatic oils containing heavy aromatics content ≥ 50 wt%, polycyclic aromatics, partially or fully hydrogenated polycyclic One or more of aromatic oils. 50. The method according to claim 42, wherein the neutral component is selected from heavy aromatic oils containing heavy aromatics content ≥ 50 wt%, polycyclic aromatics, partially or fully hydrogenated polycyclic Two or more of aromatic oils. 51. The method of claim 42, wherein said solvent comprises heavy aromatic oil as base mineral spirits of the solvent. 52. The method according to claim 42, characterized in that, the solvent contains 60wt%-90wt% of the total amount of the solvent as heavy aromatic oil as the base spirit of the solvent. 53. The method according to claim 1 or 2, wherein the complexing agent is selected from the group consisting of heterocyclic compounds comprising heteroatoms and optionally substituted, C ₁ -C ₁₈ aliphatic alcohols, aliphatic amines, Aliphatic carboxylic acids and aliphatic sulfonic acids each optionally substituted by one or more hydroxyl, carboxyl or mercapto groups, and thiourea or thiourea derivatives. 54. The method of claim 53, wherein the heteroatom is N, O or S. 55. The method of claim 53, wherein the heterocyclic compound has 6-40 carbon atoms. 56. The method of claim 53, wherein said heterocyclic compound has 6-30 carbon atoms. 57. The method of claim 53, wherein the heterocyclic compound is substituted with a hydroxyl or mercapto group. 58. The method of claim 57, wherein the complexing agent is selected from one or more of the following: 1,10-phenanthroline, EDTA, dimercaptopropanol, dimercapto Sodium Propane Sulfonate, Mercaptoethylamine, Thioglycolic Acid, Thiourea, 8-Hydroxyquinoline. 59. The method according to claim 1 or 2, wherein the complexing aid is selected from cyanide, citric acid, tartaric acid, oxalic acid, sulfosalicylic acid, triethanolamine, sodium alkoxide, methylsilanol One or more of sodium, NaOH, KOH. 60. The method according to claim 1 or 2, characterized in that, the hydrogenation reaction conditions when catalyzing and supplying hydrogen to the heavy raw material catalytic slurry are: reaction pressure 5MPa-30MPa and reaction temperature 380°C- 520°C. 61. The method according to claim 1 or 2, characterized in that, the heavy raw material catalytic slurry is an oil-based heavy raw material catalytic slurry, and the hydrogenation reaction conditions when it is catalyzed and supplied with hydrogen are as follows: The pressure is 8.0MPa-18.0MPa and the reaction temperature is 380°C-470°C. 62. The method according to claim 1 or 2, characterized in that, the heavy raw material catalytic slurry is a coal-based heavy raw material catalytic slurry, and the hydrogenation reaction conditions when it is catalyzed and supplied with hydrogen are as follows: The pressure is 12.0MPa-18.0MPa and the reaction temperature is 400°C-470°C. 63. The method according to claim 1 or 2, characterized in that, the heavy raw material is an oil-based raw material, which is selected from heavy crude oil, processed heavy oil, coal tar, biological waste oil and their Mixed oil products, wherein the distillate content of ≥350°C is >90wt%. 64. The method according to claim 1 or 2, characterized in that, the heavy raw material is coal-based raw material, which is selected from sapropelite with maturity R°≤0.85 and sapropelite with vitrinite content of 30-70wt%. Humic coals and their mixtures of different coal qualities. 65. The method according to claim 64, wherein the heavy raw material is a coal-based raw material selected from sapropelite with a maturity R°≤0.75 and humic coal with a vitrinite content of 30-70wt%. And their mixed coals of different coal qualities. 66. The method according to claim 1 or 2, characterized in that, the heavy raw material is a bio-based raw material, which is selected from high calorific value organic raw materials with a hydrogen content ≥ 6.5 wt% and an oxygen content ≤ 30%. substance. 67. The method according to claim 1 or 2, characterized in that, the heavy feedstock is a mixed base feedstock, which is an oil-based feedstock as claimed in claim 63, a coal-based feedstock as described in claim 64 Feedstock, any mixture of the three types of heavy feedstock of bio-based feedstock as claimed in claim 66. 68. A heavy raw material catalytic slurry is characterized in that it dissolves, disperses and/or dilutes the heavy raw material by the catalytic fluid as defined in any one of claims 1, 27 to 59, and then passes through Prepared after treatment, it has a Fann viscosity at 80°C of ≤2000MPa·s, a static shear stress at 80°C of ≤35MPa·m ^-2 and an industrial stability ratio of ≥0.80; Wherein said industrial stability ratio is obtained by following experiments and calculations: pour fully stirred catalytic slurry into a 1000mm hydrostatic pipe, flow and stand still for 10 minutes and then lead fluid from the middle of the hydrostatic pipe to measure the fluid density D ₀ ; static settlement After 24h, the fluid is derived from the upper 100mm, and the average density D ^{upper part} (24h) is measured; the fluid is derived from the lower 100mm, and the average density D ^{lower part} (24h) is measured, and the industrial stability ratio is calculated by the following formula: 69. The catalytic slurry of claim 68, wherein the slurry is homogeneously stable on the colloidal scale. 70. The catalytic slurry according to claim 68 or 69, characterized in that, in the catalytic slurry, the mixing ratio of oil-based heavy raw material and catalytic fluid is 40-70wt%: 60-30wt%, The mixing ratio of powdery coal-based or bio-based heavy feedstock to catalytic fluid is 30-55wt%: 70-45wt%, or the mixing ratio of any mixture of oil-based, coal-based and bio-based heavy feedstock to catalytic fluid is 40 ~70wt%: 60~30wt%.