CN104789252B

CN104789252B - A kind of universal heavy charge catalysis slurry hyd lightening method and device

Info

Publication number: CN104789252B
Application number: CN201410028794.2A
Authority: CN
Inventors: 金军
Original assignee: Beijing Jingeite Energy Technology Co Ltd
Current assignee: Zhongxinghang (Shanghai) Business Service Co.,Ltd.
Priority date: 2014-01-21
Filing date: 2014-01-21
Publication date: 2018-06-12
Anticipated expiration: 2034-01-21
Also published as: CN106554793A; CN104789252A; CN106554793B

Abstract

The present invention relates to a kind of method of universal heavy charge catalysis slurry hyd lighting and the devices of implementation this method, are additionally related to suitable for a kind of catalysis fluid of this method and thus obtained heavy charge catalysis slurry.The heavy charge can be oil base, coal base, biology base and its mixed base heavy charge.

Description

A kind of universal heavy charge catalysis slurry hyd lightening method and device

Invention field

The method of slurry hyd lighting is catalyzed the present invention relates to a kind of universal heavy charge and implements this method Device is additionally related to a kind of catalysis fluid and thus obtained heavy charge catalysis slurry.The heavy charge can be Oil base, coal base, biology base and its mixed base heavy charge.

Background technology

Routinely fossil energy classification is divided into the mink cell focus of oil base or petroleum base, i.e. API severe≤25 ° to heavy charge Product, usual hydrogen content≤11.0%；Coal base, the i.e. sapropelic coal of R ° of maturity≤0.75 and vitrinite's content >=50%, such as >=60% Humic coal, and organic phase (daf) is by >=-30 ° of oil API severes extrapolation and hydrogeneous usually in organic phase in coal base heavy charge Measure 4.3-7.0%；The matrix precursor of biology base, i.e. fossil energy（R°≈0）, such as bio-oil, cyanobacteria, pine needle, it is typically Oxygen content 5wt%-30wt% and hydrogen content >=6.5wt% high burning-value component；And there is the heavy original of their mixed base Material.

Existing heavy charge lighting engineering is generally divided into heavy oil decarburization or hydrogenation technique according to type of feed, Direct coal liquefaction process, the Hydrogenation liquefaction process of biomass and their mixed base add hydrogen to be total to sweetening process.

China is the country based on continental sedimentary basin, and coal accounts for the 99% of fossil energy total resources, conventional gas and oil resource Amount only accounts for 1% or so of fossil energy total resources, this also means that heavy charge (fuel) and unconventional petroleum resources (coal petrography Oil, shale gas, coal bed gas) it is abundant, therefore, Chinese fossil energy resources characteristic determines heavy charge lighting, purifying Critical role in Chinese energy industry.

There are mainly two ways for processing of heavy oil at present：Decarburization adds hydrogen.Delayed coking is typical decarbonization process, Ke Yijia The various inferior heavy oils of work and residual oil, but its liquid product yield is low, of poor quality, it is also restrained in petroleum coke application aspect.Cause This, to improve the yield of refinery's light fraction oil, at present generally using hydrogen addition technology processing residual oil or heavy oil.This hydrogen addition technology Mainly include fixed bed, moving bed, ebullated bed (slurry bed system) and floating bed hydrogenation technology.Wherein, heavy oil fixed bed hydrogenating skill When the shortcomings that art is processing high metal, the inferior heavy oil of high asphalt content, the operation cycle is too short.Moving bed, ebullated bed heavy oil Hydrogen addition technology can handle raw material relatively inferior, but the technical sophistication, operating cost are higher.

Coking of coal technique is that the carbon sequestration that coal is processed in coal industry takes off liquid technique.Coal tar as the byproduct in technique, It is a kind of liquid hydrocarbon-containing product very inferior, is widely used as primary industrial chemicals or fuel.

The direct liquefaction technique of coal and biomass is by coal under the conditions of temperature (400-500 DEG C) and pressure (15-30MPa) Or biomass, solvent react with hydrogen with the mixture of catalyst and generate product liquid, catalyst used have cobalt, molybdenum, tungsten, The oxide or halide of tin, iron and lead etc..Direct coal liquefaction process mainly have U.S.'s H-coal techniques, Japan's NEDOL techniques, German IGOR techniques and the Shenhua technique in China etc., but existing coal Direct Hydrogenation liquefaction technology, it is complicated there are technological process, Conversion cost is high, hinders the industrialization development of the technique.

It is proposed in Canadian Patent CA1073389 and United States Patent (USP) US4214977 and coal or coal base is added in processing of heavy oil The method of additive reduces the coke settling amount in hydrocracking heavy oil technique.It is solid after feedstock oil conversion but in this technology Body powder can be stayed in unconverted residue, and separating difficulty is larger, reduced the purposes of unconverted residual oil and also environmental protection is brought to ask Topic.

The forties in last century, Canada have started tar asphalt and have faced the research that hydrogen produces fluid product with ub-bituminous coal, added and take Canmet techniques and hydrocarbonylation object company of the U.S. that coal-tar asphalt refines altogether are proposed in big patent CA1160586 in H-Coal With the HRI techniques for kerosene is proposed on H-Oil Process ba- sis refining altogether, Japan Patent 8045703,8023407 proposes solvent point Solution technique.Last century eight, middle nineteen nineties where Chinese Liaohe Oil Field and Shanxi coalification are public with Canada and U.S. HRT respectively Department cooperation carried out viscous crude, super-viscous oil, decompression residuum kerosene refine commerical test technology transfer altogether, but fail to realize industrial dress The operation put.

The later stage eighties in last century, each major oil companies of the world competitively research and develop homogeneous catalyst.Representative technology There is Canadian (HC) 3 technology (using oil-soluble organo-metallic catalyst), water-soluble homogeneous catalyst Ze You Exxon companies Phosphomolybdic acid catalyst and the ammonium molybdate catalyst of Chevron companies etc..Homogeneous catalyst is due to being all during the reaction with gold The form for belonging to particle and its sulfide exists, so its activity is high, additive amount is few, small to reaction system abrasion, but their valencys Lattice are expensive and catalyst way of recycling is complicated.

CN1778871A proposes the Direct Hydrogenation liquefaction that the catalyst of γ-FeOOH that coal particle supports is used for coal, the U.S. The kerosene that patent US4338183 proposes using metal-organic complex as catalyst is total to sweetening process, and CN101020834A is carried Coal direct hydro-liquefaction method of the iron pentacarbonyl as catalyst is gone out to use, CN1089037C, which is proposed, is catalyzed heteropolyacid salt Agent is used for the heat treatment of super―heavy oil, and CN102041017A, CN102233279A propose lignin sulfonic acid metal coordination catalysis Agent and complexing humic acid and by dispersing type metallic catalyst for coal and decompression residuum plus hydrogen lighting.

Part Hydrogenated aromatic cycloalkanes hydrocarbon diluent is proposed in United States Patent (USP) US2848530, US3238118, US4090947 The method for handling poor hydrogen Petroleum Production liquid hydrocarbon, thermal tar, gas oil, higher coking gas oil, coal derived liquid and catalysis follow Ring oil is preferred hydrogen donor diluent precursor.United States Patent (USP) US6702936 comes by using the partial oxidation of asphaltene product Hydrogen donor diluent cracking method is produced, CN1032669A proposes complete ion liquid solvent process.

CN102041015A proposes a kind of method from coal oil-gas reservoir preparing liquid fuel, in this method by coal dust with Heavy oil mixing is aged, after heat of solution and dispersion, produces stable coal colloidal sol phase slurry through phase separation, coal colloidal sol phase slurry is big The big stability and transport property for improving fluid, consequently facilitating the side of light oil is produced in the operation in residual oil cracking hydrogenation plant Method.

In existing heavy oil boiling bed hydrogenation conversing technology, direct hydrogenation liquefaction of coal technology etc., reactant Material is three-phase mass transport process, this causes transporting for material that need to use high temperature and pressure multiphase circulating pump.In addition, by reaction mass into Row cycle causes processing unit (plant), and the wall thickness of particularly large high-temperature high-pressure reactor is big, tonnage weight, manufacture difficulty is big, is manufactured into The problem of this is high, this seriously constrains the lighting of heavy charge and cleans process.

In existing heavy oil floating bed hydrogenation transformation technology, direct hydrogenation liquefaction of coal technology, light fraction oily product The oily catalyst amount of ton is huge, and the water consumption in preparation or recycling catalyst process occupies the main use of hydroconversion process Water increases the lighting of heavy charge and cleans the Environmental costs of process.

Summary of the invention

The present invention task be to overcome in the prior art to oil base, coal base, biology base heavy charge and they appoint Mixture of anticipating carries out following defect present in hydroconversion process：(1) existing plus hydrogen lighting technique raw material is single；(2) Solvent of the prior art is low with dispersed ability to the dissolving of heavy charge solute and applicable heavy charge narrow range；(3) The rheology of slurry and thixotropy are poor；(4) preparation of catalyst is numerous and diverse with recovery process and water consumption is high；(5) traditional catalyst pair The catalysis adaptability of hydrogenating materials composition is narrow, the technological problems such as low, poor quality of conversion ratio of distillate.Meanwhile for corresponding Process engineering, task of the invention are to overcome in the prior art that system flow is complicated, utilization rate is low, and reaction unit is mostly high temperature High pressure multiphase circulating reaction system, reaction system device and device fabrication difficulty are big, and safety difference of device control etc. is a series of Problem.

It has surprisingly been found that slurry hyd lighting is catalyzed by a kind of universal heavy charge provided by the present invention Method, catalysis fluid and heavy charge catalysis slurry, that the present invention is based on, as described above appoint can be completed well Business.

Therefore, the present invention relates to a kind of method of universal heavy charge catalysis slurry hyd lighting, this method includes： Heavy charge is dissolved, disperseed and/or is diluted using the catalysis fluid with catalysis, obtained heavy after treated Catalytic material slurry is then catalyzed and hydrogen supply heavy charge catalysis slurry under hydrogenation conditions, is thus made Obtain lighting distillate and cracking gas.

Fan Shi viscosity≤2000MPas of heavy charge catalysis slurry wherein after processing（80℃）, quiet shearing stress≤ 35MPa·m^-2（80℃）With stabilization of industry ratio >=0.80.

On the other hand, it the present invention relates to a kind of catalysis fluid with catalysis, is formed it includes or by following component： Multi-component starting and/or cycle solvent, the multi-element metal compound containing two or more metallic element, complexing agent With optional complexing auxiliary agent, wherein total content of the metallic element in fluid is catalyzed for it is described catalysis fluid 0.05wt%- 5.0wt% and the multi-element metal compound and complexing agent formation complex compound or chelate.The catalysis fluid can especially be used In the method for universal heavy charge catalysis slurry hyd lighting as described above.

In another aspect, the present invention relates to a kind of heavy charges to be catalyzed slurry, which is characterized in that it is by above-mentioned catalysis fluid Heavy charge is dissolved, disperseed and/or is diluted, and is treated rear obtained, with Fan Shi viscosity≤2000MPas （80℃）, quiet shearing stress≤35MPam^-2（80℃）With stabilization of industry ratio >=0.80.

Finally, the invention further relates to a kind of for implementing the device of method as described above.

Detailed description of the invention

It, will be by the different type heavy charge of oil base, coal base, biology base and mixed base and catalysis in this patent scope The catalysis slurry that fluid is mixed with carries out the process for adding hydrogen lighting under hydrogenation conditions, is collectively referred to as heavy charge Plus hydrogen lighting technique, it is not limited to whether the type of reactor, structure have filler or inner member etc. in reactor.

In scope, it is oil base, coal base, biology to be adapted to the present invention plus hydrogen lightening method heavy charge Base heavy charge and their any mixture（Also referred to as mixed base heavy charge）, wherein oil base heavy charge for example attaches most importance to The fluid fuels such as matter crude oil, processing heavy oil, coal tar, biologic garbage grease, coal base heavy charge is for example, low, middle maturity is rotten The humic coal of mud coal and high vitrinite's content, biology base heavy charge are, for example, algae in fossil fuel precursor biomass, life The high heating values component such as object lipid, barkinite, lignin.

Oil base raw material in the heavy charge can be API °≤25 heavy crude, processing heavy oil, coal tar, life Object rubbish grease etc. and their mixing oil product.In general, oil base raw material oil product mid-boiling point>350 DEG C of ends content> 90wt%, such as>95wt%.Preferably, selected oil base raw material is API °≤15.0 super-viscous oil, super―heavy oil, depressurizes slag Oil, coal tar and biologic garbage grease etc. or their mixing oil product；Oil base raw material oil product mid-boiling point>350 DEG C of fraction Content 100wt%, water content≤0.2wt%, solid residue≤0.2wt%.

In addition, the coal-based feedstocks being suitable for the invention in heavy charge can be such as R ° of maturity≤0.85, such as R °≤0.75 sapropelic coal and the humic coal of vitrinite's content >=50wt% and the Mixture Density Networks of their different coals quality.Coal base The powder granularity of material is suitably 80-400 mesh, such as 80-200 mesh, and pulverized coal water content is suitably≤15.0wt%（Such as< 10.0wt%）And ash content≤15wt%（Such as≤10wt%）.Advantageously, selected coal-based feedstocks can be R ° of maturity≤ 0.70 sapropelic coal and the humic coal of vitrinite's content >=65wt% and their different types of coal, the Mixture Density Networks of coal quality.

In addition, the organism-based raw material being suitable for the invention in heavy charge may, for example, be hydrogen content >=6.5wt%, contain The high heating value organic biomass of oxygen amount≤30%.The powder granularity of organism-based raw material can be 80-400 mesh（Such as 80-200 mesh）, it is raw The powder water content of object based raw material can be for example≤15.0% and/or content of ashes≤5%.Preferably, selected biology base Raw material is hydrogen content >=7.0wt%, the lignin of oxygen content≤26wt%, bolt plastid biomass.

In the methods of the invention, in the heavy charge mix based raw material can be, for example, more than oil base, coal base, life Any mixture of three classes heavy charge in object base.Likewise, the powder granularity of solid material can be in mixed base heavy charge For 80-400 mesh, content of ashes≤10% and water content≤15.0wt% in powder.

On the one hand, subject of the present invention is a kind of method of universal heavy charge catalysis slurry hyd lighting, the party Method includes：Heavy charge is dissolved, disperseed and/or is diluted using the catalysis fluid with catalysis, after treated Heavy charge catalysis slurry is made, then heavy charge catalysis slurry is catalyzed and is supplied under hydrogenation conditions Thus lighting distillate and cracking gas is made in hydrogen, wherein the Fan Shi viscosity of heavy charge catalysis slurry after processing≤ 2000MPa·s（80℃）, quiet shearing stress≤35MPam^-2（80℃）With stabilization of industry ratio >=0.80, more preferably >=0.90 or >= 0.93。

In one preferred embodiment, it is required respectively for different types of heavy charge catalysis slurry as follows Preferred scope：

1st, Fan Shi viscosity≤200MPas of oil base heavy charge catalysis slurry（80℃）, quiet shearing stress≤5MPam^-2 （80℃）With stabilization of industry ratio >=0.95, more preferably >=0.98 or 1.0.

2nd, Fan Shi viscosity≤1200MPas of coal base weight matter catalytic material slurry（80℃）, quiet shearing stress≤20MPa m^-2（80℃）, preferably≤10MPam^-2（80℃）With stabilization of industry ratio >=0.93, more preferably >=0.95 or >=0.98.

3rd, Fan Shi viscosity≤500MPas of kerosene mixed base heavy charge catalysis slurry（80℃）, quiet shearing stress≤ 10MPa·m^-2（80℃）, preferably≤5MPam^-2（80℃）With stabilization of industry ratio >=0.93, more preferably >=0.95 or >=0.98.

On the other hand, correspondingly, the present invention relates to a kind of for implementing the device of the above method, the device is at least successively Including following three technique units：It is catalyzed fluid preparation unit, catalysis slurry preparation unit and adds hydrogen lighting reaction member.Its In particularly catalysis slurry preparation unit and plus hydrogen lighting reaction member in respectively carry out using catalysis fluid to heavy original Material is dissolved, disperseed and/or is diluted and the step of treated obtained heavy charge catalysis slurry and in hydrogenation conditions Under heavy charge catalysis slurry is catalyzed and the step of hydrogen supply.

Particularly, at least five can be included successively as a relatively complete embodiment, the method and device Technique unit, i.e. heavy charge preprocessing unit, catalysis fluid preparation unit, catalysis slurry preparation unit plus hydrogen lighting Reaction member, product postpositive disposal unit, so as to produce lighting distillate and cracking gas for example≤350 DEG C.

The method of the present invention is theoretical and biological with fossil energy resource deposition distribution according to biocoene in nature Development and inheritance between matter and variety classes fossil resource, the multicomponent distribution character with heavy charge, and based on more Component raw material catalytic hydrogenation reaction and the technology theory of kinetics basis.An outstanding feature in this method is with work The multicomponent catalysis dispersed paste that industry is stablized is working fluid, can be provided in industrial reaction device and defeated add hydrogen homogeneously to pump Thus the reaction engineering system of lighting greatly simplifies the operating condition for adding hydrogen lighting and brings higher security reliability.

Due to these advantages, method of the invention is excellent in catalysis slurry preparation unit and in adding hydrogen lighting reaction member It is selected in catalysis fluid preparation unit, catalysis slurry preparation unit and adds in hydrogen lighting reaction member under dehydration or water-less environment It carries out, more preferably the method whole process is completed under dehydration or water-less environment.

To the present invention be further elaborated on according to above-mentioned more complete technological process below.

Heavy charge preprocessing unit

The present invention's plus in hydrogen lightening method, the heavy charge preprocessing unit technological process be raw material into Before entering to be catalyzed slurry unit raw material import, the storage and transportation of the summation of material treatment process flow, i.e. heavy charge, powder processed, dehydration, The purified treatments such as deliming and raw material mixing and deposit etc..

The heavy charge preprocessing unit device refers to entering before catalysis slurry preparation unit material inlet, raw material The summation of all devices on route is flowed through in processing technological flow, such as the combined purifying system and device of oil base heavy charge, coal base, The crushing of biology base heavy charge, powder processed, sorting, dehydration, gas separator, powder stocking system device and relevant control Control equipment and security system etc..

In the specific embodiment of the present invention, material of the heavy charge preprocessing unit according to heavy charge Type, which with state is divided into fluid, to be preserved and is preserved with powder.Wherein, it for the fluid reservoir system of oil base heavy charge, can select The heavy oil storage and transportation apparatus and technique of petroleum industry national standard.And for coal base, biology base and the solid powder for mixing based raw material Body reservoir system can select cement, the coal dust storage and transportation apparatus of power industry national standard and technique, for wanting for these materials Seeking Truth such as powder granularity is -200 mesh of 80 mesh, material moisture≤10.0wt%, inorganic content≤10.0wt%.Powder preserves Tank needs nitrogen to protect, and powder is arranged by nitrogen wind or conveyed under nitrogen protection by screw conveyor.

It is catalyzed fluid preparation unit

The present invention's plus in hydrogen lightening method, catalysis fluid is prepared in fluid preparation unit is catalyzed.

In the present invention, the catalysis fluid for being suitable for the invention method can be any conventional in the prior art in principle The Direct Hydrogenation liquefaction process for heavy charge, particularly coal base heavy charge in catalysis fluid, such as include coal γ-FeOOH the catalyst and the catalysis fluid of dispersion solvent that grain supports.

But a kind of novel catalysis fluid is proposed in the present invention, the technique that can be preferably applicable in the present invention.Institute State catalysis fluid include following component and preferably it is composed of the following components：Multi-component solvent, containing two or more Multi-element metal compound, complexing agent and the optional complexing auxiliary agent of metallic element, wherein the metallic element is in fluid is catalyzed Total content for it is described catalysis fluid 0.05wt%-5.0wt%, such as 0.05wt%-4.0wt% or 0.07wt%-3.0wt% and The multi-element metal compound forms complex compound or chelate with complexing agent.

As a preferred embodiment, although complexing is desired, in general multi-element metal chemical combination as far as possible The complexing degree of object is >=40%, is preferably >=50%, more preferably >=60% or 70%, therefore the multi-element metal in the catalysis fluid Element will be dissolved or dispersed in the solvent with ionic condition, molecular state, complex status and/or polymolecular polymerization state In.

The present invention catalysis fluid be by multi-component solvent be complexed be dissolved or dispersed in it is polynary organic in the solvent The fluid with catalytic performance of metallic compound composition.Although in the process according to the present invention using it is of the prior art that The slurries that a little traditional catalysts and solvent are formed can also realize the improvement of technique and the promotion of performance, but by using basis The selected catalysis fluid of the present invention can be more conducive to that homogeneous stability is made on colloid scale after mixing with heavy charge Catalysis slurry.For coal-based feedstocks, compared with traditional direct coal liquefaction technology, avoid unstable, easy The multiphase transmission processing procedure of separation is precipitated, is overcome in the transmission process of coal slurry storage and transportation river and is deposited caused by two-phase laminated flow, is serious The problems such as abrasion, coking, blocking.In addition, catalysis fluid is formed due to employing the catalyst containing ionic liquid in the present invention, Therefore liquefaction effect is enhanced, has prevented the γ-FeOOH catalyst systems that solid such as coal particle supports in conventional liquefaction technology Standby complicated technology and huge water power consumption.

In the catalysis fluid of the present invention, the solvent may be preferred that the starting of system and/or cycle solvent, be By the solvent entered plus the starting of hydrogen lighting system is prepared（Such as fraction >=300 DEG C）Or the cycle solvent run in system Or both mixture form, the composition of the two can be identical or different.It for example can be present invention process method to recycle solvent In take off slag and add the bottom of towe oil that hydrogen slurry fraction section is 320 DEG C -550 DEG C, it is appropriate to supplement according to the type difference for adding hydrogen heavy charge Heterocyclic compound and/or solubilized dosage 0-5.0wt%.The solvent has multicomponent distribution characteristics and the not such as prior art Employed in the relatively single solvent of component, must have existing to the dissolving of heavy charge, dispersion, diluted fluid work( Can, and have and hydrogen storage, activation, the response function for shifting hydrogen supply are dissolved under hydrogenation conditions.Therefore, in the catalysis stream of the present invention It can not essentially be added in body such as pre-add hydrogen solvent common in routine techniques.

Specifically, the present invention catalysis fluid used in solvent include neutral component, acidic components, basic component and Ionic liquid.Solvent it is multigroup be grouped as in generally with hetero atom in heavy charge（Such as N, O, S）The reduction of content, polarity Ingredient is reduced, but neutral component must formation base component with ionic liquid in a solvent.

In an advantageous embodiment, the solvent includes>40 weight %, preferably>45 weight %, more preferably>50 The neutral component of weight %, the acidic components of the weight % of the weight %, preferably 5 weight % of 3 weight %~25~22, the weight of 3 weight %~25 Measure the weight % of %, preferably 5 weight %~20 basic component and the weight % of the weight %, preferably 3 weight % of 3 weight %~15~10 from Sub- liquid.

As neutral component, it may be considered that more selected from amount containing heavy arene（Such as heavy arene content >=50wt%）'s It is one or more in heavy arene class oil, polycyclic aromatic hydrocarbon, multiring aromatic hydrocarbon oil for partly or entirely hydrogenating etc., preferably two kinds or It is more kinds of.

As acidic components, it may be considered that one kind in phenol, C3-C4 alkyl phenols, naphthols and indenols, high carbolic oil etc. Or it is a variety of, preferably two or more.

As basic component, it may be considered that selected from nitrogen heterocyclics such as phenyl amines, quinolines, indoles, pyridine, acridine etc. In it is one or more, preferably two or more.

As ionic liquid, it may be considered that one in imidazole salt, pyridine salt, quaternary ammonium salt and quaternary phosphonium salt class etc. Kind or it is a variety of, preferably two or more.

Alternatively, it is also possible to be directly used in industrial common such as wax tailings or add 330 DEG C of fraction section in hydrogen slurry Themselves it is one or more mixtures that complicated component still contains above-mentioned four kinds of components to 541 DEG C of distillate.

In the preferred embodiment of the present invention, respectively from improve solvent to the suspension of dispersing solid object, carry Height prepare catalysis slurry transport property, meet plus hydrogen lighting reaction in hydrogen migration characteristic and improve heavy charge it is molten From the aspect of solution property, it is desirable that density >=0.95 of the solvent, preferably 0.95-1.02g/cm³, particularly 0.96-0.99g/cm³, Fan Shi viscosity for >=5MPas, preferably 15-35MPas, such as 15-28MPas (50 DEG C) and average virtue rate fa be >=0.60, the total content of organic hetero atom N, S, O in preferably 0.65-0.72, particularly 0.67-0.70, wherein solvent for≤ 8.0th, preferably 3.0-8.0wt%, especially such as 4.0-6.5wt%.

Preparation for solvent, the ratio of polar compound increases in the type and Group Component generally according to heavy charge, Polar compound ratio improves in the solvent.

As a preferred embodiment, heavy arene class oil is included in the solvent, preferably accounts for solvent total amount 70wt%-90wt% heavy arene class oil as solvent base solvent oil.

Preferably, in the solvent of the present invention, the dissolubility property parameter distribution of solvent and the type of heavy charge It is directly related with the dissolubility property parameter distribution of Group Component.In general, in the present invention, the solubility characteristics of the solvent The intermediate value solubility characteristics parameter difference Δ δ of parameter intermediate value and heavy charge^1/2≤ 5, preferably Δ δ^1/2≤3。

In the present invention, the solvent can be by those skilled in the art by known method, such as by matching It mixes and prepares.In one preferred embodiment, will such as heavy arene class base solvent oil, polycyclic aromatic hydrocarbon, part or complete The secondary solvent oil of portion's hydrogenation multiring aromatic hydrocarbon, heterocyclic compound or solubilizer etc. at -80 DEG C of temperature 50 C, stir in order It mixes mixture and the non-aqueous initial solvent of multicomponent is made.

In the present invention, the metallic element is selected from the IA races of the periodic table of elements to VA races, IB races to VIIB races and VIII Two or more of race and lanthanide series rare-earth elements.Preferably, the metallic element be selected from iron, nickel, molybdenum, copper, zinc, tin, aluminium, Tungsten, manganese, titanium, vanadium, chromium, cobalt, gold, cadmium, mercury, cerium and lanthanide series rare-earth elements are more preferably selected from iron, nickel, molybdenum, tungsten, titanium, zinc, aluminium And lanthanide series rare-earth elements, it is especially selected from iron, nickel, aluminium, titanium and lanthanide series rare-earth elements.

As a very favorable embodiment, in terms of the weight of all metallic elements of multi-element metal compound, iron, Aluminium and/or titanium elements（It is preferred that ferro element）Content is>50wt%, preferably>65wt%, particularly>70wt% and such as 70wt- 80wt%, and the content of lanthanide series rare-earth elements be based on 0~5wt% of weight meter of all metallic elements, preferably 0.1~3wt%, More preferable 0.1~1wt% and particularly 0.2~0.5wt%.

In addition, in one preferred embodiment, total content of the metallic element in fluid is catalyzed is urged to be described Change the 0.05wt%-3.0wt%, preferably 0.05wt%-2.0wt% of fluid.

Multi-element metal compound is not particularly limited, it should be able to be compatible with solvent and can be subsequent anti- The complexing agent formation that Ying Zhongyu is added is dissolved or dispersed in complex compound or chelate in solvent.Those skilled in the art can Suitable multi-element metal compound is selected accordingly.Suitable multi-element metal compound is, for example, inorganic salts and/or organic salt, excellent Select hydrochloride, sulfate, nitrate, carbonate, carboxylate, C₁-C₁₈Aliphatic acid salt and/or C₆-C₂₀Aromatics hydrochlorate etc..

Here, need further complexing agent group to form complex compound or chelate in the solvent with metal ion Point.In principle, all and above-mentioned metal ion all can be applicable, ability with stable complexation or the morphogenetic complexing agent of chelating Field technique personnel can reasonably select suitable complexing agent according to the production practices common sense of itself.

In a specific embodiment, as complexing agent it is contemplated that including the heterocyclic compound of hetero atom such as N, O or S Object（Such as with 6-40 or 6-30 carbon atom）And it can be optionally substituted（Such as hydroxyl or sulfydryl）, C₁-C₁₈Fat Race's alcohol, aliphatic amine, aliphatic carboxylic acid and aliphatic sulfonic acid and its can respectively be replaced by one or more hydroxyls, carboxyl or sulfydryl, with And such as thiocarbamide or thiourea derivative.As example it can be cited for example that it is following these：1,10- Phen, EDTA, dimercapto Propyl alcohol, Sodium Dimercapto Sulfonate, mercaptoethylmaine, thioacetic acid, thiocarbamide, 8-hydroxyquinoline etc..The complexing agent can be single Solely use, can also a variety of forms be applied in combination.

According to selected complexing agent and multi-element metal compound, complexing auxiliary agent optionally can be optionally added, such as The one of cyanide, citric acid, tartaric acid, oxalic acid, sulfosalicylic acid, triethanolamine and sodium alkoxide, methyl silicon sodium alcoholate, NaOH, KOH etc. Kind is several.

In order to prepare the catalysis fluid of the present invention, the solvent is made in advance as described above, then adds in institute thereto The complexing agent and optional complexing auxiliary agent and multi-element metal compound stated, fully react and discharge uncondensable gas with Desired catalysis fluid is obtained after water.

For example, in a specific embodiment, in order to prepare the catalysis fluid, preparation and adjustment is provided previously The good solvent adjusts the PH ranges of solvent in 7.0- in 20-100 DEG C of temperature, at preferably 30 DEG C -80 DEG C by the way that auxiliary agent is complexed 11.0th, it preferably after 8.0-10.0, is proportionally added into complexing agent and sequentially adds above-described multi-element metal compound（Such as F_e ²⁺、Ni²⁺、Al³⁺With the multi-element metal salt of a small amount of lanthanide series rare-earth elements）After mixture, 120 DEG C -150 DEG C are warming up to, is being stirred It mixes down（It such as stirs 30-120 minutes）, it is warming up to 180 DEG C -250 DEG C again after uncondensable gas and water is detached, continues to stir Reaction（It is such as stirred for 30-180 minutes）, thus prepare the catalysis fluid containing multi-element metal compound.

It is catalyzed slurry preparation unit

In the catalysis slurry preparation unit of the present invention plus hydrogen lightening method, heavy charge is carried out using catalysis fluid Dissolving, swelling, dispersion and/or dilution（Such as it can be realized by simply being mixed）, being made after treated improves The heavy charge catalysis slurry of fluid property.

Advantageous, the present invention claims the fluid properties parameters of catalysis slurry prepared according to both methods to be：Stream of slurry Fan Shi viscosity≤2000MPa.s (80 DEG C) of body, quiet shearing stress≤35MPa × m^-2(80 DEG C), stabilization of industry ratio >=0.90；It is preferred that Ground, fluid Fan Shi viscosity≤2000MPa.s (80 DEG C), quiet shearing stress≤30MPam-2 (80 DEG C) and stabilization of industry ratio >= 0.95.It is further advantageous that solid content is 0-65wt%, preferably 0-55wt%, more preferable 0-42wt% in catalysis slurry fluid. Catalysis slurry fluid obtained in this way obtains remarkable machinability and is therefore particularly suited for subsequent plus hydrogen lighting step Suddenly.

The catalysis paste industry stabilization ratio is by testing with being calculated.Experimental method is：In 1000mm hydrostatics The catalysis slurry being sufficiently stirred is poured into pipe, fluid is exported in the middle part of hydrostatic pipe after flowing static 10min, measures fluid density D₀；Quiescent settling for 24 hours after, from top 100mm export fluid, measure averag density D^Top(24h)；It exports and flows from lower part 100mm Body measures averag density D^{Lower part}(for 24 hours), stabilization of industry ratio is calculated by following formula：

In order to realize above-mentioned desired Fan Shi viscosity, quiet shearing stress and stabilization of industry ratio, the processing procedure is advantageously Including following two committed steps, i.e., oil base heavy charge is mixed and will contained with the catalysis fluid according to obtained by the present invention Coal base, biology base and the mixed base heavy charge of solid carry out maturation process.It will be appreciated by those skilled in the art that described is ripe Change processing is referred to heavy charge in ager（Such as tubular reactor）In be subjected to certain time pressure and temperature place Reason, so as to adjust the maturity of heavy charge and organic component contained therein etc..In the method for the invention, advantageously make It must cure and be carried out at a temperature of the operating pressure of 0.1-5.0MPa and 120 DEG C -300 DEG C, and the maturation process time can protect It holds at such as 0.5 hour or more, preferably 1 hour or 2 hours or more, and as expected the length of maturation process time can be Performance is adjusted, such as measured stabilization of industry ratio.

Therefore, the catalysis slurry preparation method can be divided into oil base heavy charge in proportion by the type of heavy charge Mix with catalysis fluid and prepare obtain Newtonian fluid oil base heavy charge be catalyzed slurry technique and coal base containing solid, The two step preparation methods with catalysis fluid, later approach can prepare non-ox in proportion for biology base and mixed base heavy charge Coal base, biology base and the mixed base heavy charge catalysis slurry of fluid.For example, the catalysis slurry preparation method can divide Slurry is catalyzed for lysotype oil base catalytic material slurry preparation method with dispersing type mixed base, coal base, biology base powder material to match Method processed.

In the catalysis slurry preparation unit, catalysis slurry is mixed by catalysis fluid in proportions and different type heavy charge With composition, the oil base based on solubilised state can be prepared according to the mutual dissolution method of fluid mixing and is catalyzed slurry, is disperseed according to powder The kerosene mixed base that mixed method prepares low dispersion phase refines catalysis slurry altogether, the coal base catalysis of high dispersive phase dissolved colloidal state is starched The biology base catalysis slurry of material, high score dephasing suspended state.

For the coal base containing solid, biology base and mixed base heavy charge in proportion be catalyzed fluid two step preparation methods In, heavy charge with catalysis fluid in proportions is simply mixed prepares initial catalyst slurry first, then initial slurry is made to exist Operating pressure 0.1-5.0MPa and 120 DEG C -300 DEG C of temperature, preferably operating pressure 1.0-3.5MPa and 180 DEG C -280 DEG C of temperature, Through curing and the optional step that homogenizes at 210 DEG C -280 DEG C of more preferable (such as 1.1) -3.0MPa of operating pressure 1.0 and temperature Suddenly, the non-newtonian fluid catalysis slurry of the coal base of stable work in work, biology base and mixed base is prepared.Wherein solid phase weight Content of the matter raw material in slurry is catalyzed advantageously≤65wt%, preferably≤55wt%, more preferably≤42wt%.

In general, in order to prepare the catalysis slurry of heavy charge, the heavy charge and the catalysis fluid is abundant Mixing, be then according to circumstances allowed to it is degassed, dehydration, curing and/or homogenize process, wherein it is further advantageous that the catalysis The total content of S elements can be with≤2.0wt% in slurry, and solid content can be that 0~65wt% and water content can be with≤0.2wt%. In the catalysis slurry, the mixed proportion of heavy charge is 10~65wt%, such as 20~55wt% or 30~45wt%.

As described above, it is preferred to and it is crucial, the processing is included to catalysis fluid obtained and heavy charge（Particularly contain Coal base, biology base and the mixed base heavy charge of solid）Mixture carry out maturation stage and more preferably optionally also into Row homogenization step.Degassing and dehydration can occur for mixture in maturation stage（Although it is also not excluded for being additionally carried out it Degassing and the possibility of dehydration）, so that the free water in such as coal-based feedstocks is removed and be reduced low-maturity coal base The oxygen content of organic phase in raw material properly increases R ° of the average maturity of coal-based feedstocks, particularly reduces the dispersion of maturity, So as to improve the content of (C+H) effective element in coal base heavy charge organic phase.This technical process, especially for R °≤ 0.55 lignite, ub-bituminous coal effect are especially pronounced.In addition, it is found that after by such maturation stage, the mobile performance of slurry Accessing greatly improves, and thus makes it possible to simplifying subsequent operation.

It is typically by the raw material of heavy charge such as coal base powder drying and dehydrating directly processed and by dewatered coal in the prior art Powder, which is sufficiently mixed, to homogenize, and is then mixed with catalyst, solvent and produces slurry；It prepares in drying and dehydrating powder and homogenizes with raw material In the process, although by the dry water content for reducing coal original washing powder body raw material, the safety problems such as spontaneous combustion of pulverized coal are increased simultaneously, It thus needs complicated safe ancillary method and requirement for raw material is very high.Compared with the prior art, technique of the invention Special requirement carry out slurry curing operation, therefore also just eliminate drying steps and avoid the danger of spontaneous combustion, expand simultaneously The engineering scope of application of coal-based feedstocks is opened up.

In one preferred embodiment, the mixture of the catalysis fluid and heavy charge is further carried out 1 Hour or more, preferably 2 hours or more, the homogenize process of such as 12-48 hours or 12-24 hours.Particularly, it is such equal The matter time depends on the type and the homogenization degree of itself of heavy charge, such as degree of homogenizing is preferably oily in itself for some Homogenization step can be saved for base heavy charge.In an advantageous embodiment, it is preferred for oil base heavy charge Homogenize process 2-4 hours, such as coal base, biology base or the mixed base heavy charge of the heavy charge for solid or containing solid are excellent Select homogenize process >=24 hour, for example >=48 hour.

In the catalysis slurry preparation unit, when preparing oil base heavy charge catalysis slurry, it is only necessary to will be catalyzed Fluid is mixed by arbitrary different proportion with the heavy crude of oil base heavy charge such as API≤25 ° and optionally selectively carried out It homogenizes.In the present invention, according to the limitation to being catalyzed slurry fluid property, mixing of the oil base heavy charge in slurry is catalyzed Ratio is 40wt%-70wt%, such catalysis slurry fluid is in Newtonian fluid at a temperature of >=30 DEG C.

In addition, the coal base heavy charge that high dispersive phase dissolved colloidal state can be prepared in the catalysis slurry preparation unit is urged Slurrying material, wherein heavy charge are coal base 80-200 mesh powder materials, and the stabilization group, vitrinite point in coal dust have pole in a solvent Good dissolubility, swellability, peptization and dispersibility.Coal base is catalyzed slurry fluid, and larger difference is distributed with coal powder size, with The increase of concentration, non-Newtonianism enhancing.In the present invention, the mixed proportion of coal-based feedstocks is 30wt%- in coal base catalysis slurry 55wt%。

In addition, the biology base heavy charge of high score dephasing suspended state can be prepared in the catalysis slurry preparation unit Slurry is catalyzed, wherein heavy charge is the 80-200 mesh powders for being dehydrated biomass, and the suspension that it has only had in fluid is catalyzed divides Property is dissipated, in non newtonian plastic fluid, and with the increase of dehydration biomass powder bulk concentration, fluid touches such catalysis slurry fluid Denaturation increases quickly.In the present invention, the mixed proportion of organism-based raw material is 30wt%-50wt% in biology base catalysis slurry.

More specifically, in order to which method according to the present invention prepares oil base heavy charge catalysis slurry, a kind of illustrative side Method is：In atmospheric conditions, in proportion（Compounding ratio such as oil base heavy charge and catalysis fluid is 40wt%-70wt%： 60wt%-30wt%）Heavy oil is mixed with catalysis fluid at a temperature of 50 DEG C -250 DEG C, preferably 50 DEG C -100 DEG C of ranges（Such as In static mixer）, then add in 0.5wt-2.0wt%, preferably 0.5wt-1.0wt% co-catalyst such as liquid sulfur or sulphur powder (>100 mesh), CS2, at -250 DEG C of temperature 50 C, the good ox of fluidised form is prepared in presulfurization 2-5 hours, preferably 2-4 hours Pause fluid catalyst slurry, is conveyed into catalysis slurry output surge tank.

In order to prepare coal base, biology base powder material catalysis slurry in catalysis slurry preparation unit according to the present invention, A kind of illustrative method is：In atmospheric conditions, by inert gas by coal dust or biomass powder raw material in proportion（Such as Powder material：It is catalyzed fluid=30wt%-55wt%：70wt%-45wt%）It is blown into 120 DEG C of -250 DEG C of ranges of temperature（Such as from At a temperature of 150 DEG C to 250 DEG C）Catalysis fluid in, and continue to be dispersed with stirring 10-60 minutes.Then product pump is sent into ripe Change in reactor, reacted 2-4 hours at 230 DEG C -280 DEG C of temperature, pressure 2.2-3.5MPa, in abjection gas and moisture（Example Such as through flash distillation and condenser）Afterwards, it cures material and adds in helping for amount of slurry 0.5wt-2.0wt%, preferably 0.5wt%-2.0wt% and urge Agent such as liquid sulfur or sulphur powder (>100 mesh) or CS2, it is then pumped into homogeneous, ageing, pre-vulcanizing tank and is recycled, in temperature Under pressure 0.1MPa, homogeneous, ageing >=12 hours is carried out according to the homogenieity of raw material for 150 DEG C -250 DEG C of degree, preferably >=24 small When, it is preferred >=48 hours, prepare non-ox of the stabilization of industry of the fluid in 50 DEG C of -250 DEG C of working ranges than >=0.90 Pause fluid catalyst slurry, is sent to catalysis slurry output surge tank.

In addition, the method for specific illustrative preparation mixed base catalytic material slurry can be the letter of both of the aforesaid method Single group is closed, and can accordingly be adjusted according to production practices by those skilled in the art.

For example, in the catalysis slurry preparation unit, the kerosene mixed base that can prepare low dispersion phase refines urge altogether Slurrying material, wherein heavy charge are heavy oil, coal dust can mixture in any proportion mixing based raw material, such catalysis slurry fluid exists It is in Newtonian fluid after heating in non-newtonian fluid under room temperature.In the present invention, heavy oil in based raw material is mixed：The weight ratio of coal dust Example can be 65-75:25-35 or 25-35:65-75, the ratio for being catalyzed oily coal mixing based raw material in slurry can be 30wt%- 60wt%。

Kerosene mixed base according to the present invention is refined in hydrogenation modifying process altogether, it is preferable that heavy charge mixed ratio is attached most importance to Oil：Coal dust=68wt%-75wt%：25wt%-32wt% or 25wt%-32wt%：68wt%-75wt%；Additionally preferably, mixed base The mixed ratio of heavy charge and catalysis fluid is=40wt%-70wt%：60wt%-30wt%, and add in amount of slurry into the material 0.5wt%-2.0wt% co-catalyst sulphur powder (>100 mesh) or liquid sulfur, CS2, it is mixed repeatedly into catalysis slurry homogeneous tank It homogenizes, cure 12-24h hours, material is then inputted into catalysis slurry tank.

In a preferred embodiment, in coal base weight matter catalytic material slurry, particularly in coal base weight matter material content During≤60wt%, the working reaction temperature of the slurry in the range of 120 DEG C -250 DEG C, the stabilization of industry ratio of slurry fluid >= 0.93 and fluidised form be in low thixotroping（Quiet shearing stress≤20MPam^-2（80℃））Non-newtonian fluid；It is urged in biology base heavy charge In slurrying material, particularly in biology base heavy charge content≤50wt%, the working reaction temperature of the slurry 120 DEG C- In the range of 250 DEG C, stabilization of industry ratio >=0.90 of slurry fluid and fluidised form are in middle thixotroping（Quiet 10~30MPam of shearing stress^-2 （80℃））Non-newtonian fluid；It is catalyzed in slurry in mixed base heavy charge, the coal base weight matter particularly in mixed base heavy charge During material content≤30wt%, for the working reaction temperature of the slurry in the range of 120 DEG C -250 DEG C, the industry of slurry fluid is steady It is in Newtonian fluid or low thixotroping to determine ratio >=0.95 and fluidised form（Quiet shearing stress≤10MPam^-2（80℃））Non-newtonian fluid.

It is catalyzed in slurry preparation unit in the heavy charge, the mixing, curing and homogenization process any can be closed It is carried out in suitable reactor, mixer or ager, these devices are those skilled in the art understand that with well known.Particularly, These processes can carry out in the tubular reactor for being suitble to fluid operation.

Add hydrogen lighting reaction member

Heavy charge according to the present invention is catalyzed slurry hyd lighting reaction member, be by catalysis mashing pump it is defeated, be flushed with hydrogen Mixing, heating process are with adding hydrogen lighting reaction process composition.

The catalysis slurry pumping, to be flushed with hydrogen mixing with the flow that heating process forms be to be flushed with hydrogen catalysis slurry and enter to react The summation of technological process before device, the collection including being catalyzed slurry is defeated, high-pressure pump is defeated and fills mixed compression hydrogen, heating furnace is warming up to work Make temperature etc..In addition, hydrogen operating condition is added to be generally described plus in hydrogen lighting reaction member：Reaction pressure 5MPa- 380 DEG C -520 DEG C of 30MPa and reaction temperature.Heavy charge is catalyzed the volumetric spaces speed of slurry in the reactor from 0.1h^-1It arrives 10h^-1, and hydrogen or high Gas Mixtures Containing Hydrogen are catalyzed slurry with heavy charge under standard state（Hereinafter also referred to hydrogen slurry ratio） Volume ratio be 100Nm³/m³-10000Nm³/m³。

Thus, for example in the catalysis slurry pumping, being flushed with hydrogen in mixing and heating process method, slurry is catalyzed from storage The operating temperature being pumped into tank through thickened-oil pump can be 25 DEG C -250 DEG C, and the pump pressure after pump is hydrogenation reaction operating pressure 10.0- 20.0MPa, preferably 12.0-20.0MPa.After high pressure hydrogen is filled in proportion, heated stove is warming up to plus hydrogen operating temperature 420 DEG C -465 DEG C, preferably 430 DEG C -465 DEG C.

Correspondingly, the catalysis slurry pumping, the device for being flushed with hydrogen the flow that mixing is formed with heating process are to be flushed with hydrogen to urge Before slurrying material enters reactor, material flows through the summation of all devices and equipment on route, is such as catalyzed slurry gathering and transporting device and collection Defeated tank, high pressure thickened-oil pump, hydrogen gas compressor, hydrogen mixer, heating furnace, control system and relevant safety equipment etc..

Described plus hydrogen lighting reaction process flow is：It is pumped up, is flushed with hydrogen mixing and heating process entrance plus hydrogen lightweight Chemical industry make under the conditions of mixed hydrogen catalysis slurry, reacted device inlet control valve enters reactor, and the heavy in fluid mechanics is former Expect to carry out cracking, hydrogenation reaction in reactor with the suspended state of laminar flow or turbulent flow.It is required according to purpose product, completes institute The reacted device discharge control valve of product is discharged after the reaction time needed, so as to prepare the slurry of lighting.

In the hydrogenation reaction lighting technique, main design library part editor and reuse is hydrogenation reactor, reacts fixture system Select high-temperature and high-pressure hydrogenation safety control standed.The type of the reactor can be tubular reactor, also empty reactor, full back-mixing Circulation flow reactor, trickle bed reactor, reverse convection formula reactor, slurry bed reactor, suspended-bed reactor and underground are anti- Answer one or more of device.

Therefore, in an illustrative specific embodiment, the hydrogen lighting reaction process flow that adds is：Adding Under hydrogen working condition, the high-pressure catalytic slurry of mixed hydrogen heating through interior tube valve in the control valve group of ground enter underground reactor into Row hydrogenation reaction then goes through next reactor or technique unit.

Further, in the hydrogenation reaction lighting technique, hydrogen lighting is added for oil base catalysis slurry, selection Working condition may be, for example,：Reaction pressure=8.0-18.0MPa（It is preferred that 10.0-18.0MPa, more preferable 12.0-18.0MPa）, instead Answer -470 DEG C of temperature=380 DEG C（It is preferred that 420 DEG C -465 DEG C, it is 440 DEG C -455 DEG C more preferable）；Hydrogen slurry ratio=500Nm³/m³– 1200Nm³/m³（It is preferred that 600Nm³/m³–950Nm³/m³）, the volumetric spaces speed of slurry is catalyzed from 0.5h^-1To 5h^-1（It is preferred that from 0.5h^-1To 2.0h^-1, more preferably from 0.8h^-1To 1.2h^-1）.

In addition, in the hydrogenation reaction lighting technique, hydrogen lighting, the operating mode of selection are added for coal base catalysis slurry Condition may be, for example,：Reaction pressure=12.0-18.0MPa（It is preferred that 15.0-18.0MPa）, -470 DEG C of reaction temperature=400 DEG C（It is excellent Select 420 DEG C -455 DEG C, it is 440 DEG C -455 DEG C more preferable）；Hydrogen slurry ratio=1000Nm³/m³-2500Nm³/m³（It is preferred that 1200Nm³/ m³-1700Nm³/m³, more preferable 1300Nm³/m³-1700Nm³/m³）, the volumetric spaces speed of slurry is catalyzed from 0.5h^-1To 5h^-1 （It is preferred that from 0.5h^-1To 2.0h^-1, more preferably from 0.8h^-1To 1.5h^-1）.

In addition, in the hydrogenation reaction lighting technique, hydrogen lighting, the work of selection are added for biology base catalysis slurry Condition condition may be, for example,：Reaction pressure=8.0-16.0MPa（It is preferred that 12.0-18.0MPa, preferably 12.0-16.0MPa）, reaction temperature =350 DEG C -470 DEG C of degree（It is preferred that 420 DEG C -445 DEG C, it is 420 DEG C -435 DEG C more preferable）；Hydrogen slurry ratio=1200Nm³/m³– 3000Nm³/m³（It is preferred that 1500Nm³/m³–2000Nm³/m³, more preferable 1500Nm³/m³–1800Nm³/m³）, it is catalyzed the volume of slurry Space velocity is from 0.5h^-1To 5h^-1（It is preferred that from 0.5h^-1To 2.0h^-1, more preferably from 1.0h^-1To 2.0h^-1）.

In the hydrogenation reaction lighting technique, slurry can also be catalyzed to kerosene mixed base and carries out adding hydrogen lighting, Working condition in the case of this may be, for example,：Operating pressure=12.0-18.0MPa, -460 DEG C of reaction temperature=400 DEG C（It is preferred that 420 DEG C -460 DEG C, it is 440 DEG C -460 DEG C more preferable）；Hydrogen slurry ratio=700Nm³/m³–2000Nm³/m³（It is preferred that 900Nm³/m³– 1500Nm³/m³）, the volumetric spaces speed of slurry is catalyzed from 0.5h^-1To 5h^-1（It is preferred that from 0.5h^-1To 2.0h^-1, more preferably from 1.0h^-1To 1.5h^-1）.

Described plus hydrogen lighting technique under running conditions, calculates the lightweight rate and lightweight of heavy charge according to the following formula Oil cut rate and add hydrogen slurry in residual solid concentration：

Product postpositive disposal unit

Technological process in hydrogenation products postpositive disposal unit according to the present invention is to add hydrogen lighting reaction member After product discharge mouth, product flows through the summation of processing technological flow, i.e., the following process that such as reaction product is flowed through：Gas-liquid Separation, degasification add hydrogen slurry separation of solid and liquid, slagging-off to add purpose product light fraction oil/gas (fraction section≤350 DEG C) in hydrogen slurry With as cycle solvent basis, auxiliary oil >=330 DEG C（Such as 350 DEG C -550 DEG C）The separation and recycling of the oil of fraction and/or general The techniques such as unreacted hydrogen upgrading and supercharging recycling.

In the hydrogenation products postpositive disposal unit, the reaction cracking gas isolated from hydrogenation products enters storage Tank, it is outer defeated or as fuel gas, it separates residue and enters residue tank as fuel and by unreacted hydrogen upgrading With being pressurized recycling.It simultaneously also will be >=330 DEG C（Such as 350 DEG C -550 DEG C）Fraction oil pump it is defeated to cycle solvent materials tank, Lightweight oil pump is defeated to light oil tank, it is outer defeated or enter oil hydrogenation refined unit.

Process unit in hydrogenation products postpositive disposal unit according to the present invention is to add hydrogen lighting reaction member After product discharge mouth, the summation of all devices on the route that product flows through, such as gas separator, stripping tower, solid-liquid centrifugation point Slag tower, relevant control system and safety equipment etc. are taken off from device, fractionating column, heat exchanger, solvent.

Involved each technological parameter and performance parameter measure and computational methods in addition to illustrating everywhere above Except, it can be determined by those skilled in the art according to oil development and refining API engineering specifications method or GB standard.

In addition, the content of each substance in the composition is all by weight percentage, unless otherwise specifically in the application It is bright；Temperature expression measures at such a temperature in bracket after parameters data.

Description of the drawings

Fig. 1 is the device technique stream for implementing universal heavy charge catalysis slurry hyd lightening method according to the present invention Journey schematic diagram.

It is single that the complete process shows prepared by heavy charge preprocessing unit, catalysis fluid preparation unit, catalysis slurry The sequencing of member plus hydrogen lighting reaction member and product postpositive disposal unit.Wherein, the cycle solvent in system can be with It recycles to enter in catalysis fluid preparation unit and is catalyzed fluid for preparing.

Embodiment

The present invention will be described further with reference to following embodiment, but these embodiments should not be construed as to this The limitation of invention.

Embodiment 1

1st, the preparation of raw material and catalysis fluid used

In an embodiment according to the present invention, 1.5t/d commerical test system and devices, the process unit system, by weight are selected Matter raw material preprocessing unit, catalysis fluid preparation unit, catalysis slurry preparation unit plus hydrogen lighting reaction member and product Postpositive disposal unit form, wherein the high-temperature high-pressure craft device of the commerical test system and device for horizontal endless tube heating furnace with The heat-insulated also empty suspended-bed reactors of 1.5t/d and the heat-insulated also empty suspended-bed reactor in underground.

Selected following heavy charge is handled in heavy charge preprocessing unit：

Oil base heavy charge is Yumen refinery decompression residuum,

Coal base heavy charge is dehydrated coal dust (>=120 mesh) for Xinjiang Tu Hanao maos of lake ore deposit 2# steam coal,

Mixed base heavy charge subtracts slag for Yumen and subtracts slag according to mixed ratio Yumen with 2# coal dewaterings coal dust (>=120 mesh)： 2# coal dewaterings coal dust=72.7wt%:The mixture coal of 27.3wt%, raw material 1-3 during heavy charge property is shown in Table 1.

The initial solvent being catalyzed in fluid is wax tailings, high carbolic oil, organic nitrogen-containing heterocyclic compound and imidazole salts and pyrrole Pyridine salt compound presses 60:20:20:5（Imidazole salts+pyridinium compound adds up to）Ratio is stirred at 20 DEG C -50 DEG C of temperature It is formulated.The H/C atomic ratios of initial solvent are 1.36, oxygen-containing, nitrogenous compound content in initial solvent（With oxygen and nitrogen Content meter）Respectively 2.26wt% and 2.37wt%.

For the cycle solvent in catalysis fluid, the distillate of 330 DEG C -541 DEG C of fraction section in selection plus hydrogen slurry, cycle The H/C atomic ratios of solvent are 1.39, recycle oxygen-containing, nitrogenous compound content in solvent（In terms of oxygen and nitrogen element content）Respectively 2.51wt% and 2.42wt%.

In order to prepare catalysis fluid, ferrous sulfate, nickel nitrate, nitric acid molybdenum, titanium sulfate, aluminum sulfate and lanthanide series metal are selected The compound of oxalates is made containing Fe according to ratio as described below with containing Ni, Mo, Ti, Al metal ion and a small amount of lanthanum The mixed solution of the compound of series rare earth element is as multi-element metal compound component, wherein with Fe in mixed metal element²⁺For The elements total content about 26.6wt% such as main and described iron content 73.2wt%, Al, Ti, Ni, Mo and lanthanide series rare-earth elements contain Measure about 0.2wt%；In addition, by 1,10- Phens, dimercaprol dimercaptopropanol complexing agent with a small amount of methyl silicon sodium alcoholate auxiliary agent, with it is a concentration of The multi-element metal group mixed liquor (total metallic element concentration 21.7wt%) of 10wt% is added sequentially to the starting of 100wt% or recycles molten In agent, fluid-mixing is formed.

Fluid-mixing is warming up to 120 DEG C -150 DEG C under stiring, after dehydration, degassing, 210 DEG C is warming up to, continues thereafter with It is stirred to react the polynary gold containing metallic element total amount~0.83wt% received for 30-60 minutes to be catalyzed 104.7wt% in terms of slurry Belong to compound for catalysis fluid, be pumped into catalysis fluid reservoir.The feedstock property of heavy charge and starting catalytic fluid is shown in Table in 1 Raw material 4-5.

The property of 1 heavy charge of table and catalysis fluid

2nd, the preparation of the catalysis slurry of heavy charge

In order to prepare the catalysis slurry of the oil base heavy charge shown in table 2, by oil base heavy original at 80 DEG C of temperature Expect to mix to obtain oil base heavy charge in ratio shown in " slurry 1 " row with " the catalysis fluid 2 " described in part 1 Content is the catalytic slurry of 51.1wt%.

In order to prepare the catalysis slurry of the kerosene mixed base heavy charge shown in table 2, in 80 DEG C of fluid temperature (F.T.) of catalysis Under the conditions of 34.1 parts of coal base weight matter material powders of 120 mesh and 75.9 parts of oil base heavy charge and 100 parts are existed first " catalysis fluid 2 " described in part 1, mixed preparing goes out 210 parts of the initial of kerosene mixed base heavy charge and urges at 80 DEG C Then slurrying material reacts 90min under the conditions of 210 DEG C and pressure 1.2MPa are warming up to, after curing degassing and dehydration, further Add in 0.5wt% co-catalyst sulphur powder (>100 mesh), then homogeneous and the ageing, pre- again at 150 DEG C of pressure 0.1MPa and temperature The catalysis slurry that 205 parts of kerosene mixed base heavy charge average contents are 51.2wt% is prepared in vulcanization 24 hours.

In order to prepare the catalysis slurry of the coal base heavy charge shown in table 2, under the conditions of 100 DEG C of fluid temperature (F.T.) is catalyzed First by 103 parts of coal base weight matter material powders of 120 mesh and 100 parts of " the catalysis fluid 2 " described in part 1 150 It is mixed at a temperature of DEG C, so as to make 203 parts of coal base heavy charge initial catalyst slurries, is then warming up to 250 DEG C and in pressure React 150min under 2.5MPa, through curing degassing and dehydration after, further add in 0.8wt% co-catalyst sulphur powder (>100 mesh), Then homogeneous and ageing, presulfurization 48 hours again at 170 DEG C of pressure 0.1MPa and temperature, prepare 187.6 parts of coal base weight matter Raw material average content is the catalysis slurry of 46.7wt%.

2 heavy charge of table is catalyzed slurry properties and flow pattern

3rd, be catalyzed slurry adds hydrogen lighting

In the embodiment of the present invention plus hydrogen lighting technique unit is by 1.5t/d tubular reactors and the industry of underground reactor Experimental rig is formed, and each catalysis slurry for being obtained from part 2 is carried out wherein plus hydrogen lighting is handled.For being obtained from the 2nd Partial oil base, coal base, mixed base heavy charge plus hydrogen lighting duty parameter be shown in Table in 3 plus hydrogen example with result of the test 1-3。

Table 31.5t/d tubular reactors add hydrogen lighting duty parameter and result with underground reactor

4th, the postpositive disposal of product

In this embodiment, product postpositive disposal unit according to the present invention by 1.5t/d commerical test device postpositions at Device is managed to run, obtaining oil base, coal base, mixed base heavy charge from third portion adds hydrogen light fraction oily, wherein light fraction The fundamental property of oil is shown in Table the lighting product 1-3 in 4.

Table 41.5t/d commerical test devices add the fundamental property of hydrogen lighting result and light fraction oil

In an embodiment according to the present invention, pass through heat-insulated also empty suspended-bed reactor (the ground and underground) industry of 1.5t/d The obtained oil base of operation, coal base, the mixed base heavy charge of experimental rig add hydrogen lighting distillate, can add hydrogen as refinery Refined or hydroformer raw material produces the tank oils such as qualified gasoline, kerosene, diesel oil.

It, below will be with regard to the tradition of process according to the invention and the prior art in order to further embody the superiority of the present invention Technique is compared.

Comparative example 1

The heavy charge of the present invention adds the comparison of hydrogen lighting process and conventional hydrogenation process

Coal base heavy charge in the comparative example is to spit Kazakhstan for the Xinjiang in the same manner as in Example 1 of following proposal 2 and 3 Mire hair lake ore deposit 2# steam coals powder (>=120 mesh)（Raw material 6）With the nitrogen of the conventional hydrogenation liquefaction raw material for following proposal 1 Drying and dehydrating coal dust (>=120 mesh)（Raw material 7）, coal dust property is shown in Table 5.

Table 52# thermal coals coal dust and dry base coal dust property

It is used in scheme 1,2 by FeSO₄·7H₂O, the γ-FeOOH/ that ammonium hydroxide, 2# power coal dusts are prepared in aqueous solution Coal supported catalyst is as catalyst, and solvent reforms slurry oil and wax tailings (1 for Yumen refinery:1) 430 DEG C of temperature, Pressure 12.0MPa and air speed 1.0h^-1The DCL/Direct coal liquefaction routine pre-add hydrogen solvent of lower preparation.It is then used in scheme 3 according to implementation " catalysis fluid 2 " prepared by example 1.

In addition, scheme 1 selects the raw material slurry preparation process of DCL/Direct coal liquefaction common process and routine, wherein being particularly DCL/Direct coal liquefaction routine pre-add hydrogen solvent containing γ-FeOOH/ coal supported catalysts as described above is mixed with coal-based feedstocks It closes；Scheme 2 and 3 includes the curing coal base weight matter raw material slurry preparation process according to present invention process, and preparation process is in addition under It is identical in embodiment 1 except cooking conditions and homogenization conditions described in table 6.It is described routine pre-add hydrogen solvent be typically The mixture of wax tailings and arenes catalytic slurry oil and by advance hydrotreating.Result of the comparison is shown in Table 6.

6 coal base weight matter raw material slurry of table prepares and slurry properties

Then, coal base weight matter raw material slurry prepared in scheme 1-3 is carried out plus hydrogen lighting (liquefaction), result arranges In table 7.

The different coal base weight matter raw material slurries of table 7 add hydrogen result

As can be seen from the above table, under identical plus hydrogen working condition, although conversion ratio (daf)/% bases of coal base heavy charge This is identical, but lightweight rate has significant difference with the property that lightweight oil cut rate has bigger difference, particularly liquefaction oil, and routinely coal is direct Oxygen content reaches 4.66wt% in liquefaction oil prepared by liquefaction process work, suitable with Shenhua demonstration project liquefaction oil nature.Different process The liquefaction oil fundamental property that method is produced is shown in Table 8.

8 coal base weight matter raw material slurry of table liquefies the fundamental property of oil product in different process method

Comparative example 2

Influence of the different component of the catalysis fluid of the present invention to heavy catalytic material slurry

Scheme 4 and 5 is to prepare coal base weight matter in the 1st and 2 parts for repeat embodiment 1 for the preparation process of slurry 3 The catalysis slurry of raw material, but the catalysis fluid of different compositions is wherein respectively adopted.

Fluid is catalyzed used in scheme 4, coal is mainly supported and according to reality by the γ-FeOOH/ in the scheme 1 of comparative example 1 Apply initial solvent obtained by 1 part 1 of example and mixed as solvent and formed, and be catalyzed used in scheme 5 fluid 3 with by basis Catalysis fluid 1 obtained by 1 part 1 of embodiment is identical, but wherein adjusts the amount of initial solvent so that the Fe in scheme 4 Total metal contents in soil in constituent content and scheme 5 is 1.8wt%.

The catalysis fluid of difference composition and its stabilization of industry of the coal base heavy charge caused by under same operation are than knot Fruit is shown in the following table 9.

The different catalysis fluid composition of table 9 and its caused different stabilization of industry ratios

Claims

1. a kind of method of universal heavy charge catalysis slurry hyd lighting, this method include：Use catalysis fluid counterweight Matter raw material is dissolved, disperseed and/or is diluted, obtained heavy charge catalysis slurry after treated, then in hydrogenation reaction item Heavy charge catalysis slurry is catalyzed and hydrogen supply under part, lighting distillate and cracking gas is thus made,

Fan Shi viscosity≤2000MPas at heavy charge catalysis 80 DEG C of slurry wherein after processing, quiet at 80 DEG C are cut Stress≤35MPam^-2With stabilization of industry ratio >=0.80；

The wherein described catalysis fluid includes：Multi-component solvent, the multi-element metal containing the metallic element of two or more Compound, complexing agent and optional complexing auxiliary agent, wherein the metallic element be selected from iron, nickel, molybdenum, copper, zinc, tin, aluminium, tungsten, manganese, Titanium, vanadium, chromium, cobalt, gold, cadmium, mercury and lanthanide series rare-earth elements, the total content in fluid is catalyzed are the catalysis fluid 0.05wt%-5.0wt% and the multi-element metal compound and complexing agent formation complex compound or chelate；

Wherein described multi-element metal compound is dissolved or is divided with ionic condition, molecular state, complex status, polymolecular polymerization state It dissipates in the solvent；With

Wherein described stabilization of industry ratio is by testing and being calculated as follows：Pour into what is be sufficiently stirred in 1000mm hydrostatic pipes Slurry is catalyzed, fluid is exported in the middle part of hydrostatic pipe after flowing static 10min, measures fluid density D₀；Quiescent settling for 24 hours after, from Top 100mm exports fluid, measures averag density D^Top(24h)；Fluid is exported from lower part 100mm, measures averag density D^{Lower part} (for 24 hours), stabilization of industry ratio is calculated by following formula：

2. method as claimed in claim 1, which is characterized in that the metallic element selected from cerium.

3. method as claimed in claim 1, which is characterized in that the processing includes the mixture to catalysis fluid and heavy charge The step of being cured and optionally homogenization step.

4. such as the method for claims 1 or 2, which is characterized in that total content≤2.0wt% of S elements wherein in the catalysis slurry, Solid content is 0~65wt% and water content≤0.2wt%.

5. such as the method for claims 1 or 2, which is characterized in that the coal base containing solid, biology base and the arbitrary of theirs are mixed Object is closed, heavy charge and catalysis fluid are mixed with out initial catalyst slurry first, then make initial catalyst slurry in pressure After maturation stage 0.5 hour or more at 120 DEG C -300 DEG C of 0.1-5.0MPa and temperature；It, will or for oil base heavy charge The oil base heavy charge is mixed with catalysis fluid.

6. method as claimed in claim 5, which is characterized in that the pressure is 1.0-3.5MPa.

7. method as claimed in claim 5, which is characterized in that the temperature is 180-280 DEG C.

8. method as claimed in claim 5, which is characterized in that make initial catalyst slurry also after degassing and/or dehydration.

9. such as the method for claims 1 or 2, which is characterized in that the mixture of the catalysis fluid and heavy charge was after 1 hour Above homogenize process.

10. method as claimed in claim 9, which is characterized in that for oil base heavy charge homogenize process 2-4 hours.

11. method as claimed in claim 9, which is characterized in that homogenize place for coal base, biology base or their any mixture Reason >=24 hours.

12. such as the method for claim 11, which is characterized in that homogenize for coal base, biology base or their any mixture Processing >=48 hours.

13. such as the method for claims 1 or 2, which is characterized in that in the catalysis slurry, the mixed proportion of heavy charge For 10~80wt%.

14. such as the method for claim 13, which is characterized in that the mixed proportion of heavy charge is 20~70wt%.

15. such as the method for claim 13, which is characterized in that the mixed proportion of heavy charge is 30~70wt%.

16. such as the method for claims 1 or 2, which is characterized in that in the catalysis slurry, oil base heavy charge and catalysis The mixed proportion of fluid is 40~70wt%：60~30wt%.

17. such as the method for claims 1 or 2, which is characterized in that in the catalysis slurry, powder coal base or biological base weight The mixed proportion of matter raw material and catalysis fluid is 30~55wt%：70~45wt%.

18. such as the method for claims 1 or 2, which is characterized in that in the catalysis slurry, oil base, coal base and biological base weight Any mixture of matter raw material and the mixed proportion of catalysis fluid are 40~70wt%：60~30wt%.

19. such as the method for claims 1 or 2, which is characterized in that in coal base weight matter catalytic material slurry, the work of the slurry Make temperature in the range of 120 DEG C -250 DEG C, stabilization of industry ratio >=0.93 of slurry and fluidised form in quiet shearing stress at 80 DEG C≤ 20MPa·m^-2Low thixotroping non-newtonian fluid.

20. such as the method for claims 1 or 2, which is characterized in that it is catalyzed in slurry in biology base heavy charge, the slurry Operating temperature is in the range of 120 DEG C -250 DEG C, and stabilization of industry ratio >=0.90 of slurry and fluidised form are in quiet shearing stress 10 at 80 DEG C ~30MPam^-2Middle thixotroping non-newtonian fluid.

21. such as the method for claims 1 or 2, which is characterized in that in the arbitrary mixing of oil base, coal base and biology base heavy charge In the catalysis slurry of object, the operating temperature of the slurry is in the range of 120 DEG C -250 DEG C, and stabilization of industry ratio >=0.95 of slurry is simultaneously And fluidised form is in quiet shearing stress≤10MPam at Newtonian fluid or 80 DEG C^-2Low thixotroping non-newtonian fluid.

22. such as the method for claims 1 or 2, which is characterized in that the method includes at least following three technique units successively, That is catalysis fluid preparation unit, catalysis slurry preparation unit and plus hydrogen lighting reaction member.

23. such as the method for claims 1 or 2, which is characterized in that the method further includes heavy charge preprocessing unit and production Object postpositive disposal unit.

24. such as the method for claims 1 or 2, which is characterized in that the method is in catalysis slurry preparation unit and plus hydrogen lighting It is carried out under dehydration or water-less environment in reaction member.

25. such as the method for claim 24, which is characterized in that the method is prepared in catalysis fluid preparation unit, catalysis slurry Unit and plus hydrogen lighting reaction member in carried out under dehydration or water-less environment.

26. such as the method for claim 24, which is characterized in that the method whole process is completed under dehydration or water-less environment.

27. such as the method for claims 1 or 2, which is characterized in that the catalysis fluid is by the multi-component solvent, institute Multi-element metal compound, the complexing agent and the optional complexing for the metallic element containing two or more stated Auxiliary agent forms.

28. as claims 1 or 2 method, which is characterized in that the metallic element be selected from iron, nickel, molybdenum, tungsten, titanium, zinc, aluminium with And lanthanide series rare-earth elements.

29. such as the method for claims 1 or 2, which is characterized in that it is dilute that the metallic element is selected from iron, nickel, aluminium, titanium and group of the lanthanides Earth elements.

30. such as the method for claims 1 or 2, which is characterized in that with the weight of all metallic elements of multi-element metal compound Meter, iron, aluminium and/or titanium elements content are>50wt%, and the content of lanthanide series rare-earth elements is the weight based on all metallic elements 0~5wt% of gauge.

31. such as the method for claim 30, which is characterized in that iron content is>50wt%.

32. such as the method for claim 30, which is characterized in that iron, aluminium and/or titanium elements content are>65wt%.

33. such as the method for claim 30, which is characterized in that iron, aluminium and/or titanium elements content are>70wt%.

34. such as the method for claim 30, which is characterized in that iron, aluminium and/or titanium elements content are 70wt-80wt%.

35. such as the method for claim 30, which is characterized in that the content of lanthanide series rare-earth elements is the weight based on all metallic elements 0.1~3wt% of gauge.

36. such as the method for claim 30, which is characterized in that the content of lanthanide series rare-earth elements is the weight based on all metallic elements 0.1~1wt% of gauge.

37. such as the method for claim 30, which is characterized in that the content of lanthanide series rare-earth elements is the weight based on all metallic elements 0.2~0.5wt% of gauge.

38. such as the method for claims 1 or 2, which is characterized in that the multi-element metal compound is inorganic salts and/or organic salt.

39. such as the method for claim 38, which is characterized in that the multi-element metal compound is hydrochloride, sulfate, nitric acid Salt, carbonate and/or carboxylate.

40. such as the method for claim 38, which is characterized in that the multi-element metal compound is C₁-C₁₈Aliphatic acid salt and/or C₆-C₂₀Aromatics hydrochlorate.

41. such as the method for claims 1 or 2, which is characterized in that average fragrant rate fa >=0.60 that the solvent has, density ≥0.95g/cm³With Fan Shi viscosity >=5MPas at 50 DEG C, the total content of organic hetero atom N, S, O wherein in solvent≤ 8.0wt%.

42. such as the method for claims 1 or 2, which is characterized in that the solvent includes>The neutral component of 40 weight %, 5 weights Measure the acidic components of the weight % of %~25, the weight % of the basic component of the weight % of 5 weight %~25 and 5 weight %~15 from Sub- liquid.

43. method as claimed in claim 42, which is characterized in that the acidic components be selected from phenol, C3-C4 alkyl phenols, It is one or more in naphthols and indenols, high carbolic oil.

44. method as claimed in claim 42, which is characterized in that the acidic components be selected from phenol, C3-C4 alkyl phenols, Two or more in naphthols and indenols, high carbolic oil.

45. method as claimed in claim 42, which is characterized in that the basic component is selected from phenyl amines, quinolines, Yin Diindyl, pyridine, acridine nitrogen heterocyclic in it is one or more.

46. method as claimed in claim 42, which is characterized in that the basic component is selected from phenyl amines, quinolines, Yin Diindyl, pyridine, acridine nitrogen heterocyclic in two or more.

47. method as claimed in claim 42, which is characterized in that the ionic liquid be selected from imidazole salt, pyridine salt, It is one or more in quaternary ammonium salt and quaternary phosphonium salt class.

48. method as claimed in claim 42, which is characterized in that the ionic liquid be selected from imidazole salt, pyridine salt, Two or more in quaternary ammonium salt and quaternary phosphonium salt class.

49. method as claimed in claim 42, which is characterized in that the neutral component be selected from content containing heavy arene >= It is one or more in the heavy arene class oil of 50wt%, polycyclic aromatic hydrocarbon, the multiring aromatic hydrocarbon oil that partly or entirely hydrogenates.

50. method as claimed in claim 42, which is characterized in that the neutral component be selected from content containing heavy arene >= Two or more in the heavy arene class oil of 50wt%, polycyclic aromatic hydrocarbon, the multiring aromatic hydrocarbon oil that partly or entirely hydrogenates.

51. method as claimed in claim 42, which is characterized in that comprising heavy arene class oil as molten in the solvent The base solvent oil of agent.

52. method as claimed in claim 42, which is characterized in that included in the solvent and account for solvent total amount Base solvent oil of the heavy arene class oil of 60wt%-90wt% as solvent.

53. such as the method for claims 1 or 2, which is characterized in that the complexing agent be selected from comprising heteroatomic heterocyclic compound and It is optionally substituted, C₁-C₁₈Aliphatic alcohol, aliphatic amine, aliphatic carboxylic acid and aliphatic sulfonic acid and it is respectively optionally one or more Hydroxyl, carboxyl or sulfydryl substitution and thiocarbamide or thiourea derivative.

54. such as the method for claim 53, which is characterized in that the hetero atom is N, O or S.

55. such as the method for claim 53, which is characterized in that the heterocyclic compound has 6-40 carbon atom.

56. such as the method for claim 53, which is characterized in that the heterocyclic compound has 6-30 carbon atom.

57. such as the method for claim 53, which is characterized in that the heterocyclic compound is replaced by hydroxyl or sulfydryl.

58. method as claimed in claim 57, which is characterized in that the complexing agent is selected from these following one kind or more Kind：1,10- Phen, EDTA, dimercaprol dimercaptopropanol, Sodium Dimercapto Sulfonate, mercaptoethylmaine, thioacetic acid, thiocarbamide, 8- hydroxyls Base quinoline.

59. such as the method for claims 1 or 2, which is characterized in that the complexing auxiliary agent is selected from cyanide, citric acid, winestone Acid, oxalic acid, sulfosalicylic acid, triethanolamine, sodium alkoxide, methyl silicon sodium alcoholate, NaOH, KOH one or more.

60. such as the method for claims 1 or 2, which is characterized in that heavy charge catalysis slurry is catalyzed and during hydrogen supply The hydrogenation conditions are：380 DEG C -520 DEG C of reaction pressure 5MPa-30MPa and reaction temperature.

61. such as the method for claims 1 or 2, which is characterized in that the heavy charge catalysis slurry is urged for oil base heavy charge Slurrying material, is catalyzed it and hydrogenation conditions during hydrogen supply are：Reaction pressure 8.0MPa-18.0MPa and reaction temperature 380℃-470℃。

62. such as the method for claims 1 or 2, which is characterized in that the heavy charge catalysis slurry is urged for coal base heavy charge Slurrying material, is catalyzed it and hydrogenation conditions during hydrogen supply are：Reaction pressure 12.0MPa-18.0MPa and reaction temperature 400℃-470℃。

63. as claims 1 or 2 method, which is characterized in that the heavy charge is oil base raw material, selected from API °≤ 25 heavy crude, processing heavy oil, coal tar, biologic garbage grease and their mixing oil product, wherein >=350 DEG C of fraction Content>90wt%.

64. such as the method for claims 1 or 2, which is characterized in that the heavy charge is coal-based feedstocks, is selected from maturity R °≤0.85 sapropelic coal and the Mixture Density Networks with the humic coal of vitrinite 30~70wt% of content and their different coals quality.

65. such as the method for claim 64, which is characterized in that the heavy charge is coal-based feedstocks, is selected from R ° of maturity ≤ 0.75 sapropelic coal and the Mixture Density Networks with the humic coal of vitrinite 30~70wt% of content and their different coals quality.

66. method as claimed in claim 1 or 2, which is characterized in that the heavy charge is organism-based raw material, is selected from The high heating value organic biomass of hydrogen content >=6.5wt%, oxygen content≤30%.

67. such as the method for claims 1 or 2, which is characterized in that the heavy charge is mixing based raw material, is such as right It is required that the oil base raw material described in 63, the coal-based feedstocks as described in claim 64, the biology as described in claim 66 Any mixture of the three classes heavy charge of based raw material.

68. a kind of heavy charge is catalyzed slurry, which is characterized in that it is by as defined in claim 1,27 to 59 any one Catalysis fluid dissolves heavy charge, disperseed and/or is diluted, and treated rear obtained, has the Fan Shi at 80 DEG C Viscosity≤2000MPas, quiet shearing stress≤35MPam at 80 DEG C^-2With stabilization of industry ratio >=0.80；

69. catalysis slurry as recited in claim 68, which is characterized in that the slurry is the homogeneous stability on colloid scale.

70. the catalysis slurry as described in claim 68 or 69, which is characterized in that in the catalysis slurry, oil base heavy The mixed proportion of raw material and catalysis fluid is 40~70wt%：60~30wt%, powder coal base or biology base heavy charge are with urging The mixed proportion for changing fluid is 30~55wt%：70~45wt% or oil base, the arbitrary of coal base and biology base heavy charge mix It is 40~70wt% that object, which is closed, with the mixed proportion for being catalyzed fluid：60~30wt%.