CN104789252A

CN104789252A - Universal heavy raw material catalytic slurry hydrogenation lightening method and device

Info

Publication number: CN104789252A
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: 2015-07-22
Anticipated expiration: 2034-01-21
Also published as: CN104789252B; CN106554793B; CN106554793A

Abstract

The invention relates to a universal heavy raw material catalytic slurry hydrogenation lightening method, a device used for the universal heavy raw material catalytic slurry hydrogenation lightening method, a catalytic fluid suitable for the universal heavy raw material catalytic slurry hydrogenation lightening method, and a heavy raw material catalytic slurry prepared via the universal heavy raw material catalytic slurry hydrogenation lightening method. Heavy raw materials used in the universal heavy raw material catalytic slurry hydrogenation lightening method can be selected from an oil-based heavy raw material, a coal-based heavy raw material, a biology-based heavy raw material, and a hybrid-base heavy raw material of the oil-based heavy raw material, the coal-based heavy raw material and the biology-based heavy raw material.

Description

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

Invention field

The present invention relates to the method for a kind of universal heavy feed stock catalysis slurry hyd lighting and implement the device of the method, relating to a kind of catalysis fluid and heavy feed stock catalysis slurry obtained thus in addition.Described heavy feed stock can be oil base, coal-based, bio-based and mixed base heavy feed stock thereof.

Background technology

Heavy feed stock routinely fossil energy classification is divided into oil base or petroleum base, i.e. the heavy oil product of API severe≤25 °, usual hydrogen content≤11.0%; Coal-based, namely ripening degree R °≤0.75 sapropelinite and vitrinite's content >=50%, humic coal as >=60%, and organic phase (daf) by oil API severe extrapolation >=-30 ° and usually hydrogen content 4.3-7.0% in organic phase in coal-based heavy feed stock; Bio-based, i.e. the matrix precursor (R ° of ≈ 0) of fossil energy, as bio-oil, blue-green algae, pine needle etc., its normally oxygen level in 5wt%-30wt% and the hydrogen content high burning-value component at >=6.5wt%; And also have their heavy feed stock of mixed base.

Existing heavy feed stock lighting engineering, is divided into heavy oil decarburization or hydrogenation technique, direct coal liquefaction process, the Hydrogenation liquefaction process of biomass usually according to type of feed, and the hydrogenation of their mixed base sweetening process altogether.

China for continental sedimentary basin be lead country, coal accounts for 99% of fossil energy total resources, conventional gas and oil stock number only accounts for about 1% of fossil energy total resources, this also means that heavy feed stock (fuel) and unconventional petroleum resources (coal petrography oil, shale gas, coal-seam gas) enrich, therefore, the fossil energy resources characteristic of China, determines heavy feed stock lighting, purifying critical role in China energy industry.

Current heavy oil upgrading mainly contains two approach: decarburization or hydrogenation.Delayed coking is typical decarbonization process, can process various inferior heavy oil and residual oil, but its liquid product yield is low, of poor quality, is also restricted in refinery coke application aspect.Therefore, for improving the yield of refinery's light ends oil, generally hydrogen addition technology process residual oil or heavy oil is adopted at present.This hydrogen addition technology mainly comprises fixed bed, moving-bed, ebullated bed (slurry bed system) and floating bed hydrogenation technology.Wherein, the shortcoming of heavy oil fixed bed hydrogenating technology be the high metal of processing, high asphalt content inferior heavy oil time, the operational cycle is too short.Moving-bed, boiling bed heavy oil hydrogenation technology can process raw material relatively inferior, but this technical sophistication, process cost are higher.

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

The direct liquefaction technique of coal and biomass is that catalyzer used has oxide compound or the halogenide of cobalt, molybdenum, tungsten, tin, iron and lead etc. by the mixture of coal or biomass, solvent and catalyzer and hydrogen reaction and produce liquid product at temperature (400-500 DEG C) and pressure (15-30MPa) condition.Direct coal liquefaction process mainly contains the Shenhua technique etc. of U.S. H-coal technique, Japanese NEDOL technique, German IGOR technique and China, but existing coal Direct Hydrogenation liquefaction technology, all there is technical process complexity, transform cost high, hinder the industrialization development of this technique.

Propose in heavy oil upgrading the method for adding coal or coal-based additive in Canadian Patent CA1073389 and US Patent No. 4214977, reduce the coke sinkability in hydrocracking heavy oil technique.But in this technology, after stock oil transforms, pressed powder can be stayed in unconverted residue, and separating difficulty is comparatively large, reduces the purposes of unconverted residual oil, and also brings environmental issue.

The forties in last century, Canada starts tar-bitumen and sub-bituminous coal faces the research that hydrogen produces liquid product, the Canmet technique that coal-tar-bitumen refines altogether is proposed in Canadian Patent CA1160586, and hydrocarbonylation thing company of the U.S. proposes the HRI technique that kerosene refines altogether on H-Coal and H-Oil Process ba-sis, Japanese Patent 8045703,8023407 proposes solvolysis technique.China Liaohe Oil Field and coalification place, Shanxi last century eight, middle nineteen nineties cooperate with Canada and HRT company of the U.S. respectively to have carried out viscous crude, super-viscous oil, vacuum residuum kerosene refine commerical test technology introduction altogether, but all fail to realize the operation of full scale plant.

In the later stage eighties in last century, each major oil companies of the world competitively research and develop homogeneous catalyst.Representational technology has Canadian (HC) 3 technology (using oil soluble organo-metallic catalyst), the water-soluble phospho-molybdic acid catalyzer of homogeneous catalyst Ze You Exxon company and the ammonium molybdate catalyst etc. of Chevron company.Homogeneous catalyst owing to being all exist with the form of metal particle and sulfide thereof in reaction process, so its activity is high, addition is few, little to reactive system wearing and tearing, but they are expensive and catalyst recovery mode complicated.

CN1778871A proposes the Direct Hydrogenation liquefaction of catalyzer for coal of the γ-FeOOH that coal particle supports, US Patent No. 4338183 proposes the kerosene sweetening process altogether using organometallic complex as catalyzer, CN101020834A proposes the coal direct hydro-liquefaction method using pentacarbonyl iron as catalyzer, CN1089037C proposes thermal treatment heteropolyacid salt catalyst being used for super―heavy oil, CN102041017A, CN102233279A proposes lignosulfonic acid metal complex catalyst and complexing humic acid and decentralized metal catalyst is used for the hydrogenation lighting of coal and vacuum residuum.

Propose the method for partial hydrogenation aromatic ring alkane diluent process poor hydrogen oil production liquid hydrocarbon in US Patent No. 2848530, US3238118, US4090947, thermal tar, gas oil, higher coking gas oil, coal derived liquid and catalytic cycle oil are preferred hydrogen donor diluent precursors.US Patent No. 6702936 carrys out production hydrogen donor diluent cracking method by utilizing the partial oxidation of asphaltene product, and CN1032669A proposes complete ion liquid solvent processing method.

CN102041015A proposes a kind of method from coal oil-gas reservoir preparing liquid fuel, in the method, coal dust is mixed with heavy oil, ageing, through heat of solution and dispersion after, stable coal colloidal sol phase slurry is produced through being separated, coal colloidal sol phase slurry substantially improves stability and the transport property of fluid, thus is convenient to the method producing lightweight oil in the operation of heavy oil cracking hydrogenation unit.

In existing heavy oil boiling bed hydrogenation conversing technology, direct hydrogenation liquefaction of coal Technology etc., reaction mass is three-phase mass transfer process, and this makes transporting of material need use the heterogeneous recycle pump of High Temperature High Pressure.In addition, circulated by reaction mass, cause processing unit (plant), the problem that particularly wall thickness of large high-temperature high-pressure reactor is large, tonnage heavy, manufacture difficulty is large, manufacturing cost is high, this seriously constrains the lighting of heavy feed stock and cleans process.

In existing heavy oil floating bed hydrogenation transformation technology, direct hydrogenation liquefaction of coal technology, the ton oil catalyst levels of light ends oil product is huge, and preparation or the water loss reclaimed in catalyst process occupy the main water consumption of hydroconversion process, add the lighting of heavy feed stock and clean the Environmental costs of process.

Normally by the direct powder process drying and dehydrating of raw material that heavy feed stock is such as coal-based in prior art, and dehydration coal dust is fully mixed homogenize, then produce slurry with catalyzer, solvent; In the preparation of drying and dehydrating powder with raw material Homogenization, although by the dry water content reducing coal-based powder raw material, add the safety problems such as spontaneous combustion of pulverized coal simultaneously, thus need complicated safe assist measure and requirement for raw material is very high.Compared to prior art, technique of the present invention special requirement carry out slaking operation to slurry, therefore also just eliminate drying step and avoid the danger of spontaneous combustion, extending the engineering scope of application of coal-based feedstocks simultaneously.

In one preferred embodiment, further the mixture of described catalysis fluid and heavy feed stock is carried out more than 1 hour, preferably more than 2 hours, the process that homogenizes of such as 12-48 hour or 12-24 hour.Especially, such time of homogenizing depends on the type of heavy feed stock and homogenization degree own, such as, can save homogenization step for the good oil base heavy feed stock of some homogenizing degree own.In a favourable embodiment, oil base heavy feed stock is preferably homogenized process 2-4 hour, for solid or the heavy feed stock containing solid as coal-based, bio-based or mixed base heavy feed stock preferably homogenize process >=24 hour, such as >=48 hours.

Preparing in unit at described catalysis slurry, when preparing oil base heavy feed stock catalysis slurry, only needing catalysis fluid and oil base heavy feed stock to be mixed by any different ratios as the heavy crude of API≤25 ° and optionally optionally homogenizes.In the present invention, according to the restriction to catalysis slurry fluid character, the blending ratio of oil base heavy feed stock in catalysis slurry is 40wt%-70wt%, and such catalysis slurry fluid is Newtonian fuid at the temperature of >=30 DEG C.

In addition, the coal-based heavy feed stock catalysis slurry can preparing high dispersive phase dissolved colloidal state is prepared in unit at described catalysis slurry, wherein heavy feed stock is coal-based 80-200 order powder raw material, stable group in coal dust, vitrinite divides fabulous solvability, swelling property, peptization and dispersiveness in a solvent.Coal-based catalysis slurry fluid, is distributed with larger difference with coal powder size, and with the increase of concentration, non-Newtonianism strengthens.In the present invention, in coal-based catalysis slurry, the blending ratio of coal-based feedstocks is 30wt%-55wt%.

In addition, the bio-based heavy feed stock catalysis slurry can preparing high dispersive phase suspended state is prepared in unit at described catalysis slurry, wherein heavy feed stock is the 80-200 order powder of dehydration biomass, the suspended dispersed that it has only had in catalysis fluid, such catalysis slurry fluid is non newtonian plastic fluid, and with the increase of dehydration biomass powder bulk concentration, the thixotropy increase of fluid is very fast.In the present invention, in bio-based catalysis slurry, the blending ratio of organism-based raw material is 30wt%-50wt%.

More specifically, in order to prepare oil base heavy feed stock catalysis slurry according to the inventive method, a kind of exemplary method is: in atmospheric conditions, (the compounding ratio as oil base heavy feed stock and catalysis fluid is 40wt%-70wt%:60wt%-30wt%) is at 50 DEG C-250 DEG C in proportion, by heavy oil and catalysis fluid chemical field (such as in static mixer) at the temperature of preferred 50 DEG C of-100 DEG C of scopes, then 0.5wt-2.0wt% is added, the promotor of preferred 0.5wt-1.0wt% is as liquid sulfur or sulphur powder (>100 order), CS2, at temperature 50 C-250 DEG C, prevulcanized 2-5 hour, preferred 2-4 hour, prepare the Newtonian fuid catalysis slurry that fluidised form is good, delivered into catalysis slurry and exported surge tank.

Coal-based, bio-based powder raw material catalysis slurry is prepared in order to prepare in unit at catalysis slurry according to the present invention, a kind of exemplary method is: in atmospheric conditions, by rare gas element by coal dust or biomass powder raw material in proportion (such as powder raw material: catalysis fluid=30wt%-55wt%:70wt%-45wt%) be blown in the catalysis fluid of temperature 120 DEG C of-250 DEG C of scopes (such as from the temperature of 150 DEG C to 250 DEG C), and continue dispersed with stirring 10-60 minute.Then product pump is sent in slaking reaction device, temperature 230 DEG C-280 DEG C, 2-4 hour is reacted under pressure 2.2-3.5MPa, after deviating from gas and moisture (such as through flash distillation and condenser), slaking material also adds amount of slurry 0.5wt-2.0wt%, the promotor of preferred 0.5wt%-2.0wt% is as liquid sulfur or sulphur powder (>100 order) or CS2, be pumped into homogeneous subsequently, ageing, circulate in pre-vulcanizing tank, temperature 150 DEG C-250 DEG C, under pressure 0.1MPa, uniformity according to raw material carries out homogeneous, ageing >=12 hour, preferably >=24 hours, preferred >=48 hour, prepare the non-Newtonian fluid catalysis slurry of stabilization of industry than >=0.90 at 50 DEG C-250 DEG C working range inner fluids, sent into catalysis slurry and exported surge tank.

In addition, the method for concrete exemplary preparation mixed base catalytic material slurry can be the simple combination of aforementioned two methods, and can by those skilled in the art's corresponding adjustment according to production practice.

Such as, prepare in unit at described catalysis slurry, the kerosene mixed base can preparing low dispersion phase refines catalysis slurry altogether, wherein heavy feed stock is heavy oil, coal dust can the mixed base raw material of mixture in any proportion, such catalysis slurry fluid, at normal temperatures in non-Newtonian fluid, is Newtonian fuid after heating up.In the present invention, heavy oil in mixed base raw material: the part by weight of coal dust can be 65-75:25-35 or 25-35:65-75, in catalysis slurry, the ratio of oily coal mixed base raw material can be 30wt%-60wt%.

Kerosene mixed base according to the present invention refines in hydrogenation modifying process altogether, and preferably, heavy feed stock mixed ratio is heavy oil: coal dust=68wt%-75wt%:25wt%-32wt% or 25wt%-32wt%:68wt%-75wt%; In addition preferably, the mixed ratio of mixed base heavy feed stock and catalysis fluid is=40wt%-70wt%:60wt%-30wt%, and in this material, add promotor sulphur powder (>100 order) or liquid sulfur, the CS2 of amount of slurry 0.5wt%-2.0wt%, to enter in catalysis slurry homogeneous tank that mixing repeatedly homogenizes, slaking 12-24h hour, subsequently material is inputted catalysis slurry tank.

In a preferred embodiment, in coal-based heavy feed stock catalysis slurry, particularly when coal-based heavy feed stock content≤60wt%, the working reaction temperature of described slurry is within the scope of 120 DEG C-250 DEG C, and the stabilization of industry of slurry fluid is than>=0.93 and fluidised form is low thixotroping (quiet shearing stress≤20MPam ^-2(80 DEG C)) non-Newtonian fluid; In bio-based heavy feed stock catalysis slurry, particularly when bio-based heavy feed stock content≤50wt%, the working reaction temperature of described slurry is within the scope of 120 DEG C-250 DEG C, and the stabilization of industry of slurry fluid is than>=0.90 and fluidised form is middle thixotroping (quiet shearing stress 10 ~ 30MPam ^-2(80 DEG C)) non-Newtonian fluid; In mixed base heavy feed stock catalysis slurry, particularly in mixed base heavy feed stock during coal-based heavy feed stock content≤30wt%, the working reaction temperature of described slurry is within the scope of 120 DEG C-250 DEG C, and the stabilization of industry of slurry fluid is than>=0.95 and fluidised form is Newtonian fuid or low thixotroping (quiet shearing stress≤10MPam ^-2(80 DEG C)) non-Newtonian fluid.

Prepare in unit at this heavy feed stock catalysis slurry, described mixing, slaking and homogenization process can be carried out in any suitable reactor, mixing tank or ager, and these devices are that those skilled in the art understand and know.Especially, these processes can be applicable to carrying out in fluid-operated tubular reactor.

hydrogenation lighting reaction member

According to heavy feed stock catalysis slurry hyd lighting reaction member of the present invention, defeated by catalysis mashing pump, fill hydrogen mixing, heating process and hydrogenation lighting reaction process form.

Described catalysis slurry pumping, to fill flow process that hydrogen mixing forms with heating process be fill the summation that hydrogen catalysis slurry enters the technical process before reactor, the collection comprising catalysis slurry is defeated, high-pressure pump defeated with fill mixed compression hydrogen, process furnace is warmed up to working temperature etc.In addition, the hydrogenation working conditions in described hydrogenation lighting reaction member is generally: reaction pressure 5MPa-30MPa and temperature of reaction 380 DEG C-520 DEG C.Heavy feed stock catalysis slurry volumetric spaces speed is in the reactor from 0.1h ^-1to 10h ^-1, and under standard state, the volume ratio of hydrogen or high Gas Mixtures Containing Hydrogen and heavy feed stock catalysis slurry (hereinafter also referred to hydrogen slurry ratio) is 100Nm ³/ m ³-10000Nm ³/ m ³.

Therefore, such as described catalysis slurry pumping, fill hydrogen mixing with heating process method in, the working temperature that catalysis slurry pumps into through thickened-oil pump from hold-up vessel 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 being filled with high pressure hydrogen in proportion, through process furnace be warmed up to hydrogenation working temperature 420 DEG C-465 DEG C, preferably 430 DEG C-465 DEG C.

Accordingly, described catalysis slurry pumping, the device filling the flow process that hydrogen mixing forms with heating process fill before hydrogen catalysis slurry enters reactor, the summation of streams all devices and equipment on route, as catalysis slurry gathering and transporting device and collection defeated tank, high pressure thickened-oil pump, hydrogen gas compressor, hydrogen mixing tank, process furnace, Controlling System and relevant safety equipment etc.

Described hydrogenation lighting reaction process flow process is: through pumping, fill hydrogen mixing and to enter mixed hydrogen catalysis slurry under hydrogenation lighting working conditions with heating process, enter into reactor through reactor inlet control valve, the heavy feed stock in fluid mechanics carries out cracking, hydrogenation reaction with the suspended state of laminar flow or turbulent flow in reactor.According to object product requirements, after completing the required reaction times, product is discharged through reactor outlet control valve, thus prepare the slurry of lighting.

In described hydrogenation reaction lighting technique, main design library part editor and reuse is hydrogenator, and reaction fixture system selects high-temperature and high-pressure hydrogenation safety control standed.The type of this reactor can be tubular reactor, go back Empty reactor, one or more in full back-mixing loop reactor, trickle-bed reactor, reverse convection formula reactor, slurry bed reactor, suspended-bed reactor and down-hole reactor.

Therefore, in an exemplary embodiment, described hydrogenation lighting reaction process flow process is: under hydrogenation working condition, the high-pressure catalytic slurry of mixed hydrogen heating in the control valve group of ground in tube valve enter into down-hole reactor and carry out hydrogenation reaction, enter into next reactor or technique unit subsequently.

Further, in this hydrogenation reaction lighting technique, for the hydrogenation lighting of oil base catalysis slurry, the working condition selected such as can be: the preferred 10.0-18.0MPa of reaction pressure=8.0-18.0MPa(, more preferably 12.0-18.0MPa), temperature of reaction=380 DEG C-470 DEG C (preferably 420 DEG C-465 DEG C, more preferably 440 DEG C-455 DEG C); Hydrogen slurry ratio=500Nm ³/ m ³– 1200Nm ³/ m ³(preferred 600Nm ³/ m ³– 950Nm ³/ m ³), the volumetric spaces speed of catalysis slurry is from 0.5h ^-1to 5h ^-1(preferably from 0.5h ^-1to 2.0h ^-1, more preferably from 0.8h ^-1to 1.2h ^-1).

In addition, in this hydrogenation reaction lighting technique, for the hydrogenation lighting of coal-based catalysis slurry, the working condition selected such as can be: the preferred 15.0-18.0MPa of reaction pressure=12.0-18.0MPa(), temperature of reaction=400 DEG C-470 DEG C (preferably 420 DEG C-455 DEG C, more preferably 440 DEG C-455 DEG C); Hydrogen slurry ratio=1000Nm ³/ m ³-2500Nm ³/ m ³(preferred 1200Nm ³/ m ³-1700Nm ³/ m ³, more preferably 1300Nm ³/ m ³-1700Nm ³/ m ³), the volumetric spaces speed of catalysis slurry is from 0.5h ^-1to 5h ^-1(preferably from 0.5h ^-1to 2.0h ^-1, more preferably from 0.8h ^-1to 1.5h ^-1).

In addition, in this hydrogenation reaction lighting technique, for the hydrogenation lighting of bio-based catalysis slurry, the working condition selected such as can be: the preferred 12.0-18.0MPa of reaction pressure=8.0-16.0MPa(, preferably 12.0-16.0MPa), temperature of reaction=350 DEG C-470 DEG C (preferably 420 DEG C-445 DEG C, more preferably 420 DEG C-435 DEG C); Hydrogen slurry ratio=1200Nm ³/ m ³– 3000Nm ³/ m ³(preferred 1500Nm ³/ m ³– 2000Nm ³/ m ³, more preferably 1500Nm ³/ m ³– 1800Nm ³/ m ³), the volumetric spaces speed of catalysis slurry is from 0.5h ^-1to 5h ^-1(preferably from 0.5h ^-1to 2.0h ^-1, more preferably from 1.0h ^-1to 2.0h ^-1).

In this hydrogenation reaction lighting technique, hydrogenation lighting can also be carried out to kerosene mixed base catalysis slurry, working condition in the case such as can be: operating pressure=12.0-18.0MPa, temperature of reaction=400 DEG C-460 DEG C (preferably 420 DEG C-460 DEG C, more preferably 440 DEG C-460 DEG C); Hydrogen slurry ratio=700Nm ³/ m ³– 2000Nm ³/ m ³(preferred 900Nm ³/ m ³– 1500Nm ³/ m ³), the volumetric spaces speed of catalysis slurry is from 0.5h ^-1to 5h ^-1(preferably from 0.5h ^-1to 2.0h ^-1, more preferably from 1.0h ^-1to 1.5h ^-1).

Described hydrogenation lighting technique under running conditions, calculates lightweight rate and the lightweight oil rate of heavy feed stock according to following formula, and the residual solid load in hydrogenation slurry:

product postpositive disposal unit

After the product discharge mouth of hydrogenation lighting reaction member according to the technical process in hydrogenation products postpositive disposal unit of the present invention, the summation of the treated technical process of product stream, the i.e. following operation that flows through of such as reaction product: gas-liquid separation, degasification hydrogenation slurry solid-liquid separation, object product light ends oil/gas (fraction section≤350 DEG C) and as circulating solvent basis in slagging-off hydrogenation slurry, auxiliary oil >=oil separating of 330 DEG C of (as 350 DEG C-550 DEG C) cuts and recovery, and/or by techniques such as unreacted hydrogen upgrading and supercharging recyclings.

In described hydrogenation products postpositive disposal unit, from hydrogenation products, isolated reaction splitting gas enters storage tank, it is outer defeated or as fuel gas, separate residue and enter into residue tank as fuel, and by unreacted hydrogen upgrading and supercharging recycling.Simultaneously also the cut oil pump of >=330 DEG C (as 350 DEG C-550 DEG C) is passed to circulating solvent head tank, lightweight oil pump is passed to light oil tank, outer defeated or enter into oil hydrogenation refined unit.

After process unit in hydrogenation products postpositive disposal unit according to the present invention is the product discharge mouth of hydrogenation lighting reaction member, the summation of all devices on the route of product stream warp, as gas separator, gas stripping column, solid-liquid centrifugation separator, separation column, interchanger, solvent take off slag tower, relevant Controlling System and safety equipment etc.

Below each involved everywhere processing parameter and performance perameter, except special instruction measurements and calculations method, can be determined according to oil development and refining API engineering specification method or GB standard by those skilled in the art.

In addition, in the application, each material content is in the composition all by weight percentage, unless expressly stated otherwise; In bracket after parameters data, thermometer shows and records at such a temperature.

Summary of the invention

Task of the present invention is to overcome in prior art carries out to oil base, coal-based, bio-based heavy feed stock and their any mixture the following defect that exists in hydroconversion process: the raw material of (1) existing hydrogenation lighting technique is single; (2) solvent of the prior art is to the dissolving of heavy feed stock solute and dispersed ability is low and applicable heavy feed stock narrow range; (3) stream of slurry becomes poor with thixotropy; (4) catalyzer preparation and recovery process is numerous and diverse and water loss is high; (5) the catalysis adaptability that forms hydrogenating materials of traditional catalyst is narrow, the technological problems such as low conversion rate, poor quality of distillate.Simultaneously, for the process engineering of correspondence, task of the present invention is to overcome system flow complexity in prior art, utilization ratio is low, and reaction unit mostly is the heterogeneous circulating reaction system of High Temperature High Pressure, the series of problems such as reactive system device and device fabrication difficulty are large, the poor stability that device controls.

Be surprisingly found out that, by the method for a kind of universal heavy feed stock catalysis slurry hyd provided by the present invention lighting, catalysis fluid and heavy feed stock catalysis slurry, can complete well the present invention based on, task as above.

Therefore, the present invention relates to the method for a kind of universal heavy feed stock catalysis slurry hyd lighting, the method comprises: use the catalysis fluid with catalysis to dissolve heavy feed stock, disperse and/or dilute, obtain heavy feed stock catalysis slurry after treatment again, under hydrogenation conditions, catalysis and hydrogen supply are carried out to described heavy feed stock catalysis slurry subsequently, thus obtained lighting distillate and splitting gas.

The wherein Fan Shi viscosity≤2000MPas(80 DEG C of heavy feed stock catalysis slurry after treatment), quiet shearing stress≤35MPam ^-2(80 DEG C) and stabilization of industry are than>=0.80.

On the other hand, the present invention relates to a kind of catalysis fluid with catalysis, it comprises or is made up of following component: multi-component initial and/or circulating solvent, multi-element metal compound, complexing agent and optional complexing auxiliary agent containing two or more metallic element, the total content of wherein said metallic element in catalysis fluid is the 0.05wt%-5.0wt% of described catalysis fluid and described multi-element metal compound and complexing agent form complex compound or inner complex.Described catalysis fluid may be used for the method for universal heavy feed stock catalysis slurry hyd as above lighting especially.

Again on the one hand, the present invention relates to a kind of heavy feed stock catalysis slurry, it is characterized in that, it is dissolved heavy feed stock by above-mentioned catalysis fluid, disperse and/or is diluted, and obtain after treatment again, it has Fan Shi viscosity≤2000MPas(80 DEG C), quiet shearing stress≤35MPam ^-2(80 DEG C) and stabilization of industry are than>=0.80.

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

Detailed Description Of The Invention

In this patent category, by catalysis slurry prepared by dissimilar heavy feed stock and the catalysis fluid chemical field by oil base, coal-based, bio-based and mixed base, the process of hydrogenation lighting is carried out under hydrogenation conditions, be collectively referred to as the hydrogenation lighting technique of heavy feed stock, be not limited in the type of reactor, structure, reactor whether have filler or inner member etc.

In scope, the heavy feed stock being adapted to hydrogenation lightening method of the present invention is oil base, coal-based, bio-based heavy feed stock and their any mixture (also referred to as mixed base heavy feed stock), wherein oil base heavy feed stock is such as the fluid fuels such as heavy crude, processing heavy oil, coal tar, biologic garbage grease, coal-based heavy feed stock is such as the humic coal of low, middle ripening degree sapropelinite and high vitrinite content, and bio-based heavy feed stock is such as the high heating value components such as the algae in fossil oil precursor biomass, biological lipid, barkinite, xylogen.

Oil base raw material in described heavy feed stock can be heavy crude, processing heavy oil, coal tar, biologic garbage grease etc. and their the mixing oil product of API °≤25.Generally speaking, ends content >90wt%, the such as >95wt% of oil base raw material oil product mid-boiling point >350 DEG C.Preferably, selected oil base raw material be API °≤15.0 super-viscous oil, super―heavy oil, vacuum residuum, coal tar and biologic garbage grease etc. or their mixing oil product; The ends content 100wt% of oil base raw material oil product mid-boiling point >350 DEG C, water content≤0.2wt%, solid residue≤0.2wt%.

In addition, be applicable to coal-based feedstocks in heavy feed stock of the present invention can for such as ripening degree R °≤0.85, the such as R °≤sapropelinite of 0.75 and the humic coal of vitrinite content >=50wt%, and the Mixture Density Networks of their different atures of coal.The powder granularity of coal-based feedstocks is 80-400 order suitably, as 80-200 order, pulverized coal water content is suitably≤15.0wt%(is as <10.0wt%) and ash content≤15wt%(as≤10wt%).Advantageously, selected coal-based feedstocks can be the sapropelinite of ripening degree R °≤0.70 and the humic coal of vitrinite content >=65wt%, and their Coal ranks, ature of coal Mixture Density Networks.

In addition, the organism-based raw material be applicable in heavy feed stock of the present invention can be such as the high heating value organic-biological matter of hydrogen content >=6.5wt%, oxygen level≤30%.The powder granularity of organism-based raw material can be 80-400 order (as 80-200 order), and the powder water content of organism-based raw material can be such as≤15.0% and/or ash oontent≤5%.Preferably, selected organism-based raw material is hydrogen content >=7.0wt%, the xylogen of oxygen level≤26wt%, bolt plastid biomass.

In the methods of the invention, in described heavy feed stock, mixed base raw material can be such as any mixture of three class heavy feed stocks in above oil base, coal-based, bio-based.Same, in mixed base heavy feed stock, the powder granularity of solid material can be 80-400 order, ash oontent≤10% and water content≤15.0wt% in powder.

On the one hand, theme of the present invention is the method for a kind of universal heavy feed stock catalysis slurry hyd lighting, the method comprises: use the catalysis fluid with catalysis to dissolve heavy feed stock, disperse and/or dilute, obtain heavy feed stock catalysis slurry after treatment again, under hydrogenation conditions, catalysis and hydrogen supply are carried out to described heavy feed stock catalysis slurry subsequently, obtained lighting distillate and splitting gas thus, wherein the Fan Shi viscosity≤2000MPas(80 DEG C of heavy feed stock catalysis slurry after treatment), quiet shearing stress≤35MPam ^-2(80 DEG C) and stabilization of industry are than>=0.80, more preferably>=0.90 or>=0.93.

In one preferred embodiment, require that there is following preferable range respectively for dissimilar heavy feed stock catalysis slurry:

1, the Fan Shi viscosity≤200MPas(80 DEG C of oil base heavy feed stock catalysis slurry), quiet shearing stress≤5MPam ^-2(80 DEG C) and stabilization of industry are than>=0.95, more preferably>=0.98 or 1.0.

2, the Fan Shi viscosity≤1200MPas(80 DEG C of coal-based heavy feed stock catalysis slurry), quiet shearing stress≤20MPam ^-2(80 DEG C), preferably≤10MPam ^-2(80 DEG C) and stabilization of industry are than>=0.93, more preferably>=0.95 or>=0.98.

3, the Fan Shi viscosity≤500MPas(80 DEG C of kerosene mixed base heavy feed stock catalysis slurry), quiet shearing stress≤10MPam ^-2(80 DEG C), preferably≤5MPam ^-2(80 DEG C) and stabilization of industry are than>=0.93, more preferably>=0.95 or>=0.98.

On the other hand, accordingly, the present invention relates to a kind of device for implementing aforesaid method, this device comprises following three technique units at least successively: catalysis fluid prepares unit, unit prepared by catalysis slurry and hydrogenation lighting reaction member.Wherein particularly prepare in unit and hydrogenation lighting reaction member at catalysis slurry and carry out respectively using catalysis fluid dissolve, disperse and/or dilute also again the step of treated obtained heavy feed stock catalysis slurry to heavy feed stock and described heavy feed stock catalysis slurry carried out to the step of catalysis and hydrogen supply under hydrogenation conditions.

Especially, as a relatively complete embodiment, described method and apparatus can comprise at least five technique units successively, namely heavy feed stock preprocessing unit, catalysis fluid prepares unit, unit prepared by catalysis slurry, hydrogenation lighting reaction member, product postpositive disposal unit, thus can produce lighting distillate and the splitting gas of such as≤350 DEG C.

Method of the present invention is according to occurring in nature coenosis and fossil energy resource deposition distribution theory, and development between biomass and different sorts fossil resource and inheritance, with the polycomponent distribution character of heavy feed stock, and basic based on the technology theory of multi-component feedstock catalytic hydrogenation reaction and reaction kinetics.An outstanding feature in the method is for working fluid with the polycomponent catalysis dispersed paste of stabilization of industry, can provide with the reaction engineering system of the defeated hydrogenation lighting of homogeneous phase pump in industrial reaction device, greatly simplify the operational condition of hydrogenation lighting thus and bring higher safe reliability.

Due to these advantages, method of the present invention is prepared in unit and hydrogenation lighting reaction member at catalysis slurry, preferably prepare unit at catalysis fluid, unit prepared by catalysis slurry and carry out under dehydration or water-less environment in hydrogenation lighting reaction member, more preferably described method is omnidistance completes under dehydration or water-less environment.

The present invention is elaborated further below by according to above-mentioned comparatively complete technical process.

heavy feed stock preprocessing unit

In hydrogenation lightening method of the present invention, described heavy feed stock preprocessing unit technical process is before raw material enters the import of catalysis slurry unit raw material, the summation of material treatment process flow process, the mixing of the i.e. purifying treatment such as accumulating, powder process, dehydration, deliming of heavy feed stock, and raw material and deposit etc.

This heavy feed stock preprocessing unit device refers to and enters before catalysis slurry prepares unit raw material import, the summation of all devices on route is flowed through in material treatment process flow process, as the combined purifying system and device of oil base heavy feed stock, coal-based, the fragmentation of bio-based heavy feed stock, powder process, sorting, dehydration, gas separator, powder storage system device, and relevant operating device and security system etc.

In a concrete embodiment of the present invention, heavy feed stock preprocessing unit is divided into fluid to preserve according to the material type of heavy feed stock and state preserving with powder.Wherein, for the fluid reservoir system of oil base heavy feed stock, heavy-oil reservoir shipping unit and the technique of petroleum industry national standard can be selected.And for the solid powder reservoir system of coal-based, bio-based and mixed base raw material, can select coal dust storage and transportation apparatus and the technique of cement, power industry national standard, the requirement for these materials is such as powder granularity is 80 order-200 orders, material moisture≤10.0wt%, inorganic content≤10.0wt%.Powder storage cylinder needs nitrogen protection, and powder is arranged by nitrogen wind or carried by worm conveyor under nitrogen protection.

catalysis fluid prepares unit

In hydrogenation lightening method of the present invention, prepare in unit at catalysis fluid and prepare catalysis fluid.

In the present invention, the catalysis fluid being applicable to method of the present invention can be conventional for the catalysis fluid in the Direct Hydrogenation liquefaction process of heavy feed stock, particularly coal-based heavy feed stock in any prior art in principle, such as, comprise the catalysis fluid of γ-FeOOH catalyzer that coal particle supports and dispersion solvent.

But propose a kind of novel catalysis fluid in the present invention, it can be suitable for technique of the present invention better.Described catalysis fluid comprises following component and preferably composed of the following components: multi-component solvent, multi-element metal compound, complexing agent and optional complexing auxiliary agent containing two or more metallic element, and the total content of wherein said metallic element in catalysis fluid is 0.05wt%-5.0wt%, the such as 0.05wt%-4.0wt% of described catalysis fluid or 0.07wt%-3.0wt% and described multi-element metal compound and complexing agent form complex compound or inner complex.

As one preferred embodiment, although complexing expects as far as possible, but generally speaking the complexing degree of multi-element metal compound is >=40%, is preferably >=50%, more preferably >=60% or 70%, and therefore in described catalysis fluid, multi-metal element will be dissolved or dispersed in described solvent with ionic condition, molecularity, complex status and/or polymolecular polymerization state.

The fluid with catalytic performance that the polynary organometallic compound that catalysis fluid of the present invention is dissolved or dispersed in this solvent by multi-component solvent and complexing forms.Although the slurries adopting those traditional catalyst of the prior art and solvent to be formed in the process according to the present invention also can realize the improvement of technique and the lifting of performance, but by adopting the catalysis fluid selected by the present invention, the catalysis slurry of obtained homogeneous stability on colloid yardstick more can be contributed to after mixing with heavy feed stock.Particularly for coal-based feedstocks, compared with traditional direct coal liquefaction technology, avoid the multiphase transmission treating processes of instability, easily precipitate and separate, overcome the problem such as deposition, heavy wear, coking, blocking that in the course of conveying of coal slurry accumulating river, two-phase laminated flow causes.In addition, because the catalyzer that have employed in the present invention containing ionic liquid forms catalysis fluid, therefore enhance liquefaction effect, stop the complicated technology of the γ-FeOOH catalyst preparing that such as coal particle solid-state in conventional liquefaction technology supports and huge water power consumption.

In catalysis fluid of the present invention, described solvent can be preferably the initial of system and/or circulating solvent, it is made up of the circulating solvent run in the solvent of the initial preparation entering hydrogenation lighting system (such as cut >=300 DEG C) or system or both mixtures, and both compositions can be identical or different.Circulating solvent can be such as that in present invention process method, de-slag hydrogenation slurry fraction section is oil at the bottom of the tower of 320 DEG C-550 DEG C, according to the type difference of hydrogenation heavy feed stock, and appropriate supplementary heterogeneous ring compound and/or solubilising dosage 0-5.0wt%.Described solvent has polycomponent distribution characteristics and is not solvent as relatively single in component used in the prior art, it must possess the fluid function of the existing dissolving to heavy feed stock, dispersion, dilution, has again the response function dissolving storage hydrogen, activation, transfer hydrogen supply under hydrogenation conditions.Therefore, in catalysis fluid of the present invention, in fact can not add pre-hydrogenation solvent conventional in as routine techniques.

Specifically, in catalysis fluid of the present invention, solvent used comprises neutral component, acidic components, basic component and ionic liquid.Generally along with the reduction of heteroatoms in heavy feed stock (as N, O, S) content in the polycomponent composition of solvent, the composition of polarity reduces, but neutral component and ionic liquid must formation base components in a solvent.

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

As neutral component, can consider to be selected from containing one or more in the polycyclic aromatic hydrocarbons wet goods of the heavy arene class oil of heavy arene amount more (such as heavy arene content >=50wt%), polycyclic aromatic hydrocarbons, partly or entirely hydrogenation, preferably two or more.

As acidic components, can consider to be selected from phenol, C3-C4 alkylphenol, naphthols and indenols, high carbolic oil etc. one or more, preferably two or more.

As basic component, can consider to be selected from nitrogen heterocyclics such as phenyl amines, quinoline, indoles, pyridine, acridine etc. one or more, preferably two or more.

As ionic liquid, can consider to be selected from imidazole salt, pyridine salt, quaternary ammonium salt and season phosphonium salt class etc. one or more, preferably two or more.

In addition, also can be directly used in the distillate of fraction section 330 DEG C to 541 DEG C in industrial common such as wax tailings or hydrogenation slurry, but they itself are complicated component contain one or more mixture of above-mentioned four kinds of components.

Of the present invention one preferred embodiment in, from improving solvent, the suspension of dispersible solid thing, the transport property improving the catalysis slurry of preparation, the solvability aspect that meets the hydrogen transference characteristic hydrogenation lighting reaction and improve heavy feed stock being considered respectively, requiring density>=0.95 of described solvent, preferably 0.95-1.02g/cm ³, particularly 0.96-0.99g/cm ³fan Shi viscosity is>=5MPas, preferably 15-35MPas, such as 15-28MPas (50 DEG C), and average fragrant rate fa be>=0.60, preferably 0.65-0.72, particularly 0.67-0.70, the total content of organic heteroatoms N, S, O wherein in solvent be≤8.0, preferably 3.0-8.0wt%, especially as 4.0-6.5wt%.

For the preparation of solvent, usually increase according to the type of heavy feed stock and the ratio of Group Component Semi-polarity component, improve at described solvent Semi-polarity component ratio.

As a preferred embodiment, in described solvent, comprise heavy arene class oil, preferably account for the base solvent oil of the heavy arene class oil of the 70wt%-90wt% of solvent total amount as solvent.

Preferably, in described solvent of the present invention, the dissolubility property parameter distribution of solvent is directly related with the dissolubility property parameter distribution of Group Component with the type of heavy feed stock.Generally speaking, in the present invention, the solubility characteristics parameter intermediate value of described solvent and the intermediate value solubility characteristics parameter difference Δ δ of heavy feed stock ^1/2≤ 5, preferred Δ δ ^1/2≤ 3.

In the present invention, described solvent can by those skilled in the art by known method, such as, by compounding and prepare.In one preferred embodiment, by oily for such as heavy arene class base solvent, the secondary solvent oil of polycyclic aromatic hydrocarbons, partly or entirely hydrogenation polycyclic aromatic hydrocarbons, heterogeneous ring compound or solubilizing agent etc., at temperature 50 C-80 DEG C, stir mixture in order and obtain the non-water initial solvent of polycomponent.

In the present invention, the described metallic element IA race that is selected from the periodic table of elements is to VA race, IB race to two or more of VIIB race and VIII and lanthanide series rare-earth elements.Preferably, described metallic element chosen from Fe, nickel, molybdenum, copper, zinc, tin, aluminium, tungsten, manganese, titanium, vanadium, chromium, cobalt, gold, cadmium, mercury, cerium and lanthanide series rare-earth elements, more preferably chosen from Fe, nickel, molybdenum, tungsten, titanium, zinc, aluminium and lanthanide series rare-earth elements, particularly chosen from Fe, nickel, aluminium, titanium and lanthanide series rare-earth elements.

As a very favorable embodiment, with the weighing scale of all metallic elements of multi-element metal compound, iron, aluminium and/or titanium elements (preferred ferro element) content are >50wt%, preferably >65wt%, particularly >70wt% and such as 70wt-80wt%, and the content of lanthanide series rare-earth elements is based on the weighing scale 0 ~ 5wt% of all metallic elements, preferably 0.1 ~ 3wt%, more preferably 0.1 ~ 1wt% and particularly 0.2 ~ 0.5wt%.

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

For the not special restriction of multi-element metal compound, it should be able to be compatible and can be formed with added complexing agent in follow-up reaction and be dissolved or dispersed in complex compound in solvent or inner complex with solvent.Those skilled in the art can select suitable multi-element metal compound accordingly.Suitable multi-element metal compound is such as inorganic salt and/or organic salt, preferably salt hydrochlorate, vitriol, nitrate, carbonate, carboxylate salt, C ₁-C ₁₈aliphatic hydrochlorate and/or C ₆-C ₂₀aromatics hydrochlorate etc.

At this, in order to form complex compound with metal ion in described solvent or inner complex needs further complexing agent component.In principle, all and above-mentioned metal ion can be all applicable with stable complexation or the morphogenetic complexing agent of chelating, and those skilled in the art can reasonably select applicable complexing agent according to the production practice general knowledge of self.

In a concrete embodiment, as complexing agent can consider to comprise heteroatoms as the heterogeneous ring compound (such as have 6-40 or 6-30 carbon atom) of N, O or S and its can be optionally substituted (as hydroxyl or sulfydryl), C ₁-C ₁₈fatty alcohol, aliphatic amine, aliphatic carboxylic acid and aliphatic sulfonic acid and its can be optionally substituted with one or more hydroxyl separately, carboxyl or sulfydryl replace, and such as thiocarbamide or thiourea derivative.Can enumerate as an example such as following these: 1,10-phenanthroline, EDTA, dimercaprol dimercaptopropanol, Sodium Dimercapto Sulfonate, mercaptoethylamine, Thiovanic acid, thiocarbamide, oxine etc.Described complexing agent can be used alone, and also can multiple form combinationally use.

According to selected complexing agent and multi-element metal compound, optionally can optionally add complexing auxiliary agent, as prussiate, citric acid, tartrate, oxalic acid, sulphosalicylic acid, trolamine and sodium alkoxide, methyl silicon sodium alcoholate, NaOH, KOH etc. one or more.

In order to prepare catalysis fluid of the present invention, obtain described solvent in advance as described above, then add described complexing agent and optional complexing auxiliary agent and multi-element metal compound wherein, after fully reacting and discharge uncondensable gas and water, obtain desired catalysis fluid.

Such as, in a concrete embodiment, in order to prepare described catalysis fluid, preparation and the described solvent adjusted are provided in advance, at temperature 20-100 DEG C, preferably 30 DEG C-80 DEG C by the PH scope of complexing auxiliary agent adjustment solvent after 7.0-11.0, preferably 8.0-10.0, add complexing agent in proportion and add above-described multi-element metal compound (such as F successively _e ²⁺, Ni ²⁺, Al ³⁺with the multi-element metal salt of a small amount of lanthanide series rare-earth elements) after mixture, be warmed up to 120 DEG C-150 DEG C, under agitation (as stirred 30-120 minute), 180 DEG C-250 DEG C are warmed up to again after the uncondensable gas of separation and water, continuing stirring reaction (as stirred 30-180 minute again), preparing the catalysis fluid containing multi-element metal compound thus.

unit prepared by catalysis slurry

Prepare in unit at the catalysis slurry of hydrogenation lightening method of the present invention, use catalysis fluid to dissolve heavy feed stock, swelling, dispersion and/or dilution (such as can realize by mixing simply), the more obtained heavy feed stock catalysis slurry improving fluid property after treatment.

Favourable, application claims according to the fluid properties parameter of the catalysis slurry of these two kinds of method preparations is: the Fan Shi viscosity≤2000MPa.s (80 DEG C) of slurry fluid, quiet shearing stress≤35MPa × m ^-2(80 DEG C), stabilization of industry is than>=0.90; Preferably, fluid Fan Shi viscosity≤2000MPa.s (80 DEG C), quiet shearing stress≤30MPam-2 (80 DEG C) and stabilization of industry are than>=0.95.In addition advantageously, in catalysis slurry fluid, solid content is 0-65wt%, preferably 0-55wt%, more preferably 0-42wt%.Catalysis slurry fluid obtained like this obtains remarkable workability and is therefore particularly suitable for hydrogenation lighting step subsequently.

Described catalysis paste industry stabilization ratio be by experiment with calculate.Experimental technique is: in 1000mm quiet liquid pipe, pour well-beaten catalysis slurry into, derive fluid, record fluid density D after the static 10min that flows in the middle part of quiet liquid pipe ₀; After quiescent settling 24h, derive fluid from top 100mm, record mean density D ^top(24h); Derive fluid from bottom 100mm, record mean density D ^bottom(24h), 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, described treating processes advantageously comprises following two committed steps, carries out maturation process by oil base heavy feed stock and the catalysis fluid chemical field obtained by the present invention and by containing coal-based, the bio-based of solid and mixed base heavy feed stock.Those skilled in the art can understand, described maturation process refers to process heavy feed stock being stood in ager (such as tubular reactor) pressure and temperature of certain hour, thus regulates the ripening degree of heavy feed stock and wherein contained organic constituent etc.In the method for the invention, slaking is advantageously made to carry out at the temperature of the operating pressure of 0.1-5.0MPa and 120 DEG C-300 DEG C, and the maturation process time can remain on such as more than 0.5 hour, preferably more than 1 hour or 2 hours, and the length of maturation process time can regulate according to desired performance, such as measured stabilization of industry ratio.

Therefore, described catalysis slurry preparation method can be divided into by the type of heavy feed stock prepares with catalysis fluid chemical field the oil base heavy feed stock catalysis slurry technique obtaining Newtonian fuid in proportion by oil base heavy feed stock, and containing coal-based, the bio-based of solid and mixed base heavy feed stock in proportion with two step compound methods of catalysis fluid, a kind of rear method can prepare coal-based, bio-based and the mixed base heavy feed stock catalysis slurry of non-Newtonian fluid.Such as, described catalysis slurry preparation method can be divided into lysotype oil base catalytic material slurry preparation method and decentralized mixed base, coal-based, bio-based powder raw material catalysis slurry preparation method.

Prepare in unit at this catalysis slurry, catalysis slurry is made up of catalysis fluid in proportions and dissimilar heavy feed stock mixture, can dissolving each other according to fluid chemical field, to prepare solubilised state be main oil base catalysis slurry to method, refines catalysis slurry, the coal-based catalysis slurry of high dispersive phase dissolved colloidal state, the bio-based catalysis slurry of high dispersive phase suspended state altogether according to the kerosene mixed base preparing low dispersion phase with powder dispersion mixing process.

For containing the coal-based of solid, bio-based and mixed base heavy feed stock are in proportion with two step compound methods of catalysis fluid, first heavy feed stock and catalysis fluid in proportions are simply mixed with out initial catalyst slurry, then make initial slurry in operating pressure 0.1-5.0MPa and temperature 120 DEG C-300 DEG C, preferred operating pressure 1.0-3.5MPa and temperature 180 DEG C-280 DEG C, more preferably at operating pressure 1.0 (such as 1.1)-3.0MPa and temperature 210 DEG C-280 DEG C through slaking and optional homogenization step, and prepare the coal-based of stable work in work, the non-Newtonian fluid catalysis slurry of bio-based and mixed base.Wherein the content of solid phase heavy feed stock in catalysis slurry advantageously≤65wt%, preferably≤55wt%, more preferably≤42wt%.

Generally speaking, in order to prepare the catalysis slurry of heavy feed stock, described heavy feed stock is fully mixed with described catalysis fluid, then according to circumstances make it through degassed, dehydration, slaking and/or the process that homogenizes, wherein further advantageously in this catalysis slurry S element total content can≤2.0wt%, solid content can be 0 ~ 65wt% and water content can≤0.2wt%.In described catalysis slurry, the blending ratio of heavy feed stock is 10 ~ 65wt%, such as 20 ~ 55wt% or 30 ~ 45wt%.

As mentioned above, preferably and key, described process comprises carries out maturation stage to the mixture of obtained catalysis fluid and heavy feed stock (particularly containing coal-based, bio-based and the mixed base heavy feed stock of solid), and more preferably optionally also carries out homogenization step.Can be there is degassed and dehydration (carrying out possibility that is degassed and processed in addition to it although also do not get rid of) in mixture in maturation stage, thus the free-water in such as coal-based feedstocks is removed, and reduce the oxygen level of organic phase in low-maturity coal-based feedstocks, the average maturity R ° of suitable raising coal-based feedstocks, particularly reduce the plastisied dispersion of ripening degree, thus improve the content of (C+H) effective element in coal-based heavy feed stock organic phase.This technological process is particularly particularly remarkable for brown coal, the sub-bituminous coal effect of R °≤0.55.Find in addition, after maturation stage like this, the flowing property of slurry accesses to be improved greatly, thus makes likely to simplify follow-up operation.

Accompanying drawing explanation

Fig. 1 implements the device technique schematic flow sheet according to universal heavy feed stock catalysis slurry hyd lightening method of the present invention.

This complete process shows heavy feed stock preprocessing unit, catalysis fluid prepares unit, unit prepared by catalysis slurry, the sequencing of hydrogenation lighting reaction member and product postpositive disposal unit.Wherein, the circulating solvent in system can be recycled and enter catalysis fluid and prepare in unit for preparation catalysis fluid.

Embodiment

The present invention is described further with reference to following embodiment, but these embodiments should not be understood to be limitation of the present invention.

Embodiment 1

1, the raw material adopted and the preparation of catalysis fluid

In an embodiment according to the present invention, select 1.5t/d commerical test system and device, this process unit system, prepare unit by heavy feed stock preprocessing unit, catalysis fluid, unit prepared by catalysis slurry, hydrogenation lighting reaction member and product postpositive disposal unit form, wherein the high-temperature high-pressure craft device of this commerical test system and device is the heat insulation also empty suspended-bed reactor of the heat insulation also empty suspended-bed reactor of horizontal endless tube process furnace and 1.5t/d and down-hole.

The following heavy feed stock for the treatment of of selected in heavy feed stock preprocessing unit:

Oil base heavy feed stock is Yumen refinery vacuum residuum,

Coal-based heavy feed stock is Tu Hanao Mao Hu ore deposit, Xinjiang 2# steam coal dehydration coal dust (>=120 order),

Mixed base heavy feed stock is that Yumen subtracts slag and 2# coal dewatering coal dust (>=120 order) subtracts slag according to mixed ratio Yumen: the mixture coal oil mixture of 2# coal dewatering coal dust=72.7wt%:27.3wt%, heavy feed stock character is in table 1 Raw 1-3.

Initial solvent in catalysis fluid is wax tailings, high carbolic oil, organic nitrogen-containing heterogeneous ring compound and imidazole salts and pyridinium compound add up in 60:20:20:5(imidazole salts+pyridinium compound) ratio is uniformly mixed formulated at temperature 20 DEG C-50 DEG C.The H/C atomic ratio of initial solvent is 1.36, is respectively 2.26wt% and 2.37wt% in initial solvent containing oxygen, nitrogenous compound content (in oxygen and nitrogen element content).

For the circulating solvent in catalysis fluid, the distillate of fraction section 330 DEG C-541 DEG C in selec-tive hydrogenation slurry, the H/C atomic ratio of circulating solvent is 1.39, is respectively 2.51wt% and 2.42wt% in circulating solvent containing oxygen, nitrogenous compound content (in oxygen and nitrogen element content).

In order to prepare catalysis fluid, select the compound of ferrous sulfate, nickelous nitrate, nitric acid molybdenum, titanium sulfate, Tai-Ace S 150 and lanthanide series metal oxalate to go out mixing solutions containing Fe and the compound containing Ni, Mo, Ti, Al metal ion and a small amount of lanthanide series rare-earth elements as multi-element metal compound component according to proportions as described below, wherein in hybrid metal element with Fe ²⁺be main and described iron content 73.2wt%, the element total contents such as Al, Ti, Ni, Mo are about 26.6wt%, and lanthanide series rare-earth elements content is about 0.2wt%; In addition, by 1,10-phenanthroline, dimercaprol dimercaptopropanol complexing agent and a small amount of methyl silicon sodium alcoholate auxiliary agent, be that the multi-element metal group mixed solution (total metallic element concentration 21.7wt%) of 10wt% joins in the initial of 100wt% or circulating solvent successively with concentration, form mixed stream.

Mixed stream is under agitation warmed up to 120 DEG C-150 DEG C, dehydration, degassed after, be warmed up to 210 DEG C, continuation stirring reaction receives the multi-element metal compound for catalysis fluid containing metallic element total amount ~ 0.83wt% in catalysis slurry 104.7wt% for 30-60 minute subsequently, pumps into catalysis fluid reservoir.The feedstock property of heavy feed stock and starting catalytic fluid is in the raw material 4-5 in table 1.

The character of table 1 heavy feed stock and catalysis fluid

2, the preparation of the catalysis slurry of heavy feed stock

In order to be formulated in the catalysis slurry of the oil base heavy feed stock shown in table 2, shown in oil base heavy feed stock and " the catalysis fluid 2 " described in part 1 being arranged in " slurry 1 " at temperature 80 DEG C, ratio mixes thus obtains oil base heavy feed stock content is the catalytic slurry of 51.1wt%.

In order to be formulated in the catalysis slurry of the kerosene mixed base heavy feed stock shown in table 2, first by coal-based for 120 object 34.1 parts heavy feed stock powder and the oil base heavy feed stock of 75.9 parts and " the catalysis fluid 2 " described in part 1 of 100 parts under catalysis fluid temperature (F.T.) 80 DEG C of conditions, at 80 DEG C, mixed preparing goes out the initial catalyst slurry of 210 parts of kerosene mixed base heavy feed stocks, then 90min is reacted being warmed up under 210 DEG C and pressure 1.2MPa condition, through slaking degassed and dehydration after, add the promotor sulphur powder (>100 order) of 0.5wt% further, homogeneous and ageing again at pressure 0.1MPa and temperature 150 DEG C subsequently, prevulcanized 24 hours, prepare the catalysis slurry that 205 parts of kerosene mixed base heavy feed stock average contents are 51.2wt%.

In order to be formulated in the catalysis slurry of the coal-based heavy feed stock shown in table 2, first by coal-based for 120 object 103 parts heavy feed stock powder and 100 parts mix at 150 DEG C of temperature at " the catalysis fluid 2 " described in part 1 under catalysis fluid temperature (F.T.) 100 DEG C of conditions, thus make 203 parts of coal-based heavy feed stock initial catalyst slurries, then 250 DEG C and react 150min under pressure 2.5MPa are warmed up to, through slaking degassed and dehydration after, add the promotor sulphur powder (>100 order) of 0.8wt% further, homogeneous and ageing again at pressure 0.1MPa and temperature 170 DEG C subsequently, prevulcanized 48 hours, prepare the catalysis slurry that 187.6 parts of coal-based heavy feed stock average contents are 46.7wt%.

Table 2 heavy feed stock catalysis slurry properties and flow pattern

3, the hydrogenation lighting of catalysis slurry

Hydrogenation lighting technique unit in the embodiment of the present invention is made up of 1.5t/d tubular reactor and down-hole reactor commerical test device, carries out hydrogenation lighting process wherein to each catalysis slurry available from part 2.For available from the oil base of part 2, the hydrogenation lighting duty parameter of coal-based, mixed base heavy feed stock and test-results in the hydrogenation example 1-3 in table 3.

The hydrogenation lighting duty parameter of table 31.5t/d tubular reactor and down-hole reactor and result

4, the postpositive disposal of product

In this embodiment, product postpositive disposal unit according to the present invention is run by 1.5t/d commerical test device postpositive disposal device, obtain oil base, coal-based, mixed base heavy feed stock hydrogenation light ends oil from the 3rd part, wherein the essential property of light ends oil is in the lighting product 1-3 in table 4.

The essential property of table 41.5t/d commerical test device hydrogenation lighting result and light ends oil

In an embodiment according to the present invention, the oil base obtained by the operation of 1.5t/d heat insulation also empty suspended-bed reactor (ground and down-hole) commerical test device, coal-based, mixed base heavy feed stock hydrogenation lighting distillate, can be used as refinery's hydrofining or hydroformer raw material, produce the tank oils such as qualified gasoline, kerosene, diesel oil.

In order to embody superiority of the present invention further, below putting up with and contrasting according to the traditional technology of technique of the present invention and prior art.

Comparative example 1

heavy feed stock hydrogenation lighting processing method of the present invention compares with conventional hydrogenation process

Coal-based heavy feed stock in this comparative example is dewater coal dust (>=120 order) (raw material 7) with the nitrogen drying for the hydrogenation liquefaction raw material of the routine of following proposal 1 in the Tu Hanao Mao Hu ore deposit, Xinjiang 2# steam coal powder (>=120 order) (raw material 6) in the same manner as in Example 1 for following proposal 2 and 3, and its coal dust character is in table 5.

Table 52# steam coal coal dust and dry base coal dust character

Adopt by FeSO in scheme 1,2 ₄7H ₂γ-FeOOH/ coal the supported catalyst that O, ammoniacal liquor, 2# power coal dust are prepared in aqueous is as catalyzer, and solvent is that Yumen refinery reformation slurry oil and wax tailings (1:1) are at temperature 430 DEG C, pressure 12.0MPa and air speed 1.0h ^-1the conventional pre-hydrogenation solvent of DCL/Direct coal liquefaction of lower preparation." the catalysis fluid 2 " prepared by embodiment 1 is then adopted in scheme 3.

In addition, scheme 1 selects the raw material slurry preparation technology of DCL/Direct coal liquefaction common process and routine, is wherein particularly mixed with coal-based feedstocks by conventional for the DCL/Direct coal liquefaction containing γ-FeOOH/ coal supported catalyst as above pre-hydrogenation solvent; Scheme 2 and 3 comprises according to the coal-based heavy feed stock slurry preparation step of the slaking of present invention process, and its preparation process is except identical with embodiment 1 except homogenization conditions of the cooking conditions described in following table 6.The pre-hydrogenation solvent of described routine normally wax tailings and arenes catalytic slurry oil mixture and by hydrotreatment in advance.That compares the results are shown in Table 6.

The coal-based heavy feed stock slurry preparation of table 6 and slurry properties

Subsequently, coal-based heavy feed stock slurry prepared in scheme 1-3 is carried out hydrogenation lighting (liquefaction), and the results are shown in Table 7 for it.

The hydrogenation result of the different coal-based heavy feed stock slurry of table 7

As can be seen from the above table, under identical hydrogenation working condition, although the transformation efficiency of coal-based heavy feed stock (daf)/% is substantially identical, but lightweight rate and lightweight oil rate have bigger difference, the oil properties that particularly liquefies has significant difference, direct coal liquefaction process is made oxygen level in the liquefaction oil prepared and is reached 4.66wt% routinely, suitable with Shenhua demonstration project liquefaction oil character.The liquefaction oil essential property that different process method is produced is in table 8.

The essential property of the coal-based heavy feed stock slurry of table 8 liquefaction oil product in different process method

Comparative example 2

the different components of catalysis fluid of the present invention is on the impact of heavy feed stock catalysis slurry

Scheme 4 and 5 be in the 1st and 2 parts of repetition embodiment 1 for the preparation process of slurry 3 to prepare the catalysis slurry of coal-based heavy feed stock, but wherein adopt the catalysis fluid of different composition respectively.

Catalysis fluid used in scheme 4 supports coal primarily of the γ-FeOOH/ in the scheme 1 of comparative example 1 and the initial solvent obtained by embodiment 1 part 1 forms as solvent, and catalysis fluid 3 used in scheme 5 is identical with by the catalysis fluid 1 obtained by embodiment 1 part 1, but wherein regulate the amount of initial solvent, make the Fe constituent content in scheme 4 and the total metal contents in soil in scheme 5 be 1.8wt%.

The stabilization of industry of the different catalysis fluid formed and the coal-based heavy feed stock caused under same operation thereof is shown in following table 9 than result.

The catalysis fluid composition that table 9 is different and the different stabilization of industry ratios caused thereof

Claims

1. the method for universal heavy feed stock catalysis slurry hyd lighting, the method comprises: use catalysis fluid to dissolve heavy feed stock, disperse and/or dilute, obtain heavy feed stock catalysis slurry after treatment again, under hydrogenation conditions, catalysis and hydrogen supply are carried out to described heavy feed stock catalysis slurry subsequently, obtained lighting distillate and splitting gas thus

2. method as claimed in claim 1, is characterized in that, described process comprises the step and the optionally homogenization step that the mixture of catalysis fluid and heavy feed stock are carried out to slaking.

3. the method as described in aforementioned any one of claim, is characterized in that, wherein total content≤the 2.0wt% of S element in this catalysis slurry, and solid content is 0 ~ 65wt% and water content≤0.2wt%.

4. the method as described in aforementioned any one of claim, it is characterized in that, for containing coal-based, the bio-based of solid and mixed base heavy feed stock, first heavy feed stock and catalysis fluid chemical field are prepared initial catalyst slurry, then make initial slurry go through maturation stage more than 0.5 hour at pressure 0.1-5.0MPa, preferably 1.0-3.5MPa and temperature 120 DEG C-300 DEG C, preferably 180-280 DEG C; Or for oil base heavy feed stock, by described oil base heavy feed stock and catalysis fluid chemical field.

5. the method as described in aforementioned any one of claim, is characterized in that, makes initial catalyst slurry also go through degassed and/or dehydrating step.

6. the method as described in aforementioned any one of claim, it is characterized in that, the mixture of described catalysis fluid and heavy feed stock goes through the process that homogenizes of more than 1 hour, preferably oil base heavy feed stock is preferably homogenized process 2-4 hour, for coal-based, bio-based or mixed base heavy feed stock homogenize process >=24 hour, such as >=48 hours.

7. the method as described in aforementioned any one of claim, is characterized in that, in described catalysis slurry, the blending ratio of heavy feed stock is 10 ~ 80wt%, such as 20 ~ 70wt% or 30 ~ 70wt%.

8. the method as described in aforementioned any one of claim, is characterized in that, in described catalysis slurry, the blending ratio of oil base heavy feed stock and catalysis fluid is 40 ~ 70wt%:60 ~ 30wt%.

9. the method as described in aforementioned any one of claim, is characterized in that, in described catalysis slurry, coal-based or bio-based heavy feed stock and catalysis fluid the blending ratio of powder is 30 ~ 55wt%:70 ~ 45wt%.

10. the method as described in aforementioned any one of claim, is characterized in that, in described catalysis slurry, the blending ratio of mixed base heavy feed stock and catalysis fluid is 40 ~ 70wt%:60 ~ 30wt%.

11. methods as described in aforementioned any one of claim, is characterized in that, in coal-based heavy feed stock catalysis slurry, the working temperature of described slurry is within the scope of 120 DEG C-250 DEG C, and the stabilization of industry of slurry is than>=0.93 and fluidised form is quiet shearing stress≤20MPam ^-2the non-Newtonian fluid of the low thixotroping of (80 DEG C).

12. methods as described in aforementioned any one of claim, it is characterized in that, in bio-based heavy feed stock catalysis slurry, the working temperature of described slurry is within the scope of 120 DEG C-250 DEG C, and the stabilization of industry of slurry is than>=0.90 and fluidised form is quiet shearing stress 10 ~ 30MPam ^-2the middle thixotroping non-Newtonian fluid of (80 DEG C).

13. methods as described in aforementioned any one of claim, it is characterized in that, in mixed base heavy feed stock catalysis slurry, the working temperature of described slurry is within the scope of 120 DEG C-250 DEG C, and the stabilization of industry of slurry is than>=0.95 and fluidised form is Newtonian fuid or quiet shearing stress≤10MPam ^-2the low thixotroping non-Newtonian fluid of (80 DEG C).

14. methods as described in aforementioned any one of claim, is characterized in that, described method comprises at least following three technique units successively, and namely catalysis fluid prepares unit, unit prepared by catalysis slurry and hydrogenation lighting reaction member.

15. methods as described in aforementioned any one of claim, it is characterized in that, described method also comprises heavy feed stock preprocessing unit and product postpositive disposal unit.

16. methods as described in aforementioned any one of claim, it is characterized in that, described method is prepared in unit and hydrogenation lighting reaction member at catalysis slurry, preferably prepare unit at catalysis fluid, unit prepared by catalysis slurry and carry out under dehydration or water-less environment in hydrogenation lighting reaction member, more preferably described method is omnidistance completes under dehydration or water-less environment.

17. methods as described in aforementioned any one of claim, it is characterized in that, described catalysis fluid comprises or is made up of following component: multi-component solvent, multi-element metal compound, complexing agent and optional complexing auxiliary agent containing two or more metallic element, the total content of wherein said metallic element in catalysis fluid is the 0.05wt%-5.0wt% of described catalysis fluid and described multi-element metal compound and complexing agent form complex compound or inner complex.

18. methods as described in aforementioned any one of claim, is characterized in that, the IA race that described metallic element is selected from the periodic table of elements is to VA race, IB race to VIIB race and VIII and lanthanide series rare-earth elements.

19. methods as described in aforementioned any one of claim, it is characterized in that, described metallic element chosen from Fe, nickel, molybdenum, copper, zinc, tin, aluminium, tungsten, manganese, titanium, vanadium, chromium, cobalt, gold, cadmium, mercury, cerium and lanthanide series rare-earth elements, be preferably selected from iron, nickel, molybdenum, tungsten, titanium, zinc, aluminium and lanthanide series rare-earth elements, particularly chosen from Fe, nickel, aluminium, titanium and lanthanide series rare-earth elements.

20. methods as described in aforementioned any one of claim, it is characterized in that, described multi-element metal compound is inorganic salt and/or organic salt, preferably salt hydrochlorate, vitriol, nitrate, carbonate, carboxylate salt, C ₁-C ₁₈aliphatic hydrochlorate and/or C ₆-C ₂₀aromatics hydrochlorate.

21. methods as described in aforementioned any one of claim, it is characterized in that, described multi-element metal compound is dissolved or dispersed in described solvent with ionic condition, molecularity, complex status, polymolecular polymerization state.

22. methods as described in aforementioned any one of claim, is characterized in that, average fragrant rate fa>=0.60 that described solvent has, density>=0.95g/cm ³with Fan Shi viscosity>=5MPas(50 DEG C), the total content≤8.0wt% of organic heteroatoms N, S, O wherein in solvent.

23. methods as described in aforementioned any one of claim, it is characterized in that, described solvent comprises the neutral component of >40 % by weight, the acidic components of 5 % by weight ~ 25 % by weight, the basic component of 5 % by weight ~ 25 % by weight and the ionic liquid of 5 % by weight ~ 15 % by weight.

24. methods as described in aforementioned any one of claim, is characterized in that, the hydrogenation conditions described in when carrying out catalysis and hydrogen supply to described heavy feed stock catalysis slurry is: reaction pressure 5MPa-30MPa and temperature of reaction 380 DEG C-520 DEG C.

25. methods as described in aforementioned any one of claim, it is characterized in that, described heavy feed stock catalysis slurry is oil base heavy feed stock catalysis slurry, and hydrogenation conditions when carrying out catalysis and hydrogen supply to it is: reaction pressure 8.0MPa-18.0MPa and temperature of reaction 380 DEG C-470 DEG C.

26. methods as described in aforementioned any one of claim, it is characterized in that, described heavy feed stock catalysis slurry is coal-based heavy feed stock catalysis slurry, and hydrogenation conditions when carrying out catalysis and hydrogen supply to it is: reaction pressure 12.0MPa-18.0MPa and temperature of reaction 400 DEG C-470 DEG C.

27. methods as described in aforementioned any one of claim, it is characterized in that, described heavy feed stock is oil base raw material, it is selected from heavy crude, processing heavy oil, coal tar, biologic garbage grease etc. and their the mixing oil product of API °≤25, the ends content >90wt% of wherein >=350 DEG C.

28. methods as described in aforementioned any one of claim, it is characterized in that, described heavy feed stock is coal-based feedstocks, it is selected from ripening degree R °≤0.85, sapropelinite as R °≤0.75 from the Mixture Density Networks of the humic coal of vitrinite content 30 ~ 70wt% and their different atures of coal.

29. the method for claim 1, is characterized in that, described heavy feed stock is organism-based raw material, and it is selected from the high heating value organic-biological matter of hydrogen content >=6.5wt%, oxygen level≤30%.

30. methods as described in aforementioned any one of claim, it is characterized in that, described heavy feed stock is mixed base raw material, and it is any mixture of three class heavy feed stocks of oil base as claimed in claim 25, as claimed in claim 26 bio-based coal-based, as claimed in claim 27.

31. 1 kinds for implementing the device of the method as described in any one of the claims, this device comprises following three technique units at least successively: catalysis fluid prepares unit, unit prepared by catalysis slurry and hydrogenation lighting reaction member.

32. devices as claimed in claim 31, wherein prepare in unit and hydrogenation lighting reaction member at catalysis slurry and carry out respectively using catalysis fluid dissolve, disperse and/or dilute also again the step of treated obtained heavy feed stock catalysis slurry to heavy feed stock and described heavy feed stock catalysis slurry carried out to the step of catalysis and hydrogen supply under hydrogenation conditions.

33. devices as described in aforementioned any one of claim, described device comprises at least five technique units successively, namely heavy feed stock preprocessing unit, catalysis fluid prepares unit, unit prepared by catalysis slurry, hydrogenation lighting reaction member, product postpositive disposal unit, thus produces lighting distillate and the splitting gas of such as≤350 DEG C.

34. devices as described in aforementioned any one of claim, it is characterized in that, comprise hydrogenator at described hydrogenation lighting reaction member, this reactor be selected from tubular reactor, go back Empty reactor, one or more in full back-mixing loop reactor, trickle-bed reactor, reverse convection formula reactor, slurry bed reactor, suspended-bed reactor or down-hole reactor.

35. devices as described in aforementioned any one of claim, it is characterized in that, described hydrogenator is the reactor being arranged at down-hole.

36. 1 kinds of catalysis fluids, it is characterized in that, described catalysis fluid comprises or is made up of following component: multi-component solvent, multi-element metal compound, complexing agent and optional complexing auxiliary agent containing two or more metallic element, the total content of wherein said metallic element in catalysis fluid is the 0.05wt%-5.0wt% of described catalysis fluid and described multi-element metal compound and complexing agent form complex compound or inner complex.

37. catalysis fluids as claimed in claim 36, it is characterized in that, described metallic element chosen from Fe, nickel, molybdenum, copper, zinc, tin, aluminium, tungsten, manganese, titanium, vanadium, chromium, cobalt, gold, cadmium, mercury, cerium and lanthanide series rare-earth elements, be preferably selected from iron, nickel, molybdenum, tungsten, titanium, zinc, aluminium and lanthanide series rare-earth elements, particularly chosen from Fe, nickel, aluminium, titanium and lanthanide series rare-earth elements.

38. catalysis fluids as described in aforementioned any one of claim, it is characterized in that, with the weighing scale of all metallic elements of multi-element metal compound, iron, aluminium and/or titanium elements (preferred ferro element) content are >50wt%, preferably >65wt%, particularly >70wt% and such as 70wt-80wt%, and the content of lanthanide series rare-earth elements is based on the weighing scale 0 ~ 5wt% of all metallic elements, preferably 0.1 ~ 3wt%, more preferably 0.1 ~ 1wt% and particularly 0.2 ~ 0.5wt%.

39. catalysis fluids as described in aforementioned any one of claim, is characterized in that, average fragrant rate fa>=0.60 that described solvent has, density>=0.95g/cm ³with Fan Shi viscosity>=5MPas(50 DEG C), the total content≤8.0wt% of organic heteroatoms N, S, O wherein in solvent.

40. catalysis fluids as described in aforementioned any one of claim, it is characterized in that, described solvent comprises the neutral component of >40 % by weight, the acidic components of 5 % by weight ~ 25 % by weight, the basic component of 5 % by weight ~ 25 % by weight and the ionic liquid of 5 % by weight ~ 15 % by weight.

41. catalysis fluids as claimed in claim 40, is characterized in that, described acidic components be selected from phenol, C3-C4 alkylphenol, naphthols and indenols, high carbolic oil etc. one or more, preferably two or more.

42. catalysis fluids as claimed in claim 40, is characterized in that, described basic component be selected from nitrogen heterocyclics such as phenyl amines, quinoline, indoles, pyridine, acridine etc. one or more, preferably two or more.

43. catalysis fluids as claimed in claim 40, is characterized in that, described ionic liquid be selected from imidazole salt, pyridine salt, quaternary ammonium salt and season phosphonium salt class etc. one or more, preferably two or more.

44. catalysis fluids as claimed in claim 40, it is characterized in that, described neutral component is selected from containing one or more in the polycyclic aromatic hydrocarbons wet goods of the heavy arene class oil of heavy arene content >=50wt%, polycyclic aromatic hydrocarbons, partly or entirely hydrogenation, preferably two or more.

45. catalysis fluids as claimed in claim 40, is characterized in that, comprise heavy arene class oil, preferably account for the base solvent oil of the heavy arene class oil of the 60wt%-90wt% of solvent total amount as solvent in described solvent.

46. catalysis fluids as described in aforementioned any one of claim, it is characterized in that, described complexing agent be selected from comprise heteroatoms as the heterogeneous ring compound (such as have 6-40 or 6-30 carbon atom) of N, O or S and its can be optionally substituted (as hydroxyl or sulfydryl), C ₁-C ₁₈fatty alcohol, aliphatic amine, aliphatic carboxylic acid and aliphatic sulfonic acid and its can be optionally substituted with one or more hydroxyl separately, carboxyl or sulfydryl replace, and thiocarbamide or thiourea derivative.

47. catalysis fluids as claimed in claim 46, is characterized in that, described complexing agent is selected from these one or more following: 1,10-phenanthroline, EDTA, dimercaprol dimercaptopropanol, Sodium Dimercapto Sulfonate, mercaptoethylamine, Thiovanic acid, thiocarbamide, oxine.

48. catalysis fluids as described in aforementioned any one of claim, is characterized in that, described complexing auxiliary agent for being selected from prussiate, citric acid, tartrate, oxalic acid, sulphosalicylic acid, trolamine, sodium alkoxide, methyl silicon sodium alcoholate, NaOH, KOH one or more.

49. 1 kinds of heavy feed stock catalysis slurries, it is characterized in that, it is dissolved heavy feed stock by the catalysis fluid as described in any one of claim 36 to 48, disperse and/or is diluted, and obtains after treatment again, and it has Fan Shi viscosity≤2000MPas(80 DEG C), quiet shearing stress≤35MPam ^-2(80 DEG C) and stabilization of industry are than>=0.80.

50. catalysis slurries as claimed in claim 49, it is characterized in that, this slurry is homogeneous stability on colloid yardstick.

51. catalysis slurries as described in claim 49 or 50, it is characterized in that, in described catalysis slurry, the blending ratio of oil base heavy feed stock and catalysis fluid is 40 ~ 70wt%:60 ~ 30wt%, coal-based or bio-based heavy feed stock and catalysis fluid the blending ratio of powder is 30 ~ 55wt%:70 ~ 45wt%, or the blending ratio of mixed base heavy feed stock and catalysis fluid is 40 ~ 70wt%:60 ~ 30wt%.