CN1446888A - Suspension bed hydrocracking technique for producing gasoline with high octane number and diesel oil with high cetane number simultaneously - Google Patents

Suspension bed hydrocracking technique for producing gasoline with high octane number and diesel oil with high cetane number simultaneously Download PDF

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CN1446888A
CN1446888A CN 03112099 CN03112099A CN1446888A CN 1446888 A CN1446888 A CN 1446888A CN 03112099 CN03112099 CN 03112099 CN 03112099 A CN03112099 A CN 03112099A CN 1446888 A CN1446888 A CN 1446888A
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reactor
floating bed
hydrogen
bed hydrocracking
technology
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周家顺
阙国和
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China University of Petroleum East China
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China University of Petroleum East China
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Abstract

A suspension-bed hydrocracking process for preparing both the gasoline with high octane number and the diesel oil with high cetane number at same time includes adding the aqueous solution of alcohol, which contains catalytic active component and assistant and is used as high-dispersity catalyst, to heavy hydrocarbon as raw material, cracking to generate olefin while reaction of the olefin on alcohol to obtain the oxygen-contained compound with high octane number. and hydrocracking to obtain said diesel oil. Its advantages are high output rate and high quality of products.

Description

Can produce the floating bed hydrocracking technology of the high conversion of stop bracket gasoline and high hexadecane value diesel oil simultaneously
Technical field:
The invention belongs to the heavy oil hydroprocessing process in the petroleum refining process, also can be used for the hybrid process process of gelatin liquefaction process and coal and oil.
Background technology:
Producing stop bracket gasoline at present is to adopt different technological processs with high hexadecane value diesel oil:
(1) produces stop bracket gasoline
In China, the production of gasoline mainly relies on catalytic cracking process, 70% gasoline is arranged approximately from catalytic cracking process.Catalytic cracking process has with the distillate to be the fluid catalytic cracking process of raw material and to be the fluid catalytic cracking of heavy oil process of raw material with heavy oil, and they are referred to as catalytic cracking process.The catalyzer acidic zeolite that supports some rare earth elements commonly used in catalytic cracking process, what also have sieves as catalyzer (as patent US4859314) with nonzeolite.Traditional catalytic cracking process is to adopt to promote tubular reactor.In order to improve conversion of raw material and liquid yield, reduce olefin content in gasoline, the technology that has changes reactor into two sections placed in-line riser tubes (as Chinese patent application 00134054.9), is called two-stage catalytic cracking technology; Also have when adopting two-stage catalytic cracking, a hydrotreating reactor (as patent US5152883) is added in back at first section reactor, perhaps adds a hydrotreating reactor (as patent CA2356628 or Chinese patent application 99815275.7) respectively in the front and back of first section reactor.These effort finally can improve conversion of raw material and liquid yield, improve the content of isoparaffin in the gasoline, reduce olefin(e) centent, the octane value of product gasoline improves 1～2 unit, and the octane value RON of gasoline is generally about 90 ± 3, but liquid yield is lower, generally 75～80%.Diesel-fuel cetane number is about 30, and is lower.Do not have in the gasoline that the catalytic cracking process of hydrotreatment process produces, alkene, aromatic hydrocarbons, sulphur content do not reach the standard of clean gasoline, differ greatly with European II standard.This mainly is by the decision of the reaction mechanism of catalytic cracking process.
Catalytic cracking process is under the effect of molecular sieve catalyst and heat, makes the process of raw material generation cracking reaction and isomerization reaction, and the carbonium ion reaction mechanism is deferred in reaction.C in the gas of product 1, C 2Content be lower than C 3, C 4Content.The content height of alkene, aromatic hydrocarbons and isomery hydro carbons in the product, because the octane value of these hydro carbons is higher, cetane value is lower.Therefore, the gasoline octane rating that catalytic cracking process is produced is higher, can reach No. 90, and diesel-fuel cetane number is lower.Because the alkene instability, easily oxidized, so the stability of catalytically cracked gasoline, diesel oil is poor.
Production stop bracket gasoline method preferably is to add oxygenatedchemicals (ethers or alcohols) and isomeric alkane hydro carbons in gasoline.But rely on interpolation aromatic hydrocarbons component at present usually, increase the olefines components contents, also will add the higher lighter hydrocarbons of vapour pressure sometimes.Like this, though the octane value of gasoline reaches high grade, vapour pressure is higher, the content of alkene and aromatic hydrocarbons is higher.These all are scabrous problems in the present gasoline producing process.
(2) produce high hexadecane value diesel oil
High hexadecane value diesel oil need be produced (perhaps low cetane number diesel is through unifining process production) usually with the fixed bed hydrogenation cracking process.The catalyzer that hydrocracking process is commonly used is that Co-Mo-Ni-W isoreactivity component is supported on γ-Al 2O 3Or on the molecular sieve, the carbonium ion reaction mechanism is deferred in reaction, but variant again with catalytic cracking process.The alkene that generates in hydrocracking process is unlike in that works in the catalytic cracking process and continues isomerization and cracking, but saturated by hydrogenation.Sulfocompound, nitrogenous compound and undersaturated aromatic hydrocarbons in the while raw material are also by hydrogenation or partly by hydrogenation.Therefore, sulfide and nitrogen compound are less in the product of hydrocracking process, and alkene and aromatic hydrocarbons are less, and saturated hydrocarbons is many.Like this, the octane value of gasoline fraction is lower, has only about 70.The cetane value of diesel oil distillate is higher, can reach about 50 ± 5.As can be seen, the fixed bed hydrogenation cracking process can be produced the diesel oil of high hexadecane value, but can't produce stop bracket gasoline simultaneously.
(3) floating bed hydrocracking
Floating bed hydrocracking is meant that catalyzer is evenly dispersed in the raw material, is in the hydrocracking process of suspended state in reactor.Catalyzer commonly used has inorganic salt, organic salt or the heteropolyacid salt of transition element such as Co, Mo, Ni, Fe, W, Mn, and the aqueous solution of these materials or organic compound are dispersed in the raw material, have just formed the catalytic active substance of hydrocracking process of suspended bed.
Chinese patent application 95118354.0,96102879.3 is used the solution compositing catalyst that contains molybdenum, nickel, phosphorus; Chinese patent 96102880.7 uses the solution compositing catalyst that contains molybdenum, nickel, cobalt, phosphorus; Chinese patent 97121791.2 uses the mixed aqueous solution of nickelous nitrate, manganous nitrate, iron nitrate, Xiao Suangu as catalyzer; Chinese patent application 97121844.7 uses molybdenum, nickel, cobalt, the tungsten aqueous solution as catalyzer; Chinese patent 97121845.5 uses molybdenum, nickel, the cobalt aqueous solution as catalyzer; Chinese patent application 99113301.3 uses the aqueous solution of two or more metallic compounds in periodic table of elements VIB, VIIB and the group VIII as catalyzer, comprising the aqueous solution of molybdenum, nickel, cobalt, tungsten, chromium, iron; Suspension bed residual oil hydrogenation catalyzer in the Chinese patent application 00110715.1 uses the aqueous solution of molybdenum, nickel, phosphorus as catalyzer; Weight among the Chinese patent application 00110716.X, dreg-oil suspension bed catalyzer use the aqueous solution of molybdenum, nickel, phosphorus as catalyzer; The aqueous solution that adopts molybdenum, nickel, tungsten, cobalt in the Chinese patent application 00123153.7 is catalyzer; Chinese patent application 01109276.9 adopts the solution compositing catalyst of iron, nickel, cobalt, molybdenum.The common issue with that the catalyzer that relates in the above-mentioned patent application exists is: 1. catalyzer is the aqueous solution that contains metal, and raw material is a heavy raw oil, and the two is immiscible.Metallic catalyst constituents is difficult in the effect that reaches high dispersive in the heavy raw oil, and the utilization ratio of metallic catalyst constituents is low.2. aqueous catalyzer also must remove water by brute force stirring, shear agitation or after being distributed in the mink cell focus under the effect of tensio-active agent, with hydrogen partial pressure that improves reactive system or the Hydrobon catalyst of protecting post-processing unit.3. the disposable often use of the catalyzer of floating bed hydrocracking, the aqueous solution that uses molybdenum, nickel, cobalt, tungsten etc. is as catalyzer, and cost is too high, is restricted in industrial application.
Adopt pressed powder, water-soluble catalyst or oil-soluble catalyst in the Chinese patent application 01106011.5.Chinese patent application 01106017.4 adopts one or more oil solubles and water-soluble catalyst, adds solid powder th-1 catalyst simultaneously.Only with regard to fine catalyst, the powder of adding can be used as the place of sedimentation of coke in the reaction process, prevents to form big lump coke.If the powder that adds is a coal dust, can reach coal and the oily effect of refining altogether, but the problem that it exists is: 1. a large amount of powder causes deposition and obstruction easily in unit such as reactor, separator, separation column.2. a large amount of powder causes wearing and tearing to fresh feed pump, discharging pump, liquid reducing valve etc.Just because of these insoluble practical problemss, but not technical reason, people have just begun to use the floating bed hydrocracking research of liquid catalyst.
Chinese patent application 00110711.9 is used one or more metals in periodic table of elements VIB, VIIB and the group VIII and is contained the formed complex compound of heteroatomic heterocycle sulfo group compound, and metallic element wherein includes iron, cobalt, nickel, chromium, molybdenum, tungsten; Chinese patent application 00123148.0 is used the promotor of one or more compounds of metal in the periodic table of elements group VIII as catalyzer in the floating bed hydrogenation process, wherein includes muriate, nitrate, prussiate, oxide compound, halohydrocarbon, ethers, amine, quinones, the azo class of Ru, Rh, Pd, Os, Ir, Pt and contains the organism of carbonyl, thiocarbonyl group.Chinese patent application 01106013.1 is about a kind of hydrocracking catalyst for oil-soluble suspension bed, two or more metals in use periodic table of elements VIB, VIIB and the group VIII and the compound of phenylhydroxylamine and derivatives reaction gained thereof, wherein metallic element includes molybdenum and tungsten.With the metallic compound that contains organic group as disperse type catalyzer, the dispersion effect in mink cell focus be improved significantly because it is a kind of oil-soluble material, can dissolve each other with stock oil.Directly as product, do not need to separate after the organic group reaction.But the problem that it exists is: relative and atoms metal, the molecular weight of organic group is very big, adds the very metal of small concentration, needs to add relatively large organometallic compound.After organometallic compound enters into reactive system, just be decomposed, the main effect of organic group is the dispersed metal ion.Use the effect of oil-soluble catalyst better, but the cost of catalyzer also is higher than water-soluble catalyst far away than water-soluble catalyst.
At the floating bed hydrocracking process aspect, Chinese patent application 99113301.3 discloses a kind of processing method of handling inferior heavy, residual oil, the steps include: small amounts of water soluble metal catalyst and heavy, residual oil raw material are sent into the floating bed hydrogenation reactor after mixing; Isolate distillate and unconverted tail oil from the material that suspended-bed reactor comes out through tripping device; Distillate advances the further hydrogenation of fixed bed hydrogenation device; Part or all of tail oil be as the solvent extraction raw material, and obtaining more light ends oil, the pitch that removes is directly as the blend component of qualified product or other trade mark.The catalyzer that uses in this processing method is water-soluble catalyst, and from the material that the floating bed hydrogenation reactor comes out, after high-pressure separator was separated, lighting end entered fixed bed hydrogenation refining reaction device, tail oil C 2～C 6Normal paraffin carries out solvent deasphalting.Water in the water-soluble catalyst can enter into hydrofining reactor together along with the lighting end that high-pressure separator is told, and can shorten the running period of hydrofining reactor like this., the catalyzer that add higher when the transformation efficiency of stock oil more for a long time, granules of catalyst in the tail oil and coke granule can have influence on the bituminous ductility.
Chinese patent application 00110720.8 discloses a kind of heavy hydrocarbon feeding and hydrogenating process, it comprises: heavier hydrocarbon feeds is under the condition that hydrogen exists, at first in suspended-bed reactor, relax the thermally splitting pre-treatment, the gained reactant is under the condition that hydrogen exists, enter fixed-bed reactor and contact, carry out fixed bed hydrogenation and handle with catalyzer.Be provided with separator behind suspended-bed reactor, catalyzer that adds in the suspended-bed reactor and additive are discharged from the bottom of this separator, and gas and product liquid enter into fixed bed hydrogenation refining reaction device.Suspended-bed reactor is the up-flow reactor that goes out on advancing under, and used catalyzer or additive are useless hydrogenation catalysts, and promptly solid particle catalyst stops up reactor in the reactor bottom deposition easily.The separator of suspended-bed reactor back; also be difficult to gas, liquid are separated with solid particulate; owing to separate incomplete and entrainment, can enter in the fixed bed hydrogenation refining reaction device in company with liquid product by a part of solid particulate, easily reaction bed is stopped up.
Chinese patent application 00123992.9 discloses a kind of normal pressure suspension bed hydrogenation process that adopts liquid multiple-metal catalyst, the reactor that adopts is full backmixed reactor, slurries in the reactor are constantly to be circulated to keep full back-mixing state by recycle pump, the material of reaction enters the floating bed hydrocracking reactor by the bottom, the effluent of reactor head enters high pressure hot separator to be separated, vapor phase stream enters online hydrofining reactor, liquid phase stream enters the low pressure separation system, and isolated liquid phase stream also enters online fixed bed hydrogenation refining reaction device.The full back-mixing mode of reactor relies on recycle pump to keep in this technology, and existing solid particulate in the material, the hydrogen that dissolved is arranged again and be inhaled into is easy to recycle pump is caused wearing and tearing and produces vapour lock.This recycle pump is to work under the high temperature and high pressure, keep the long-term operation of reactor, and certain difficulty is arranged.The high pressure hot separator that this technology is used can be brought into the dispersed catalyzer of floating bed hydrogenation in the fixed bed hydrogenation refining reaction device owing to entrainment equally.
Chinese patent application 00110715.1 discloses a kind of heavy, residual oil treatment process, this method comprises: stock oil is with after recycle hydrogen mixes, enter fixed bed hydrogenation pretreatment reaction device, contact with catalyzer, directly enter the suspension bed residual oil hydrogenation device after the reaction and carry out the high conversion conversion, after reaction finishes, generate oil and leave suspended-bed reactor and enter downstream unit and further handle.Adopting the purpose of fixed bed hydrogenation pretreatment reaction device in this processing method is colloid, the bituminous matter of taking off the easy green coke in the charging, to prolong the running life of suspension bed residual oil hydrogenation device.We know that floating bed hydrocracking technology usually is used for handling the reluctant raw material of fixed bed hydrogenation technology, as the raw material of high carbon residue, high metal content.
Chinese patent application 00110716.X discloses a kind of heavy, residuum hydroconversion, this method comprises: reaction raw materials is at first under the condition that hydrogen exists, entering first section low temperature long residence time floating bed hydrogenation device handles, reaction effluent directly enters second section high temperature short residence time(SRT) floating bed hydrogenation device and carries out the high conversion reaction, fixed bed hydrogenation pretreatment reaction device, contact with catalyzer, directly enter the suspension bed residual oil hydrogenation device after the reaction and carry out the high conversion conversion, after reaction finishes, generate oil and leave suspended-bed reactor and enter downstream unit and further handle.
Chinese patent application 00123222.3 discloses a kind of processing method of handling inferior heavy, residual oil, and this method at first is dispersed in hydrogenation catalyst in the stock oil, enters multistage suspension bed hydroprocessing reactor then.Multistage suspension bed hydroprocessing reactor is one or more pyroreaction sections and one or more low-temp reaction section, and the pyroreaction section is positioned at before the low-temp reaction section and the low-temp reaction section is interspersed.The temperature of reaction of pyroreaction section is 400～500 ℃, and liquid hourly space velocity is 0.2～4.0h -1The temperature of reaction of low-temp reaction section is 300～420 ℃, and liquid hourly space velocity is 0.2～4.0h -1First section high temperature section of this technology is close with the liquid hourly space velocity of second section low-temperature zone, and first section temperature of reaction is higher than second section, coking easily comparatively speaking, and the 3rd section is the another one high temperature section.In first and second sections reacted materials, comprise lighter hydrocarbons, catalyzer and the coke granule of a large amount of hydrogen, cracking generation, can use the electric furnace heat temperature raising in the laboratory, and continue again to heat up with process furnace industrial, acquire a certain degree of difficulty.
Above-mentioned disclosed hydrocracking catalyst for suspension bed and floating bed hydrocracking technology, the focus of being paid close attention to mainly contains 2 points: the transformation efficiency that 1. improves heavier hydrocarbon feeds; 2. reduce green coke amount in the reaction process.Do not relate to the quality that improves the light-end products that generate after the feedstock conversion as yet, the operability of cost when the catalyzer that has is not considered practical application yet, some technical process also lacks to be considered the feasibility of industrial practical application.
Technology involved in the present invention is to defer to free radical reaction according to floating bed hydrocracking reaction, and reaction process is a kind ofly to turn to the master with hot tearing, and hydrogenation and isomery turn to auxilliary reaction mechanism and design.In hydrocracking process of suspended bed, the isomery hydro carbons is less in the product, and the product hydrogenation is incomplete, the olefin(e) centent height, and therefore, the octane value of gasoline component is not very low in the product, octane value RON is generally about 75.Diesel-fuel cetane number is higher, but is lower than the diesel-fuel cetane number of the fixed bed hydrogenation cracking process that uses same materials, generally about 40.By suitable catalyzer, improve the octane value of gasoline, just can produce stop bracket gasoline and high hexadecane value diesel oil simultaneously with the method for floating bed hydrocracking.In the technological process involved in the present invention, in raw material, add and contain the alcohol solution of catalytic activity thing and catalytic activity auxiliary agent as high dispersive type catalyzer, when raw material generation cracking generates alkene, the alkene of generation and the alcohols of interpolation are reacted, generate high-octane oxygenatedchemicals, both reduce the olefin(e) centent of gasoline, improved the octane value of gasoline again.Because catalyzer can dissolve each other with raw material, the dispersity in raw material is very high, the catalytic activity height, and the temperature of reaction is also high, and conversion of raw material and liquid yield are also just very high.And the diesel-fuel cetane number that hydrocracking process of suspended bed is produced was just higher originally, therefore can produce the purpose of stop bracket gasoline and high hexadecane value diesel oil simultaneously under very high feed stock conversion condition.
In the related scope of this patent, every disperse type catalyzer is suspended in the hydrocracking process in the reactant, all is called hydrocracking process of suspended bed, and whether be not limited to has filler or inner member in the type, structure, reactor of reactor.
Summary of the invention:
The present invention be directed to present catalytic cracking and produce the technology of gasoline and the deficiency that the technology of diesel oil is produced in hydrocracking, reaction rule according to hydrocracking process of suspended bed, and the floating bed hydrocracking technology that can produce stop bracket gasoline and high hexadecane value diesel oil simultaneously that proposes is called for short HHH technology.This technology can solve the low problem of content of olefin in gasoline height, diesel cetane-number that catalytic cracking process is produced, and can solve the low problem of gasoline octane rating that hydrocracking process is produced simultaneously again.
HHH technological process provided by the present invention is raw material with the heavy hydrocarbon, in the presence of the mixed gas of high dispersive type catalyzer, hydrogen or hydrogen and other gas, under higher pressure and temperature effect, produce stop bracket gasoline and high hexadecane value diesel oil simultaneously, and conversion of raw material is very high.This technology comprises raw materials pretreatment unit, three unit of floating bed hydrocracking reaction member and product postprocessing unit at least.The major parts of its floating bed hydrocracking reaction member is the floating bed hydrocracking reactor, and this floating bed hydrocracking reaction member comprises following consecutive steps:
(a) mixed gas of heavier hydrocarbon feeds, high dispersive type catalyzer, hydrogen or hydrogen and other gas of crossing through the raw materials pretreatment cell processing, mix after entering into the floating bed hydrocracking reactor after the mixing or entering into the floating bed hydrocracking reactor, form the charging of floating bed hydrocracking reactor.
(b) charging of floating bed hydrocracking reactor is reacted in the floating bed hydrocracking reactor, forms the floating bed hydrocracking product.
(c) the floating bed hydrocracking product is discharged from the floating bed hydrocracking reactor, enters into the product postprocessing unit and handles.
HHH technology provided by the invention, the catalyzer that uses is high dispersive type catalyzer, wherein contains catalytic activity thing, catalytic activity auxiliary agent, alcohols and water.After heavier hydrocarbon feeds and the high dispersive type catalyst mix, high dispersive type catalyzer high dispersing is in suspended state in heavier hydrocarbon feeds.Under the floating bed hydrocracking reaction conditions, catalyzer is promoting the heavier hydrocarbon feeds cracked simultaneously, and the alkene that also promotes alcohols and heavier hydrocarbon feeds cracking to generate reacts, and generates octane value RON at 110 left and right sides oxygenatedchemicalss.So both reduce the content of alkene, improved the octane value and the stability of gasoline again.Because the diesel-fuel cetane number that hydrocracking process of suspended bed is produced was just higher originally, again because the dispersity of catalyzer in heavy hydrocarbon feedstocks is very high, the catalytic activity height, the temperature of reaction is also high, and conversion of raw material and liquid yield are also just very high.So just reached with very high feed stock conversion, produced the purpose of stop bracket gasoline and high hexadecane value diesel oil simultaneously.
Description of drawings:
Accompanying drawing is the principle schematic of a kind of preferred embodiment of floating bed hydrocracking technology proposed by the invention.
Embodiment:
Floating bed hydrocracking technology usually is used for the processing of heavier hydrocarbon feeds, catalyzer is used the aqueous solution, organic compound, inorganic or organic complex compound, the heteropolyacid salt of transition element such as Co, Mo, Ni, Fe, W, Mn always, natural mineral dust, coal dust, special earth powder and the spent catalyst powder of other technological process.These said catalyzer are dispersed in the heavier hydrocarbon feeds, and major part is in suspended state.According to reaction bed is that fixed just is called fixed bed; Reaction bed be fluidized state just be called fluidized-bed.Reaction bed is to be in suspended state, just is called suspension bed naturally.
Catalyzer mainly plays two effects in hydrocracking process of suspended bed: 1. promote hydrogen transference, produce the condensation that hydroperoxyl radical suppresses the condensed ring free radical of cracking reaction generation, just suppress the generation of coke; 2. as the medium that carries coke.Certainly lead to coke in the reaction process, if do not carry its place, they will flock together and form bulk, finally stop up reactor.Catalyzer adds reactor and the subsequent disposal system equally also can stopped up too much.
Think that usually radical reaction mechanism is deferred in the floating bed hydrocracking reaction, reaction process is a kind of based on heat cracking reaction, and hydrogenation reaction and isomerization reaction are the process of assisting.In hydrocracking process of suspended bed, the isomerisation degree of product is very low, because used catalyzer usually is no acidic, even acidity is arranged, the ratio of catalyzer and stock oil is too little, and the ratio of isomerization reaction is also well below the ratio of heat cracking reaction.Therefore, in hydrocracking process of suspended bed, the cetane value of diesel oil distillate is higher, contains a large amount of alkene in the gasoline fraction.
Describe the present invention in detail below in conjunction with drawings and Examples.Accompanying drawing is a kind of synoptic diagram of preferred embodiment wherein.HHH technological process provided by the present invention is to be raw material with the heavy hydrocarbon, in the presence of the mixed gas of high dispersive type catalyzer, hydrogen or hydrogen and other gas, under higher pressure and temperature effect, the process of hydrocracking reaction takes place.Contain alcohols in the high dispersive type catalyzer that adopts, when this catalyzer mixed with heavier hydrocarbon feeds, they were dispersed in the heavier hydrocarbon feeds with high dispersity.Catalyzer is in the catalysis heavier hydrocarbon feeds cracked while, and also the alkene of catalyzing alcohols and heavier hydrocarbon feeds cracking generation reacts, and generates oxygenatedchemicals.The octane value RON of these oxygenatedchemicalss is generally about 110.Because the diesel-fuel cetane number that hydrocracking process of suspended bed is produced was just higher originally, therefore can produce stop bracket gasoline and high hexadecane value diesel oil simultaneously.
HHH technology involved in the present invention comprises raw materials pretreatment unit, three unit of floating bed hydrocracking reaction member and product postprocessing unit at least.The raw materials pretreatment unit is meant that raw material flows on the route of process, is positioned at the summation of all devices before the floating bed hydrocracking reaction member opening for feed, as mixing tank, process furnace, interchanger, hydrogenation pretreatment reaction device, pre-decarburizing reaction device etc.The unitary effect of raw materials pretreatment is to make charging (mixed gas of heavier hydrocarbon feeds, high dispersive type catalyzer, hydrogen or hydrogen and other gas) after entering the floating bed hydrocracking reaction member, reach the reaction conditions of effective generation hydrocracking reaction.In the raw materials pretreatment unit, enter from stock oil inlet (2) after heavier hydrocarbon feeds and the high dispersive type catalyst mix, with from the hydrogen partial of circulating hydrogen compressor (21) and hydrogen make-up inlet (1) or hydrogen with after the mixed gas of other gas mixes, enter into stock oil process furnace (4).The mixed gas of heavier hydrocarbon feeds, high dispersive type catalyzer, hydrogen partial or hydrogen and other gas that process stock oil process furnace (4) heated, enter into floating bed hydrogenation pretreatment reaction device (5), this reactor also is called first section floating bed hydrogenation reactor, enters into the stock oil opening for feed (7) of the floating bed hydrocracking reactor (6) of floating bed hydrocracking reaction member then.High dispersive type catalyzer also can mix with heavier hydrocarbon feeds in the outlet of stock oil process furnace (4).Floating bed hydrogenation pretreatment reaction device (5) is an optional response device, can not use this reactor.From circulating hydrogen compressor (21) and another part hydrogen of hydrogen make-up inlet (1) or the mixed gas of hydrogen and other gas, enter into hydrogen process furnace (3), after heating, enter into the hydrogen feed mouth (8) of the floating bed hydrocracking reactor (6) of floating bed hydrocracking reaction member.
In the raw materials pretreatment unit, need a process furnace at least and come heating raw, stock oil and hydrogen can adopt same process furnace to heat, but preferably adopt two process furnace to heat respectively.An optional floating bed hydrogenation pretreatment reaction device (5) can also be arranged in the raw materials pretreatment unit, and this reactor is littler than floating bed hydrocracking reactor (6) volume of floating bed hydrocracking reaction member, length-to-diameter ratio is big, temperature of reaction is high, liquid-volume hourly space velocity (LHSV) is high.The upflowing plug flow reactor that the preferably two or more reactor parallel connections of floating bed hydrogenation pretreatment reaction device (5) are used alternatingly.Because easy coking under the high temperature when one of them coking and blocking, can be switched and use other parallel reactor.Floating bed hydrogenation pretreatment reaction device (5) also can be full back-mixing loop reactor, trickle-bed reactor, reverse convection type reactor, moving-burden bed reactor, expanded bed reactor and slurry bed reactor.
Floating bed hydrogenation pretreatment reaction device (5) turns round under the reaction conditions between high temperature, short time, can improve the cracking rate of raw material, reduces the generation of coke.Under identical feed stock conversion, the reaction conditions of the floating bed hydrocracking reactor (6) of floating bed hydrocracking reaction member can relax, thereby can prolong the on-stream time of device.The operational condition of floating bed hydrogenation pretreatment reaction device (5) is: preferred hydrogen partial pressure is 2MPa～30MPa, and preferred hydrogen partial pressure is 8MPa～16MPa; The preferred volumetric spaces speed of heavier hydrocarbon feeds in reactor is 4.01h -1～100h -1, preferred space velocity is 5.0h -1～25h -1Preferred temperature of reaction is 360 ℃～530 ℃, and the temperature of reaction in the preferred reactor is 450 ℃～505 ℃.
The product postprocessing unit is meant the summation of all devices on the product discharge port that is positioned at the floating bed hydrocracking reaction member route afterwards, the mobile process of product, takes off slag tower etc. as separator, interchanger, separation column, gas stripping column, stabilizer tower, hydrofining reactor, catalyst cracker, centrifuge separator, solid-liquid separator, tail oil coking tower, solvent.At least to include separator that the product that will produce in the floating bed hydrocracking reaction member carries out gas-liquid separation in the product postprocessing unit, will compress circulating hydrogen compressor that supercharging recirculation uses behind the unreacted hydrogen upgrading, product liquid be carried out fractionation to obtain the separation column of gasoline and diesel oil.
The unitary effect of product postprocessing is that the product that comes out from the floating bed hydrocracking reaction member is made with extra care, separated or transforms, with the raw material that obtains can be used as the component of commodity or transforming.In the product postprocessing unit, benzoline product from the top discharge mouth (11) of the floating bed hydrocracking reactor (6) of floating bed hydrocracking reaction member, be separated into gaseous component and liquid composition through separator (12), this part gaseous component is the lighting end that separated with separator (12) two-stage through floating bed hydrogenation reactor (6), substantially do not contain granules of catalyst, this part lighting end enters into hydrofining reactor (14) and carries out hydrofining.Liquid composition is discharged from the bottom of separator (12), after product from the lower discharge port (10) of the floating bed hydrocracking reactor (6) of floating bed hydrocracking reaction member mixes, enter into fractionator (13), this fractionator can be gas stripping column, atmospheric fractional tower and vacuum fractionation tower.The isolated light constituent of fractionator (13) enters into hydrofining reactor (14), isolated heavy constituent with from (29) take off residue supplementing solvent, recovery solvent from solvent recovery tower (17) after, enter solid-liquid separator (15).Taking off the residue supplementing solvent and can take from the lighting end of separation column (20) (23) (24) and (25) from (29).Component from removing of coming out of solid-liquid separator (15) after residual enters into solvent recovery tower (17).Tail oil in the solvent recovery tower (17) behind the recovery solvent is discharged from (27).From the residue that solid-liquid separator (15) comes out, enter residue coking tower (16), the light constituent that residue coking tower (16) produces enters into hydrofining reactor (14), and the residue of generation is discharged from (28).The product that hydrofining reactor (14) produces is separated into liquid hydrocarbon (23), gasoline (24), diesel oil (25) and wax oil (26) by separator (19) and separation column (20).The isolated gas of separator (19) enters into circulating hydrogen compressor (21) and exhaust port (22) after removing hydrogen sulfide and ammonia through deammoniation tower (18).
HHH technology involved in the present invention, be a kind of under hydrogen atmosphere and in the presence of the dispersed catalysts, the floating bed hydrocracking technology of heavier hydrocarbon feeds lighting, the operational condition of the floating bed hydrocracking reaction member of this technology is: preferred hydrogen partial pressure is 2MPa～30MPa, and preferred hydrogen partial pressure is 8MPa～16MPa; The preferred volumetric spaces speed of heavier hydrocarbon feeds in reactor is 0.1h -1～10h -1, preferred space velocity is 0.4h -1～2.0h -1Preferred temperature of reaction is 350 ℃～520 ℃, and the temperature of reaction in the preferred reactor is 400 ℃～470 ℃; The addition that contains the alcohol solution of high dispersive type catalytic activity thing and catalytic activity auxiliary agent, account for total feed 0～85%, preferred ratio is 2～20%; (0 ℃, the 1 normal atmosphere) volume of heavier hydrocarbon feeds and the volume ratio of hydrogen are 1: 100～1: 10000 under the standard state.
The floating bed hydrocracking reaction member is meant on the route of feedstream through passing through, and is positioned at after the raw materials pretreatment unit, and is positioned at a product postprocessing unit processing unit before, and its major equipment is floating bed hydrocracking reactor (6).The mixed gas of heavier hydrocarbon feeds, high dispersive type catalyzer, hydrogen partial or hydrogen and other gas mixes, after the raw materials pretreatment cell processing, be warmed up to can make the temperature that hydrocracking takes place after, enter into inside reactor from the stock oil opening for feed (7) of the floating bed hydrocracking reactor (6) of floating bed hydrocracking reaction member; The mixed gas of another part hydrogen or hydrogen and other gas enters reactor by hydrogen feed mouth (8), and through hydrogen sparger (9) this part hydrogen is distributed in the reactor.Require this hydrogen partial to have certain temperature, make that this part hydrogen enters in the reactor after, the medial temperature in the reactor can reach the condition of effective generation hydrocracking.Enter into heavier hydrocarbon feeds, dispersed catalysts, hydrogen or the hydrogen of inside reactor and the mixed gas of other gas, be in the back-mixing state in reactor, temperature is even relatively.Reacted product, used granules of catalyst and unreacted hydrogen are discharged to the product postprocessing unit from discharge port (10) and (11).
The reactor of the floating bed hydrocracking reaction member of the HHH technology that the present invention relates to can be the reactor of any kind.All can make reactant mix, can make maximum temperature and minimum response temperature in the reactor to differ less than 20 ℃ and can make the catalytic activity thing of high dispersive be suspended in the reactor of any kind in the reactant, can be applied to this technology.Reactor comprises trickle-bed reactor, reverse convection type reactor, moving-burden bed reactor, expanded bed reactor and slurry bed reactor.No matter adopt the reactor of which kind of type, reactor has a discharge gate at least, so that discharge the product of reactor bottom off and on or continuously or be deposited on the catalyzer and the coke granule of reactor bottom, perhaps off and on or discharge the product or the settling of reaction continuously from reactor bottom.
The floating bed hydrocracking reaction member of HHH technology provided by the invention, it is heavier hydrocarbon feeds generation cracked main place, splitting this reaction member and other technology merges, for example merge: the floating bed hydrocracking technology of other type with following technology, multistage suspension bed hydroprocessing cracking technology, hydrodesulfurization, hydrodenitrification technology, hydrogenation deoxidation technology, hydrodemetallation (HDM) technology, hydrogenation takes off carbon residue technology, hydroisomerisation process, hydrofining technology, hydrocracking process, hydrodewaxing technology, face the hydrogen condensation process, hydrovisbreaking technology, face hydrogen coking process or other one or more combination process in technological process that added hydrogen exists, perhaps above-mentioned one or more technologies and catalytic reforming process are arranged, solvent deasphalting technology, solvent takes off carbon residue technology, solvent extraction process, solvent treatment technology, viscosity breaking technology, thermocracking process, delay coking process, catalytic cracking process, the multistage catalytic cracking process, overcritical accurate separating technology or other do not have one or more the combination process in the technology that added hydrogen exists.Perhaps before or after this reaction member, add treater or separator, also within the scope of the invention.This reaction member comprises following consecutive steps,
(a) mixed gas of heavier hydrocarbon feeds, hydrogen or hydrogen and other gas, high dispersive type catalyst mix form the charging of floating bed hydrocracking reactor.Heavier hydrocarbon feeds is with after the alcohol solution that contains decentralized catalytic activity thing, hydrogen partial mix, by interchanger or process furnace heating, be warmed up to 350 ℃～520 ℃ after, enter in the reactor.Can take the mode of heating separately by some hydrogen, mix with above-mentioned raw materials in reactor the heating back.This part separately temperature of the hydrogen of heating will be controlled, make that all chargings mix in reactor after, the interior medial temperature of reactor does not exceed 350 ℃～520 ℃ scope.
(b) charging of floating bed hydrocracking reactor is reacted in the floating bed hydrogenation reactor, forms the floating bed hydrocracking product.Under the condition of charging 350 ℃～520 ℃ of medial temperatures in reactor, with 0.1h -1～10h -1Space velocity pass through reactor.The condensation green coke reaction of the reaction of the alkene of the hydrogenation reaction of the olefin hydrocarbon molecules that in reactor, the macromolecular scission reaction of hydro carbons takes place, partly generates, part generation and the alcohols of adding and hydrocarbon molecules.The coke that generates is wrapped on the high dispersive catalytic activity thing, attached on the inert filler or flock together and form the coke of larger particles.
(c) the floating bed hydrocracking product is discharged from reactor.For trickle-bed reactor, product can all be discharged from reactor bottom.For reverse convection type reactor, moving-burden bed reactor, expanded bed reactor and slurry bed reactor, can discharge from top and bottom.The product that discharge at the top comprises most of responseless hydrogen, and the product that discharge the bottom comprises most of reacted granules of catalyst.From the product that reactor is discharged, what possible processing unit or separating unit of can no longer holding the post again is to be further processed and to separate.
The used heavier hydrocarbon feeds of HHH technology that the present invention relates to, be atmospheric gas oil, vacuum gas oil, atmospheric residue, vacuum residuum, the product or the product heavy oil of crude oil, synthetic crude, deasphalted oil, other process (as UOP RCD Unibon process, viscosity breaking process), contain one or several the mixture in the coal dust slurry of coal tar or gas oil, perhaps above-mentioned one or several and boiling point are lower than the mixture of 400 ℃ lightweight oil.The common feature of these hydrocarbon raw materials is the content of their boiling points of containing at 350 ℃～650 ℃ cut, is not less than 10%, and preferred condition is not less than 30% for this content.
In HHH technology provided by the invention, enter into that the material of reaction member is made up of the mixed gas of heavier hydrocarbon feeds, high dispersive type catalyzer, hydrogen or hydrogen and other gas.High dispersive type catalyzer is meant in all materials that enter the floating bed hydrocracking reaction member, do not comprise under heavier hydrocarbon feeds, hydrogen and the atmospheric pressure at room summation for all other materials of the material of gas.
The used high dispersive type catalyzer of the present invention is made up of catalytic activity thing, catalytic activity auxiliary agent, alcohols and water.The catalytic activity auxiliary agent is meant in the high dispersive type catalyzer, the summation that does not comprise other all components of catalytic activity thing, alcohols and water comprises vulcanizing agent, acid cracking agent, basic cracking agent, emulsifying agent, vapour pressure improving agent, specific conductivity improving agent, refractive index improving agent, surface tension improving agent etc.
Alcohols in the high dispersive type catalyzer is one or more a mixture of the alcohols of no more than 10 carbon atoms in the molecule, and preferred alcohols is methyl alcohol and ethanol.
Catalytic activity thing in the high dispersive type catalyzer, be that periodic table of elements IA family arrives in VIIB family (first subgroup to the, seven subgroups) and the VIII family (the 8th family) to VA family (first main group to the, five main groups), IB family, all can be with ionic condition, molecularity, hydration status, complex status, polymolecular polymerization state, forms one or more of inorganic salts, organic salt, complex compound or inner complex of the metal of true solution, milk sap or suspension with the aqueous solution of alcohols or alcohols.Preferably one or more mixing of the inorganic salt of lanthanum, cerium, titanium, vanadium, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, copper, zinc, silver, gold, cadmium, mercury, tin, organic salt, complex compound or inner complex.The material that more preferably contains copper and zinc element.The material that most preferably contains cupric nitrate.
This technology is development on traditional floating bed hydrocracking technology basis, and its technical characterstic reaches with traditional floating bed hydrocracking technology difference and is:
(a) HHH technology involved in the present invention, variant with the reaction principle of existing floating bed hydrocracking technology.Existing floating bed hydrocracking technology is to utilize the effect of disperse type catalyzer, produces activation hydrogen, and the generation that comes coke in the inhibited reaction process promotes the lighting of raw material.Reaction process is thermal process reactor basically, and the degree of unsaturation of product is big, the olefin(e) centent height.The octane value of gasoline is low, and about 70～75; Technology involved in the present invention utilizing disperse type catalyzer to promote cracked simultaneously, also promotes the alkene of generation and the alcohols of adding to react, generate high-octane oxygenatedchemicals, reach reduction alkene, the purpose of boosting of octane rating, the octane value RON of gasoline reaches more than 85.
(b) HHH technological process involved in the present invention is different with flowing to of the structure of the reactor of existing floating bed hydrocracking technology and material.Existing floating bed hydrocracking technology, the normal sky tube up-flow reactor that adopts, just material enters from the lower end of reactor, flows out from top.Also have and use the up-flow reactor that relies on recycle pump to keep full back-mixing state; And technological process involved in the present invention can be used any type of reactor.The preferred full back-mixing loop reactor of discharge simultaneously that uses up and down, also can adopt the full backmixed reactor of empty cartridge type, or employing is filled with the trickle-bed reactor of filler, as long as disperse type catalyzer is in suspended state in reactant, all can be used for the described hydrocracking process of suspended bed of patent of the present invention.
(c) the used catalyzer of HHH technological process involved in the present invention, be different from existing water-soluble and oil soluble liquid catalyzer, it is a kind of alcohol solution that contains metal active component, catalytic activity auxiliary agent, it both can dissolve each other with water, can dissolve each other with oil again, be a kind of water oil mutual solubility liquid catalyst.This catalyzer needs brute force to mix unlike water-soluble catalyst, only utilizes the pipeline static mixer just can reach the water-soluble catalyst high degree of dispersion that is beyond one's reach, and alcohols does not need to remove yet.Simultaneously, it is expensive unlike oil-soluble catalyst again.After being worth lower alcohols and participating in reaction, gasoline that generating value is higher or diesel oil have reduced the cost of catalyzer.Alcohols participates in reaction simultaneously, also has the effect of hydrogen supply agent, can reduce the hydrogen consumption of reaction process, reduces running cost.
(d) HHH technological process involved in the present invention, owing to do not have water or seldom water is arranged in the catalyzer, raw material does not need processed in the raw materials pretreatment unit; Catalyzer in the unitary hydrofining reactor of product postprocessing can be owing to the influence of water reduction of service life.
(e) effect of the unitary hydrofining reactor of product postprocessing in the HHH technological process involved in the present invention has difference with existing technology.Hydrofining reactor in the existing technology is the benzoline in the product that is used for producing in the refining reaction unit, benzoline mainly comes self-heating high score or hot high score and follow-up low pressure separating device, and the hydrofining reactor in this technology is except that having above-mentioned effect, also be used for benzoline in the conversion process again in the refined products post-processing unit, produce after the tailings coking as solvent removal benzoline, and can reclaim light naphtha residual in the tailings simultaneously.
(f) first section reactor of the floating bed hydrogenation pretreatment reaction device in the raw materials pretreatment unit in the HHH technological process involved in the present invention and existing multistage suspension bed hydroprocessing cracking case or the fixed bed pretreatment reaction device before the floating bed hydrocracking reactor are different.Floating bed hydrogenation pretreatment reaction device preferably uses the upflowing plug flow reactor that is used alternatingly by two or more reactor parallel connections among the present invention, when one of them coking and blocking, can switch and use other parallel reactor.In addition, the floating bed hydrogenation pretreatment reaction device operational condition of this technology is also different with existing processes, and its preferred hydrogen partial pressure is 2MPa～30MPa, and the volumetric spaces speed of heavier hydrocarbon feeds in reactor is 4.01h -1～100h -1Preferred temperature of reaction is 360 ℃～530 ℃.
The present invention further describes with reference to the following example, but these embodiment should not be considered to limit use range of the present invention.
Raw material adopts boiling point at 360 ℃～520 ℃ vacuum gas oil, and its character sees Table 1.
Table 1 Application Example feedstock property
Boiling range scope/℃ density (20 ℃)/gcm -3Viscosity (100 ℃)/mm 2·s -1Condensation point/℃ carbon residue/m% basic nitrogen/μ gg -1 ????360～520 ????0.9182 ????7.1 ????10 ????0.10 ????1370
H/C atomic ratio S/m% N/m% ????1.73 ????0.079 ????0.46
Saturated part/m% fragrance part/m% colloid/m% ????75.8 ????17.1 ????7.1
Testing apparatus is the medium-sized long run test device of 3 liters loop reactor for using volume; Floating bed hydrogenation pretreatment reaction actuator temperature is 430 ℃～450 ℃, liquid-volume hourly space velocity (LHSV) 20h -1The temperature of floating bed hydrocracking reactor is 430 ℃～450 ℃, liquid-volume hourly space velocity (LHSV) 0.6～1.0h -1In an embodiment, floating bed hydrogenation pretreatment reaction device is identical with the temperature of reaction of floating bed hydrocracking reactor.The hydrogen dividing potential drop is 10MPa～11MPa; Alcohols in the high dispersive type catalyzer adopts methyl alcohol; The catalytic activity thing is the cupric nitrate crystal; The catalytic activity auxiliary agent is a dithiocarbonic anhydride.Conversion of raw material is higher than 95%, and liquid yield is 90%.Now illustrate as follows:
(1) high dispersive type catalyzer is formed
With cupric nitrate crystal [Cu (NO 3) 22H 2O] join in the methanol aqueous solution, in the methanol aqueous solution of this cupric nitrate, add dithiocarbonic anhydride then.The blue clear solution that forms is exactly a high dispersive type catalyzer used in the application example.In this high dispersive type catalyzer, copper accounts for 3m%～4m%, and water accounts for 10m%, and dithiocarbonic anhydride is 2: 1 with cupric nitrate crystalline molecule number ratio.
(2) process feeds composition, flow process and products distribution
Test with 97.42% is with the above-mentioned high dispersive type catalyzer of vacuum gas oil and 2.58%, by entering process furnace after the fresh feed pump mixing.Need to inject hydrogen partial before the process furnace, to improve the flow velocity of raw material in boiler tube.Vacuum gas oil after the heating and high dispersive type catalyzer enter full backmixed reactor and react.After some hydrogen heats separately in addition, enter reactor.Reacted product is discharged from reactor, and through obtaining the gasoline that boiling point is lower than 180 ℃ after the fractionation, 180～350 ℃ of diesel oil and boiling point are higher than 350 ℃ residue tail oil.
The medial temperature of reactor is respectively 430 ℃, 440 ℃ and 450 ℃.When temperature of reaction is 450 ℃, the amount of methyl alcohol in the deduction high dispersive type catalyzer, the transformation efficiency of vacuum gas oil is 95.66%, the yield of gasoline and diesel oil is 90.30%, the weight ratio of diesel oil and gasoline (diesel and gasoline ratio) is 1.85, boiling point is higher than sulphur that contains in 350 ℃ the tail oil and the sulphur that is removed, and accounts for 82.27% of total sulfur content in the charging.See Table 2 and table 3.
Table 2 feed composition and products distribution
Feed composition The product that temperature of reaction is 430 ℃ is formed The product that temperature of reaction is 440 ℃ is formed The product that temperature of reaction is 450 ℃ is formed
High dispersive type catalyzer/m% ??2.58 ??- - ??-
C 1～C 4Gas/m% ??- ??5.63 5.90 ??5.95
C 5～180 ℃ of gasoline/m% ??- ??20.45 27.31 ??31.73
180～350 ℃ of diesel oil/m% ??- ??46.46 53.11 ??58.57
＞350 ℃ of decompressed wax oil/m% ??97.42 ??27.91 14.14 ??4.23
Wax oil transformation efficiency/m% ??- ??71.35 85.49 ??95.66
The sulphur content of table 3 charging and product (450 ℃ of temperature of reaction)
The charging wax oil ??C 5～180 ℃ of product gasoline 180～350 ℃ of product diesel oil
Weight of material percentage ratio/m% ??97.42 ????31.73 ????58.57
Sulphur content/m% ??0.079 ????0.0181 ????0.0135
Account for charging total sulfur percentage ratio/m% ??100 ????7.46 ????10.27
(3) character of gasoline, diesel oil
When table 4, table 5 are 450 ℃ for temperature of reaction, the gasoline of generation and the character of diesel oil.The aromaticity content of gasoline, olefin(e) centent, sulphur content can both reach the new gasoline standard of country, and octane value RON is 89.The sulphur content of diesel oil is also very low, and cetane value reaches country and is not less than 40 standard, can further improve cetane value by hydrofining.
The character of table 4 product gasoline
Aromaticity content/m% ????17.6
Normal paraffin content/m% ????15.4
Isoparaffin/m% ????19.5
Naphthenic hydrocarbon/m% ????11.8
Alkene/m% ????14.3
Methyl alcohol/m% ????0.024
Oxygenatedchemicals/m% ????10.0
Octane value RON ????89
Sulphur content/m% ????0.0181
The character of table 5 product diesel oil
Density (20 ℃)/gcm -3 ????0.8824
Aniline point/℃ ????55
Sulphur content/m% ????0.0135
Cetane index ????41
Condensation point/℃ ????-38
(4) distribution situation of catalyzer in the floating bed hydrocracking reactor
With reaction product, the high dispersive type catalyzer of the reaction of discharging from the floating bed hydrocracking reactor still has high dispersity, and diameter surpasses 80% less than the granule number of the catalyzer of 1 μ m.Table 6 is with the granules of catalyst in the product liquid after the laser particle analyzer analytical reaction, the particle size distribution data that obtains.Granules of catalyst is little, be evenly distributed one of reason that this also is the catalyst activity height, feed stock conversion is high.
The size distribution of catalyzer and granule number distribute in table 6 reaction product
Particle size distribution range/μ m Relative granule number/% Particle size distribution range/μ m Relative granule number/%
????＜0.375 ????5.12 ????1.520～1.668 ????1.44
????0.375～0.412 ????6.81 ????1.668～1.832 ????1.08
????0.412～0.452 ????7.73 ????1.832～2.011 ????0.79
????0.452～0.496 ????8.71 ????2.011～2.207 ????0.57
????0.496～0.545 ????8.92 ????2.207～2.423 ????0.41
????0.545～0.598 ????8.61 ????2.423～2.660 ????0.28
????0.598～0.656 ????8.10 ????2.660～2.920 ????0.20
????0.656～0.721 ????7.45 ????2.920～3.205 ????0.14
????0.721～0.791 ????6.73 ????3.205～3.519 ????0.09
????0.791～0.868 ????5.97 ????3.519～3.863 ????0.07
????0.868～0.953 ????5.19 ????3.863～4.240 ????0.05
????0.953～1.047 ????4.41 ????4.240～4.655 ????0.03
????1.047～1.149 ????3.68 ????4.655～5.110 ????0.03
????1.149～1.261 ????3.01 ????5.110～5.610 ????0.02
????1.261～1.384 ????2.41 ????5.610～6.158 ????0.01
????1.384～1.520 ????1.88 ????＞6.158 ????0.06
(5) cost of catalyzer
Should be lower than the price that methyl alcohol participates in the gasoline of reaction back generation with the price of the methyl alcohol in the example.Therefore, the cost of high dispersive type catalyzer is very low, even can accomplish zero cost.In certain scope, the high dispersive type catalytic amount of adding is big more, and the cost of catalyzer is just more little, and the octane value of gasoline is also high more.This has fundamentally solved the cost problem of the catalyzer of restriction floating bed hydrocracking technology.

Claims (52)

1. the floating bed hydrocracking technology that can produce the high conversion of stop bracket gasoline and high hexadecane value diesel oil simultaneously is characterized in that this technology needs raw materials pretreatment unit, three unit of floating bed hydrocracking reaction member and product postprocessing unit at least.
After the raw materials pretreatment cell processing, the material that enters into the floating bed hydrocracking reaction member includes: (a) heavier hydrocarbon feeds; (b) mixed gas of hydrogen or hydrogen and other gas; (c) other additive except the mixed gas of heavier hydrocarbon feeds, hydrogen or hydrogen and other gas, this additive is called high dispersive type catalyzer again.
Heavier hydrocarbon feeds, high dispersive type catalyzer, hydrogen or hydrogen mix in the raw materials pretreatment unit with the mixed gas of other gas and handle after enter into the floating bed hydrocracking reaction member, perhaps after the mixed gas of heavier hydrocarbon feeds, high dispersive type catalyzer, hydrogen or hydrogen and other gas process raw materials pretreatment cell processing, enter into the floating bed hydrocracking reaction member and mix; The above-mentioned material that enters into the floating bed hydrocracking reaction member reacts under the condition that the floating bed hydrocracking reaction effectively takes place; Reacted product enters into the product postprocessing unit, after the product postprocessing cell processing, can obtain stop bracket gasoline and high hexadecane value diesel oil simultaneously, and conversion of raw material is very high.
2. technology according to claim 1, it is characterized in that said floating bed hydrocracking reaction member is the described heavier hydrocarbon feeds of claim 1, under the mixed gas effect of high dispersive type catalyzer, hydrogen or hydrogen and other gas, the main place of cracking reaction and lighting reaction takes place.The major parts of said floating bed hydrocracking reaction member is the floating bed hydrocracking reactor.Said floating bed hydrocracking reaction member comprises following consecutive steps:
(a) the described heavy hydrocarbon of crossing through the described raw materials pretreatment cell processing of claim 1 of claim 1
The mixed gas of class raw material, high dispersive type catalyzer, hydrogen or hydrogen and other gas is after the mixing
Mix after entering into the floating bed hydrocracking reactor or entering into the floating bed hydrocracking reactor,
Form the charging of floating bed hydrocracking reactor.
(b) shape is reacted in the charging of floating bed hydrocracking reactor in the floating bed hydrocracking reactor
Become the floating bed hydrocracking product.
(c) the floating bed hydrocracking product is discharged from the floating bed hydrocracking reactor, enters into claim 1
Described product postprocessing unit is handled.
3. floating bed hydrocracking reaction member according to claim 1 and 2, it is characterized in that its operational condition is: pressure is from 2MPa to 30MPa; Temperature of reaction is from 350 ℃ to 520 ℃; The volumetric spaces speed of heavier hydrocarbon feeds in reactor is from 0.1h -1To 10h -1The volume ratio of the mixed gas of the volume of (0 ℃, 1 normal atmosphere) heavier hydrocarbon feeds and hydrogen or hydrogen and other gas is from 1: 100 to 1: 10000 under the standard state.
4. floating bed hydrocracking reaction member according to claim 2 is characterized in that said floating bed hydrocracking reactor is one or more in full back-mixing loop reactor, trickle-bed reactor, reverse convection type reactor, moving-burden bed reactor, expanded bed reactor and the slurry bed reactor.
5. floating bed hydrocracking reaction member according to claim 2, it is characterized in that said floating bed hydrocracking reactor is one or more in full back-mixing loop reactor, reverse convection type reactor, moving-burden bed reactor, expanded bed reactor and the slurry bed reactor, this reactor has a discharge gate at least, discharge the product or the settling of reactor bottom off and on or continuously, perhaps discharge product or settling from reactor bottom off and on or continuously.
6. floating bed hydrocracking reaction member according to claim 2, it is characterised in that it is one of them processing unit in the described floating bed hydrocracking technology of claim 1.
7. floating bed hydrocracking reaction member according to claim 2, it is characterised in that it is a processing unit in the shortening combination process.
8. floating bed hydrocracking reaction member according to claim 1, it is characterised in that it is a processing unit in the shortening combination process.
9. according to claim 7 or 8 described shortening combination procesies, it is characterised in that it is a floating bed hydrocracking technology, multistage suspension bed hydroprocessing cracking technology, hydrodesulfurization, hydrodenitrification technology, hydrogenation deoxidation technology, hydrodemetallation (HDM) technology, hydrogenation takes off carbon residue technology, hydroisomerisation process, hydrofining technology, hydrocracking process, hydrodewaxing technology, face the hydrogen condensation process, hydrovisbreaking technology, face hydrogen coking process or other one or more combination process in technological process that added hydrogen exists, perhaps above-mentioned one or more technologies and catalytic reforming are arranged, solvent deasphalting technology, solvent takes off carbon residue technology, solvent extraction process, solvent treatment technology, viscosity breaking technology, thermocracking process, delay coking process, catalytic cracking process, the multistage catalytic cracking process, overcritical accurate separating technology or other do not have one or more the combination process in the technology that added hydrogen exists.
10. technology according to claim 1, it is characterised in that described raw materials pretreatment unit is that raw material flows on the route of process, is positioned at the summation of all devices before the opening for feed of claim 1,2,6,7 or 8 described floating bed hydrocracking reaction members, wherein can include mixing tank, process furnace, interchanger, floating bed hydrogenation pretreatment reaction device, operating device and safety equipment.
11. technology according to claim 1, it be characterised in that said product postprocessing unit be after the product discharge port of claim 1,2,6,7 or 8 described floating bed hydrocracking reaction members, the flow summation of all devices on the route of process of product, wherein can include separator, interchanger, separation column, gas stripping column, stabilizer tower, hydrofining reactor, catalyst cracker, centrifuge separator, spinning liquid solid-liquid separator, tail oil coking tower, solvent and take off slag tower, operating device and safety equipment.
12. technology according to claim 1, it is characterised in that said floating bed hydrocracking reaction member is on the route of the mobile process of raw material, be positioned at after the described raw materials pretreatment of claim 10 unit, and be positioned at the summation of all devices before the described product postprocessing of claim 11 unit, its major equipment is claim 4 and 5 described floating bed hydrocracking reactors.
13. technology according to claim 1, it is characterised in that described raw materials pretreatment unit can make the mixed gas of the described heavier hydrocarbon feeds of claim 1, high dispersive type catalyzer and hydrogen or hydrogen and other gas, when entering into the described floating bed hydrocracking reaction member of claim 12, reach the described operational condition of claim 3.
14. technology according to claim 1, it is characterised in that said product postprocessing unit can be with the product of the described floating bed hydrocracking reaction member of claim 12, make with extra care, separate or transform again, maybe can be with the component that obtains can be used as commodity as other unit of raw material of conversion process again.
15. according to claim 1,10 or 13 described technologies, it is characterised in that and needs the mixed gas that a process furnace is used for heating the described heavier hydrocarbon feeds of claim 1, high dispersive type catalyzer and hydrogen or hydrogen and other gas in the described raw materials pretreatment unit at least.The material that includes heavier hydrocarbon feeds that was heated is from the outlet of process furnace, after entering into the floating bed hydrogenation pretreatment reaction device of raw materials pretreatment unit, enter into claim 1,2,6,7,8 or 12 described floating bed hydrocracking reaction members again.
16. according to claim 1,10 or 13 described technologies, it is characterised in that and needs the mixed gas that a process furnace is used for heating the described heavier hydrocarbon feeds of claim 1, high dispersive type catalyzer and hydrogen or hydrogen and other gas in the described raw materials pretreatment unit at least.The material that includes heavier hydrocarbon feeds that was heated enters into claim 1,2,6,7,8 or 12 described floating bed hydrocracking reaction members from the outlet of process furnace.
17. raw materials pretreatment according to claim 15 unit, it is characterised in that the operational condition of described floating bed hydrogenation pretreatment reaction device is: hydrogen partial pressure is 2MPa～30MPa; The volumetric spaces speed of heavier hydrocarbon feeds in reactor is 4.01h -1～100h -1Temperature of reaction is 360 ℃～530 ℃; The volume ratio of the mixed gas of the volume of (0 ℃, 1 normal atmosphere) heavier hydrocarbon feeds and hydrogen or hydrogen and other gas is from 1: 100 to 1: 10000 under the standard state.
18. raw materials pretreatment according to claim 15 unit, it is characterised in that described floating bed hydrogenation pretreatment reaction device is that raw material enters the effusive up-flow reactor from top by reactor lower part.
19. raw materials pretreatment according to claim 15 unit, it is characterised in that described floating bed hydrogenation pretreatment reaction device is that raw material enters the effusive up-flow reactor from top by reactor lower part, and reactor is provided with the bottom precipitation relief outlet.
20. raw materials pretreatment according to claim 15 unit, it is characterised in that described floating bed hydrogenation pretreatment reaction device is one or more in full back-mixing loop reactor, trickle-bed reactor, reverse convection type reactor, moving-burden bed reactor, expanded bed reactor and the slurry bed reactor.
21. raw materials pretreatment according to claim 15 unit, it is characterised in that described floating bed hydrogenation pretreatment reaction device is one or more in full back-mixing loop reactor, reverse convection type reactor, moving-burden bed reactor, expanded bed reactor and the slurry bed reactor.This reactor has a discharge gate at least, discharges the product or the settling of reactor bottom off and on or continuously, perhaps discharges product or settling from reactor bottom off and on or continuously.
22. raw materials pretreatment according to claim 15 unit, it is characterised in that described floating bed hydrogenation pretreatment reaction device, by forming after two or more reactor parallel connections, and alternately switches and to use.In process operation, have at least one of them reactor in parallel to be in standby to be switched state.
23. raw materials pretreatment according to claim 22 unit, it is characterised in that described floating bed hydrogenation pretreatment reaction device is that raw material enters the effusive up-flow reactor from top by reactor lower part.
24. raw materials pretreatment according to claim 22 unit, it is characterised in that described floating bed hydrogenation pretreatment reaction device is that raw material enters the effusive up-flow reactor from top by reactor lower part, and reactor is provided with the bottom precipitation relief outlet.
25. raw materials pretreatment according to claim 22 unit, it is characterised in that described floating bed hydrogenation pretreatment reaction device is one or more in full back-mixing loop reactor, trickle-bed reactor, reverse convection type reactor, moving-burden bed reactor, expanded bed reactor and the slurry bed reactor.
26. raw materials pretreatment according to claim 22 unit, it is characterised in that described floating bed hydrogenation pretreatment reaction device is one or more in full back-mixing loop reactor, trickle-bed reactor, reverse convection type reactor, moving-burden bed reactor, expanded bed reactor and the slurry bed reactor.This reactor has a discharge gate at least, discharges the product or the settling of reactor bottom off and on or continuously, perhaps discharges product or settling from reactor bottom off and on or continuously.
27. according to claim 18,19,20,21,22,23,24,25 or 26 described raw materials pretreatment unit, it is characterised in that the operational condition of described floating bed hydrogenation pretreatment reaction device is: hydrogen partial pressure is 2MPa～30MPa; The volumetric spaces speed of heavier hydrocarbon feeds in reactor is 4.01h -1～100h -1Temperature of reaction is 360 ℃～530 ℃; The volume ratio of the mixed gas of the volume of (0 ℃, 1 normal atmosphere) heavier hydrocarbon feeds and hydrogen or hydrogen and other gas is from 1: 100 to 1: 10000 under the standard state.
28. according to claim 1,2,6,7,8 or 12 described technologies, it is characterised in that and includes a floating bed hydrocracking reactor in the described floating bed hydrocracking reaction member at least that this floating bed hydrocracking reactor is claim 4 and 5 described floating bed hydrocracking reactors.
29. according to claim 1,11 or 14 described technologies, it is characterised in that the separator that includes the product that will produce in the floating bed hydrocracking reaction member in the described product postprocessing unit at least and carry out gas-liquid separation, will compresses circulating hydrogen compressor that supercharging recirculation uses behind the unreacted hydrogen upgrading, product liquid be carried out fractionation to obtain the separation column of gasoline and diesel oil.
30. technology according to claim 1, it is characterised in that said heavier hydrocarbon feeds contains weight percentage and is not less than 10% the cut of boiling point between 350 ℃ to 650 ℃.
31. according to claim 1 or 30 described technologies, it is characterised in that described heavier hydrocarbon feeds is atmospheric gas oil, vacuum gas oil, atmospheric residue, vacuum residuum, the product of crude oil, synthetic crude, deasphalted oil, other process or product heavy oil, contain one or several the mixture in the coal dust slurry of coal tar or gas oil, perhaps above-mentioned one or several and boiling point are lower than the mixture of 400 ℃ lightweight oil.
32. technology according to claim 1, it is characterised in that in the mixed gas of said hydrogen or hydrogen and other gas, the shared percent by volume of hydrogen is not less than 60%.Said other gas for do not comprise hydrogen, be the material of gas under the atmospheric pressure at room.
33. technology according to claim 1, it is characterised in that said high dispersive type catalyzer is all materials that enter into the described floating bed hydrocracking reaction member of claim 1, does not comprise under the described heavier hydrocarbon feeds of claim 1, hydrogen and the atmospheric pressure at room summation for all other materials of the material of gas.
34. technology according to claim 1, it is characterised in that said high dispersive type catalyzer is all materials that enter into claim 1,2,6,7,8 or 12 described floating bed hydrocracking reaction members, does not comprise under hydrogen, the atmospheric pressure at room summation for all other materials of the material of gas and claim 30 and 31 described heavier hydrocarbon feeds.
35. according to claim 1,33 and 34 described high dispersive type catalyzer, it is characterised in that it is made up of following component: catalytic activity thing, alcohols, water and other auxiliary agent except catalytic activity thing, alcohols, water, this auxiliary agent is called the catalytic activity auxiliary agent again.The shared therein weight percent of water is from 0% to 99.8%.The shared therein weight percent of alcohols is from 0% to 99.8%.
36. high dispersive type catalyzer according to claim 35, it is characterised in that said alcohols is one or more the mixture that contains the alcohol of 1 to 10 carbon atom in the molecule.
37. high dispersive type catalyzer according to claim 35, it is characterised in that said alcohols is one or more the mixture in methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol and the hexanol.
38. high dispersive type catalyzer according to claim 35, it is characterised in that said alcohols is one or both the mixture in methyl alcohol and the ethanol.
39. high dispersive type catalyzer according to claim 35, it is characterised in that said catalytic activity thing is that periodic table of elements IA family is to VA family, IB family is to VIIB family and VIII family, i.e. first main group to the, five main groups, in first subgroup to the, seven subgroups and the 8th family, can be with ionic condition, molecularity, hydration status, complex status, the polymolecular polymerization state, with claim 36, the solution of 37 and 38 said alcohols or this alcohols and water forms true solution, the inorganic salt of the metal of milk sap or suspension, organic salt, complex compound, the mixing of one or more of inner complex.
40. according to the described catalytic activity thing of claim 39, it is characterised in that it is selected from one or more mixing of the inorganic salt of lanthanum, cerium, titanium, vanadium, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, copper, zinc, silver, gold, cadmium, mercury, tin, organic salt, complex compound, inner complex.
41. according to the described catalytic activity thing of claim 39, it is characterised in that its a kind of element wherein is a copper.
42. according to the described catalytic activity thing of claim 39, it is characterised in that its a kind of component wherein is cupric nitrate or cupric nitrate crystal.
43. high dispersive type catalyzer according to claim 35, it is characterised in that said catalytic activity thing is selected from one or more mixing of the inorganic salt of lanthanum, cerium, titanium, vanadium, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, copper, zinc, silver, gold, cadmium, mercury, tin, organic salt, complex compound, inner complex.
44. high dispersive type catalyzer according to claim 35, it is characterised in that the wherein a kind of element in the said catalytic activity thing is a copper.
45. high dispersive type catalyzer according to claim 35, it is characterised in that the wherein a kind of component in the said catalytic activity thing is cupric nitrate or cupric nitrate crystal.
46. high dispersive type catalyzer according to claim 35, it is characterised in that said catalytic activity auxiliary agent is in the high dispersive type catalyzer, does not comprise the summation of other all components of water, alcohols and catalytic activity thing.
47. high dispersive type catalyzer according to claim 35, it is characterised in that said catalytic activity auxiliary agent is in claim 33 or the 34 described high dispersive type catalyzer, does not comprise the summation of other all components of water, claim 36,37 and 38 described alcohols and claim 39,43,44 and 45 described catalytic activity things.
48. according to claim 46 or 47 described catalytic activity auxiliary agents, it is characterised in that adds this catalytic activity auxiliary agent in claim 1,33, the 34 and 35 described high dispersive type catalyzer to, and one or more in the sulphur content of corresponding high dispersive type catalyzer, acidity, density, vapour pressure, specific conductivity, refractive index, the surface tension can change.Simultaneously, one or more in the sulphur content of the octane value of the coke content of the product of the transformation efficiency of heavier hydrocarbon feeds, floating bed hydrocracking reaction member, product gasoline, product diesel-fuel cetane number, product gasoline and diesel oil can change.
49. high dispersive type catalyzer according to claim 35, it is characterised in that the percentage ratio that said catalytic activity auxiliary agent accounts for high dispersive type catalyst weight is from 0% to 99.8%.
50. according to claim 33 or 34 described high dispersive type catalyzer, it be characterised in that claim 46 that it is wherein contained and 48 or the weight percentage of 47 and 48 said catalytic activity auxiliary agents be from 0% to 99.8%.
51. technology according to claim 1, it is characterised in that the add-on of said high dispersive type catalyzer, account for the weight percentage of the total feed of claim 1,2,6,7,8 or 12 described floating bed hydrocracking reaction members, be no more than 85%.
52. according to claim 1,2,6,7,8 or 12 described technologies, it is characterised in that in the total feed of said floating bed hydrocracking reaction member, contains weight percentage and is no more than 85% claim 33 or 34 described high dispersive type catalyzer.
CN 03112099 2003-04-07 2003-04-07 Suspension bed hydrocracking technique for producing gasoline with high octane number and diesel oil with high cetane number simultaneously Pending CN1446888A (en)

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101962571A (en) * 2010-10-29 2011-02-02 大连理工大学 Coal tar heavy fraction suspension-bed hydrocracking method and system thereof
CN103789036A (en) * 2012-10-26 2014-05-14 中国石油化工股份有限公司 Combination processing method of inferior heavy oil
CN103789027A (en) * 2012-10-26 2014-05-14 中国石油化工股份有限公司 Heavy oil hydrogenating and modifying method
CN105602643A (en) * 2010-02-19 2016-05-25 恩尔彼有限公司 Methods and procedures for producing useful products from waste materials
CN106281427A (en) * 2016-10-14 2017-01-04 北京神雾环境能源科技集团股份有限公司 A kind of system and method that coal tar is processed
CN107641525A (en) * 2016-07-29 2018-01-30 北京华石联合能源科技发展有限公司 A kind of floating bed hydrogenation group technology and system
CN110023461A (en) * 2016-10-28 2019-07-16 环球油品有限责任公司 The flexible hydrotreating of slurry hydrocracking product
CN111315849A (en) * 2017-09-30 2020-06-19 环球油品有限责任公司 Method and apparatus for hydroprocessing hydrocarbon streams
CN112592731A (en) * 2020-10-10 2021-04-02 中国科学院青岛生物能源与过程研究所 Method for producing second-generation biodiesel by liquid catalyst
CN113786859A (en) * 2021-10-21 2021-12-14 福州大学 Hydrocracking catalyst, and preparation method and application thereof

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105602643A (en) * 2010-02-19 2016-05-25 恩尔彼有限公司 Methods and procedures for producing useful products from waste materials
CN101962571A (en) * 2010-10-29 2011-02-02 大连理工大学 Coal tar heavy fraction suspension-bed hydrocracking method and system thereof
CN103789036A (en) * 2012-10-26 2014-05-14 中国石油化工股份有限公司 Combination processing method of inferior heavy oil
CN103789027A (en) * 2012-10-26 2014-05-14 中国石油化工股份有限公司 Heavy oil hydrogenating and modifying method
CN103789027B (en) * 2012-10-26 2015-04-29 中国石油化工股份有限公司 Modifying method for heavy oil hydrogenating
CN103789036B (en) * 2012-10-26 2015-09-23 中国石油化工股份有限公司 A kind of inferior heavy oil combinational processing method
CN107641525B (en) * 2016-07-29 2020-07-14 北京三聚环保新材料股份有限公司 Suspension bed hydrogenation combined process and system
CN107641525A (en) * 2016-07-29 2018-01-30 北京华石联合能源科技发展有限公司 A kind of floating bed hydrogenation group technology and system
CN106281427A (en) * 2016-10-14 2017-01-04 北京神雾环境能源科技集团股份有限公司 A kind of system and method that coal tar is processed
CN110023461A (en) * 2016-10-28 2019-07-16 环球油品有限责任公司 The flexible hydrotreating of slurry hydrocracking product
CN110023461B (en) * 2016-10-28 2021-07-20 环球油品有限责任公司 Flexible hydroprocessing of slurry hydrocracking products
CN111315849A (en) * 2017-09-30 2020-06-19 环球油品有限责任公司 Method and apparatus for hydroprocessing hydrocarbon streams
CN111315849B (en) * 2017-09-30 2022-11-15 环球油品有限责任公司 For treating hydrocarbon streams carrying out hydrogenation method and device for machining
CN112592731A (en) * 2020-10-10 2021-04-02 中国科学院青岛生物能源与过程研究所 Method for producing second-generation biodiesel by liquid catalyst
CN113786859A (en) * 2021-10-21 2021-12-14 福州大学 Hydrocracking catalyst, and preparation method and application thereof

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