CN104449836B

CN104449836B - The trans hydrocracking process of a kind of full cut of coal tar

Info

Publication number: CN104449836B
Application number: CN201410544912.5A
Authority: CN
Inventors: 白建明; 陈松; 单小勇; 苏玉更
Original assignee: Huadian Heavy Industries Co Ltd
Current assignee: Huadian Heavy Industries Co Ltd
Priority date: 2014-10-15
Filing date: 2014-10-15
Publication date: 2016-05-18
Anticipated expiration: 2034-10-15
Also published as: CN104449836A

Abstract

The invention discloses the trans hydrocracking process of the full cut of a kind of coal tar, comprise the full cut of coal tar is carried out obtaining cold high score gas, cold low point of gas, low point of oil of heat and cold low point of oil after pretreatment, hydrofinishing, separation, wherein cold high score gas is hydrogen-rich gas, after recovery together with new hydrogen the hydrogen source as hydrogenation reaction; Cold low point of oil obtains fuel gas, gasoline fraction, diesel oil distillate and tail oil through fractionation, carries out hydrocracking by tail oil and after low point of oily mixing of part heat, and crackate returns to hydrofining reactor and carry out refining reaction together with pretreatment generation oil. Not only technological process is simple for the trans hydrocracking process of the full cut of coal tar of the present invention, hydrogenation plant run stability is good, high to the utilization rate of coal tar, and sulphur in the gasoline that obtains of hydrogenation, diesel oil, nitrogen content are low, meets the quality standard of clean fuel.

Description

The trans hydrocracking process of a kind of full cut of coal tar

Technical field

The present invention relates to a kind of coal tar hydrogenation process, particularly one is produced clean taking the full cut of coal tar as raw materialThe process of light-weight fuel oil, belongs to technical field of coal chemical industry.

Technical background

Along with the sustainable development of China's economy, the domestic demand to liquid fuel is growing, lacks but China is oneThe country that oil, weak breath, coal resources enrich relatively, under existing situation, exploitation is produced available liquid by solid fuels such as coalsThe method of fuel has positive realistic meaning. Coal tar is the accessory substance that coal forms in coking, gasification and retort process, orderBefore taking coal tar as raw material, adopt suitable processing scheme, improve the stability of coal tar, reduce its impurity content, thereby obtainThe low-sulfur naphtha and the clean fuel oil that obtain high added value are the approach of a very effective prepare liquid fuel.

Because coal tar oil composition is extremely complicated, contain unsaturated hydro carbons such as a large amount of alkene, polycyclic aromatic hydrocarbon etc. and oxygen, sulphur,Nitrogen compound and solid impurity, and colloid and bitumen content also quite high, therefore, in actual production process, conventionally adopt hydrogenation essenceSystem/method for hydrogen cracking realizes that deoxidation, desulfurization, denitrogenation and the unsaturated hydrocarbons of coal tar saturated etc. cleans, lighting object,Thereby obtain naphtha and clean fuel oil. For example, Chinese patent literature CN1676583A discloses high temperature coal-tar in oneHydrocracking process, this technique comprises: middle high temperature coal-tar is introduced to heating furnace and mix with hydrogen after to send into hydrofinishing anti-Answer device, the generation oil of refining reaction device effluent after separating enters fractionating column, isolates gasoline, diesel oil, lubricating oil and tail oil,Tail oil is introduced cracker, and its generation oil enters fractionating column and carry out fractionation together with hydrofinishing generation oil.

Above-mentioned prior art is passed through to adopt hydrofinishing-hydrocracking process, by further hydrorefined tail oil cracking,Although improved to a certain extent the utilization rate of coal tar raw material, but still the defect existing is: prior art is to coal tarFull cut carries out hydrofinishing-cracking to be processed in the oil product obtaining and still contains more sulphur, makes oil quality not up to standard. CauseHow this, improve to overcome the defect that prior art exists to the hydrogenation technique of coal tar, be those skilled in the art urgentlyTechnical barrier to be solved.

Summary of the invention

In what the present invention solved is light ends that coal tar hydrogenation process of the prior art exists, sulfur content exceeds standardProblem, and then provide that a kind of utilization rate to coal tar is high, hydrogenation plant run stability is good and light ends meets clean combustionThe coal tar hydrogenation process of material standard.

The technical scheme that the present invention solves the problems of the technologies described above is:

The trans hydrocracking process of a kind of full cut of coal tar, comprises the steps:

(a) under the condition existing in hydrogenation protecting agent, the full cut of coal tar is added to hydrogen pretreatment, obtain pretreatment rawBecome oil;

(b) described pretreatment is generated to oil and carry out hydrofinishing, obtain hydrotreated product;

(c) described hydrotreated product is carried out to thermal high separation and obtain thermal high gas phase and thermal high liquid phase; Again to instituteStating thermal high gas phase carries out cold anticyclone and separates and obtain cold high score gas and cold anticyclone liquid phase; Described thermal high liquid phase is carried out to heat lowSeparation obtains heat low gas phase and low point of oil of heat; Carry out cold low to the mixture of described heat low gas phase and described cold anticyclone liquid phasePress to separate and obtain cold low point of gas and cold low point of oil;

(d) described cold low point of oil is carried out to fractionation, cut out tail oil and fuel that gasoline, diesel oil, boiling point are greater than 370 DEG CGas;

(e) a low described heat point of oily part and described tail oil are mixed to get to miscella, described miscella is addedHydrogen cracking reaction, is cracking high score gas and cracking high score oil by the product separation of hydrocracking, wherein said cracking high score oil withThe described pretreatment preparing in step (a) generates after oil mixes carries out hydrofinishing together.

Low point of oily part of described heat and described tail oil are made miscella and are carried out hydrocracking reaction, another part withHydrogenation pretreatment is carried out in the full cut mixing of described coal tar in step (a).

In step (a), carrying out the pretreated temperature of hydrogenation is 300～450 DEG C, and pressure is 18Mpa, and hydrogen to oil volume ratio is 800～1500: 1, volume space velocity is 0.1～5.0h^-1。

The hydrogenation protecting agent using in step (a) is compound or the aqueous solution that contains active metal element, described activityMetallic element is one or more in VB, VIB, VIII family metallic element; Active metal in every gram of described hydrogenation protecting agentThe content of element is 50～200 μ g.

In step (b), carrying out hydrorefined temperature is 330～390 DEG C, and pressure is 18Mpa, hydrogen to oil volume ratio 800～1500: 1, volume space velocity was 0.5～5.0h^-1。

Molybdenum oxide, 1 that described in step (b), hydrofinishing Hydrobon catalyst used comprises 5～25wt%～The nickel oxide of 10wt%, surplus is silica support or alumina support, the pore volume of described catalyst for refining is 0.20～0.50mL/g, specific area are 100～200m²/g。

In step (c), the operating pressure that carries out described thermal high separation is that 17.3MPa, operating temperature are 310 DEG C; Carry outThe operating pressure that described cold anticyclone separates is that 17.2MPa, operating temperature are 48 DEG C; Carry out the operating pressure of described heat low separationFor 2.0MPa, operating temperature are 310 DEG C; The operating pressure that carries out described cold low separation is that 2.0MPa, operating temperature are 45 DEG C.

Mixing of the described cracking high score gas that in step (e), separation obtains and described heat low gas phase and described cold anticyclone liquid phaseCompound jointly carries out cold low separation and obtains cold low point of gas and cold low point of oil.

The pressure that carries out described hydrocracking in step (e) is that 17MPa, hydrogen to oil volume ratio are 800～3000: 1, temperature is260～340 DEG C, volume space velocity are 0.1～4.0h^-1。

While carrying out hydrocracking reaction in step (e), flow through successively cracking protective agent bed, cracking of described miscella located in advanceReason agent bed and Cracking catalyst bed, wherein said cracking protective agent, cracking pretreating agent and Cracking catalyst all with Mo, W,Any one or a few in Co or Ni is active component, taking aluminium oxide and/or molecular sieve as carrier. Cracking of the present invention is protectedProtect agent, cracking pretreating agent and Cracking catalyst be preferably Fu Yan institute develop the single hop such as FC-28, FC-14, ZHC-01 addHydrogen Cracking catalyst, the hydrocracking catalyst such as DHC39, DHC-8 of Uop Inc.'s exploitation.

Described cold high score gas is mixed with hydrogen as adding hydrofinishing and step in hydrogen pretreatment, step (b) in step (a)Suddenly the hydrogen source of hydrocracking in (e).

The trans hydrogenation system of a kind of full cut of coal tar, comprising:

Connect the pre-hydrogenation protecting reactor and the hydrofining reactor that arrange; The outlet of described pre-hydrogenation protecting reactorFeed(raw material)inlet pipe by described hydrofining reactor is connected with the entrance of described hydrofining reactor;

High pressure hot separator, is connected setting with the outlet of described hydrofining reactor;

Cold high pressure separator, is connected setting with the gaseous phase outlet of described high pressure hot separator;

Thermal low-pressure separators, is connected setting with the liquid-phase outlet of described high pressure hot separator;

Cold low separator, with the liquid-phase outlet of described cold high pressure separator and the gaseous phase outlet of described thermal low-pressure separatorsConnect and arrange;

Fractionating column, is connected setting with the liquid-phase outlet of described cold low separator;

Hydrocracking reactor, simultaneously with the liquid-phase outlet of described thermal low-pressure separators and the outlet of the tail oil of described fractionating columnConnect and arrange;

Cracking high-pressure separator, with the outlet setting of described hydrocracking reactor;

The liquid-phase outlet of described cracking high-pressure separator is communicated with setting with the feed(raw material)inlet of described hydrofining reactor pipe.

The liquid-phase outlet of described thermal low-pressure separators is communicated with the feed(raw material)inlet pipe of described pre-hydrogenation protecting reactor simultaneouslyArrange, enter together with after being suitable for the liquid phase of described cracking high-pressure separator and the generation of described pre-hydrogenation protecting reactor oil and mixingRow hydrofinishing.

The gaseous phase outlet of described cracking high-pressure separator is connected setting with described cold low separator.

Be connected with circulating hydrogen compressor with the gaseous phase outlet of described cold high pressure separator, described circulating hydrogen compressorCompressed Gas outlet enters with the hydrogen of described pre-hydrogenation protecting reactor, hydrofining reactor and hydrocracking reactor respectivelyMouth is communicated with setting.

In step of the present invention (a), hydrogenation pretreatment reaction is to enter in single beds fixed bed reactorsRow, the top of this reactor is provided with cold hydrogen inlet, and to control the temperature of beds, this beds is filled with, there is demetalization reaction and hydrogenation of olefins presaturation reaction in hydrogenation protecting agent, prevents that alkene is at high temperature because polymerization coking blocks upPlug beds, affects the normal operation of device. The hydrofining reactor that the hydrofining reaction of step (b) adoptsTop is provided with cold hydrogen inlet, by regulating cold hydrogen the controlling of injecting quantity reaction bed temperature, prevents bed temperature runaway. In addition,The Cracking catalyst that the present invention uses is taking aluminium oxide and/or molecular sieve as carrier, with in Mo, W, Co or Ni any one or severalKind for active component, its reason is for the aromatic hydrocarbons in coal tar, and it is fine that its lighting needs Cracking catalyst to haveOpen loop activity, but in mode, be not the lytic activity center that increases merely Cracking catalyst, but want in balance B, L acidThe heart, so that L acid coordinates B acid to realize better open loop, the cracking of aromatic hydrocarbons to the anchorage effect of conjugated system molecule.

Compared with coal tar hydrogenation process of the prior art, the trans hydrocracking work of the full cut of coal tar of the present inventionThe advantage of skill is:

(1) the trans hydrocracking process of the full cut of coal tar of the present invention is that full cut using coal tar is as raw materialCarry out hydrofinishing, the tail oil that refined products obtains through fractionation further carries out hydrocracking, and isocrackate is not directFractionation in addition, but carry out hydrofinishing processing together with adding hydrogen pretreatment product, further to remove in isocrackateThe sulphur-containing substance existing, thus effectively avoid the mercaptan of hydrocracking stage generation in prior art because having little time hydro-conversionThe sulfur content that causes cracking to generate in oil exceeds standard, and directly this cracking is generated to oil and carries out fractionation, can cause each light ends qualityProblem not up to standard. That is to say, adopt gasoline that the trans hydrocracking process of the full cut of coal tar of the present invention obtains andSulphur, nitrogen content in diesel oil are lower, all meet the quality standard of clean fuel.

The content that is tail oil due to heavy constituent in coal tar (370 DEG C of >) is generally 50-60%, and the present invention will occupy coal tarThe tail oil hydrocracking over half of oil gross weight, and then be converted into light-end products, promote largely the warp of coal tarJi is worth, thus the adaptability and the production flexibility that have improved coal tar raw material. And before above-mentioned hydrofinishing, the present inventionAlso coal tar raw material is added to hydrogen pretreatment, make the olefins hydrogenation in coal tar, prevent that alkene is at high temperature because of polymerizationCoking and blocking catalyst bed, thereby the normal operation of assurance device; Simultaneously the present invention uses before adding hydrogen pretreatment above-mentionedLow point of oil of part heat dilutes coal tar raw material, and its reason is to reduce density, the carbon residue of coal tar raw materialValue and hydrogenation difficulty, can also control the temperature rise of beds.

(2) the trans hydrocracking process of the full cut of coal tar of the present invention, described hydrotreated product is through thermal highFour separators such as separator, cold high pressure separator, thermal low-pressure separators and cold low separator separate, the rich hydrogen obtainingGas reclaims and then mixes the hydrogen source as hydrogenation reaction with new hydrogen, so can reduce the new hydrogen supply in whole system, reducesProduction cost.

Brief description of the drawings

Fig. 1 is the flow chart of the trans hydrocracking process of the full cut of coal tar of the present invention;

Wherein, Reference numeral is as follows:

1-booster; 2-heat exchanger; The pre-hydrogenation protecting reactor of 3-; 4-hydrofining reactor; 5-high pressure hot separator;6-cold high pressure separator; 7-thermal low-pressure separators; 8-cold low separator; 9-fractionating column; 10-cracked charge heat exchanger; 11-addsHydrogen cracker; 12-cracking high-pressure separator; 13-circulating hydrogen compressor.

Detailed description of the invention

Below in conjunction with specific embodiment, the trans hydrocracking process of the full cut of coal tar provided by the invention is carried out in detailExplanation.

Embodiment 1

Realize the trans hydrogenation system of the full cut of coal tar of the trans hydrocracking process of the full cut of coal tar in the present embodiment,Comprise:

Connect the pre-hydrogenation protecting reactor 3 and the hydrofining reactor 4 that arrange;

High pressure hot separator 5, is connected setting with the outlet of described hydrofining reactor 4;

Cold high pressure separator 6, is connected setting with the gaseous phase outlet of described high pressure hot separator 5;

Thermal low-pressure separators 7, is connected setting with the liquid-phase outlet of described high pressure hot separator 5;

Cold low separator 8, with the gas phase of liquid-phase outlet and the described thermal low-pressure separators 7 of described cold high pressure separator 6Outlet connects setting;

Fractionating column 9, is connected setting with the liquid-phase outlet of described cold low separator 8;

Hydrocracking reactor 11, simultaneously with the liquid-phase outlet of described thermal low-pressure separators 7 and the tail oil of described fractionating column 9Outlet connects setting;

Cracking high-pressure separator 12, with the outlet setting of described hydrocracking reactor 11; Described cracking high-pressure separator12 liquid-phase outlet is communicated with setting with the feed(raw material)inlet pipe of described hydrofining reactor 4.

The trans hydrocracking process of the full cut of coal tar described in the present embodiment, as shown in Figure 1, comprises the steps:

(a) in pre-hydrogenation protecting reactor 3, pressure be 18MPa, hydrogen to oil volume ratio be 1500: 1, temperature be 300 DEG C,Volume space velocity is 2.5h^-1Condition under, use vanadic anhydride, as hydrogenation protecting agent, the full cut of coal tar is carried out to hydrogenation pre-Process, obtain pretreatment and generate oil, the consumption of this hydrogenation protecting agent is counted 50 μ g/g with v element;

(b) described pretreatment generation oil is sent into hydrofining reactor 4 and carry out hydrofinishing, obtain hydrofinishing and produceThing; Described hydrorefined condition is: pressure 18MPa, hydrogen to oil volume ratio 800: 1,390 DEG C of temperature, volume space velocity 0.5h^-1; InstituteState Hydrobon catalyst that hydrofinishing the uses molybdenum oxide that is 25wt%, the nickel oxide of 1wt%, surplus is that silica carriesBody, and the pore volume of this catalyst for refining is that 0.20mL/g, specific area are 200m²/g；

(c) utilize high pressure hot separator 5 to described hydrotreated product carry out thermal high separate obtain thermal high gas phase andThermal high liquid phase; Recycling cold high pressure separator 6 carries out cold anticyclone separation to described thermal high gas phase and obtains cold high score gas and coldHigh pressure liquid phase, utilizes thermal low-pressure separators 7 to carry out heat low separation to described thermal high liquid phase and obtains heat low gas phase and hot lowDivide oil; Utilizing cold low separator 8 to carry out cold low to described heat low gas phase with the mixture of described cold anticyclone liquid phase separatesObtain cold low point of gas and cold low point of oil; Wherein, the operating pressure that described thermal high separates is that 17.3MPa, operating temperature are 310DEG C; The operating pressure that carries out described cold anticyclone separation is that 17.2MPa, operating temperature are 48 DEG C; Carry out described heat low separationOperating pressure is that 2.0MPa, operating temperature are 310 DEG C; The operating pressure that carries out described cold low separation is 2.0MPa, operation temperatureDegree is 45 DEG C;

(d) described cold low point of oil is sent into fractionating column 9, described cold low point of oil is carried out to fractionation, cut out boiling point and be less than 150DEG C gasoline, tail oil and the fuel gas that diesel oil, boiling point that boiling point is 150～370 DEG C are greater than 370 DEG C;

(e) a low described heat point of oily part and described tail oil are made to miscella and sent into hydrocracking reactor 11 and enterRow hydrocracking reaction, the condition of described hydrocracking is: pressure 17MPa, hydrogen to oil volume ratio 3000: 1,300 DEG C of temperature, volumeAir speed 0.25h^-1, the Cracking catalyst that described hydrocracking is used is the DHC39 hydrocracking catalyst of Uop Inc.'s exploitation;Utilizing cracking high-pressure separator 12 is cracking high score gas and cracking high score oil, wherein said cracking by the product separation of hydrocrackingTogether with after high score oil generates oil mixing with the described pretreatment preparing in step (a), sending into hydrofining reactor 4 enters againRow hydrofinishing.

Described in the present embodiment, the character of the full cut of coal tar is as shown in table 1, the trans hydrocracking of the full cut of described coal tarThe reaction condition of technique is as shown in table 2, and the gasoline that fractionation obtains and bavin oil properties are as shown in table 3.

Embodiment 2

Be communicated with the booster 1 and the heat exchanger 2 that arrange;

Connect the pre-hydrogenation protecting reactor 3 and the hydrofining reactor 4 that arrange, described pre-hydrogenation protecting reactor 3Feed(raw material)inlet is connected with the material outlet of described heat exchanger 2;

Cold high pressure separator 6, is connected setting with the gaseous phase outlet of described high pressure hot separator 5, described cold high pressure separator 6Gaseous phase outlet be connected with circulating hydrogen compressor 13, the Compressed Gas of described circulating hydrogen compressor 13 exports respectively with describedThe hydrogen inlet of pre-hydrogenation protecting reactor 3, hydrofining reactor 4 and hydrocracking reactor 11 is communicated with setting;

Thermal low-pressure separators 7, is connected setting with the liquid-phase outlet of described high pressure hot separator 5, described thermal low-pressure separators 7The feed(raw material)inlet pipe of liquid-phase outlet and described pre-hydrogenation protecting reactor 3 be communicated with setting;

Cracking high-pressure separator 12, with the outlet setting of described hydrocracking reactor 11; Described cracking high-pressure separator12 liquid-phase outlet is communicated with setting with the feed(raw material)inlet pipe of described hydrofining reactor 4; Described cracking high-pressure separator 12Gaseous phase outlet is connected setting with described cold low separator 8.

(a) the full cut of coal tar is sent into pre-hydrogenation protecting reactor 3 after booster 1 and heat exchanger 2 pressurization intensifications,Pressure is that 18MPa, hydrogen to oil volume ratio are that 1150: 1, temperature are that 450 DEG C, volume space velocity are 0.1h^-1Condition under, use ammonium molybdateThe aqueous solution adds hydrogen pretreatment as hydrogenation protecting agent to the full cut of coal tar after pressurization heats up, and obtains pretreatment and generatesOil, the consumption of this hydrogenation protecting agent is counted 200 μ g/g with molybdenum element;

(b) described pretreatment generation oil is sent into hydrofining reactor 4 and carry out hydrofinishing, obtain hydrofinishing and produceThing; Described hydrorefined condition is: pressure 18MPa, hydrogen to oil volume ratio 1500: 1,360 DEG C of temperature, volume space velocity 5h^-1; DescribedThe molybdenum oxide that the Hydrobon catalyst that hydrofinishing is used is 5wt%, the nickel oxide of 5wt%, surplus is alumina support,And the pore volume of this catalyst for refining is that 0.35mL/g, specific area are 150m²/g；

(c) utilize high pressure hot separator 5 to described hydrotreated product carry out thermal high separate obtain thermal high gas phase andThermal high liquid phase; Recycling cold high pressure separator 6 carries out cold anticyclone separation to described thermal high gas phase and obtains cold high score gas and coldHigh pressure liquid phase, utilizes thermal low-pressure separators 7 to carry out heat low separation to described thermal high liquid phase and obtains heat low gas phase and hot lowPoint oil, can be used as after wherein said cold high score gas mixes with hydrogen and in step (a), adds hydrogen pretreatment, the middle hydrofinishing of step (b)And the hydrogen source of hydrocracking in step (e); Utilize cold low separator 8 to described heat low gas phase and described cold anticyclone liquid phaseMixture carries out cold low separation and obtains cold low point of gas and cold low point of oil; Wherein, the operating pressure that described thermal high separates is17.3MPa, operating temperature are 310 DEG C; The operating pressure that carries out described cold anticyclone separation is that 17.2MPa, operating temperature are 48 DEG C;The operating pressure that carries out described heat low separation is that 2.0MPa, operating temperature are 310 DEG C; Carry out the operation of described cold low separationPressure is that 2.0MPa, operating temperature are 45 DEG C;

(d) described cold low point of oil is sent into fractionating column 9 and carry out fractionation, cut out gasoline, the boiling point that boiling point is less than 150 DEG C and beTail oil and fuel gas that diesel oil, the boiling point of 150～370 DEG C is greater than 370 DEG C;

(e) a low described heat point of oily part and described tail oil are made to miscella and sent into hydrocracking reactor 11 and enterRow hydrocracking, in described hydrocracking reactor 11, flow through successively cracking protective agent bed, cracking of described miscella located in advanceReason agent bed and Cracking catalyst bed carry out hydrocracking reaction, and wherein said cracking protective agent is that Fu Yan institute developsFC-28 Catalyst For Single-stage Hydrocracking, described cracking pretreating agent and Cracking catalyst be respectively Uop Inc. exploitation DHC39,DHC-8 hydrocracking catalyst, the condition of described hydrocracking is: pressure 17MPa, hydrogen to oil volume ratio 3000: 1, temperature 300DEG C, volume space velocity 0.25h^-1; Cracking high-pressure separator 12 is cracking high score gas and cracking high score by the product separation of hydrocrackingOil, the mixture of wherein said cracking high score gas and described heat low gas phase and described cold anticyclone liquid phase jointly carries out cold low and dividesFrom, described cracking high score oil enters hydrofinishing together with after the described pretreatment generation oil mixing preparing in step (a)Reactor 4 carries out hydrofinishing; And low point of oily another part of described heat mixes with the full cut of described coal tar in step (a)Add hydrogen pretreatment.

Embodiment 3

(a) full coal tar cut being sent into pre-hydrogenation protecting reactor 3, is that 18MPa, hydrogen to oil volume ratio are 800 at pressure:1, temperature is that 375 DEG C, volume space velocity are 5h^-1Condition under, use nickel nitrate and cobalt acetate jointly as hydrogenation protecting agent to coalThe full cut of tar adds hydrogen pretreatment, obtains pretreatment and generates oil, and the consumption of this hydrogenation protecting agent is counted 60 μ g/ with nickel elementG, count 40 μ g/g with cobalt element;

(b) described pretreatment generation oil is sent into hydrofining reactor 4 and carry out hydrofinishing, obtain hydrofinishing and produceThing; Described hydrorefined condition is: pressure 18MPa, hydrogen to oil volume ratio 1150: 1,330 DEG C of temperature, volume space velocity 2.75h^-1，The molybdenum oxide that described hydrofinishing Hydrobon catalyst used is 15wt%, the nickel oxide of 10wt%, surplus is silicaCarrier, and the pore volume of this Hydrobon catalyst is that 0.5mL/g, specific area are 100m²/g；

(c) utilize high pressure hot separator 5 to described hydrotreated product carry out thermal high separate obtain thermal high gas phase andThermal high liquid phase; Recycling cold high pressure separator 6 carries out cold anticyclone separation to described thermal high gas phase and obtains cold high score gas and coldHigh pressure liquid phase, utilizes thermal low-pressure separators 7 to carry out heat low separation to described thermal high liquid phase and obtains heat low gas phase and hot lowDivide oil; Utilizing cold low separator 8 to carry out cold low to described heat low gas phase with the mixture of described cold anticyclone liquid phase separatesObtain cold low point of gas and cold low point of oil; Wherein, the operating pressure that described thermal high separates is that 17.3MPa, operating temperature are 310DEG C; The operating pressure that carries out described cold anticyclone separation is that 17.2MPa, operating temperature are 48 DEG C; Carry out described heat low separationOperating pressure is that 2.0MPa, operating temperature are 310 DEG C; The operating pressure that carries out described cold low separation is 2.0MPa, operation temperatureDegree is 45 DEG C.

(e) a low described heat point of oily part and described tail oil are made to miscella, described miscella is sent into hydrogenation and splitChange reactor 11, in described hydrocracking reactor 11, miscella flow through successively cracking protective agent bed, cracking pretreating agentBed and Cracking catalyst bed carry out hydrocracking reaction, and wherein said cracking protective agent is that the DHC-8 of Uop Inc.'s exploitation addsHydrogen Cracking catalyst, described cracking pretreating agent is the ZHC-01 Catalyst For Single-stage Hydrocracking that Fu Yan institute develops, described inCracking catalyst is the FC-14 Catalyst For Single-stage Hydrocracking that Fu Yan institute develops, and the condition of described hydrocracking is: pressure17MPa, hydrogen to oil volume ratio 1900: 1,340 DEG C of temperature, volume space velocity 4h^-1; Utilize cracking high-pressure separator 12 by hydrocrackingProduct separation is cracking high score gas and cracking high score oil, wherein said cracking high score gas and described heat low gas phase and described cold heightThe mixture of hydraulic fluid phase carries out cold low separation jointly, the described pre-place preparing in described cracking high score oil and step (a)After reason generation oil mixes, enter together hydrofining reactor 4 and carry out hydrofinishing; And low point of oily another part of described heat withAfter the full cut of described coal tar in step (a) mixes, enter pre-hydrogenation protecting reactor 3 and add hydrogen pretreatment.

Embodiment 4

(a) full coal tar cut being sent into pre-hydrogenation protecting reactor 3, is that 18MPa, hydrogen to oil volume ratio are 1200 at pressure: 1, average reaction temperature is that 350 DEG C, volume space velocity are 2.5h^-1Condition under, use potassium dichromate aqueous solution as hydrogenation protectingAgent adds hydrogen pretreatment to the full cut of coal tar, obtains pretreatment and generates oil, and the consumption of this hydrogenation protecting agent is in chromium elementBe 80 μ g/g;

(b) described pretreatment generation oil is sent into hydrofining reactor 4 and carry out hydrofinishing, obtain hydrofinishing and produceThing; Described hydrorefined condition is: pressure 18MPa, hydrogen to oil volume ratio 1200: 1,350 DEG C of temperature, volume space velocity 2.5h^-1; InstituteState Hydrobon catalyst that hydrofinishing the uses molybdenum oxide that is 22wt%, the nickel oxide of 8wt%, surplus is carrying aluminaBody, and the pore volume of this catalyst for refining is that 0.4mL/g, specific area are 190m²/g；

(e) a low described heat point of oily part and described tail oil are made to miscella, described miscella is sent into hydrogenation and splitChange reactor 11, flow through successively in described hydrocracking reactor 11 cracking protective agent bed, cracking of described miscella located in advanceReason agent bed and Cracking catalyst bed carry out hydrocracking reaction, and wherein said cracking protective agent and cracking pretreating agent are respectivelyFor FC-14, ZHC-01 Catalyst For Single-stage Hydrocracking that Fu Yan institute develops, described Cracking catalyst is Uop Inc.'s exploitationDHC39 hydrocracking catalyst, the condition of described hydrocracking is: pressure 17MPa, hydrogen to oil volume ratio 2000: 1, temperature 340DEG C, volume space velocity 4h^-1; Be cracking high score gas and cracking high score oil by the product separation of hydrocracking, wherein said cracking high scoreGas jointly carries out cold low with the mixture of described heat low gas phase and described cold anticyclone liquid phase and separates, described cracking high score oil withThe described pretreatment preparing in step (a) generates after oil mixes carries out hydrofinishing together; And oily another of low point of described heatA part is mixed and is carried out hydrogenation pretreatment with the full cut of described coal tar in step (a).

Comparative example

The trans hydrocracking process of the full cut of coal tar described in this comparative example, comprises the steps:

(e) a low described heat point of oily part and described tail oil are made to miscella, described miscella is sent into hydrogenation and splitChange reactor 11, flow through successively in described hydrocracking reactor 11 cracking protective agent bed, cracking of described miscella located in advanceReason agent bed and Cracking catalyst bed carry out hydrocracking reaction, and wherein said cracking protective agent and cracking pretreating agent are respectivelyFor FC-14, ZHC-01 Catalyst For Single-stage Hydrocracking that Fu Yan institute develops, described Cracking catalyst is Uop Inc.'s exploitationDHC39 hydrocracking catalyst, the condition of described hydrocracking is: pressure 17MPa, hydrogen to oil volume ratio 2000: 1, temperature 340DEG C, volume space velocity 4h^-1; Be cracking high score gas and cracking high score oil by the product separation of hydrocracking, wherein said cracking high scoreGas jointly carries out cold low with the mixture of described heat low gas phase and described cold anticyclone liquid phase and separates, and described cracking high score oil is straightTap into into fractionating column 9 and carry out fractionation; And the full cut of described coal tar in low point of oily another part of described heat and step (a) is mixedClose and add hydrogen pretreatment.

Described in this comparative example, the character of the full cut of coal tar is as shown in table 1, the trans hydrocracking of the full cut of described coal tarThe reaction condition of technique is as shown in table 2, and the gasoline that fractionation obtains and bavin oil properties are as shown in table 3.

The character of the full cut of coal tar described in table 1 embodiment 1-4 and comparative example

Project	The full cut of coal tar
		Density (20 DEG C), g/cm³	1.0981
Carbon residue, wt%	5.11
		Elementary analysis, wt%
C	81.31
		H	9.82
S	0.23
		N	0.76
O	7.83
		Metallic element, μ g/g
Fe	66.28
		Na	0.63
Ni	0.0483

V	0.0282
		Colloid, wt%	37.4
Water, wt%	5.4
		360 DEG C of tail oils of >, wt%	51.5

The reaction condition of the trans hydrocracking process of the full cut of coal tar described in table 2 embodiment 1-4 and comparative example

Gasoline, bavin oil properties that in table 3 embodiment 1-4 and comparative example, fractionation obtains

As can be seen from Table 2, adopt the trans hydrocracking process of the full cut of coal tar of the present invention complete to coal tarCut carries out hydrotreatment, more than the total amount of fuel gas that fractionation obtains, gasoline, diesel oil accounts for the 88.6wt% of coal tar consumption,The total amount of the fuel gas that obtains with comparative example fractionation, gasoline, diesel oil accounts for compared with the 79.6wt% of coal tar consumption, of the present inventionHydrocracking process has obviously improved the utilization rate of coal tar raw material. As shown in Table 3, adopt coal tar of the present invention entirely to heat up in a steamerDivide trans hydrocracking process to carry out hydrotreatment to coal tar, the sulfur content in gasoline that fractionation obtains is not higher than 8.5 μ gg^-1，Nitrogen content is not higher than 1.2 μ gg^-1, in the diesel oil simultaneously obtaining, sulfur content is not higher than 9.2 μ gg^-1, nitrogen content is not higher than 2.2 μg·g^-1, therefore the two all meets the quality standard of clean fuel.

Obviously, above-described embodiment is only for example is clearly described, and the not restriction to embodiment. RightIn those of ordinary skill in the field, can also make on the basis of the above description other multi-form variation orVariation. Here without also giving exhaustive to all embodiments. And the apparent variation of being extended out thus orVariation is still among the protection domain in the invention.

Claims

1. the trans hydrocracking process of the full cut of coal tar, comprises the steps:

(a) under the condition existing in hydrogenation protecting agent, the full cut of coal tar is added to hydrogen pretreatment, obtain pretreatment and generateOil;

(c) described hydrotreated product is carried out to thermal high separation and obtain thermal high gas phase and thermal high liquid phase; Again to described heatHigh pressure vapor is carried out cold anticyclone separation and is obtained cold high score gas and cold anticyclone liquid phase; Described thermal high liquid phase is carried out to heat low separationObtain heat low gas phase and low point of oil of heat; The mixture of described heat low gas phase and described cold anticyclone liquid phase is carried out to cold low to be dividedFrom obtaining cold low point of gas and cold low point of oil;

(d) described cold low point of oil is carried out to fractionation, cut out tail oil and fuel gas that gasoline, diesel oil, boiling point are greater than 370 DEG C;

(e) a low described heat point of oily part and described tail oil are mixed to get to miscella, described miscella are carried out to hydrogenation and splitChanging reaction, is cracking high score gas and cracking high score oil by the product separation of hydrocracking, wherein said cracking high score oil and step(a) the described pretreatment preparing in generates after oil mixes carries out hydrofinishing together.

2. the trans hydrocracking process of the full cut of coal tar according to claim 1, is characterized in that, low point of oil of described heatA part and described tail oil make miscella and carry out hydrocracking reaction, the described coal tar in another part and step (a)Hydrogenation pretreatment is carried out in the full cut mixing of oil.

3. the trans hydrocracking process of the full cut of coal tar according to claim 1, is characterized in that, in step (a), entersThe pretreated temperature of row hydrogenation is 300～450 DEG C, and pressure is 18MPa, and hydrogen to oil volume ratio is 800～1500:1, and volume space velocity is0.1～5.0h^-1。

4. the trans hydrocracking process of the full cut of coal tar according to claim 3, is characterized in that, in step (a), makesWith hydrogenation protecting agent be compound or the aqueous solution that contains active metal element, described active metal element be VB, VIB,One or more in VIII family metallic element; In every gram of described hydrogenation protecting agent, the content of active metal element is 50～200 μg。

5. the trans hydrocracking process of the full cut of coal tar according to claim 1, is characterized in that, in step (b), entersThe hydrorefined temperature of row is 330～390 DEG C, and pressure is 18MPa, hydrogen to oil volume ratio 800～1500:1, and volume space velocity is 0.5～5.0h^-1。

6. the trans hydrocracking process of the full cut of coal tar according to claim 5, is characterized in that, institute in step (b)State the molybdenum oxide that hydrofinishing Hydrobon catalyst used comprises 5～25wt%, the nickel oxide of 1～10wt%, surplus isSilica support or alumina support, the pore volume of described catalyst for refining be 0.20～0.50mL/g, specific area be 100～200m²/g。

7. the trans hydrocracking process of the full cut of coal tar according to claim 1, is characterized in that, in step (c), entersThe operating pressure that the described thermal high of row separates is that 17.3MPa, operating temperature are 310 DEG C; Carry out the operation of described cold anticyclone separationPressure is that 17.2MPa, operating temperature are 48 DEG C; The operating pressure that carries out described heat low separation is that 2.0MPa, operating temperature are310 DEG C; The operating pressure that carries out described cold low separation is that 2.0MPa, operating temperature are 45 DEG C.

8. according to the trans hydrocracking process of the full cut of coal tar described in claim 1-7 any one, it is characterized in that step(e) the described cracking high score gas that in, separation obtains and the mixture of described heat low gas phase and described cold anticyclone liquid phase carry out jointlyCold low separates and obtains cold low point of gas and cold low point of oil.

9. the trans hydrocracking process of the full cut of coal tar according to claim 1, is characterized in that, in step (e), entersThe pressure of the described hydrocracking of row is that 17MPa, hydrogen to oil volume ratio are that 800～3000:1, temperature are 260～340 DEG C, volume space velocityBe 0.1～4.0h^-1。

10. the trans hydrocracking process of the full cut of coal tar according to claim 9, is characterized in that, in step (e), entersWhen row hydrocracking reaction, described miscella flow through successively cracking protective agent bed, cracking pretreating agent bed and cracking catalysisAgent bed, wherein said cracking protective agent, cracking pretreating agent and Cracking catalyst are all with any one in Mo, W, Co or NiOr several be active component, taking aluminium oxide and/or molecular sieve as carrier.

11. according to the trans hydrocracking process of the full cut of coal tar described in claim 1,2,3,4,5,6,7,9 or 10, its spyLevy and be, described cold high score gas is mixed with hydrogen as adding hydrofinishing and step in hydrogen pretreatment, step (b) in step (a)Suddenly the hydrogen source of hydrocracking in (e).

12. 1 kinds of trans hydrogenation systems of the full cut of coal tar, comprising:

Connect the pre-hydrogenation protecting reactor (3) and the hydrofining reactor (4) that arrange; Described pre-hydrogenation protecting reactor (3)The feed(raw material)inlet pipe of outlet by described hydrofining reactor (4) be connected with the entrance of described hydrofining reactor (4)Connect;

High pressure hot separator (5), is connected setting with the outlet of described hydrofining reactor (4);

Cold high pressure separator (6), is connected setting with the gaseous phase outlet of described high pressure hot separator (5);

Thermal low-pressure separators (7), is connected setting with the liquid-phase outlet of described high pressure hot separator (5);

Cold low separator (8), with the liquid-phase outlet of described cold high pressure separator (6) and the gas of described thermal low-pressure separators (7)Outlet connects setting mutually;

Fractionating column (9), is connected setting with the liquid-phase outlet of described cold low separator (8);

Hydrocracking reactor (11), simultaneously with the liquid-phase outlet of described thermal low-pressure separators (7) and the tail of described fractionating column (9)Oil export connects setting;

Cracking high-pressure separator (12), is connected setting with the outlet of described hydrocracking reactor (11);

It is characterized in that the raw material of the liquid-phase outlet of described cracking high-pressure separator (12) and described hydrofining reactor (4)Inlet tube is communicated with and arranges, and is suitable for the liquid phase of described cracking high-pressure separator (12) and described pre-hydrogenation protecting reactor (3)Generate after oil mixes and carry out together hydrofinishing.

The trans hydrogenation system of the full cut of 13. coal tar according to claim 12, is characterized in that, described heat low separatesThe liquid-phase outlet of device (7) is communicated with setting with the feed(raw material)inlet pipe of described pre-hydrogenation protecting reactor (3) simultaneously.

14. according to the trans hydrogenation system of the full cut of the coal tar described in claim 12 or 13, it is characterized in that, described cracking is highPress the gaseous phase outlet of separator (12) to be connected setting with described cold low separator (8).

15. according to the trans hydrogenation system of the full cut of the coal tar described in claim 12 or 13, it is characterized in that, with described cold heightPress the gaseous phase outlet of separator (6) to be connected with circulating hydrogen compressor (13), the compressed gas of described circulating hydrogen compressor (13)Body outlet respectively with the hydrogen of described pre-hydrogenation protecting reactor (3), hydrofining reactor (4) and hydrocracking reactor (11)Gas entrance is communicated with setting.

The trans hydrogenation system of the full cut of 16. coal tar according to claim 14, is characterized in that, divides with described cold anticycloneBe connected with circulating hydrogen compressor (13) from the gaseous phase outlet of device (6), the Compressed Gas of described circulating hydrogen compressor (13) goes outMouth enters with the hydrogen of described pre-hydrogenation protecting reactor (3), hydrofining reactor (4) and hydrocracking reactor (11) respectivelyMouth is communicated with setting.