CN109554188A

CN109554188A - Heavy-oil hydrogenation thermal cracking and the concatenated oily coal of direct hydrogenation liquefaction of coal are total to smelting method

Info

Publication number: CN109554188A
Application number: CN201710969382.2A
Authority: CN
Inventors: 何巨堂
Original assignee: Individual
Current assignee: Individual
Priority date: 2017-09-27
Filing date: 2017-09-27
Publication date: 2019-04-02

Abstract

Heavy-oil hydrogenation thermal cracking and the concatenated oily coal of direct hydrogenation liquefaction of coal are total to smelting method, the heavy oil miscella that hydrogen supply dissolvent is prepared is converted into product AR1P in the first heavy-oil hydrogenation heat cracking reaction section AR1, hydrocarbonaceous liquid material flow A R1PX based on product AR1P, the second heavy-oil hydrogenation heat cracking reaction section AR2 is blended in as hydrogen supply dissolvent BDS and coal dust XS-FS, it carries out the second heavy-oil hydrogenation heat cracking reaction and Coal Liquefaction reaction AR2R is converted into product AR2P, it uses and carries out deep hydrogenation heat cracking reaction for material flow A R1PX bis- times, direct hydrogenation liquefaction of coal reaction process is reduced to the consumption of fresh hydrogen supply dissolvent oil, to reduce system gross investment, improve economy；The hydrogen logistics for being typically based on product AR1P enters AR2 reuse.

Description

Heavy-oil hydrogenation thermal cracking and the concatenated oily coal of direct hydrogenation liquefaction of coal are total to smelting method

Technical field

The present invention relates to the concatenated oily coals of heavy-oil hydrogenation thermal cracking and direct hydrogenation liquefaction of coal to be total to smelting method, and hydrogen supply dissolvent is matched The heavy oil miscella of system is converted into product AR1P in the first heavy-oil hydrogenation heat cracking reaction section AR1, based on the hydrocarbonaceous of product AR1P Liquid material flow A R1PX is blended in the second heavy-oil hydrogenation heat cracking reaction section AR2 as hydrogen supply dissolvent BDS and coal dust XS-FS, carries out Second heavy-oil hydrogenation heat cracking reaction and Coal Liquefaction reaction AR2R are converted into product AR2P, and material flow A R1PX bis- times using simultaneously Deep hydrogenation heat cracking reaction is carried out, reduces direct hydrogenation liquefaction of coal reaction process to the consumption of fresh hydrogen supply dissolvent oil, To reduce system gross investment, improve economy；The hydrogen logistics for being typically based on product AR1P enters AR2 reuse.

Background technique

Oily coal refines altogether, refers to carrying out total processing to coal and non-coal derived oils simultaneously.

It is total to smelting method about existing oily coal, a document for recording this kind of data is shown in document A01: 1. publication title: " Modern Coal-based Chemical technical manual ", page 1060 to page 1063；2. retrieval is encoded with books: ISBN coding: 978-7-122- 09636-4, Chinese depository library CIP data core word (2010) the 197010th；3. writing: He Yongde chief editor；4. publishing house: Chemical Industry Press.

Oily coal refines feedstock oil FD used in process, the usually high boiling substance of low value altogether, such as comes from PETROLEUM PROCESSING Pitch, extra-heavy crude oil or the petroleum residue or tar liquid hydrocarbon of industry, shale oil heavy oil or the husky heavy oil of oil.

Oily coal under traditional definition refines process altogether, and feedstock oil FD is used to prepare coal slurry and the pumped (conveying) medium as coal, not make With hydrogen supply dissolvent oil, there is no hydrogen supply dissolvent oil return line, basic technology can be single hop or two sections.Process, big portion are refined altogether in oily coal Divide derived from liquid product from oil rather than be made from coal, certain small part liquid product is made from coal.Oily coal refines process altogether, always Target is that petroleum derivative upgrading is reduced the investment and operating cost of unit product while coal liquefaction.But non-coal spreads out Raw solvent is poor to the solubility property of coal, and hydrogen supply capacity is also very low, and therefore, coal is converted into the development of evil in febrile disease rate of liquid product relatively It is low.

In fact, the oily coal under traditional definition is total to the research history of sweetening process more than 45 years, but so far still without business Change plant construction and operation.

Oily coal under existing traditional definition refines process for selective hydrogenation altogether, in order to realize the mesh of Low investment and low operating cost Mark, the condition premised on without using circulation hydrogen supply dissolvent；And hydrogenation process, the free radical that coal liquefaction generates are refined altogether in oily coal Stablize and need a large amount of reactive hydrogens, stablizing for the free radical that feedstock oil thermal cracking generates needs a large amount of reactive hydrogens, deviates from miscellaneous element As oxygen, sulphur, nitrogen plus hydrogen dissociation reaction need a large amount of reactive hydrogens, the wilderness demand of reactive hydrogen refines hydrogenation reaction mistake with oily coal altogether Cheng Wufa provides the essential contradiction that constitutes and can not balance between the inherent characteristics of a large amount of reactive hydrogens, lacks the reaction condition of reactive hydrogen Lower macromolecular hydrocarbon thermal cracking free radical high temperature thermal condensation reaction is a large amount of to be occurred, and a large amount of thermal condensation object such as coke, therefore, oily coal are generated When refining hydrogenation process altogether or coal conversion ratio be extremely low, and improving conversion ratio then a large amount of cokings cause reaction process long Between continuous operation.

As seen from the above analysis, the essential defect that the oily coal under existing traditional definition refines process for selective hydrogenation altogether exists It, can be in a large amount of reactive hydrogens that can not be provided reaction and need, and by using the hydrogen supply dissolvent oil that can be released effectively reactive hydrogen It significantly improves existing oily coal and refines hydrogenation process altogether, still, if anti-using existing direct hydrogenation liquefaction of coal is analogous to The a large amount of circulation hydrogen supply dissolvents oil for answering process to use, is used to hydrogen supply dissolvent oil to prepare coal slurry, mix with heavy oil and as coal Pumped (conveying) medium then will lead to investment and operating cost substantial increase that oily coal refines the unit product of overall process altogether, lose " the phase What the oily coal of prestige refined altogether " economic competitiveness, key reason is that hydrogen supply dissolvent oil dosage is excessive.

Independent heavy oil is especially the heat from hydrogenation cracking process for being rich in the heavy oil of aromatic hydrocarbons, what heavy oil feedstock oil thermal cracking generated Stablizing for free radical needs a large amount of reactive hydrogens, deviate from miscellaneous element for example oxygen, sulphur, nitrogen plus hydrogen dissociation reaction need a large amount of reactive hydrogens, The wilderness demand of reactive hydrogen, it is desirable that just can guarantee operation steady in a long-term using circulation hydrogen supply dissolvent, no person generates a large amount of thermal condensations Object such as coke, and generate huge temperature rise and increase control difficulty, therefore its economy is lower.

In fact, the direct hydrogenation liquefaction of coal process of economic high conversion must use hydrogen supply dissolvent oil, this is being recognized On the basis of one objective fact, the present invention wishes to propose that a kind of oily coal of reasonable is total to smelting method, reduces construction investment, simultaneous The optimization of heavy-oil hydrogenation thermal cracking process, the operating condition of direct hydrogenation liquefaction of coal process is cared for, therefore, it is an object of the present invention to such as What building combination process, reduces the total dosage of hydrogen supply dissolvent.

Demand of the different location of following analysis direct hydrogenation liquefaction of coal reaction process to hydrogen supply agent.

It is well known that coal adds hydrogen direct liquefaction reaction process, the pyrolysis of coal is generally undergone, adds hydrogen and further decomposes Etc. processes, eventually become stable pot liquor molecule.

The pyrolytic process of coal will convert coal into liquid, it is necessary to the macromolecular structure for destroying coal, make its be decomposed into be suitble into The size of one step processing.So the first step of DCL/Direct coal liquefaction is exactly to destroy the macromolecular structure of coal.Due to direct liquefaction raw material In the macromolecular structure of coal, the bridged bond intensity for connecting basic structural unit is weaker, when the outer active force of application is more than the intensity of bridged bond When, the bridged bond for connecting basic structural unit can be broken, and free radical fragment is decomposed into, since this process is generally by mentioning High-temperature is realized, is normally referred to as pyrolyzed.In pyrolytic process, coal is to be added in circulation solvent coal slurry is made to participate in later Reaction, so while pyrolysis, the physical reactions such as dissolution can also occur for coal.Different technique may be by hydrogen and solvent one It rises and uses, some possibility use catalyst.The process conditions of this step differ greatly, and temperature is at 370~470 DEG C, and pressure is 15 ~30MPa changes.

The free radical that pyrolysis of coal generates, Yi Fasheng polymerization reaction.The effect of solvent in this step is quite important, it is with two Kind approach reduces polymerization reaction.The first approach is that the free radical fragment that it physically generates reaction separates in a solvent. Therefore, this solvent will get well the solubility property of heavy aromatic substance.Second approach is release hydrogen to free radical, is become steady Determine molecule.The approach is suitble to the molecule containing polycyclic aromatic hydrocarbon structure in solvent.The aromatic hydrocarbon of partial hydrogenation can be in solvent Free radical fragment with high reactivity shifts and provides hydrogen, and reactivity ratio's Gaseous Hydrogen of the hydrogen provided in hydrogenation solvent wants height to be permitted It is more.In high-pressure catalytic system, it is considered that gas phase hydrogen is by transferring to coal with solvent reaction.Add hydrogen degree suitable Hydrogen reactivity in solvent is very high, therefore is always ensured that in solvent extremely important containing reactive hydrogen.

Although the pyrolytic process of coal is along with the dissolution of coal, the pyrolysis of coal or the key reaction in the stage.Coal with When solvent is heated to 250 DEG C nearby, just there are some weak bonds to be broken in coal, can produce small molecule product.When heating temperature is super When crossing 250 DEG C and entering coal liquefaction temperature range, the pyrolytic reaction of diversified forms occurs, the unstable key in coal starts to break Split, as carbonyl bond, carboxyl key, ehter bond, thioether bond, methene key, low bond energy hydrogen-carbon link.

In pyrolytic process, the dissolution phenomena of coal occurs coal simultaneously, the dissolution phenomena of coal referred herein be do not include heat The dissolution for solving free radical fragment, is the physical dissolution phenomenon of coal itself.The dissolution phenomena of coal can use the two phase model solution of coal It releases, macromolecular network is stationary phase, and being embedded in small molecule therein is then mobile phase.

Hydrocracking process in direct hydrogenation liquefaction of coal reaction process includes two meanings, and one is that pyrolysis generates Meta-stable free radical fragment is by adding hydrogen to become to stablize molecule, second is that the macromolecular product that cracking generates further is hydrocracked At small molecule.The substance generated during pyrolytic reaction still contains macromolecular.If using retortable liquid as final products, this A little molecules must reduce molecular dimension by being hydrocracked.It is hydrocracked also another effect, that is, is deviate from disproportionate Sulphur and nitrogen.

Hydrocracking reaction can carry out in same reactor with the pyrolytic reaction of coal, or walk as independent operation Suddenly.In the first scenario, inexpensive abandoning property Fe-series catalyst or carrier metal catalyst can be used.Second situation is logical It is often used the metallic catalyst carried on alumina.

Weak bond in the macromolecular of coal is broken after being heated to certain temperature, is produced and is with coal texture unit The fractionlet on basis, and unpaired electronics is had in breaking part, this molecular fragment with unpaired electron is in chemistry Referred to as free radical, its relative molecular weight range are 300~1000.By means of modern large-sized analytic instrument -- electron spin resonance Instrument can measure the number of free radical of pyrolysis of coal generation.The unpaired electron of free radical band has very high reactivity, it has It is combined into the trend to (i.e. composition covalent bond) with unpaired electron on neighbouring free radical, and hydrogen atom is minimum, most simple Free radical can be with if the free radical fragment after pyrolysis of coal can obtain necessary hydrogen atom from matrix of coal or solvent Free radical is set to reach stable.The process that hydrogen is obtained from the matrix of coal is actually to have carried out the reallocation of hydrogen content of coal, this to make The stable process of free radical is referred to as self-stabilization process.Hydrogen atom is obtained from solvent molecule is referred to as solvent hydrogen supply.Solvent In certain partially hydrogenated polycyclic aromatic hydrocarbons be easy to release hydrogen atom, such as the C-H bond key on 9,10 in 9,10- dihydroanthracene Can be also less high, it is easily broken off at the reaction temperatures and releases 2 hydrogen atoms and itself become anthracene molecule, it is this to have to coal The solvent of free radical fragment hydrogen supply capacity be known as hydrogen supply dissolvent.

If the free radical fragment of coal cannot get hydrogen atom and its very big concentration, these free radical fragments will phase Mutually combine and generate the bigger compound of relative molecular weight or generation coke, initial reaction stage of this phenomenon in coal liquefaction It is obvious that because coal free radical debris concentration is very high.

Free radical stablize after intermediate product relative molecular weight distribution it is very wide, relative molecular weight it is small be distillate, relatively The big referred to as asphaltene of molecular weight, the bigger referred to as preasphaltene of relative molecular weight, preasphaltene can be further by adding hydrogen point Solution is at the lesser asphaltene of relative molecular weight, distillate and gas.Same asphaltene is by adding hydrogen that can further generate distillate And hydrocarbon gas, the reaction of DCL/Direct coal liquefaction is usually known as parallel series reaction.

When Coal liquefaction is under Hydrogen Vapor Pressure atmosphere and in the presence of catalyst, hydrogen molecule is by activation of catalyst, activation Hydrogen molecule afterwards can directly be reacted with the intermediate product molecule after stabilization, and this reaction is known as plus hydrogen.Hydrogenation reaction subdivides There are aromatic hydrogenation saturation, hydrogenation deoxidation, hydrodesulfurization, hydrodenitrogeneration and is hydrocracked.

The activity difference of hydrogenation catalyst or the severity of hydroconversion condition are different, and the depth of hydrogenation reaction is also different.In coal In liquefying reactor, be only capable of complete partial hydrogenation reaction, coal liquefaction generate a liquefaction oil also contain a large amount of aromatic hydrocarbons and it is oxygen-containing, The compound of sulphur, nitrogen heteroatom, it is necessary to which further adding hydrogen to liquefaction oil just can make aromatic hydrocarbons be saturated and deviate from hetero atom, reach final The quality standard of product -- gasoline, diesel oil, the repeated hydrogenation of second step, referred to as liquefaction oil plus hydrogen upgrading.

Experimental results demonstrate when the one way reaction time of heavy-oil hydrogenation thermal cracking is generally only direct hydrogenation liquefaction of coal reaction Between 40~70%, the first one way heat from hydrogenation cracking stage is the stage of reaction of the strongest component of reactivity, the free radical of generation It is more therefore big to the demand of hydrogen supply dissolvent oil；The secondary hot tearing for causing light components excessive in order to avoid one way reaction process Solution reaction generates bulk gas, and usually controlling conversion per pass is 50~60%, and a large amount of heavy oil is needed to recycle in this way, heavy oil circulation Heavy-oil hydrogenation thermal cracking process can be deteriorated, reaction temperature is higher, green coke amount is bigger, but reaction speed adds hydrogen compared with the first one way The thermal cracking stage is much lower, and the free radical of generation is less, therefore less to the demand of hydrogen supply dissolvent oil；Heavy oil circulation adds hydrogen Thermal cracking process adsorbs coking to prevent reactor deposit coke from coke being needed to carry agent as coking center；It recycles in heavy oil Containing a large amount of hydrogen supply dissolvent, the hydrogen supply dissolvent that may be used as direct hydrogenation liquefaction of coal reaction process is used, and recycles heavy oil It is potential direct hydrogenation liquefaction of coal reaction raw materials with slurry solvent, because the high coal of coal powder density can be made such as Coal powder density is up to 70~80% coal, that is to say, that heat from hydrogenation of less amount of heavy oil or heavy oil can be used and split Metaplasia carries a large amount of coal dust and enters direct hydrogenation liquefaction of coal reaction high-pressure system at oil.

Experimental results demonstrate 20~40% initial reaction stage of conventional direct hydrogenation liquefaction of coal reaction process, i.e., complete Stablize task at the most of pyrolysis task and free radical of coal, the 40~60% of total consumption hydrogen is consumed, as coal hydrogenation is direct The time of liquefaction reaction process extends, and the quantity of the organic matter for the coal that can be pyrolyzed is fewer and fewer, therefore coal is once pyrolyzed free radical The concentration of fragment is lower and lower, and the stable molecule of pyrolysis of coal fragment resistate conversion gained is more and more, can serve as hydrogen supply dissolvent Substance it is more and more, in this way, the hydrogen supply in the initial reaction stage with the 20~40% of direct hydrogenation liquefaction of coal reaction process is molten Agent quantity is compared, the hydrogen supply dissolvent quantity of later stage occur it is relatively rich remaining, can in order to improve the utilization rate of hydrogen supply substance The heavy oil of hydrogen supply dissolvent is needed to carry out joint processing to introduce, to improve process economy.

Therefore, it is reacted in the first one way heat from hydrogenation cracking stage, the direct hydrogenation liquefaction of coal for avoiding heavy-oil hydrogenation thermal cracking Under conditions of the initial reaction stage overlapping of the 20~40% of process occurs, using one section of heavy-oil hydrogenation thermal cracking hydrocarbon products as coal Add the secondary reuse of hydrogen supply dissolvent of hydrogen direct liquefaction reaction process, it is possible to reduce the total dosage of hydrogen supply dissolvent improves technique warp Ji property；Oil coal of the invention is total to smelting method, in particular to the coal slurry workflow position that enters heavy-oil hydrogenation heat cracking reaction process, together When, under the conditions of existing for the direct hydrogenation liquefaction of coal reaction process, one section of heavy-oil hydrogenation thermal cracking Light hydrocarbon products (such as it is conventional The hydrocarbon component that 250~430 DEG C of boiling point) it is used as hydrogen supply agent, it is suppressed its secondary heat from hydrogenation cracking reaction, also reduces gas Body yield；In this way, the hydrogen supply dissolvent into one section of heavy-oil hydrogenation heat cracking reaction process is substantially to start solvent naphtha, discharge one (including starting hydrogen supply dissolvent conversion product and one section of heavy-oil hydrogenation thermal cracking produce the liquid of section heavy-oil hydrogenation heat cracking reaction process Object) be substantially the self-produced secondary solvent oil of system, present invention utilizes secondary solvent oil thus create economy.

So far, basic conception of the invention: heavy-oil hydrogenation thermal cracking and the concatenated oily coal of direct hydrogenation liquefaction of coal is proposed Smelting method altogether, the heavy oil miscella that hydrogen supply dissolvent is prepared are converted into product AR1P in the first heavy-oil hydrogenation heat cracking reaction section AR1, Hydrocarbonaceous liquid material flow A R1PX based on product AR1P is blended in the second heavy-oil hydrogenation heat as hydrogen supply dissolvent BDS and coal dust XS-FS Soaking section AR2, carries out the second heavy-oil hydrogenation heat cracking reaction and Coal Liquefaction reaction AR2R is converted into product AR2P, object It flows AR1PX bis- times and uses and carry out deep hydrogenation heat cracking reaction, reduce direct hydrogenation liquefaction of coal reaction process to fresh confession The consumption of hydrogen solvent naphtha, to reduce system gross investment, improve economy；Be typically based on the hydrogen logistics of product AR1P into Enter AR2 reuse.

Since the product of one section of heavy-oil hydrogenation heat cracking reaction process needs to reduce temperature using circulation quench oil to control The initial reaction temperature in downstream reaction area, it is therefore, also of the invention at implementation as long as replacing circulation quench oil with coal A kind of mode, compared with conventional oily coal is total to sweetening process, there are also coal raw material is heated to 350~430 by 150~200 DEG C DEG C the step of omit and directly recycle the advantage of one section of heavy-oil hydrogenation heat cracking reaction heat.Therefore, partial function of the invention, It can be described as with the outer heavy-oil hydrogenation method for thermal cracking for coal surrogate response process circulation quench oil.Certainly, portion of the invention The addition temperature for dividing coal, is heated to 350~430 DEG C by 150~200 DEG C as needed, to realize the oily coal of anticipated number Slurry is kneaded；One section of heavy-oil hydrogenation heat cracking reaction process, hydrogen supply dissolvent amount are usually 0.5~2 times of heavy oil, are kneaded coal Quantity can achieve 1~3 times of heavy oil material.

The method of the present invention is combined with the process for improving heat from hydrogenation cracking reaction process hydrogen partial pressure, and effect is more preferable, The hydrogen supply capacity of the secondary hydrogen supply dissolvent used can be improved.

The technical solution similar with the present invention has not been reported.

The first object of the present invention is to propose that heavy-oil hydrogenation thermal cracking is refined altogether with the concatenated oily coal of direct hydrogenation liquefaction of coal Method.

The second object of the present invention is to propose that heavy-oil hydrogenation thermal cracking is refined altogether with the concatenated oily coal of direct hydrogenation liquefaction of coal Method, the naphtha for voluminous Gao Fangqian.

Summary of the invention

Heavy-oil hydrogenation thermal cracking of the present invention and the concatenated oily coal of direct hydrogenation liquefaction of coal are total to smelting method, it is characterised in that include Following steps:

(1) first heavy-oil hydrogenation heat cracking reaction section AR1, the coal AR1F containing hydrogen supply dissolvent AR1-DS, heavy oil FD It carries out the first heavy-oil hydrogenation heat cracking reaction AR1R of at least part and is converted into the first heavy-oil hydrogenation heat cracking reaction product AR1P；

Hydrocarbonaceous liquid material based on the first heavy-oil hydrogenation heat cracking reaction product AR1P is used as the first series connection liquid phase stream AR1PX；

(2) enter the second heavy-oil hydrogenation thermal cracking in the second heavy-oil hydrogenation heat cracking reaction section AR2, the first material flow A R1PX Conversion zone AR2, coal slurry material XS enter the second heavy-oil hydrogenation heat cracking reaction section AR2, carry out the second heavy oil of at least part and add Hydrogen heat cracking reaction and Coal Liquefaction reaction AR2R are converted into the second heavy-oil hydrogenation heat cracking reaction product AR2P；

Coal slurry material XS is made of coal dust XS-FS and oil XS-FL with slurry；

(3) in separate section S100, the second heavy-oil hydrogenation heat cracking reaction product AR2P is recycled, hydrogen supply dissolvent predecessor is obtained Hydrocarbon MFB；

(4) stabilized hydrogenation reaction is carried out in stabilized hydrogenation reaction process MR, hydrogen supply dissolvent predecessor hydrocarbon MFB complete aromatic hydrocarbon molecule Part aromatic ring saturated reaction MRR be converted into stabilized hydrogenation reaction product MRP；

Stabilized hydrogenation reaction product MRP is recycled, hydrogen supply dissolvent DS is obtained；

At least part hydrogen supply dissolvent DS enters the first heavy-oil hydrogenation heat cracking reaction section AR1 and is used as hydrogen supply dissolvent AR1- DS。

The present invention, in general, heavy oil FD, mainly the hydro carbons by normal boiling point higher than 350 DEG C is formed.

1. in the first heavy-oil hydrogenation heat cracking reaction section AR1, based on the first heavy-oil hydrogenation heat cracking reaction product AR1P's Hydrogen material is used as the first series connection gaseous stream AR1P-HVX；

2. in the second heavy-oil hydrogenation heat cracking reaction section AR2, at least part the first series connection gaseous stream AR1P-HVX ginseng A part of the second heavy-oil hydrogenation heat cracking reaction product AR2P is converted into the second heavy-oil hydrogenation heat cracking reaction AR2R；

3. recycling the second heavy-oil hydrogenation heat cracking reaction product AR2P in separate section S100, obtaining the richness containing hydrogen Hydrogen gas stream ARH, at least part hydrogen-rich stream ARH return to the first heavy-oil hydrogenation heat cracking reaction section AR1 and/or the second weight Oily heat from hydrogenation soaking section AR2.

The present invention, in general, heavy oil FD, the usually hydro carbons mainly by normal boiling point higher than 350 DEG C are formed, are general mainly by normal Hydro carbons of the boiling point higher than 530 DEG C is advised to form.

The present invention, heavy oil FD can 1 kinds or several in following materials:

1. oil product obtained by middle coalite tar or its distillate or its hot procedure；Hot procedure is selected from coking Or catalytic cracking process or catalytic pyrolysis process or hydrogenation process；

2. oil product logistics obtained by high temperature coal-tar or its distillate or its hot procedure；Hot procedure is selected from coking Journey or catalytic cracking process or catalytic pyrolysis process or hydrogenation process；

3. oil product obtained by the distillate oil of direct hydrogenation liquefaction of coal process product or its hot procedure；Hot procedure is selected from Coking or catalytic cracking process or catalytic pyrolysis process or hydrogenation process；

4. oil product obtained by shale oil or its distillate or its hot procedure；Hot procedure is selected from coking or catalysis Cracking process or catalytic pyrolysis process or hydrogenation process；

5. oil product obtained by ethylene cracking tar or its hot procedure；Hot procedure is selected from coking or catalytic cracking Process or catalytic pyrolysis process or hydrogenation process；

6. oil product obtained by petroleum based heavy fuel oils hot procedure；Hot procedure be selected from coking or catalytic cracking process or Catalytic pyrolysis process or hydrogenation process；

7. oil product hot procedure obtained by tar sand base weight oil or its hot procedure is selected from coking or catalytic cracking Process or catalytic pyrolysis process or hydrogenation process；

8. other aromatic hydrocarbons weight contents are higher than 40% hydrocarbon ils.

The coal powder density of the present invention, coal slurry material XS are preferably higher than 70%.

The present invention, coal slurry material XS are made of coal dust XS-FS and oil XS-FL with slurry；

Oil XS-FL with slurry, can a kind or several in following materials:

1. oil identical with heavy oil FD is used as oil XS-FL with slurry；

2. the quench oil of the first heavy-oil hydrogenation heat cracking reaction product AR1P；

3. separating the low point of oil AR1P-TLPS-L of heat that the first heavy-oil hydrogenation heat cracking reaction product AR1P is obtained；

First heavy-oil hydrogenation heat cracking reaction product AR1P is separated into hot high score gas in thermal high separation process AR1P-THPS AR1P-THPS-V and hot high score oil AR1P-THPS-L, hot high score oil AR1P-THPS-L are separation process AR1P-TLPS points low in heat It is used as oil XS- with slurry from for heat low point of gas AR1P-TLPS-V and low point of oil AR1P-TLPS-L of heat, low point of oil AR1P-TLPS-L of heat FL；

4. separate that the first heavy-oil hydrogenation heat cracking reaction product AR1P obtains is mainly 350~530 DEG C by normal boiling point The wax oil of hydro carbons composition, is used as oil XS-FL with slurry；

5. separate that the first heavy-oil hydrogenation heat cracking reaction product AR1P obtains is mainly higher than 530 DEG C of hydro carbons by normal boiling point The residual oil of composition is used as oil XS-FL with slurry；

6. initial boiling point is higher than heavy oil FD initial boiling point, mean boiling point is higher than the heavy oil of heavy oil FD mean boiling point；

7. the coal powder density for preparing coal slurry material XS is higher by 20% than the heavy oil FD coal powder density for preparing coal slurry material XS Heavy oil；

The present invention, in general, in the second heavy-oil hydrogenation heat cracking reaction section AR2, the temperature of at least part coal slurry material XS Lower than the operation temperature of the first heavy-oil hydrogenation heat cracking reaction product AR1P, also below the second heavy-oil hydrogenation heat cracking reaction section The initial reaction temperature of AR2, i.e. at least part coal slurry material XS serve as the first heavy-oil hydrogenation heat cracking reaction product AR1P into Enter the coolant of the second heavy-oil hydrogenation heat cracking reaction section AR2.

The present invention, in general, (1) normal boiling point in the first heavy-oil hydrogenation heat cracking reaction section AR1, heavy oil FD is higher than 350 DEG C hydro carbons cracking conversion rate be 30~60%；The hydrogen of heavy oil FD consumes DH1, accounts for the total of heavy-oil hydrogenation heat cracking reaction process AR Hydrogen consumes the 30~60% of DH.

The present invention, in general, (1) is in the first heavy-oil hydrogenation heat cracking reaction section AR1, the weight flow rate of hydrogen supply dissolvent AR1-DS The ratio of the weight flow rate FD-W of AR1-DS-W and heavy oil FD is oil ratio K100=(AR1-DS-W)/(FD-W), K100 0.5 ~2.0.

The present invention, in general, (2) coal dust XS-FS in the second heavy-oil hydrogenation heat cracking reaction section AR2, coal slurry material XS The ratio of the weight flow rate FD-W of weight flow rate XS-FS-W and heavy oil FD is kerosene ratio K500=(XS-FS-W)/(FD-W), K500 is 0.01~3.0.

The present invention, (2) in the second heavy-oil hydrogenation heat cracking reaction section AR2, coal slurry material XS coal dust XS-FS plus hydrogen it is straight Connect the liquefied fraction of liquefaction reaction process, typically larger than 85%, generally higher than 90%；

The overall conversion of heavy oil FD, typically larger than 70%, generally higher than 80%.

The present invention, in general, (2) are in the second heavy-oil hydrogenation heat cracking reaction section AR2, the hydrogenation liquefaction that coal dust XS-FS is carried out The operating condition of reaction process XS-FS-AR2 are as follows: reaction temperature is 400~465 DEG C, and reactor pressure is 6~30MPa, gas phase Hydrogen volume concentration 50~95%, gas-liquid volume ratio are 300~1500Nm³/ t, catalyst for coal liquefaction additive amount are dry pulverized coal weight 0.1~3 mass % of amount, co-catalyst additive amount be sulphur in co-catalyst/catalyst activity metal molar ratio be 1.0~ 2.0, coal slurry solid concentration is 40~60 mass %, and reaction time is 0.5~4 hour.

The present invention, (2) were reacted in the second heavy-oil hydrogenation heat cracking reaction section AR2, the hydrogenation liquefaction that coal dust XS-FS is carried out The hydrogenation catalyst that journey XS-FS-AR2 is used can be a kind of composite hydrogenation catalyst, include high-activity component and low activity Component；The weight ratio of the high-activity component metal and low activity component metals is 1: 10 to 10: 1；The high-activity component is Or mixtures thereof water soluble salt compound of molybdenum；The low activity group is divided into ferric oxide ore or iron sulfide ore, chats Iron content is not less than 40wt% in stone, and catalyst for coal liquefaction water content is lower than 2wt%；The particle diameter of catalyst for coal liquefaction is 1 ~100 μm of powdered granule.

The present invention, (2) were reacted in the second heavy-oil hydrogenation heat cracking reaction section AR2, the hydrogenation liquefaction that coal dust XS-FS is carried out The hydrogenation catalyst that journey XS-FS-AR2 is used, can for nanometer ultra-fine grain aqua oxidation iron catalyst and/or iron oxide and/or Pyrite and/or bloodstone and/or molybdenum oxide and/or molybdenum sulfide and/or ammonium molybdate and/or nickel sulfide.

The present invention, (4) prepare hydrogen supply in stabilized hydrogenation reaction process MR, for the first heavy-oil hydrogenation heat cracking reaction section AR1 Solvent, solvent oil hydrogenation stablize the hydrogenation catalyst that the hydrogenation catalyst that reaction process MR is used is Ni-Mo, Ni-Co or Ni-W system Agent；Reaction temperature is 300~390 DEG C, and hydrogenation pressure is 10~25MPa, and gas-liquid volume ratio is 300~1000Nm³/t；In general, Normal boiling point in reaction product MRP is higher than 250 DEG C of hydro carbons: the weight content of fractional saturation aromatic hydrocarbons is greater than 15%, aromatic carbon rate and is 0.35~0.70；Generally, the normal boiling point in reaction product MRP is higher than 250 DEG C of hydro carbons: the weight content of fractional saturation aromatic hydrocarbons is big In 25%, aromatic carbon rate be 0.45~0.60.

The present invention, (2) were reacted in the second heavy-oil hydrogenation heat cracking reaction section AR2, the hydrogenation liquefaction that coal dust XS-FS is carried out Journey XS-FS-AR2, the mode of operation of the Coal Liquefaction reactor used can be selected from a kind or several of combination in following:

1. suspension bed, that is, slurry bed system；

2. ebullated bed.

The present invention, (4) stablize the operation side of reactor in the solvent oil hydrogenation in stabilized hydrogenation reaction process MR, used Formula, can be selected from a kind or several of combination in following:

1. floating bed hydrogenation reactor；

2. boiling bed hydrogenation reactor usually draws off the decreased catalysis of activity from bed bottom in an intermittent fashion Agent fills into fresh catalyst from bed top in an intermittent fashion and maintains bed catalyst reserve；

3. up flow type slight expanded-bed；

4. upflow fixed bed；

5. down-flow fixed bed；

6. the low liquid phase systemic circulation hydrogenator of hydrogen to oil volume ratio.

The second heavy-oil hydrogenation heat cracking reaction product AR2P is recycled in separate section S100 in the present invention, (3), obtains main It is the distillate that 350~530 DEG C of hydrocarbon-fractions form by conventional boiling range, the first heavy-oil hydrogenation heat cracking reaction section AR1 can be returned It carries out the first heavy-oil hydrogenation heat cracking reaction and/or the second heavy-oil hydrogenation heat cracking reaction section AR2 carries out the second heavy-oil hydrogenation hot tearing Change reaction.

The present invention, (2), can will be anti-in the second heavy-oil hydrogenation thermal cracking in the second heavy-oil hydrogenation heat cracking reaction section AR2 A section Partial Liquid Phase material for AR2 discharge is answered, the first heavy-oil hydrogenation heat cracking reaction section AR1 is introduced and carries out the first heavy-oil hydrogenation hot tearing Change reaction.

The present invention, (1) first series connection gaseous stream AR1P-HVX, can be following one or more:

1. the first series connection gaseous stream AR1P-HVX is the thermal high point of the first heavy-oil hydrogenation heat cracking reaction product AR1P The hot high score gas AR1P-THPS-V isolated from process AR1P-THPS；

2. the first series connection gaseous stream AR1P-HVX is the thermal high point of the first heavy-oil hydrogenation heat cracking reaction product AR1P What the medium temperature high pressure separation process AR1P-MHPS from the process AR1P-THPS hot high score gas AR1P-THPS-V isolated was isolated Medium temperature high pressure separates gas AR1P-MHPS-V；

3. the first series connection gaseous stream AR1P-HVX is the thermal high point of the first heavy-oil hydrogenation heat cracking reaction product AR1P Medium temperature high pressure separation process AR1P-MHPS's from the process AR1P-THPS hot high score gas AR1P-THPS-V isolated isolates Medium temperature high pressure separation gas AR1P-MHPS-V cold anticyclone separation process AR1P-LHPS isolate cold anticyclone separation gas AR1P-LHPS-V；

4. the first series connection gaseous stream AR1P-HVX is the thermal high point of the first heavy-oil hydrogenation heat cracking reaction product AR1P Cold anticyclone separation process AR1P-LHPS from the process AR1P-THPS hot high score gas AR1P-THPS-V isolated isolates cold High pressure separates gas AR1P-LHPS-V.

The present invention, in general, the operating condition of (1) first heavy-oil hydrogenation heat cracking reaction section AR1 are as follows: reaction temperature 400 ~465 DEG C, reactor pressure be 6~30MPa, gas-liquid volume ratio be 300~1500Nm³/ t, catalyst loading are heavy oil FD 0.5~3 mass % of weight, co-catalyst additive amount be sulphur in co-catalyst/catalyst activity metal molar ratio be 1.0~ 2.0。

The present invention, the hydrogenation catalyst that (1) first heavy-oil hydrogenation heat cracking reaction section AR1 is used can be a kind of compound Type hydrogenation catalyst includes high-activity component and low activity component；The high-activity component metal and low activity component metals Weight ratio is 1: 10 to 10: 1；The high-activity component is or mixtures thereof the water soluble salt compound of molybdenum；The low activity Group is divided into ferric oxide ore or iron sulfide ore, and wherein iron in ore content is not less than 40wt%, and catalyst water content is lower than 2wt%；The powdered granule that catalyst particle diameter is 1~100 μm.

The present invention, the hydrogenation catalyst that (1) first heavy-oil hydrogenation heat cracking reaction section AR1 is used, it is ultra-fine to can be nanometer Particle aqua oxidation iron catalyst and/or iron oxide and/or pyrite and/or bloodstone and/or molybdenum oxide and/or molybdenum sulfide and/or molybdenum Sour ammonium and/or nickel sulfide.

Specific embodiment

The present invention described in detail below.

Pressure of the present invention, refers to absolute pressure.

Normal boiling point of the present invention refers to vapour of the substance under an atmospheric pressure, liquid equilibrium temperature.

Routine boiling range of the present invention refers to the normal boiling point range of fraction.

Specific gravity of the present invention, unless stated otherwise, refer to normal pressure, fluid density and normal pressure under the conditions of 15.6 DEG C, The ratio of water density under the conditions of 15.6 DEG C.

The composition or concentration or content or yield value of component of the present invention are unless stated otherwise weight basis Value.

Conventional gas hydrocarbon of the present invention refers under normal condition in gaseous hydro carbons, including methane, ethane, third Alkane, butane.

Conventional liq hydrocarbon of the present invention refers to the hydro carbons being in a liquid state under normal condition, including pentane and its boiling point Higher hydro carbons.

Impurity element of the present invention, refer to non-hydrogen in feedstock oil, non-carbon, nonmetallic ingredient for example oxygen, sulphur, nitrogen, Chlorine etc..

Impurity composition of the present invention refers to hydro-conversion object such as water, ammonia, the vulcanization of non-hydrocarbon component in feedstock oil Hydrogen, hydrogen chloride etc..

Light hydrocarbon of the present invention is naphtha component, refers to that normal boiling point is lower than 200 DEG C of conventional liq hydrocarbon.

Middle matter hydrocarbon of the present invention is diesel component, refers to that normal boiling point is 200~330 DEG C of hydro carbons.

Wax oil component of the present invention refers to that normal boiling point is 330~530 DEG C of hydro carbons.

Heavy hydrocarbon of the present invention refers to that normal boiling point is higher than 330 DEG C of hydro carbons.

Hydrogen to oil volume ratio of the present invention refers to the normal of the standard state volume flow of hydrogen and specified oily logistics The ratio of pressure, 20 DEG C of volume flow.

Hydrogen supply hydrocarbon is described below.

Hydrogen supply hydrocarbon described herein refers to the hydrocarbon component in direct hydrogenation liquefaction of coal reaction process with hydrogen supply function, Hydrogen supply hydrocarbon includes the polycyclic aromatic hydrocarbon of the double ring arene of fractional saturation, fractional saturation, is the confession that direct hydrogenation liquefaction of coal process uses The ideal composition of hydrogen solvent naphtha.In hydrogen supply hydrocarbon, the hydrogen supply speed of dihydro body is all larger than tetrahydro body, the dihydro body of thrcylic aromatic hydrocarbon and double The dihydro body of cycloaromatics is compared, and it is low that hydrogen supply speed has height to have；Although test it has been proved that polycyclic aromatic hydrocarbon without hydrogen supply capacity, There is the ability of transmitting hydrogen.At 400 DEG C, the opposite hydrogen supply speed of following component is as follows:

Hydrogen supply dissolvent oil, refers to the hydrocarbon ils rich in hydrogen supply hydrocarbon.

DCL/Direct coal liquefaction process described in detail below, it includes direct hydrogenation liquefaction of coal method and other DCL/Direct coal liquefaction sides Method.

DCL/Direct coal liquefaction process of the present invention refers to the method that processing coal directly obtains hydrocarbon liquid, according to solvent The oily difference with catalyst, the difference of pyrolysis way and the difference and process conditions that add hydrogen mode, can be divided into following several Technique:

1. dissolution pyrolysis liquefaction process: low-ash extract can be made to pyrolysis of coal extracting using heavy solvent, and (Japan claims Swelling charcoal)；Extract the available oils based on mink cell focus at supercritical conditions using light solvent.This method does not have to hydrogen, Though former process yield is high but product is still solid, latter technique such as supercritical extraction (extraction) method (SCE) extract content is not It is too high；

2. solvent adds hydrogen to extract liquefaction process: if any solvent refined coal process l and II (SRC-1 and SRC-II), Exxon donor solvent process EDS, Japanese New Energy Development Organization liquefaction process (NEDOL) etc., using hydrogen, but pressure is less high, and solvent naphtha has apparent work With；

3. Hydrogenation method: such as the H coal process (H- of the old and new's liquefaction process (IG and the NewlG) and the U.S. of Germany ) etc. Coal this kind is belonged to；

4. coal and residual oil joint processing method (COprocessing): once passing through together with coal using residual oil as solvent naphtha anti- Device is answered, recycle oil is not had to.Hydrocracking occurs is converted into light oil to residual oil simultaneously.The U.S., Canada, Germany and former Soviet Union etc. are each There is different technique；

5. underground liquefaction process: solvent being injected subterranean coal, makes coal depolymerization and dissolution, in addition the impact force of fluid collapses coal It dissipates, the coal not being completely dissolved is then suspended in solvent, is extracted solution out with pump and is separated processing；

6. destructive distillation liquefaction process: coal is first pyrolyzed and obtains tar, then carries out hydrocracking and upgrading to tar；.

Direct hydrogenation liquefaction of coal process is described below.

Direct hydrogenation liquefaction of coal process of the present invention, refers to the side of the Coal Liquefaction under solvent naphtha existence condition Method, solvent naphtha, which can be, improves the hydrogen supply dissolvent oil of hydrogen supply capacity by stabilized hydrogenation process or without by stabilized hydrogenation process Modified solvent naphtha, according to the difference of solvent naphtha, the difference of catalyst and hydrogenation process conditions, there are many different process, such as with Under several techniques:

1. solvent adds hydrogen to extract liquefaction process: if any solvent refined coal process I and II (SRC-I and SRC-II), Exxon donor solvent process EDS, Japanese New Energy Development Organization liquefaction process (NEDOL) etc., using hydrogen, but pressure is less high, and solvent naphtha has apparent work With；

2. Hydrogenation method: such as the H coal process (H- of the old and new's liquefaction process (IG and the NewlG) and the U.S. of Germany ) etc. Coal this kind is belonged to；

3. coal and residual oil joint processing method (COprocessing): once passing through together with coal using residual oil as solvent naphtha anti- Device is answered, recycle oil is not had to；Hydrocracking occurs is converted into light oil to residual oil simultaneously；The U.S., Canada, Germany and former Soviet Union etc. are each There is different technique；

4. Chinese Shenhua Group coal direct liquefaction method；

5. a kind of thermally dissolving and catalytic method with lignite preparing liquid fuel that patent CN1 00547055C states clearly, belongs to lignite Medium pressure hydrogenation direct liquefaction process, including Coal liquefaction process and liquefied coal coil hydrogenation modification process totally two processes.In order to It improves the conversion ratio of coal direct liquefaction and realizes that coal feedstock enters reactor, before coal enters reactor It is usually made coal dust, is made into coal with the solvent naphtha for having good hydrogen supply capacity, coal is pressurized, enters coal liquid after heating Change reactor.

During direct hydrogenation liquefaction of coal, no matter which kind of coal faces hydrogen direct liquefaction process, and target is to obtain oil product, is chased after The function of asking is " coal turns oil ", it is necessary to which existing chemical change is " coal hydrogenation ", and the common trait of current such technology is to make With solvent naphtha and catalyst, the conventional boiling range of solvent naphtha is generally 200~530 DEG C, most is for 200~450 DEG C, the best 265~430 DEG C, solvent naphtha majority is distilled oil or its hydrogenation modification oil, and contained aromatic hydrocarbons majority is the aromatic hydrocarbons of 2~4 ring structures. Therefore, either which kind of coal faces hydrogen direct liquefaction process, the outer oil extraction or liquefied coal coil (usually coal liquefaction light oil) that it is generated Or liquefied coal coil modified oil, as long as its composition has raw material compositing characteristic of the present invention, can be used the method for the present invention into Enter high aromatic hydrogenation heat cracking reaction process to be processed.

Direct hydrogenation liquefaction of coal process of the present invention refers to using coal and molecule hydrogen that may be present as raw material, It is hydrogen supply dissolvent oil with specific oil product (the usually hydrogenation modification oil of liquefied coal coil), in certain operating condition (as operated Temperature, operating pressure, solvent naphtha/coal weight ratio, hydrogen/solvent naphtha volume ratio and suitable hydrogenation catalyst) under, coal is directly sent out The reaction process of the hydrogenation liquefactions such as raw carbon-carbon bond thermal cracking, free radical stabilized hydrogenation.

Direct hydrogenation liquefaction of coal oil of the present invention, refers to the oil product that the Coal Liquefaction reaction process generates, it It is present in Coal Liquefaction reaction effluent, is the synthesis based on hydrogen supply dissolvent oil, reaction consumption coal and reaction transfer hydrogen Reaction product.

After direct hydrogenation liquefaction of coal reaction process works well, hydrogen supply dissolvent oil generallys use Coal Liquefaction and reacted The hydrogenation modification oil of the self-produced liquefied coal coil of journey (usually conventional distillate of the boiling range higher than 165 DEG C), liquefied coal coil add hydrogen to change Property process main target be production direct hydrogenation liquefaction of coal reaction process solvent naphtha, be specifically exactly to improve in oil product The content of " component with good hydrogen supply function ", for example naphthenic base benzene class, the content of bicyclic alkyl benzene class component are improved, it is based on Liquefied coal coil contains the fact that a large amount of double ring arenes and a large amount of thrcylic aromatic hydrocarbons, and liquefied coal coil hydrogenation modification process is one " suitable The hydrogenation process of degree aromatic hydrocarbons saturation ".

The final goal of Coal liquefaction process is the outer oil product supplied of production, and usual liquefied coal coil hydrogenation modification process generates Hydrogenation modification oil be two parts: a part be used as Coal liquefaction process hydrogen supply dissolvent oil, a part be used as coal liquefaction The outer oil extraction of liquefaction process.In general, at least part coal liquefaction light oil that Coal liquefaction process generates is used as outside coal oil process Oil extraction A, it is molten that remaining liquefied coal coil is used as liquefied coal coil hydrogenation modification process feedstock oil production Coal liquefaction process hydrogen supply There is the outer oil extraction of A and B two-way in agent oil and outer oil extraction B, the final whereabouts of the outer oil extraction of A and B two-way is usually by depth at this time Hydrogen grading process is added to produce high-quality oil product such as diesel oil distillate, naphtha cut.

In direct hydrogenation liquefaction of coal reaction process, hydrogen supply dissolvent is substantially a kind of the most important of coal liquefaction positive reaction Foreground catalyst, he quickly provides most of reactive hydrogen of coal liquefaction, it directly decides pyrolysis free radical fragment The stable speed of flash hydrogcnation, thus thermal condensation is inhibited to react；In direct hydrogenation liquefaction of coal reaction process, solid catalyst A kind of retarding agent of such as pyrite, molybdenum sulfide substantially more like coal liquefaction negative reaction, it is big that solid catalyst particle adsorbs viscosity Colloid, asphaltene molecules MK, and contact MK with the reactive hydrogen of solid catalyst surface, to inhibit its pyrocondensation；In coal plus In hydrogen direct liquefaction reaction process, a kind of substantially still hydrogen supply agent dehydrogenation simultaneously such as solid catalyst such as pyrite, molybdenum sulfide The recovery catalyst of object SH-Z, solid catalyst particle adsorbs SH-Z, and connects the reactive hydrogen of SH-Z and solid catalyst surface Touching, thus plus hydrogen be restored to the hydrogen supply hydrocarbon for having hydrogen supply capacity, it directly decides the recovery speed of hydrogen supply agent dehydrogen substance SH-Z； In direct hydrogenation liquefaction of coal reaction process, substantially still a kind of target is hydrocracked solid catalyst such as pyrite etc. simultaneously The weak action catalysts of reaction such as asphaltene, preasphaltene being hydrocracked.Therefore, in direct hydrogenation liquefaction of coal reaction process In, in certain sense, solid catalyst such as pyrite, molybdenum sulfide etc. is more like a kind of catalyst of backstage running, to coal Liquefaction target product distillate plays a kind of support property and the effect of promotion property.In coal hydrogenation liquefaction reaction process, due to hydrogen supply The effect of solvent DS is extremely important, and therefore, the operating condition and effect of the stable reaction process of solvent oil hydrogenation are naturally of crucial importance.

Up flow type hydrogenator of the present invention, reaction compartment or the processing medium in hydrogenation catalyst bed Macroscopic view flowing dominant direction is from top to bottom.

Expanded bed reactor of the present invention is vertical up-flow reactor, and expanded bed catalysis is belonged to when using catalyst Reactor；The vertical central axis upright for referring to working condition reactor after installing is in ground；Up flow type refers to reacting Journey material main body flow direction travels through reaction compartment or catalyst bed or the catalyst co-flow with uplink from bottom to top；It is swollen Swollen bed refers to that working condition catalyst bed is in swelling state, and catalyst bed expansion ratio, which is defined as catalyst bed, to be had instead The ratio between the height CUH of the empty bed static condition of the maximum height CWH and catalyst bed of working condition when raw material being answered to pass through Value KBED, in general, referred to as slight expanded-bed when KBED is lower than 1.10, referred to as ebullated bed when KBED is between 1.25~1.55, and suspend Bed is considered as the expanded bed of most extreme form.

Back-mixing stream expanded bed reaction zone of the present invention, refers to the mode of operation of the reaction zone using expanded bed reactor There are liquid stream back-mixings there is circulation fluid in other words；Back-mixing stream or circulation fluid refer to the intermediate product XK or final at flow points K At least part liquid phase XK-L in product X K is as the upstream reaction zone circulating fluid XK-LR return logistics XK, circulating fluid XK- The reaction product of LR flows through K point and is present among XK.The mode for forming back-mixing stream can be any appropriate mode, such as be arranged Built-in inner ring flow cartridge, built-in outer ring flow cartridge, built-in liquid collecting cup+diversion pipe+circulating pump, external circulation pipe etc..

The liquid collecting cup or liquid trap being arranged in reactor of the present invention, refer to being arranged in reactor for collecting The container of liquid, usual top or upper side opening, bottom or lower side installation diversion pipe are for being discharged collection liquid；Expansion The top liquid trap of bed reactor, is typically mounted on the de- liquid zone of gas-liquid material, obtains liquid and gas-liquid mixed phase logistics or obtain Liquids and gases.

Suspended-bed reactor of the present invention, structure type can be any one suitable form, can be empty cylinder Suspended-bed reactor can be using internal circulation guide shell to form piston flow or the back-mixing stream there are interior circulation to shape At circulation in inside or internal outside circulation, can be makes top reaction compartment liquid flow into lower part using its outer circulating tube reacts empty Between shaper outer circulation stream back-mixing flow pattern, can be using top product liquid collect and flow guide system to by circulation plus Pressure system forms the back-mixing flow pattern for forcing inner recirculation flow.

Hot high score device of the present invention, refers to the gas-liquid separation for separating hydrogenation reaction intermediate product or final product Equipment.

Direct hydrogenation liquefaction of coal reaction process of the present invention, usually using up-flow reactor, working method be can choose:

1. floating bed hydrogenation reactor；

3. slight expanded-bed.

It is high to be commonly referred to as hydro carbons of the normal boiling point higher than 350 DEG C, generally referred to as normal boiling point for heavy hydrocarbon of the present invention It in 500 DEG C of hydro carbons, particularly refers to hydro carbons of the normal boiling point higher than 550 DEG C, but is usually higher than containing normal boiling point 550 DEG C of hydro carbons.Heavy hydrocarbon of the present invention, particularly preferably aromatic carbon rate height are such as higher than 40% hydrocarbon material, and the present invention is referred to as The heavy hydrocarbon of high aromatic hydrocarbons.

The hexa-atomic cyclic hydrocarbon of low carbon number list of the present invention, refers to C₆~C₉Benzene hydrocarbons or hexamethylene methane series hydrocarbon, normal boiling point Usually 70~180 DEG C, it is adapted for use as the raw material naphtha of catalytic reforming aromatic hydrocarbons.

Twin nuclei aromatic hydrocarbons of the present invention is referred to containing two ring structures and wherein at least one ring belongs to aromatic ring Hydro carbons, such as naphthalene, naphthane and its with the hydro carbons of side chain.

Tricyclic structure aromatic hydrocarbons of the present invention refers to the ring structure containing there are three and wherein at least one ring belongs to aromatic ring Hydro carbons, such as fluorenes, dibenzofuran, thia fluorenes, carbazole, dibenzopyridine, anthracene, phenanthrene and its with side chain hydrocarbon or part thereof adds hydrogen saturated products.

Multiring structure aromatic hydrocarbons of the present invention, is containing four or more ring structure and wherein at least one ring belongs to aromatic ring Hydro carbons.

High aromatic hydrocarbons of the present invention refers to the high hydrocarbon material of aromatic carbon rate, is commonly referred to as the hydrocarbon that aromatic carbon rate is higher than 40% Material particularly refers to that the high oil product of the density of aromatic hydrocarbon containing tricyclic structure aromatic hydrocarbons and/or multiring structure aromatic hydrocarbons such as coal tar evaporates Divide, direct hydrogenation liquefaction of coal oil distillate or oily based on their hydrogenation modification, the heat from hydrogenation cracking process of such high aromatic hydrocarbons Primary product can be the hexa-atomic cyclic hydrocarbon of low carbon number list.

Direct hydrogenation liquefaction of coal reaction process of the present invention, refers to the Coal Liquefaction under solvent naphtha existence condition Method, solvent naphtha, which can be, improves the hydrogen supply dissolvent oil of hydrogen supply capacity by stabilized hydrogenation process or without by stabilized hydrogenation mistake The modified solvent naphtha of journey, according to the difference of solvent naphtha, the difference of catalyst and hydrogenation process conditions, there are many different process.

The heat from hydrogenation cracking process of the high aromatic hydrocarbons such as coal tar of the present invention refers to carrying out in the presence of hydrogen The method of thermal cracking and pyrolysis free radical fragment stabilized hydrogenation has more according to the difference of the difference of catalyst and hydrogenation process conditions Kind different process can be used hydrogen supply agent to inhibit the thermal condensation of easy coking component such as coal tar pitch, can be expanded using up flow type Bed reactor.

High aromatic hydrocarbons of the present invention, the full distillate oil or fractionation that can be coal tar cut gained light fraction oil or fractionation Cutting gained heavy distillate or fractionation cutting gained include the heavy distillate of coal tar pitch, in order to extend operation cycle and optimization The scheduling of hydrogenation process raw material hydrocarbon, coal tar pitch preferably go Coal Liquefaction combine processes to process.

Oil product obtained by group technology direct hydrogenation liquefaction of coal of the present invention, including (60~180 DEG C of conventional boiling range evaporates naphtha Point), the first light diesel fuel (180~220 DEG C of fractions of conventional boiling range), the second light diesel fuel (220~265 DEG C of fractions of conventional boiling range), again Diesel oil (265~350 DEG C of fractions of conventional boiling range), light wax oil (350~480 DEG C of fractions of conventional boiling range), wax slop (conventional boiling range 480~530 DEG C of fractions), liquefaction residual oil (normal boiling point be higher than 530 DEG C of hydro carbons).

Naphtha (60~180 DEG C of fractions of conventional boiling range) in group technology product of the present invention, is target product fraction, root According to needs, deep hydrofinishing such as desulfurization, denitrogenation can be carried out to it, it is usually desirable to generation benzene ring hydrogenation saturation as few as possible Reaction.

The first light diesel fuel (180~220 DEG C of fractions of conventional boiling range) in group technology product of the present invention, be often unsuitable for into Enter direct hydrogenation liquefaction of coal reaction process because boiling point too it is low be easy to vaporize be difficult to serve as liquid phase solvent component；If into coal Add hydrogen direct liquefaction reaction process, the product of further heat cracking reaction is exactly to generate bulk gas and uneconomical；Therefore, unless Carburet hydrogen Huge value, the first light diesel fuel should not usually enter direct hydrogenation liquefaction of coal reaction process or Special hydrogenation thermal cracking Journey or hydrocracking process or other thermal cracking processes are processed, and can usually be entered hydrofining reaction process and be taken off Sulphur, denitrogenation, production cleaning light diesel fuel.

The second light diesel fuel (220~265 DEG C of fractions of conventional boiling range) in group technology product of the present invention, stabilized hydrogenation oil Product are the hydrogen supply dissolvent oil that the boiling point that direct hydrogenation liquefaction of coal reaction process needs is suitable, hydrogen supply capacity is excellent, in addition for coal Add hydrogen direct liquefaction process, the second light diesel fuel or its stabilized hydrogenation oil, is reacted in the front of direct hydrogenation liquefaction of coal reaction process Play a part of the basic solvent composition of liquid phase in the process, but in the rear portion reaction process of direct hydrogenation liquefaction of coal reaction process It is most of to have vaporized, and usually direct hydrogenation liquefaction of coal reaction process is there are the resource of surplus thus to belong to coal hydrogenation direct The major product of liquefaction reaction process, therefore, the second light diesel fuel of coal liquefaction products or its stabilized hydrogenation oil, usually part is used as light Matter hydrogen supply dissolvent oil is used for direct hydrogenation liquefaction of coal reaction process, is partially used as plus hydrogen upgraded material is for adding hydrogen upgrading to react Journey produces final products.

Heavy diesel fuel (265~350 DEG C of fractions of conventional boiling range) in group technology product of the present invention, stabilized hydrogenation oil product, It is the hydrogen supply dissolvent oil that the most desirable boiling point of direct hydrogenation liquefaction of coal reaction process is suitable, hydrogen supply capacity is excellent, in addition for coal Add hydrogen direct liquefaction process, heavy diesel fuel or its stabilized hydrogenation oil, is played in the whole process of direct hydrogenation liquefaction of coal reaction process The effect of the basic solvent composition of liquid phase, and usually direct hydrogenation liquefaction of coal reaction process there are the resource of surplus therefore belongs to coal Add the major product of hydrogen direct liquefaction reaction process, therefore, coal liquefaction products heavy diesel fuel or its stabilized hydrogenation oil, usually part is used Make heavy hydrogen supply dissolvent oil for direct hydrogenation liquefaction of coal reaction process, is partially used as plus hydrogen upgraded material is for adding hydrogen upgrading anti- Process is answered to produce final products.

Light wax oil (350~480 DEG C of fractions of conventional boiling range) in group technology product of the present invention, stabilized hydrogenation oil product, It is the hydrogen supply dissolvent oil that the most desirable boiling point of direct hydrogenation liquefaction of coal reaction process is suitable, hydrogen supply capacity is excellent, in addition for coal Add hydrogen direct liquefaction process, light wax oil or its stabilized hydrogenation oil, in the final high temperature stage of direct hydrogenation liquefaction of coal reaction process Play a part of the basic solvent composition of liquid phase, and usually direct hydrogenation liquefaction of coal reaction process is difficult to the rare of Equilibrium Resource, therefore, coal liquefaction products light wax oil or its stabilized hydrogenation oil are usually completely used as heavy hydrogen supply dissolvent oil for coal hydrogenation Direct liquefaction reaction process, while carrying out the heat from hydrogenation cracking reaction of its lighting process needs.

Wax slop (480~530 DEG C of fractions of conventional boiling range) in group technology product of the present invention, these contain solid The lighting process of grain, the serious material for lacking hydrogen, it is necessary in the liquid phase for being capable of providing a large amount of active hydrogen atoms for being rich in hydrogen supply hydrocarbon Under the conditions of carry out, be unlikely to quick coking just to maintain device long-term operation, liquid phase of the coal liquefaction wax slop in reactor In dispersion be also required to the dispersing and dissolving by means of a large amount of hydrogen supply hydrocarbon, the thermal condensation object or coking material of coal liquefaction wax slop are also required to Relying on liquefaction semicoke is to assemble support dispersion and carry out reaction compartment, and therefore, coal liquefaction wax slop enters the direct liquid of coal hydrogenation Changing reaction process to carry out deep conversion is reasonable inevitable choice, and coal liquefaction wax slop passes through stabilized hydrogenation reaction process in other words It is reasonable inevitable choice that gained stabilized hydrogenation oil, which enters direct hydrogenation liquefaction of coal reaction process to carry out deep conversion,；In addition for Direct hydrogenation liquefaction of coal process, wax slop or its stabilized hydrogenation oil, in the final high temperature rank of direct hydrogenation liquefaction of coal reaction process Section plays a part of the basic solvent composition of liquid phase, and usually direct hydrogenation liquefaction of coal reaction process is difficult to the dilute of Equilibrium Resource is lacked, therefore, coal liquefaction products wax slop or its stabilized hydrogenation oil are usually completely used as heavy hydrogen supply dissolvent oil and add for coal Hydrogen direct liquefaction reaction process, while carrying out the heat from hydrogenation cracking reaction of its lighting process needs.

Since the i.e. liquefaction residual oil of hydro carbons of the normal boiling point higher than 530 DEG C is present in vacuum tower in group technology product of the present invention In ground coal liquefied residue logistics, usual discharge system processes no longer cyclic process again, certainly, can partially recycle as needed It returns.

It is cracked particularly suitable for the heat from hydrogenation for optimizing the high inferior heavy oil of fragrant charcoal rate that kerosene of the present invention refines integrated technique altogether Journey is conducive to reduce green coke amount, extends the operation cycle, and inferior heavy oil high conversion rate, liquid product yield are high, can be with main product Gao Fangqian Naphtha, using aromatic hydrocarbons as downstream product.

Direct hydrogenation liquefaction of coal reaction process as circulation cracked oil generates the fraction section of oil, and preferably cracked gas produces The low fraction section of rate, such as heavy diesel fuel (265~350 DEG C of fractions of conventional boiling range), wax oil (350~530 DEG C of fractions of conventional boiling range), It can be used for voluminous naphtha.

Characteristic of the invention is described below.

Coal slurry material XS is made of coal dust XS-FS and oil XS-FL with slurry；

Oil XS-FL with slurry, can a kind or several in following materials:

1. oil identical with heavy oil FD is used as oil XS-FL with slurry；

1. suspension bed, that is, slurry bed system；

2. ebullated bed.

1. floating bed hydrogenation reactor；

3. up flow type slight expanded-bed；

4. upflow fixed bed；

5. down-flow fixed bed；

The general control principle of the gas-phase presulfiding hydrogen concentration of hydrogenation process of the invention described in detail below.

As needed, any hydrogenation process can be added in any supplement sulphur, but be typically incorporated into most upstream Hydrogenation process entrance, to guarantee reaction process necessary minimum concentration of hydrogen sulfide such as 500PPm (v) or 1000PPm (v) or the expected specified value such as 3000PPm (v), with guarantee the necessary hydrogen sulfide sectional pressure of catalyst not less than minimum specified value, with Guarantee the necessary vulcanization kenel of catalyst.The supplement sulphur can be sulfide hydrogen or can be converted into hydrogen sulfide to adding hydrogen Material of the conversion process without ill-effect, such as hydrogen sulfide containing gas or oil product, or vulcanization is generated after contacting with high-temperature hydrogen The molten sulfur or carbon disulfide of hydrogen or dimethyl disulfide etc..

The rule of the high pressure separation process of hydrogenation reaction effluent of the invention described in detail below.

The high pressure separation process of hydrogenation reaction effluent generally comprises cold high pressure separator, when hydrocarbon in hydrogenation reaction effluent When oil density big (such as close with water density) or viscosity are difficult to separate or contain solid particle greatly or with water emulsification, it is also necessary to set The high pressure hot separator that operation temperature is usually 150~450 DEG C is set, hydrogenation reaction effluent enters high pressure hot separator point at this time It by conventional liq hydrocarbon and may mainly be deposited from the hot high score gas gas being mainly made of hydrogen in volume for one and one Solid composition hot high score oil liquid body, hot high score gas enters the cold high pressure separator point that operation temperature is usually 20~80 DEG C Following target is realized: cold since a large amount of high boiling components enter in hot high score oil liquid body from for cold high score oil and cold high score gas High score oil density becomes smaller or viscosity becomes smaller or is easily isolated with water.Thermal high is arranged in the high pressure separation process of hydrogenation reaction effluent Separator is also equipped with the advantages of reducing thermal loss, because hot high score oil liquid body can be to avoid hot high score gas experience using empty The process that cools of cooler or water cooler.Meanwhile the hot high score oil liquid body in part can be returned to the hydrogenation process of upstream Be recycled, with improve receive the recycle oil hydrogenation process overall raw material property, or to the cycling hot high score oil into Row circulation plus hydrogen.

Between thermal high separate section and cold anticyclone separate section, as needed, warm high pressure separate section can be set, Become gas-liquid two-phase material after hot high score air cooling at this time, one is separated into warm high-pressure separator in volume mainly by hydrogen The warm high score gas gas and the warm high score oil liquid being mainly made of conventional liq hydrocarbon and solid that may be present of gas composition Body, warm high score gas gas enter cold anticyclone separate section and carry out cooling and gas-liquid separation.

Hydrogenation reaction effluent or hot high score gas or warm high score gas enter before cold anticyclone separate section, usually first reduce temperature (temperature should be higher than that in the hydrogenation reaction effluent gas phase degree (usually with reactive moieties feed exchange heat) to about 220~100 DEG C Crystallization temperature, the crystallization temperature of sal-ammoniac of sulphur hydrogenation ammonia), then usually injection washing water formation water filling back end hydrogenation is anti-thereto Answer effluent, it may be necessary to which 2 or multiple injection points are set, and washing water is used for absorbing ammonia and issuable other impurity such as chlorine Change hydrogen etc., and the aqueous solution after absorbing ammonia necessarily absorbs hydrogen sulfide.In cold anticyclone separate section, the water filling back end hydrogenation reaction stream Object separates out are as follows: the cold high score gas being mainly made of hydrogen in volume, one mainly by conventional liq hydrocarbon and dissolved hydrogen The cold high score oil of composition, a cold high score water be mainly made of water and dissolved with ammonia, hydrogen sulfide.The cold high score water, The content of middle ammonia is generally 0.5~15% (w), preferably 1~8% (w).One purpose of note washing water is to absorb hydrogenation reaction Ammonia and hydrogen sulfide in effluent prevent from forming sulphur hydrogenation ammonia or more sulphur ammonia Crystallization Plugging heat exchanger channels, increase system pressure Drop.The injection rate of the washing water should be determined according to following principles: on the one hand, washing water divides after injecting hydrogenation reaction effluent For vapour phase water and liquid phase water, liquid phase water has to be larger than zero, preferably washs 30% or more of water inventory；In another aspect, washing Water is washed for absorbing the ammonia in hydrogenation reaction effluent, prevents the ammonia density of high score gas too high, reduces catalyst activity, usually height Divide the ammonia volumetric concentration of gas more lower better, generally no greater than 200PPm (v), desirably no more than 50PPm (v).The cold anticyclone Separator operation pressure be hydrogenation reaction partial pressure subtract actual pressure drop, cold anticyclone separate section operating pressure with add hydrogen it is anti- The difference of pressure is answered, it is unsuitable too low or excessively high, it is usually generally 0.35~3.2MPa, 0.5~1.5MPa.The cold high score The hydrogen volume concentration value of gas, should not too low (cause device operating pressure rise), generally should not less than 70% (v), it is preferably not low In 80% (v), preferably not below 85% (v).As previously described at least part, be usually 85~100% cold high score gas return It is recycled in hydrogenation reaction part, to provide the necessary amounts of hydrogen in hydrogenation reaction part and hydrogen concentration；It is thrown to improve device Provide efficiency, it is necessary to assure circulation hydrogen concentration be not less than lower limit value above-mentioned, for this purpose, according to specific feedstock property, reaction condition, Product distribution can exclude a part of cold high score gas to exclude methane, the ethane that reaction generates.For the cold high score of discharge Gas can realize hydrogen and non-hydrogen gas component point using conventional membrane separation process or pressure swing adsorption technique or oil wash technique From, and the hydrogen of recycling is used as new hydrogen.

For direct hydrogenation liquefaction of coal reaction process, because of conventional gas hydrocarbon, CO, CO₂Yield is huge, usually most of cold Cold high score gas of the high score gas than such as from about 70~100%, after being purified as membrane separation process obtained by permeated hydrogen pressurization after return plus Hydrogen reaction process, do not permeate gas by PSA mention hydrogen or after " steam reforming hydrogen manufacturing+PSA mentions hydrogen " pressurization return plus hydrogen it is anti- Process is answered to be recycled.

New hydrogen enters plus hydrogen partial is to supplement the hydrogen that hydrogenation process consumes, and the higher the better for new hydrogen hydrogen concentration, generally Not preferably less than 95% (v), preferably not below 99% (v).All new hydrogen can be introduced any hydrogenation reaction part, be preferably introduced the One hydrogenator.

The present invention, in any reaction process, it can be entirely recycle hydrogen that the hydrogen gas stream used, which can be entirely new hydrogen, It can be the gaseous mixture of new hydrogen and recycle hydrogen.

Compared with independent Coal Liquefaction process and independent heavy hydrocarbon heat from hydrogenation cracking process, combined method of the present invention Advantage is:

1. the initial reaction condition of direct hydrogenation liquefaction of coal reaction process is optimized, when controlling heavy-oil hydrogenation heat cracking reaction Between be in reasonable interval, reduce excessive thermal condensation reaction and excessive secondary cracking react, be conducive to improve liquid yield；

2. coal also serves as the quench oil of heavy-oil hydrogenation heat cracking reaction process, directly the first heavy-oil hydrogenation thermal cracking of recycling The reaction heat of conversion zone AR1；

3. guarantee direct hydrogenation liquefaction of coal high conversion rate in 90% under the premise of, secondary use hydrogen supply dissolvent and the first weight Oily heat from hydrogenation cracking reaction generates oil, compared to individual direct hydrogenation liquefaction of coal reaction process, is kneaded coal slurry and improves economy Property, it, can fecund Gao Fang particularly suitable for being kneaded the high aromatic hydrocarbons heavy oil such as coal tar asphalt of shale oil residual oil, pulverized coal pyrolysis tar Latent naphtha.

Claims

1. heavy-oil hydrogenation thermal cracking and the concatenated oily coal of direct hydrogenation liquefaction of coal are total to smelting method, it is characterised in that include following step It is rapid:

(1) first heavy-oil hydrogenation heat cracking reaction section AR1, the coal AR1F containing hydrogen supply dissolvent AR1-DS, heavy oil FD are carried out The first heavy-oil hydrogenation heat cracking reaction AR1R is converted into the first heavy-oil hydrogenation heat cracking reaction product AR1P at least partially；

(2) enter the second heavy-oil hydrogenation heat cracking reaction in the second heavy-oil hydrogenation heat cracking reaction section AR2, the first material flow A R1PX Section AR2, coal slurry material XS enter the second heavy-oil hydrogenation heat cracking reaction section AR2, carry out at least part the second heavy-oil hydrogenation heat Cracking reaction and Coal Liquefaction reaction AR2R are converted into the second heavy-oil hydrogenation heat cracking reaction product AR2P；

Coal slurry material XS is made of coal dust XS-FS and oil XS-FL with slurry；

(3) in separate section S100, the second heavy-oil hydrogenation heat cracking reaction product AR2P is recycled, hydrogen supply dissolvent predecessor hydrocarbon is obtained MFB；

(4) portion that aromatic hydrocarbon molecule is completed in stabilized hydrogenation reaction is carried out in stabilized hydrogenation reaction process MR, hydrogen supply dissolvent predecessor hydrocarbon MFB Aromatic ring saturated reaction MRR is divided to be converted into stabilized hydrogenation reaction product MRP；

At least part hydrogen supply dissolvent DS enters the first heavy-oil hydrogenation heat cracking reaction section AR1 and is used as hydrogen supply dissolvent AR1-DS.

2. according to the method described in claim 1, it is characterized by:

Heavy oil FD, mainly the hydro carbons by normal boiling point higher than 350 DEG C forms；

1. in the first heavy-oil hydrogenation heat cracking reaction section AR1, based on the hydrogeneous of the first heavy-oil hydrogenation heat cracking reaction product AR1P Gas material is used as the first series connection gaseous stream AR1P-HVX；

2. the gaseous stream AR1P-HVX that connects of at least part first participates in the in the second heavy-oil hydrogenation heat cracking reaction section AR2 Two heavy oil heat from hydrogenation cracking reaction AR2R are converted into a part of the second heavy-oil hydrogenation heat cracking reaction product AR2P；

3. recycling the second heavy-oil hydrogenation heat cracking reaction product AR2P in separate section S100, obtaining the hydrogen rich gas containing hydrogen Material flow A RH, at least part hydrogen-rich stream ARH return to the first heavy-oil hydrogenation heat cracking reaction section AR1 and/or the second heavy oil adds Hydrogen heat cracking reaction section AR2.

3. according to the method described in claim 1, it is characterized by:

Heavy oil FD, mainly the hydro carbons by normal boiling point higher than 350 DEG C forms.

4. according to the method described in claim 1, it is characterized by:

Heavy oil FD, mainly the hydro carbons by normal boiling point higher than 530 DEG C forms.

5. according to the method described in claim 1, it is characterized by:

1 kind or several in following materials of heavy oil FD:

1. oil product obtained by middle coalite tar or its distillate or its hot procedure；Hot procedure is selected from coking or urges Change cracking process or catalytic pyrolysis process or hydrogenation process；

2. oil product logistics obtained by high temperature coal-tar or its distillate or its hot procedure；Hot procedure be selected from coking or Catalytic cracking process or catalytic pyrolysis process or hydrogenation process；

3. oil product obtained by the distillate oil of direct hydrogenation liquefaction of coal process product or its hot procedure；Hot procedure is selected from coking Process or catalytic cracking process or catalytic pyrolysis process or hydrogenation process；

4. oil product obtained by shale oil or its distillate or its hot procedure；Hot procedure is selected from coking or catalytic cracking Process or catalytic pyrolysis process or hydrogenation process；

6. oil product obtained by petroleum based heavy fuel oils hot procedure；Hot procedure is selected from coking or catalytic cracking process or catalysis Cracking process or hydrogenation process；

6. according to the method described in claim 1, it is characterized by:

The coal powder density of coal slurry material XS is higher than 70%.

7. according to the method described in claim 1, it is characterized by:

Coal slurry material XS is made of coal dust XS-FS and oil XS-FL with slurry；

Oil XS-FL with slurry, a kind or several in following materials:

1. oil identical with heavy oil FD is used as oil XS-FL with slurry；

4. separate that the first heavy-oil hydrogenation heat cracking reaction product AR1P obtains is mainly 350~530 DEG C of hydro carbons by normal boiling point The wax oil of composition is used as oil XS-FL with slurry；

5. separate that the first heavy-oil hydrogenation heat cracking reaction product AR1P obtains is mainly higher than 530 DEG C of hydro carbons by normal boiling point and forms Residual oil, be used as oil XS-FL with slurry；

7. the coal powder density for preparing coal slurry material XS is higher by 20% heavy oil than the heavy oil FD coal powder density for preparing coal slurry material XS；

8. according to the method described in claim 1, it is characterized by:

(2) in the second heavy-oil hydrogenation heat cracking reaction section AR2, the temperature of at least part coal slurry material XS adds lower than the first heavy oil Temperature is reacted in the operation temperature of hydrogen heat cracking reaction product AR1P, the starting also below the second heavy-oil hydrogenation heat cracking reaction section AR2 Degree, i.e. at least part coal slurry material XS serve as the first heavy-oil hydrogenation heat cracking reaction product AR1P into the second heavy-oil hydrogenation heat The coolant of soaking section AR2.

9. according to the method described in claim 1, it is characterized by:

(1) cracking of hydro carbons of the normal boiling point higher than 350 DEG C turns in the first heavy-oil hydrogenation heat cracking reaction section AR1, heavy oil FD Rate is 30~60%.

10. according to the method described in claim 1, it is characterized by:

(1) DH1 is consumed in the hydrogen of the first heavy-oil hydrogenation heat cracking reaction section AR1, heavy oil FD, accounts for heavy-oil hydrogenation heat cracking reaction process The 30~60% of the total hydrogen consumption DH of AR.

11. according to the method described in claim 1, it is characterized by:

(1) in the weight flow rate AR1-DS-W and heavy oil FD of the first heavy-oil hydrogenation heat cracking reaction section AR1, hydrogen supply dissolvent AR1-DS Weight flow rate FD-W ratio be oil ratio K100=(AR1-DS-W)/(FD-W), K100 be 0.5~2.0.

12. according to the method described in claim 1, it is characterized by:

(2) in the second heavy-oil hydrogenation heat cracking reaction section AR2, coal slurry material XS the weight flow rate XS-FS-W of coal dust XS-FS with The ratio of the weight flow rate FD-W of heavy oil FD is kerosene ratio K500=(XS-FS-W)/(FD-W), and K500 is 0.01~3.0.

13. according to the method described in claim 1, it is characterized by:

(2) in the second heavy-oil hydrogenation heat cracking reaction section AR2, coal slurry material XS coal dust XS-FS plus hydrogen direct liquefaction reaction The liquefied fraction of process is greater than 85%；

The overall conversion of heavy oil FD is greater than 70%.

14. according to the method described in claim 1, it is characterized by:

(2) in the second heavy-oil hydrogenation heat cracking reaction section AR2, coal slurry material XS coal dust XS-FS plus hydrogen direct liquefaction reaction The liquefied fraction of process is greater than 90%；

The overall conversion of heavy oil FD is greater than 80%.

15. according to the method described in claim 1, it is characterized by:

(2) in the second heavy-oil hydrogenation heat cracking reaction section AR2, the hydrogenation liquefaction reaction process XS-FS-AR2 that coal dust XS-FS is carried out Operating condition are as follows: reaction temperature be 400~465 DEG C, reactor pressure be 6~30MPa, vapor phase hydrogen volumetric concentration 50~ 95%, gas-liquid volume ratio is 300~1500Nm³/ t, catalyst for coal liquefaction additive amount are 0.1~3 mass % of dry pulverized coal weight, Co-catalyst additive amount is that sulphur in co-catalyst/catalyst activity metal molar ratio is 1.0~2.0, and coal slurry solid concentration is 40~60 mass %, reaction time are 0.5~4 hour.

16. according to the method described in claim 1, it is characterized by:

(2) in the second heavy-oil hydrogenation heat cracking reaction section AR2, the hydrogenation liquefaction reaction process XS-FS-AR2 that coal dust XS-FS is carried out The hydrogenation catalyst used is a kind of composite hydrogenation catalyst, includes high-activity component and low activity component；The high activity The weight ratio of component metals and low activity component metals is 1: 10 to 10: 1；The high-activity component is the water soluble salt of molybdenum Close or mixtures thereof object；The low activity group is divided into ferric oxide ore or iron sulfide ore, and wherein iron in ore content is not less than 40wt%, catalyst for coal liquefaction water content are lower than 2wt%；The powdery that the particle diameter of catalyst for coal liquefaction is 1~100 μm Grain.

17. according to the method described in claim 1, it is characterized by:

(2) in the second heavy-oil hydrogenation heat cracking reaction section AR2, the hydrogenation liquefaction reaction process XS-FS-AR2 that coal dust XS-FS is carried out The hydrogenation catalyst used is nanometer ultra-fine grain aqua oxidation iron catalyst and/or iron oxide and/or pyrite and/or bloodstone And/or molybdenum oxide and/or molybdenum sulfide and/or ammonium molybdate and/or nickel sulfide.

18. according to the method described in claim 1, it is characterized by:

(4) in stabilized hydrogenation reaction process MR, hydrogen supply dissolvent, solvent naphtha are prepared for the first heavy-oil hydrogenation heat cracking reaction section AR1 The hydrogenation catalyst that stabilized hydrogenation reaction process MR is used is the hydrogenation catalyst of Ni-Mo, Ni-Co or Ni-W system；Reaction temperature It is 300~390 DEG C, hydrogenation pressure is 10~25MPa, and gas-liquid volume ratio is 300~1000Nm³/t；It is normal in reaction product MRP Advise boiling point and be higher than 250 DEG C of hydro carbons: it is 0.35~0.70 that the weight content of fractional saturation aromatic hydrocarbons, which is greater than 15%, aromatic carbon rate,.

19. according to the method for claim 18, it is characterised in that:

(4) normal boiling point in stabilized hydrogenation reaction process MR, reaction product MRP is higher than 250 DEG C of hydro carbons: fractional saturation aromatic hydrocarbons Weight content be greater than 25%, aromatic carbon rate be 0.45~0.60.

20. according to the method described in claim 1, it is characterized by:

(2) in the second heavy-oil hydrogenation heat cracking reaction section AR2, the hydrogenation liquefaction reaction process XS-FS- that coal dust XS-FS is carried out AR2, a kind or several of the combination of the mode of operation of the Coal Liquefaction reactor used in following:

1. suspension bed, that is, slurry bed system；

2. ebullated bed.

21. according to the method described in claim 1, it is characterized by:

(4) stablize the mode of operation of reactor in the solvent oil hydrogenation that in stabilized hydrogenation reaction process MR, uses in following 1 kind or several of combination:

1. floating bed hydrogenation reactor；

2. boiling bed hydrogenation reactor usually draws off the decreased catalyst of activity from bed bottom in an intermittent fashion, with The mode of interval fills into fresh catalyst from bed top and maintains bed catalyst reserve；

3. up flow type slight expanded-bed；

4. upflow fixed bed；

5. down-flow fixed bed；

22. according to the method described in claim 1, it is characterized by:

(3) in separate section S100, recycle the second heavy-oil hydrogenation heat cracking reaction product AR2P, obtain mainly be by conventional boiling range The distillate of 350~530 DEG C of hydrocarbon-fractions composition returns to the first heavy-oil hydrogenation heat cracking reaction section AR1 and carries out the first heavy-oil hydrogenation Heat cracking reaction and/or the second heavy-oil hydrogenation heat cracking reaction section AR2 carry out the second heavy-oil hydrogenation heat cracking reaction.

23. according to the method described in claim 1, it is characterized by:

It (2), will be in the portion that the second heavy-oil hydrogenation heat cracking reaction section AR2 is discharged in the second heavy-oil hydrogenation heat cracking reaction section AR2 Liquid separation phase materials introduce the first heavy-oil hydrogenation heat cracking reaction section AR1 and carry out the first heavy-oil hydrogenation heat cracking reaction.

24. according to the method described in claim 2, it is characterized by:

(1) first series connection gaseous stream AR1P-HVX, is following one or more:

1. the first series connection gaseous stream AR1P-HVX, is that the thermal high of the first heavy-oil hydrogenation heat cracking reaction product AR1P separated The hot high score gas AR1P-THPS-V that journey AR1P-THPS is isolated；

2. the first series connection gaseous stream AR1P-HVX, is that the thermal high of the first heavy-oil hydrogenation heat cracking reaction product AR1P separated The medium temperature that the medium temperature high pressure separation process AR1P-MHPS for the hot high score gas AR1P-THPS-V that journey AR1P-THPS is isolated is isolated High pressure separates gas AR1P-MHPS-V；

3. the first series connection gaseous stream AR1P-HVX, is that the thermal high of the first heavy-oil hydrogenation heat cracking reaction product AR1P separated In the isolating of the medium temperature high pressure separation process AR1P-MHPS for the hot high score gas AR1P-THPS-V that journey AR1P-THPS is isolated The cold anticyclone separation gas AR1P- that the cold anticyclone separation process AR1P-LHPS of warm high pressure separation gas AR1P-MHPS-V is isolated LHPS-V；

4. the first series connection gaseous stream AR1P-HVX, is that the thermal high of the first heavy-oil hydrogenation heat cracking reaction product AR1P separated The cold anticyclone that the cold anticyclone separation process AR1P-LHPS for the hot high score gas AR1P-THPS-V that journey AR1P-THPS is isolated is isolated Separate gas AR1P-LHPS-V.

25. combined method according to claim 1, it is characterised in that:

The operating condition of (1) first heavy-oil hydrogenation heat cracking reaction section AR1 are as follows: reaction temperature is 400~465 DEG C, reactor pressure Power is 6~30MPa, and gas-liquid volume ratio is 300~1500Nm³/ t, catalyst loading are 0.5~3 matter of heavy oil FD weight % is measured, co-catalyst additive amount is that sulphur in co-catalyst/catalyst activity metal molar ratio is 1.0~2.0.

26. combined method according to claim 1, it is characterised in that:

The hydrogenation catalyst that (1) first heavy-oil hydrogenation heat cracking reaction section AR1 is used, is a kind of composite hydrogenation catalyst, packet Containing high-activity component and low activity component；The weight ratio of the high-activity component metal and low activity component metals is 1: 10 to 10 :1；The high-activity component is or mixtures thereof the water soluble salt compound of molybdenum；The low activity group is divided into ferric oxide ore Or iron sulfide ore, wherein iron in ore content is not less than 40wt%, and catalyst water content is lower than 2wt%；Catalyst particle is straight The powdered granule that diameter is 1~100 μm.

27. combined method according to claim 1, it is characterised in that:

The hydrogenation catalyst that (1) first heavy-oil hydrogenation heat cracking reaction section AR1 is used is that a nanometer ultra-fine grain hydrated ferric oxide is urged Agent and/or iron oxide and/or pyrite and/or bloodstone and/or molybdenum oxide and/or molybdenum sulfide and/or ammonium molybdate and/or nickel sulfide.