CN109554187A

CN109554187A - The oily coal that heavy oil enters direct hydrogenation liquefaction of coal intermediate reaction process is total to smelting method

Info

Publication number: CN109554187A
Application number: CN201710932814.2A
Authority: CN
Inventors: 何巨堂
Original assignee: Individual
Current assignee: Individual
Priority date: 2017-09-25
Filing date: 2017-09-25
Publication date: 2019-04-02

Abstract

The oily coal for entering direct hydrogenation liquefaction of coal intermediate reaction process the present invention relates to heavy oil is total to smelting method, the initial stage coal liquefaction products therefrom AR1P in 25~35% stages of initial stage hydropyrolysis stage of reaction AR1 such as coal dust hydrogenation liquefaction reaction process whole residence times of coal dust hydrogenation liquefaction reaction process is completed in the coal that hydrogen supply dissolvent is prepared, it is mixed into the oily coal of heavy oil progress and refines hydrogenation reaction completion later period coal dust hydrogenation liquefaction reaction process and heavy-oil hydrogenation thermal cracking process altogether, on the one hand making the hydrogen supply dissolvent concentration of AR1 is not reduced by heavy oil early stage dilution and prevents pyrolysis of coal free radical fragment thermal condensation, on the other hand the residence time for reacting Heavy Oil Thermal is shorter than the residence time of coal dust hydrogenation liquefaction reaction process and reduces excessive secondary heat cracking reaction, it is maintaining to be pyrolyzed the hydroperoxyl radical consumption of free radical fragment and for hydrogen amount base Under conditions of this balance, secondary use hydrogen supply dissolvent mixes refining heavy oil in right amount to reduce system gross investment, improve economy.

Description

The oily coal that heavy oil enters direct hydrogenation liquefaction of coal intermediate reaction process is total to smelting method

Technical field

The oily coal for entering direct hydrogenation liquefaction of coal intermediate reaction process the present invention relates to heavy oil is total to smelting method, in hydrogen supply dissolvent The coal of preparation completes the initial stage hydropyrolysis stage of reaction AR1 such as coal dust hydrogenation liquefaction of coal dust hydrogenation liquefaction reaction process It is total to be mixed into the oily coal of heavy oil progress by the initial stage coal liquefaction products therefrom AR1P in 25~35% stages of reaction process whole residence time It refines hydrogenation reaction and completes later period coal dust hydrogenation liquefaction reaction process and heavy-oil hydrogenation thermal cracking process, on the one hand make the hydrogen supply of AR1 Solvent strength is not reduced by heavy oil early stage dilution and prevents pyrolysis of coal free radical fragment thermal condensation, on the other hand makes Heavy Oil Thermal anti- The residence time answered is shorter than the residence time of coal dust hydrogenation liquefaction reaction process and reduces excessive secondary heat cracking reaction, is tieing up Hold pyrolysis free radical fragment hydroperoxyl radical consumption with for hydrogen amount it is in a basic balance under conditions of, secondary use hydrogen supply dissolvent is mixed in right amount Refining heavy oil is to reduce system gross investment, improve economy.

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 liquid is 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 Altogether refine hydrogenation process or conversion ratio it is extremely low, and improve conversion ratio then a large amount of cokings cause reaction process can not for a long time 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 heavy-oil hydrogenation heat The investment of cracking process takes into account the optimization of direct hydrogenation liquefaction of coal process, the operating condition of heavy-oil hydrogenation thermal cracking process, because This reduces the total dosage of hydrogen supply dissolvent it is an object of the present invention to how construct combination process.

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 one electron spin resonance of large-sized analytic instrument 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 Product -- the quality standard of 0 gasoline, diesel oil, the repeated hydrogenation of second step, referred to as liquefaction oil plus hydrogen upgrading.

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.

Experimental results demonstrate, reaction time of heavy-oil hydrogenation thermal cracking be generally only the DCL/Direct coal liquefaction reaction time 40~ 70%, therefore, the synchronous heat from hydrogenation cracking process of oily coal mixture, there are optimum response period nonsynchronous problem, suitable weights Oily heat from hydrogenation soaking time will lead to the direct hydrogenation liquefaction of coal reaction time it is too short so that coal liquefaction rate be greatly lowered from And process economy is reduced, it is too long that the suitable direct hydrogenation liquefaction of coal reaction time will lead to the heavy-oil hydrogenation heat cracking reaction time Increase excessive secondary heat cracking reaction (generating gas and coke) to reduce process economy, while hydrogen supply dissolvent can not two Secondary reuse is needed using a large amount of fresh hydrogen supply dissolvents.

Smelting method is total to the present invention relates to oily coal, in particular to the heavy oil process position that enters direct hydrogenation liquefaction of coal reaction process It sets, target is the negative effect in order to reduce the initial stage pyrolysis of coal process to Coal liquefaction process, while preventing heavy oil from reacting Overlong time causes excessive secondary cracking to react, and also reduces the total dosage of hydrogen supply dissolvent.In this way, into the direct liquid of initial stage coal hydrogenation The hydrogen supply dissolvent for changing reaction process is substantially to start solvent naphtha, and the liquid of initial stage direct hydrogenation liquefaction of coal reaction process is discharged (including hydrogen supply dissolvent conversion product and initial stage coal liquefaction products) is substantially the self-produced secondary solvent oil of system, present invention utilizes Secondary solvent oil thus create economy.

So far, propose basic conception of the invention: the present invention relates to heavy oil to enter direct hydrogenation liquefaction of coal intermediate reaction The oily coal of process is total to smelting method, completes the initial stage heat from hydrogenation of coal dust hydrogenation liquefaction reaction process in the coal that hydrogen supply dissolvent is prepared Solve the initial stage coal liquefaction institute in 25~35% stages of stage of reaction AR1 such as coal dust hydrogenation liquefaction reaction process whole residence times Product AR1P is obtained, the oily coal of heavy oil progress is mixed into and refines hydrogenation reaction completion later period coal dust hydrogenation liquefaction reaction process and heavy-oil hydrogenation altogether On the one hand thermal cracking process makes the hydrogen supply dissolvent concentration of AR1 not reduced by heavy oil early stage dilution and prevent pyrolysis of coal free radical broken Piece thermal condensation, on the other hand make Heavy Oil Thermal react residence time be shorter than coal dust hydrogenation liquefaction reaction process residence time and Reduce excessive secondary heat cracking reaction, maintain the hydroperoxyl radical consumption of pyrolysis free radical fragment with it is in a basic balance for hydrogen amount Under the conditions of, secondary use hydrogen supply dissolvent mixes refining heavy oil in right amount to reduce system gross investment, improve economy.

Since the centre of direct hydrogenation liquefaction of coal reaction process needs to reduce upstream reaction product temperature using circulation quench oil It spends to control the initial reaction temperature in downstream reaction area, therefore, as long as replacing circulation quench oil with heavy oil, also originally at implementation A kind of mode of invention, compared with conventional oily coal be total to sweetening process, heavy oil feedstock is also heated to 350 by 150~200 DEG C~ The advantages of 430 DEG C of the step of, omit and directly recycle initial reaction heat.Therefore, partial function of the invention, alternatively referred to as with outer For the direct hydrogenation liquefaction of coal method of heavy oil surrogate response process circulation quench oil.Certainly, the addition of part heavy oil of the invention Temperature is heated to 350~430 DEG C by 150~200 DEG C as needed, to realize that the heavy oil of anticipated number is kneaded；It is kneaded heavy oil Quantity can achieve 1~3 times of coal charge.

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 enters the oily coal of direct hydrogenation liquefaction of coal intermediate reaction process and refines altogether Method.

The second object of the present invention is to propose that heavy oil enters the oily coal of direct hydrogenation liquefaction of coal intermediate reaction process and refines altogether Method, the naphtha for voluminous Gao Fangqian.

Summary of the invention

The oily coal that heavy oil of the present invention enters direct hydrogenation liquefaction of coal intermediate reaction process is total to smelting method, it is characterised in that includes Following steps:

1. containing hydrogen supply dissolvent AR1-DS, coal dust in the initial reaction process AR1 of direct hydrogenation liquefaction of coal reaction process AR The coal AR1F of AR1-SF carries out at least part initial stage Coal Liquefaction reaction AR1R, and to be converted into initial stage Coal Liquefaction anti- Answer product AR1P；

Material based on initial stage Coal Liquefaction reaction product AR1P is used as the first material flow A R1PX；

2. late phase reaction the process AR2, the first material flow A R1PX and heavy oil FD in direct hydrogenation liquefaction of coal reaction process AR are mixed At least part later period Coal Liquefaction reaction AR2R is carried out after conjunction is converted into later period Coal Liquefaction reaction product AR2P；

Later period Coal Liquefaction reaction product AR2P is recycled, hydrogen supply dissolvent predecessor hydrocarbon MFB is obtained；

3. hydrogen supply dissolvent predecessor hydrocarbon MFB carries out stabilized hydrogenation reaction and completes aromatic hydrocarbon molecule in stabilized hydrogenation reaction process MR 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；

The initial reaction process AR1 that at least part hydrogen supply dissolvent DS enters direct hydrogenation liquefaction of coal reaction process, which is used as, to be supplied Hydrogen solvent A R1-DS.

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

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 present invention, in general, in the late phase reaction process AR2 of direct hydrogenation liquefaction of coal reaction process AR, at least part weight The temperature of oily FD is lower than the operation temperature of the first material flow A R1PX, also below the initial reaction temperature of late phase reaction process AR2, i.e., At least part heavy oil FD serves as the coolant that initial reaction process AR1 product AR1PX enters late phase reaction process AR2.

The present invention, in the initial reaction process AR1 of direct hydrogenation liquefaction of coal reaction process AR, the residence time T1 of coal slurry, It accounts for the ratio of the total residence time TA of direct hydrogenation liquefaction of coal reaction process AR: being usually 20~60%, generally 30~40%.

The present invention consumes DH1 in the hydrogen of the initial reaction process AR1 of direct hydrogenation liquefaction of coal reaction process AR, coal slurry, accounts for coal Add the ratio of the total hydrogen consumption DH of hydrogen direct liquefaction reaction process AR: being usually 20~60%, generally 30~50%.

The present invention, in the initial reaction process AR1 of direct hydrogenation liquefaction of coal reaction process AR, the weight of hydrogen supply dissolvent AR1-DS Measure the weight flow rate AR1-SF-W of flow rate AR1-DS-W and coal dust AR1-SF ratio be agent coal ratio K100=(AR1-DS-W)/ (AR1-SF-W), K100 is usually 0.5~2.0；

In the weight flow rate FD-W and coal of late phase reaction the process AR2, heavy oil FD of direct hydrogenation liquefaction of coal reaction process AR The ratio of the weight flow rate AR1-SF-W of powder AR1-SF is agent coal ratio K500=(FD-W)/(AR1-SF-W), and K500 is usually 0.01~4.0.

The present invention, coal dust AR1-SF plus hydrogen direct liquefaction reaction process AR overall liquefied fraction, typically larger than 85%, one As be greater than 90%；

The conversion per pass of heavy oil FD, typically larger than 60%, generally higher than 75%.

The operating condition of the present invention, Coal Liquefaction reaction process AR are usual are as follows: reaction temperature is 400~465 DEG C, reaction Device pressure is 6~30MPa, and vapor phase hydrogen volumetric concentration 50~95%, gas-liquid volume ratio is 300~1500NL/kg, liquefied catalytic Agent additive amount is 0.1~3 mass % of dry pulverized coal weight, and co-catalyst additive amount is S/ catalyst activity metal in co-catalyst Molar ratio be 1.0~2.0, coal slurry solid concentration be 40~60 mass %, reaction time TA be 0.5~4 hour.

The present invention, in Coal Liquefaction reaction process AR, the hydrogenation catalyst used can be a kind of composite hydrogenation and urge Agent includes 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 oxidation Iron ore or iron sulfide ore, wherein iron in ore content is not less than 40wt%, and catalyst ARC water content is lower than 2wt%；ARC The powdered granule that particle diameter is 1~100 μm.

The present invention, in Coal Liquefaction reaction process AR, direct hydrogenation liquefaction of coal catalyst can be 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 prepares hydrogen supply dissolvent for Coal Liquefaction reaction process AR, operates in stabilized hydrogenation reaction process MR Condition is usual are as follows: it is adding for Ni-Mo, Ni-Co or Ni-W system that solvent oil hydrogenation, which stablizes the hydrogenation catalyst that reaction process MR is used, Hydrogen catalyst；Reaction temperature is 300~390 DEG C, and hydrogenation pressure is 10~25MPa, and gas-liquid volume ratio is 300~1000NL/kg； In general, 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 greater than 15%, aromatic carbon Rate 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 of fractional saturation aromatic hydrocarbons contains It is 0.45~0.60 that amount, which is greater than 25%, aromatic carbon rate,.

The present invention can be selected in the mode of operation of Coal Liquefaction reaction process AR, the Coal Liquefaction reactor used 1 kind or several of the combination in following:

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

2. ebullated bed.

The present invention, the mode of operation that the solvent oil hydrogenation that in stabilized hydrogenation reaction process MR, uses stablizes reactor can With a kind or several of the 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.

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 group in direct hydrogenation liquefaction of coal reaction process AR with hydrogen supply function Point, hydrogen supply hydrocarbon includes the polycyclic aromatic hydrocarbon of the double ring arene of fractional saturation, fractional saturation, is that direct hydrogenation liquefaction of coal process AR is used Hydrogen supply dissolvent oil ideal composition.In hydrogen supply hydrocarbon, the hydrogen supply speed of dihydro body is all larger than tetrahydro body, the dihydro body of thrcylic aromatic hydrocarbon It is compared with the dihydro body of double ring arene, it is low that hydrogen supply speed has height to have；Although testing it has been proved that polycyclic aromatic hydrocarbon is without for Hydrogen Energy Power, but have 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 1 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 AR is described below.

Direct hydrogenation liquefaction of coal process AR 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.

In direct hydrogenation liquefaction of coal process AR, no matter which kind of coal faces hydrogen direct liquefaction process, and target is to obtain oil product, The function of pursuit is " coal turns oil ", it is necessary to which existing chemical change is " coal hydrogenation ", and the common trait of current such technology is Using 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 BR to be processed.

Direct hydrogenation liquefaction of coal process AR of the present invention is referred to coal and molecule hydrogen that may be present as original Material is hydrogen supply dissolvent oil with specific oil product (the usually hydrogenation modification oil of liquefied coal coil), in certain operating condition (as grasped Make temperature, operating pressure, solvent naphtha/coal weight ratio, hydrogen/solvent naphtha volume ratio and suitable hydrogenation catalyst) under, coal is direct The reaction process of the hydrogenation liquefactions such as carbon-carbon bond thermal cracking, free radical stabilized hydrogenation occurs.

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 AR works well, hydrogen supply dissolvent oil generallys use Coal Liquefaction reaction The hydrogenation modification oil of the self-produced liquefied coal coil of process (usually conventional distillate of the boiling range higher than 165 DEG C), liquefied coal coil add hydrogen The main target of modifying process is production direct hydrogenation liquefaction of coal reaction process AR solvent naphtha, is specifically exactly to improve oil product In " with good hydrogen supply function component " content, such as improve naphthenic base benzene class, the content of bicyclic alkyl benzene class component, base The fact that in liquefied coal coil contains a large amount of double ring arenes and a large amount of thrcylic aromatic hydrocarbons, liquefied coal coil hydrogenation modification process is one The hydrogenation process of " appropriate 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 AR, hydrogen supply dissolvent is substantially a kind of the main of coal liquefaction positive reaction Foreground catalyst, he quickly provides most of reactive hydrogen of coal liquefaction, it directly decide 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 AR, solid is urged A kind of retarding agent substantially more like coal liquefaction negative reaction such as agent such as pyrite, molybdenum sulfide, solid catalyst particle absorption are viscous Big colloid, asphaltene molecules MK are spent, and contacts MK with the reactive hydrogen of solid catalyst surface, to inhibit its pyrocondensation；? In direct hydrogenation liquefaction of coal reaction process AR, solid catalyst such as pyrite, molybdenum sulfide etc. substantially simultaneously or a kind of hydrogen supply The recovery catalyst of agent dehydrogen substance SH-Z, solid catalyst particle adsorbs SH-Z, and makes the work of SH-Z and solid catalyst surface Property hydrogen contact, thus plus hydrogen be restored to the hydrogen supply hydrocarbon for having hydrogen supply capacity, it directly decides answering for hydrogen supply agent dehydrogen substance SH-Z Former speed；In direct hydrogenation liquefaction of coal reaction process AR, solid catalyst such as pyrite etc. substantially simultaneously or a kind of mesh Mark the weak action catalysts of hydrocracking reaction such as asphaltene, preasphaltene being hydrocracked.Therefore, in direct hydrogenation liquefaction of coal In reaction process AR, in certain sense, solid catalyst such as pyrite, molybdenum sulfide etc. is more like a kind of urging for backstage running Agent plays a kind of support property and the effect of promotion property to coal liquefaction target product distillate.In coal hydrogenation liquefaction reaction process AR In, since the effect of hydrogen supply dissolvent DS is extremely important, the operating condition and effect that solvent oil hydrogenation stablizes reaction process are certainly It is so 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 AR 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 AR of the present invention refers to the coal hydrogenation liquid under solvent naphtha existence condition Change 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 The modified solvent naphtha of process, 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 AR because boiling point too it is low be easy to vaporize be difficult to serve as liquid phase solvent component；If into Direct hydrogenation liquefaction of coal reaction process AR, the product of further heat cracking reaction are 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 AR or Special hydrogenation heat Cracking process or hydrocracking process or other thermal cracking processes are processed, usually can enter hydrofining reaction process into Row desulfurization, 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 that the boiling point that direct hydrogenation liquefaction of coal reaction process AR needs is suitable, hydrogen supply dissolvent that hydrogen supply capacity is excellent oil, in addition for Direct hydrogenation liquefaction of coal process AR, the second light diesel fuel or its stabilized hydrogenation oil, before direct hydrogenation liquefaction of coal reaction process AR Play a part of the basic solvent composition of liquid phase in portion's reaction process, but it is anti-at the rear portion of direct hydrogenation liquefaction of coal reaction process AR It most of in the process should vaporize, and usually direct hydrogenation liquefaction of coal reaction process AR there are the resource of surplus therefore belongs to The major product of direct hydrogenation liquefaction of coal reaction process AR, therefore, the second light diesel fuel of coal liquefaction products or its stabilized hydrogenation oil lead to Often part is used as lightweight hydrogen supply dissolvent oil for direct hydrogenation liquefaction of coal reaction process AR, is partially used as plus hydrogen upgraded material is used for Hydrogen upgrading reaction process is added to produce 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, The most desirable boiling point of direct hydrogenation liquefaction of coal reaction process AR is suitable, hydrogen supply capacity is excellent hydrogen supply dissolvent oil, in addition for Direct hydrogenation liquefaction of coal process AR, heavy diesel fuel or its stabilized hydrogenation oil, in the whole process of direct hydrogenation liquefaction of coal reaction process AR In play a part of the basic solvent composition of liquid phase, and there are the resources of surplus by usually direct hydrogenation liquefaction of coal reaction process AR Therefore belong to the major product of direct hydrogenation liquefaction of coal reaction process AR, and therefore, coal liquefaction products heavy diesel fuel or its stabilized hydrogenation oil, Usually part is used as heavy hydrogen supply dissolvent oil for direct hydrogenation liquefaction of coal reaction process AR, is partially used as plus hydrogen upgraded material is used In add hydrogen upgrading reaction process 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, The most desirable boiling point of direct hydrogenation liquefaction of coal reaction process AR is suitable, hydrogen supply capacity is excellent hydrogen supply dissolvent oil, in addition for Direct hydrogenation liquefaction of coal process AR, light wax oil or its stabilized hydrogenation oil, in the last height of direct hydrogenation liquefaction of coal reaction process AR Thermophase plays a part of the basic solvent composition of liquid phase, and usually direct hydrogenation liquefaction of coal reaction process AR is difficult to itself and puts down The scarce resource of weighing apparatus, therefore, coal liquefaction products light wax oil or its stabilized hydrogenation oil are usually completely used as heavy hydrogen supply dissolvent oil use In direct hydrogenation liquefaction of coal reaction process AR, 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 AR to carry out deep conversion is reasonable inevitable choice, and coal liquefaction wax slop was reacted by stabilized hydrogenation in other words It is reasonable inevitable choice that stabilized hydrogenation oil obtained by journey, which enters direct hydrogenation liquefaction of coal reaction process AR to carry out deep conversion,；In addition For direct hydrogenation liquefaction of coal process AR, wax slop or its stabilized hydrogenation oil, direct hydrogenation liquefaction of coal reaction process AR most Hot stage plays a part of the basic solvent composition of liquid phase afterwards, and usually direct hydrogenation liquefaction of coal reaction process AR is difficult to certainly The scarce resource of body balance, therefore, coal liquefaction products wax slop or its stabilized hydrogenation oil are usually completely used as heavy hydrogen supply dissolvent Oil is used for direct hydrogenation liquefaction of coal reaction process AR, 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 Return to AR.

Kerosene of the present invention refines heat from hydrogenation strongization of the integrated technique particularly suitable for optimizing the high inferior heavy oil of fragrant charcoal rate 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 AR as circulation cracked oil generates the fraction section of oil, preferably cracked gas The fraction section of low yield, for example heavy diesel fuel (265~350 DEG C of fractions of conventional boiling range), (350~530 DEG C of conventional boiling range evaporates wax oil Point), it can be used for voluminous naphtha.

Characteristic of the invention is described below.

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 AR, because of conventional gas hydrocarbon, CO, CO₂Yield is huge, usually most of Cold high score gas of the cold high score gas than such as from about 70~100%, after being purified as membrane separation process obtained by permeated hydrogen pressurization after return Hydrogenation process does not permeate gas by PSA and mentions hydrogen or pressurization return plus hydrogen after " steam reforming hydrogen manufacturing+PSA mentions hydrogen " Reaction process is 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. heavy oil also serves as the quench oil of direct hydrogenation liquefaction of coal reaction process, directly recycles direct hydrogenation liquefaction of coal and reacted The initial reaction heat of journey；

3. guarantee direct hydrogenation liquefaction of coal high conversion rate in 90% under the premise of, secondary use hydrogen supply dissolvent and coal liquefaction Oil realizes the deep hydrogenation heat cracking reaction of heavy oil, when being kneaded high aromatic hydrocarbons heavy oil can fecund Gao Fangqian naphtha, compared to list Only direct hydrogenation liquefaction of coal reaction process is kneaded heavy oil and improves economy, particularly suitable for being kneaded shale oil residual oil, fine coal The coal tar asphalt of pyrolytic tar.

Claims

1. the oily coal that heavy oil enters direct hydrogenation liquefaction of coal intermediate reaction process is total to smelting method, it is characterised in that include following step It is rapid:

1. containing hydrogen supply dissolvent AR1-DS, coal dust AR1- in the initial reaction process AR1 of direct hydrogenation liquefaction of coal reaction process AR The coal AR1F of SF carries out at least part initial stage Coal Liquefaction reaction AR1R and is converted into the reaction production of initial stage Coal Liquefaction Object AR1P；

2. in the late phase reaction process AR2 of direct hydrogenation liquefaction of coal reaction process AR, after the first material flow A R1PX is mixed with heavy oil FD It carries out at least part later period Coal Liquefaction reaction AR2R and is converted into later period Coal Liquefaction reaction product AR2P；

3. hydrogen supply dissolvent predecessor hydrocarbon MFB carries out the portion that aromatic hydrocarbon molecule is completed in stabilized hydrogenation reaction in stabilized hydrogenation reaction process MR Aromatic ring saturated reaction MRR is divided to be converted into stabilized hydrogenation reaction product MRP；

It is molten that the initial reaction process AR1 that at least part hydrogen supply dissolvent DS enters direct hydrogenation liquefaction of coal reaction process is used as hydrogen supply Agent 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.

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 530 DEG C forms.

4. 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；

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

2. in the late phase reaction process AR2 of direct hydrogenation liquefaction of coal reaction process AR, the temperature of at least part heavy oil FD is lower than The operation temperature of first material flow A R1PX, also below the initial reaction temperature of late phase reaction process AR2, i.e. at least part heavy oil FD serves as the coolant that initial reaction process AR1 product AR1PX enters late phase reaction process AR2.

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

1. in the initial reaction process AR1 of direct hydrogenation liquefaction of coal reaction process AR, it is straight to account for coal hydrogenation by the residence time T1 of coal slurry Connect the 20~60% of the total residence time TA of liquefaction reaction process AR.

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

1. in the initial reaction process AR1 of direct hydrogenation liquefaction of coal reaction process AR, it is straight to account for coal hydrogenation by the residence time T1 of coal slurry Connect the 30~40% of the total residence time TA of liquefaction reaction process AR.

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

1. the hydrogen of coal slurry consumes DH1 in the initial reaction process AR1 of direct hydrogenation liquefaction of coal reaction process AR, it is direct to account for coal hydrogenation The 20~60% of the total hydrogen consumption DH of liquefaction reaction process AR.

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

1. the hydrogen of coal slurry consumes DH1 in the initial reaction process AR1 of direct hydrogenation liquefaction of coal reaction process AR, it is direct to account for coal hydrogenation The 30~50% of the total hydrogen consumption DH of liquefaction reaction process AR.

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

1. in the initial reaction process AR1 of direct hydrogenation liquefaction of coal reaction process AR, the weight flow rate of hydrogen supply dissolvent AR1-DS The ratio of the weight flow rate AR1-SF-W of AR1-DS-W and coal dust AR1-SF is agent coal ratio K100=(AR1-DS-W)/(AR1-SF- W), K100 is 0.5~2.0.

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

2. the weight flow rate FD-W and coal dust of late phase reaction process AR2, heavy oil FD in direct hydrogenation liquefaction of coal reaction process AR The ratio of the weight flow rate AR1-SF-W of AR1-SF be agent coal ratio K500=(FD-W)/(AR1-SF-W), K500 be 0.01~ 4.0。

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

1. in the initial reaction process AR1 of direct hydrogenation liquefaction of coal reaction process AR, the weight flow rate of hydrogen supply dissolvent AR1-DS The ratio of the weight flow rate AR1-SF-W of AR1-DS-W and coal dust AR1-SF is agent coal ratio K100=(AR1-DS-W)/(AR1-SF- W), K100 is 0.5~2.0；

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

Coal dust AR1-SF plus hydrogen direct liquefaction reaction process AR overall liquefied fraction, is greater than 85%；

The conversion per pass of heavy oil FD is greater than 60%.

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

Coal dust AR1-SF plus hydrogen direct liquefaction reaction process AR overall liquefied fraction, is greater than 90%；

The conversion per pass of heavy oil FD is greater than 75%.

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

The operating condition of Coal Liquefaction reaction process AR 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 are 300~1500NL/kg, and deliquescence accelerant additive amount is 0.1~3 mass % of dry pulverized coal weight, co-catalyst additive amount are that the molar ratio of S/ catalyst activity metal in co-catalyst is 1.0~2.0, coal slurry solid concentration is 40~60 mass %, and reaction time TA is 0.5~4 hour.

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

In Coal Liquefaction reaction process AR, the hydrogenation catalyst used is a kind of composite hydrogenation catalyst, includes 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；It is described 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 ARC water content is lower than 2wt%；ARC particle diameter be 1~ 100 μm of powdered granule.

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

In Coal Liquefaction reaction process AR, direct hydrogenation liquefaction of coal catalyst 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:

In stabilized hydrogenation reaction process MR, hydrogen supply dissolvent is prepared for Coal Liquefaction reaction process AR, solvent oil hydrogenation is stablized anti- The hydrogenation catalyst that the process MR of answering is used is the hydrogenation catalyst of Ni-Mo, Ni-Co or Ni-W system；Reaction temperature is 300~390 DEG C, hydrogenation pressure is 10~25MPa, and gas-liquid volume ratio is 300~1000NL/kg；Normal boiling point in reaction product MRP is 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:

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 It is 0.45~0.60 that weight content, which is greater than 25%, aromatic carbon rate,.

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

In Coal Liquefaction reaction process AR, the mode of operation of the Coal Liquefaction reactor used a kind in following or Several combinations:

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

2. ebullated bed.

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

Stablize 1 of the mode of operation of reactor in following in the solvent oil hydrogenation that in stabilized hydrogenation reaction process MR, uses Kind or several combinations:

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；