CN109796998A

CN109796998A - Match the direct hydrogenation liquefaction of coal method of defeated coal slurry with the hydrocarbon liquid containing low boiling hydrocarbon

Info

Publication number: CN109796998A
Application number: CN201711188443.8A
Authority: CN
Inventors: 何巨堂
Original assignee: Individual
Current assignee: Individual
Priority date: 2017-11-17
Filing date: 2017-11-17
Publication date: 2019-05-24

Abstract

Match the direct hydrogenation liquefaction of coal method of defeated coal slurry with the hydrocarbon liquid containing low boiling hydrocarbon, for flexible modulation or the liquid phase agent coal ratio of reduction direct hydrogenation liquefaction of coal reaction process RU, the coal slurry KMJ that the solvent naphtha KL with slurry of the KC containing low boiling hydrocarbon makes, it is to complete the vaporization of most of low boiling component KC and pass rapidly through reaction compartment with gas phase in RU initial reaction process, compared with the unvaporized high boiling component HC in solvent naphtha with slurry, it is even more that 30~60% can be shortened in the residence time of reaction process, to significantly reduce the overall cleavage rate of partial solvent oil ingredient, correspondingly increase heat cracking reaction selectivity, improve Overall Liquid yield, reduce hydrogen consumption, improve process economics；Recycling direct hydrogenation liquefaction of coal reaction product process, which obtains the hydrocarbon ils material containing low boiling component KC, to be recycled.

Description

Match the direct hydrogenation liquefaction of coal method of defeated coal slurry with the hydrocarbon liquid containing low boiling hydrocarbon

Technical field

The present invention relates to the direct hydrogenation liquefaction of coal methods for matching defeated coal slurry with the hydrocarbon liquid containing low boiling hydrocarbon, are used for flexible modulation Or the liquid phase agent coal ratio of direct hydrogenation liquefaction of coal reaction process RU is reduced, what the solvent naphtha KL with slurry of the KC containing low boiling hydrocarbon made Coal slurry KMJ is to complete the vaporization of most of low boiling component KC and pass rapidly through reaction sky with gas phase in RU initial reaction process Between, compared with the unvaporized high boiling component HC in solvent naphtha with slurry, 30 can be shortened in the residence time of reaction process~ 60% is even more, to significantly reduce the overall cleavage rate of partial solvent oil ingredient, correspondingly increase heat cracking reaction selectivity, It improves Overall Liquid yield, reduce hydrogen consumption, improve process economics；Recycling direct hydrogenation liquefaction of coal reaction product process obtains It can be recycled to the hydrocarbon ils material containing low boiling component KC.

Background technique

Existing direct hydrogenation liquefaction of coal technique, that is, gas and liquid flowing reaction equation direct hydrogenation liquefaction of coal technique, why cannot Large-scale commercial is promoted, and an important factor is a large amount of using solvent naphtha, is formed comprising as described below unavoidable scarce It falls into:

1., by direct hydrogenation liquefaction of coal reaction process, a large amount of non-targeted property will occur for excessive solvent naphtha with coal dust Liquid hydrocarbon is lost in thermal cracking negative reaction, reduces the liquid hydrocarbon yield of overall direct hydrogenation liquefaction of coal process；

2. since excessive solvent naphtha passes through direct hydrogenation liquefaction of coal reaction process with coal dust, in order to inhibit excessive hot tearing Changing reaction then necessarily leads to the reduction of coal liquefaction conversion ratio；In order to guarantee rationally high coal liquefaction conversion ratio, necessarily lead to solvent naphtha Excessive thermal cracking, iterative cycles process as a result, recycled solvent oil lazy weight and boiling point present in system tend to become Low, i.e., there are the tendencies that lazy weight, component lighten for recycled solvent oil, and external supply solvent naphtha, such case are needed when serious The long-term existence on commercial plant；

3. excessive solvent naphtha passes through direct hydrogenation liquefaction of coal reaction process with coal dust, or simultaneously by carrying out aromatic hydrocarbons The solvent oil hydrogenation of fractional saturation reaction stablizes reaction process, significantly increases course-scale, increases considerably system investments And energy consumption；

4. excessive solvent naphtha passes through direct hydrogenation liquefaction of coal reaction process with coal dust, or simultaneously by carrying out aromatic hydrocarbons Fractional saturation reaction solvent oil hydrogenation stablize reaction process, significantly increase chemical hydrogen consumption, physical dissolution amounts of hydrogen and The emission hydrogen quantity of hydrogen upgrading process, increases considerably hydrogen cost.

Therefore, on the basis of not needing to significantly alter the existing technology with defeated coal slurry, need to propose that one kind can spirit The method of the liquid phase agent coal ratio living for adjusting or reducing direct hydrogenation liquefaction of coal reaction process RU is straight thoroughly to get rid of conventional coal hydrogenation The limitation for selecting agent and defeated coal method with slurry in liquifying method is connect, the best agent coal ratio and depressant of reaction process is adjusted flexibly Coal ratio improves process operating flexibility and economy.

Direct hydrogenation liquefaction of coal reactant coal ratio of the present invention refers to that participate in reacting into reaction process comes from coal The overall conventional liq hydrocarbon of slurry solvent oil participates in the weight ratio of the coal dust reacted with reaction process is entered；Coal of the present invention adds Hydrogen direct liquefaction reacts liquid phase agent coal ratio, and being present in for referring to participating in reacting into reaction process is molten from coal slurry in liquid phase The overall conventional liq hydrocarbon of agent oil participates in the weight ratio of the coal dust reacted with reaction process is entered；Since coal dust almost all is deposited It is in liquid phase, and coal slurry solvent naphtha always can partly be vaporized into gas phase, therefore, be reacted in direct hydrogenation liquefaction of coal Journey, agent coal ratio of the reaction liquid phase agent coal than being always lower than reaction process, the present invention are formally proposed, this hair based on this feature Bright purpose is: under the premise of operating license, farthest expand reaction liquid phase agent coal than the difference with reactant coal ratio, Reduce reaction liquid phase agent coal ratio.

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

It is well known that direct hydrogenation liquefaction of coal reaction process, will generally undergo pyrolysis plus the hydrogen and further decomposition etc. of coal Process eventually becomes stable pot liquor molecule.The pyrolytic process of coal will convert coal into liquid, it is necessary to destroy coal Macromolecular structure, make its be decomposed into be suitble to further processing size.So the first step of DCL/Direct coal liquefaction is exactly to destroy coal Macromolecular structure.Since in the macromolecular structure of direct liquefaction feed coal, the bridged bond intensity for connecting basic structural unit is weaker, When applying intensity of the outer active force more than bridged bond, the bridged bond for connecting basic structural unit can be broken, and be decomposed into free radical Fragment is normally referred to as pyrolyzed since this process is realized generally by temperature is improved.In pyrolytic process, coal be by Be added in circulation solvent in be made coal slurry participates in later reaction, so coal pyrolysis while, can also occur dissolve etc. physics it is anti- It answers.Hydrogen may be used together by different technique with solvent, and some possibility use catalyst.The process conditions of this step differ Very big, temperature is usually 370~470 DEG C, and pressure is usually 15~30MPa.

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.

During pyrolysis of coal, the dissolution phenomena of coal occurs 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, first is that the Asia that pyrolysis generates Stabilized radical fragment is by adding hydrogen to become to stablize molecule, second is that the macromolecular product that cracking generates further is hydrocracking into Small molecule.The substance generated during pyrolytic reaction still contains macromolecular.If using retortable liquid as final products, these Molecule must reduce molecular dimension by being hydrocracked.It is hydrocracked also another effect, that is, is deviate from out-of-proportion 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 Classification then has 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, commonly referred to as liquefaction oil plus hydrogen upgrading.

Chinese Shenhua Erdos coal oil branch company possesses the unique a set of commercialized 1,000,000 tons/year of coals in the world and adds Hydrogen direct liquefaction device, the Coal Liquefaction Project include the stabilized hydrogenation of direct hydrogenation liquefaction of coal reaction process RU, hydrogen supply dissolvent oil Process, stabilized hydrogenation distillate plus hydrogen grading process, naphtha product quantity is far below diesel oil distillate number in overall material balance Amount, that is to say, that major product is diesel oil distillate, and a document for recording this kind of data is shown in: 1. publication title: " the direct liquid of coal Chemical industry skill and engineering ", page 182 to page 188；2. retrieval is encoded with books: ISBN coding: 9-78703-04308-23；3. writing: Wu Xiuzhang, Shu Geping, Li Kejian, Xie Shunmin；4. publishing house: Science Press.

Experimental results demonstrate be suitable for the conventional raw material coal of coal liquefaction, reach 90% with coal liquefaction rate for target, adding hydrogen 20~40% initial reaction stage of direct liquefaction reaction process total reaction time completes most of pyrolysis task of coal Stablize task with free radical, coal liquefaction rate can generally achieve 50~75%, the 40~60% of total consumption hydrogen are usually consumed, with The time of direct hydrogenation liquefaction of coal reaction process extends, and the quantity of the organic matter for the coal that can be pyrolyzed is fewer and fewer, therefore coal is primary The concentration for being pyrolyzed free radical fragment is lower and lower, and the stable molecule of pyrolysis of coal fragment resistate conversion gained is more and more, Ke Yichong When the substance of hydrogen supply dissolvent is more and more, in this way, with the 20~40% of direct hydrogenation liquefaction of coal reaction process total reaction time The hydrogen supply dissolvent quantity in initial reaction stage is compared, the hydrogen supply dissolvent quantity of later stage occur it is relatively rich remaining, in order to mention The utilization rate of high hydrogen supply substance, can be by the solid concentration of direct hydrogenation liquefaction of coal reaction process RU far below charging coal slurry solid The intermediate liquid product or final liquid product of concentration are used as charging coal slurry diluent, with fair current or adverse current echo plex mode There is provided certain road part hydrogen supply dissolvent that charging coal slurry needs during direct hydrogenation liquefaction of coal initial reaction, that is to say, that be A kind of economic means of direct hydrogenation liquefaction of coal initial reaction process that realizing the i.e. thick coal slurry of high concentration coal slurry, such coal hydrogenation Effective feed process of the high concentration coal slurry of direct liquefaction reaction process, will be with great economic value.In fact, using liquid The strong loop reactor of body product is exactly a kind of effective secondary mode using solvent naphtha or hydrogen supply dissolvent oil.

Chinese Shenhua Erdos coal oil branch company possesses the unique a set of commercialized 1,000,000 tons/year of coals in the world and adds The agent coal weight ratio of hydrogen direct liquefaction device, coal slurry is about hydrogen supply dissolvent: coal dust=54.95: 45.05, the production of many years is real It tramples and shows under the operating conditions such as its efficient catalyst for coal liquefaction used, the coal hydrogenation of the coal of the agent coal weight ratio is straight It is sufficient, superfluous for connecing the quantity of the hydrogen supply dissolvent during liquefaction reaction, because long period is found after generating shut-down, is reacted The deposit on distribution plate, liquid collecting cup, wall in device is not coking deposit but granular deposit.That is, the dress The quantity for setting the hydrogen supply dissolvent oil used is more, and causes the reason that hydrogen supply dissolvent is superfluous or utilization rate is low, is not as coal Add the intrinsic demand in hydrogen direct liquefaction reaction process, is actually primarily due to slurry select agent, coal slurry transmission process, heated Other restrictive requirements of journey cause solvent naphtha or hydrogen supply agent dosage excessively high.

Requirement and existing solvent naphtha different boiling of the following analysis direct hydrogenation liquefaction of coal reaction process to solvent naphtha evaporate Divide in the phase existing way of direct hydrogenation liquefaction of coal reaction process and to the influence of Coal liquefaction, to propose that the present invention is set Think.

Existing plus hydrogen direct liquefaction reaction process, the solvent naphtha used are the hydro carbons that conventional boiling range is 200~530 DEG C, Light hydrocarbons, 230~280 DEG C of light hydrocarbons, conventional boiling range that conventional boiling range is 200~280 DEG C, which can be greatly classified into, is The heavy hydrocarbon that 280~350 DEG C of middle matter hydro carbons, conventional boiling range are 350~530 DEG C；Adding hydrogen direct liquefaction anti-according to them Phase-state change during answering is analyzed as follows:

1. the heavy hydrocarbon that conventional boiling range is 350~530 DEG C, will not usually vaporize, be direct hydrogenation liquefaction of coal process Basic liquid phase component and optimal liquid phase component；

2. the middle matter hydro carbons that conventional boiling range is 280~350 DEG C, reaction process can vaporize on a small quantity in the early stage, in operation temperature High late phase reaction process can be vaporized partially, be the important liquid phase component of direct hydrogenation liquefaction of coal process, be that hydrogen supply function is excellent Solvent naphtha；

3. the light hydrocarbons that conventional boiling range is 230~280 DEG C, in direct hydrogenation liquefaction of coal process, reaction process in the early stage It can partially vaporize, can largely be vaporized in the high late phase reaction process of operation temperature；Therefore, conventional boiling range is 200~280 DEG C Light hydrocarbons are the conveying solvent compositions with slurry of coal dust, and still, it is simultaneously not all reaction process liquid phase component；

4. the light hydrocarbons that conventional boiling range is 200~230 DEG C, in direct hydrogenation liquefaction of coal process, reaction process in the early stage It can largely vaporize, in the high middle and later periods reaction process meeting almost all vaporization of operation temperature；Therefore, conventional boiling range be 200~ 230 DEG C of light hydrocarbons are the conveying solvent compositions with slurry of coal dust, still, its no reaction process liquid phase component, and therefore, It is not needed with good hydrogen supply capacity.

As seen from the above analysis, the light hydrocarbons or normal boiling point that conventional boiling range is 200~230 DEG C are lower often Rule liquid hydrocarbon (such as light hydrocarbons that conventional boiling range is 100~200 DEG C or conventional boiling range is 150~200 DEG C), as low boiling Point component KC is used as solvent naphtha KL with slurry and prepares coal slurry KMJ, will have characteristics that and completes big portion in RU initial reaction process Divide to all vaporizing and passing rapidly through reaction compartment with gas phase, compared with the high boiling component HC in solvent naphtha with slurry, is reacting The residence time of process can be greatly shortened such as shorten it is 30~60% even more, due to the heat of low boiling hydrocarbon at identical temperature The heat scission reaction speed of cracking reaction speed and the high boiling hydrocarbon far below homogeneous structure, therefore replace part with low boiling hydrocarbon High boiling hydrocarbon prepares coal slurry, and the thermal cracking rate of bulk solvent oil can be significantly reduced, and correspondinglys increase heat cracking reaction selectivity, mentions High Overall Liquid yield reduces hydrogen consumption, improves process economics.

As seen from the above analysis, the with slurry of direct hydrogenation liquefaction of coal reaction process coal slurry selects agent principle can change Are as follows: it the use of conventional boiling range is as much as possible 200~230 DEG C under the premise of guaranteeing reaction liquid phase agent coal than this operation condition Light hydrocarbons or the lower conventional liquid hydrocarbon of normal boiling point (for example conventional boiling range is 60~200 DEG C or conventional boiling range is 130~200 DEG C of light hydrocarbons), in this way, being reduced to the maximum extent overall under the premise of retaining the function that it matches defeated coal dust The thermal cracking rate of solvent naphtha with slurry, due to its no reaction process liquid phase component, therefore, there is no need to it is hydrogen supply dissolvent oil, Use the light hydrocarbon fraction that direct hydrogenation liquefaction of coal reaction process is self-produced；With existing direct hydrogenation liquefaction of coal technique The selection principle of coal blending slurry solvent is compared, and is at least had the advantage that

1. reducing the internal circulating load with defeated coal slurry hydrogen supply dissolvent oil, it is possible to reduce reduce the heat of the hydrogen supply dissolvent oil of part Cracking negative reaction reduces liquid hydrocarbon loss, the liquid hydrocarbon yield of overall direct hydrogenation liquefaction of coal process in contrast can be improved；

2. guaranteeing the same of rationally high coal liquefaction conversion ratio due to avoiding the use to excessive high boiling point solvent oil When, reaction liquid phase agent coal ratio can be effectively reduced, reduce the excessive thermal cracking of high boiling point solvent oil, cyclic process as a result, Recycled solvent oil quantity present in system can become relatively sufficiently or even superfluous, and the mean boiling point of recycled solvent oil can be opposite Tend to get higher, i.e., the rational state that recycled solvent oil forming quantity is abundant, boiling range is relatively high, does not need external supply solvent Oil, in fact low coal conversion ratio operating condition of the such case on commercial plant is verified；

3. direct hydrogenation liquefaction of coal can be greatly lowered and reacted due to avoiding the use to excessive hydrogen supply dissolvent oil Journey, solvent oil hydrogenation stablize the scale of reaction process, and the energy consumption of the system is accordingly greatly lowered；

4. due to avoiding the use to excessive solvent oil, can be greatly lowered direct hydrogenation liquefaction of coal reaction process, The emission that solvent oil hydrogenation stablizes the chemical hydrogen consumption of reaction process, physical dissolution amounts of hydrogen and hydrogen upgrading process is hydrogeneous Hydrogen cost is greatly lowered in destiny amount.

Basic imagination of the invention is: matching the direct hydrogenation liquefaction of coal method of defeated coal slurry with the hydrocarbon liquid containing low boiling hydrocarbon, uses In flexible modulation or the liquid phase agent coal ratio of reduction direct hydrogenation liquefaction of coal reaction process RU, the solvent naphtha with slurry of the KC containing low boiling hydrocarbon The coal slurry KMJ that KL makes, RU initial reaction process be complete the vaporization of most of low boiling component KC and with gas phase it is quick It can in the residence time of reaction process compared with the unvaporized high boiling component HC in solvent naphtha with slurry across reaction compartment Shortening 30~60% is even more, to significantly reduce the overall cleavage rate of partial solvent oil ingredient, it is anti-to correspondingly increase thermal cracking Should selectively, improve Overall Liquid yield, reduce hydrogen consumption, improve process economics；Recycle direct hydrogenation liquefaction of coal reaction Product process, which obtains the hydrocarbon ils material containing low boiling component KC, to be recycled.

Using direct hydrogenation liquefaction of coal reaction process RU of the invention, reaction can be reduced under the conditions of conveying equivalent coal dust Liquid phase agent coal is more even more than about 10~30%, thus the significantly economic benefit of lifting process process.

Enter in the high warm logistics of conventional gas-liquid parallel type direct hydrogenation liquefaction of coal reaction process, the discharge of late phase reaction section Before high pressure hot separator, it is generally necessary to which its cooling down is led to late phase reaction section reaction heat, is being damaged using chilling material While disability amount, it is necessary to using the circulatory system of chilling material, the first aspect circulatory system increases investment, second aspect because The circularly-supercharged energy consumption and heat-energy losses of chilling material are recycled, the third aspect, quench oil can be partly as high pressure hot separator Hot high score oil by hot high score oil dropping valve, and be vaporizated into gas in pressure reduction, then enter in thermal low-pressure separators Heat low separates in gas, obtains condensate liquid by condensation process, condensate liquid makes after force (forcing) pump is pressurized as chilling liquid circulation With this process increases the cavitation erosion abrasion of hot high score oil dropping valve, shortens the dropping valve service life.And it is of the invention low Boiling point solvent naphtha with slurry will not occur phase in this process and convert the release amount of heat (by gas phase condensation into liquid phase), therefore, Relevant operation can be improved, first aspect can reduce the internal circulating load of chilling material, and second aspect can reduce circulation chilling object The circularly-supercharged energy consumption and heat-energy losses of material, the third aspect will not be in the form of liquid material as the hot high score oil of high pressure hot separator By hot high score oil dropping valve, once, the opposite cavitation erosion abrasion for reducing hot high score oil dropping valve, conducive to decompression is extended The valve service life.

The present invention, the step of with the other technologies of combined application, can such as increasing the liquid scrubbing of high score gas, increase hydrogen BH gas The thermal high Disengagement zone for forming hydrogenated oil can be used to hot high score oil in the step of proposing the de- light component of hot high score oil The step of injection flux oil reduces solid concentration in net product, into hot high score oil net product, injection cooling oil reduces its temperature Step etc..

The present invention, can be by the Process flow of each section of hydrogenation process of variation, can be other suitable by joint processing In the hydrocarbon material of joint processing, a variety of groups can be formed by the downstream processing methods of hydrocarbon ils in a variety of hot high score gas of joint Close technique.

Of course, it is possible to which direct hydrogenation liquefaction of coal reaction process RU (intermediate or end reaction process) to be generated to the distillation of oil Oil introduces direct hydrogenation liquefaction of coal reaction process RU secondary cycle and uses, and may be used as to be followed with coal slurry solvent naphtha Ring thermal cracking.For example, can be by the diesel oil (normal boiling point between 260~330 DEG C of distillate) and/or wax in the generation oil of RU Oil (normal boiling point between 330~530 DEG C of distillate) returns to RU and recycles cracking, with voluminous naphtha.

Of course, it is possible to which the distilled oil that RU (intermediate or end reaction process) is generated oil, introduces the production of hydrogen supply dissolvent Journey MR is converted into the secondary use of hydrogen supply dissolvent.

The present invention, it can also be used to which kerosene refines process altogether.

In fact, solvent naphtha with slurry is mink cell focus in Coal Liquefaction device of the earlier German using IG process operation, 1 part of coal and 1~1.5 part of circulation solvent are mixed and made into coal slurry coal slurry；In the improvement technique in later period, (conventional boiling range is oil in use 200~330 DEG C): the solvent naphtha with slurry that the weight ratio of heavy oil (conventional boiling range is 330~470 DEG C) is 40:60, it is evident that this The defeated coal slurry method of kind, cannot achieve effect of the invention.

It is entirely hydrogen supply dissolvent with slurry solvent, the boiling spread of hydrogen supply dissolvent is about in EDS direct hydrogenation liquefaction of coal technique It is 200~460 DEG C, the conventional boiling range of 80% component is 200~370 DEG C in hydrogen supply dissolvent.

1,000,000 tons/year of direct hydrogenation liquefaction of coal devices of Chinese Shenhua Erdos coal oil branch company operation operation, match Slurry solvent oil all generates the hydrogen supply dissolvent oil obtained after oil distillate oil stabilized hydrogenation, the conventional boiling of hydrogen supply dissolvent using coal liquefaction 200~530 DEG C of Cheng Yuewei, with slurry dose of coal weight ratio is 1.22: 1.0, is substantially free of the component that conventional boiling range is lower than 200 DEG C.But It is that this defeated coal slurry method also cannot achieve effect of the invention.

It is obvious that the present invention, which is equivalent to, is divided into 2 parts the conveying task of coal dust, the purpose of first part be conveying all or The solvent naphtha (high boiling point solvent oil) while transport portion coal dust of the participation reaction of the overwhelming majority, the conventional coal slurry of this task Configuration and transportation scheme are completed, and take into account the thermally equilibrated needs of reaction system in this way；The purpose of second part is with the method for the present invention spirit It is living to convey remaining coal dust；2 kinds of methods are used in conjunction with, come meet reaction process demanding kinetics (control necessary solid concentration, Control liquid heat carrier quantity, reduce recycled solvent oil quantity), therefore, flexibility, precise degrees will increase substantially.It is filling Under the premise of dividing heating, dilution, hydrogen supply capacity using required solvent naphtha, it can be greatly lowered with coal slurry hydrogen supply dissolvent The ratio of oil, the present invention can be coal dust/(coal dust+hydrogen supply dissolvent oil or the high boiling point solvent oils) of the overall raw material of reaction process Ratio, be increased to 55~65% even higher levels.Effect of the invention is that existing direct hydrogenation liquefaction of coal technique can not Accomplish, process economics can be increased substantially.

So far, the solvent naphtha of all direct hydrogenation liquefaction of coal technique matches defeated coal method, is all that coal hydrogenation is direct The raw material heating temperature of liquefaction reaction process is such a to be related to the thermally equilibrated problem of reaction process, such a with coal-water fluid concentration Directly affect reaction process reaction speed, the dynamics problem that solvent efficiency relates to, and reaction liquid phase agent coal is more molten than such a Agent oil efficiency, coupling or tied up in knots and cannot achieve respective free independent control, cannot achieve each change in other words One broad range of amount is freely adjusted, is controlled, and is restricted by the physical process that coal slurry heats such a input thermal energy, this Necessarily lead to excessive use hydrogen supply dissolvent oil or high boiling point solvent oil (the two belongs to high cost solvent naphtha) above-mentioned and brings The shortcomings that, this illustrates to need a kind of effective decoupling technology.

It is said from phase conversion angle, the present invention is substantially by a low boiling point liquid material coal slurry in another high temperature higher boiling The process of gas phase hydrocarbon and coal dust to be recycled is separated into liquid material coal slurry, but the coal dust isolated is connect by higher boiling liquid material simultaneously Touching, mixing carry flowing as coal slurry or reaction slurry, avoid the generation and aggregation of high concentration coal slurry or dry pulverized coal phase, So as to complete coal dust, from for the first time, defeated coal solvent liquid phase is to the transmitting of the second defeated coal solvent liquid phase, and therefore, the present invention can also claim Be " the defeated coal method of the relay-type that coal dust shifts between slurries ".

In fact, the method for liquid conveying solid substance powder, gas conveying solid substance powder realize already it is commonly used, still, Before so far, the present invention it is this liquid conveying solid substance powder, powder are transmitted between liquid phase, the first defeated coal solvent recovery reaction heat Liquid phase is left after vaporization to enter gas phase and quickly leave high-temperature reaction process, is then recycled gas phase and is obtained first time defeated coal solvent Why is not the method that liquid phase circulation uses proposed by people? one of reason may be, in order to reduce coal slurry configuration process System leakage probability, evaporative loss of solvent, the operating pressure for reducing coal slurry configuration process, improve process operation temperature with slurry with Accelerate the thermosol reaction etc. of coal dust, low boiling point solvent oil is not reasonably with slurry solvent.

However, it has been found by the present inventors that optimization " reacts liquid phase agent coal in the direct hydrogenation liquefaction of coal reaction process Than " there is major economic value, and there is not this concept in existing direct hydrogenation liquefaction of coal technology, thus also without proposing phase The solution answered.In fact, the present inventor is exactly to propose this while clear " reaction liquid phase agent coal ratio " this concept Invention.In order to optimize " reaction liquid phase agent coal ratio ", propose that the present invention is a natural event.

For the direct hydrogenation liquefaction of coal reaction process containing at least two conversion zone, the liquid material proposed using the present inventor The reactive mode of series connection, hydrogen parallel operation, or the liquid material proposed using the present inventor are connected, have hydrogen counter-current operation step Reactive mode, then low boiling hydrocarbon KC can be greatly shortened again with strength in the stop of reaction process can such as shorten 30 ~60% is even more, replace part high boiling hydrocarbon to prepare coal slurry with low boiling hydrocarbon in this way, when the thermal cracking of this partial solvent oil Between can be reduced to 20~35% even lower numerical value of corresponding amount, hydrocarbon pyrolysis rate can be reduced to corresponding amount 7~ 15% even lower numerical value significant can correspondingly increase heat cracking reaction selectivity, raising Overall Liquid yield, reduction hydrogen and disappear Consumption improves process economics, or can be referred to as one piece of cornerstone of forth generation direct hydrogenation liquefaction of coal technique.

By taking 1,000,000 tons/year of direct hydrogenation liquefaction of coal devices of Chinese Shenhua Erdos coal oil branch company as an example, if It is 1.22: 1.0 calculating by existing with slurry dose of coal weight ratio, being equivalent to reduces with slurry dose of coal weight by 15~20% solvent naphtha Than 0.183~0.244, it is equivalent to 0.366~0.488 times of solvent naphtha of the liquefied coal coil of 50% liquefaction oil yield, according to heat The conventional gas yield of cracking rate is calculated by about 5%, and being equivalent to liquefied coal coil weight yield reduces 1.83~2.44%, for For 1000000 tons/year of direct hydrogenation liquefaction of coal devices, oil product loses 1.83~2.44 ten thousand tons/year, in addition increases hydrogen and disappears Consumption.

The present invention, low boiling point solvent naphtha KL with slurry, it can be different from the low boiling point group in existing coal blending slurry solvent oil Point, he is such as recycled normal in direct hydrogenation liquefaction of coal reaction generation oil usually using the lower non-hydrogen supply solvent of cost Advise boiling point low boiling component, the light hydrocarbons that such as 100~200 DEG C or conventional boiling range are 150~200 DEG C.

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

Raw material, the product that present invention combination direct hydrogenation liquefaction of coal reaction process uses, propose specific process, also secretly Show (in secret) possible potential flow model.

Realize that mode of the invention is unrestricted, there are many concrete mode, low boiling point solvent component KC, can be with part or complete High boiling solvent component HC mixing in portion is used as solvent naphtha with slurry, independently can also match slurry solvent used as dedicated low boiling point Oil.

Low boiling point solvent component KC, independently when solvent naphtha with slurry used as dedicated low boiling point, with high boiling solvent group The process with slurry of HC is divided to compare, operation temperature would generally be reduced to reduce volatilization, increase liquid phase viscosity, the coal of the coal slurry of preparation Concentration would generally be lower.

Realize that mode of the invention is unrestricted, there are many concrete mode, the coal slurry that low boiling point solvent component KC is prepared, can be with Synchronous with other coal slurries or asynchronous participation reaction, for example, the coal slurry that low boiling point solvent component KC is prepared, it can be with other coal slurries Intermediate reaction product mixing after association response, so as to shorten low boiling point solvent component KC reaction process residence time.

The present invention can apply in the direct hydrogenation liquefaction of coal reaction method of various processes, such as conventional liquid gas Cocurrent tandem reactor process is grasped for the reaction process of liquid material series connection, hydrogen parallel operation for liquid material series connection, hydrogen adverse current The reverse-flow reaction process made.

Therefore, the first object of the present invention is the direct hydrogenation liquefaction of coal for proposing to be matched with the hydrocarbon liquid containing low boiling hydrocarbon defeated coal slurry Method can be used for conveying solid substance material such as catalyst, coal dust.

Second purpose of the invention is the direct hydrogenation liquefaction of coal method proposed with defeated coal slurry is matched with the hydrocarbon liquid containing low boiling hydrocarbon, Hydrogen supply dissolvent oil can be used in reaction process.

The purpose of third of the present invention is the direct hydrogenation liquefaction of coal method for proposing to be matched with the hydrocarbon liquid containing low boiling hydrocarbon defeated coal slurry, instead Process is answered to use the direct hydrogenation liquefaction of coal reaction method of hydrogen cocurrent cooling operation.

4th purpose of the invention is 2 sections or multistage direct hydrogenation liquefaction of coal for proposing to be matched with the liquid of hydrocarbon containing low boiling hydrocarbon defeated coal slurry Method, reaction process use the direct hydrogenation liquefaction of coal reaction method of hydrogen counter-current operation.

Summary of the invention

The present invention with the hydrocarbon liquid containing low boiling hydrocarbon match defeated coal slurry direct hydrogenation liquefaction of coal method, it is characterised in that comprising with Lower step: (1) in coal slurry configuration process MIX10, with raw material coal dust KS, the KC containing low boiling hydrocarbon hydrocarbon liquid KL and may add its Its material makes coal slurry KMJ；

Based on the material KMJ-TORU of coal slurry KMJ KS's containing low boiling hydrocarbon by least part of coal powder KS and at least part Solvent naphtha KL delivers into direct hydrogenation liquefaction of coal reaction process RU and participates in direct hydrogenation liquefaction of coal reaction RUR；

(2) in direct hydrogenation liquefaction of coal reaction process RU, 2 of 1 conversion zone or setting liquid material serial operation are set Conversion zone or multiple conversion zones that liquid material serial operation is set；

One conversion zone refers to that the gas-liquid separation comprising slurry hyd reaction step and the step gas-liquid product walks Rapid technical process；

In direct hydrogenation liquefaction of coal reaction process RU, there are hydrogen, hydrocarbon liquid phase, there may be the conditions of catalyst simultaneously Under, the direct hydrogenation liquefaction of coal for carrying out three phase materials of gas, liquid, solid reacts RUR, material KMJ-TORU and that may be present other contains Coal dust material carries out at least part direct hydrogenation liquefaction of coal reaction RUR and is converted into direct hydrogenation liquefaction of coal final reacting product RUP；Recycle final hydrogenation reaction product RUP；Final hydrogenation reaction product RUP is 1 tunnel or 2 tunnels or multichannel material；

Material KMJ-TORU is characterized in that by direct hydrogenation liquefaction of coal reaction process RU: from material KMU-TORU's When low boiling hydrocarbon KC leaves reactor as final reacting product, vaporized with weight basis, at least 50% into gas phase In；

In material KMJ-TORU, 200 DEG C of conventional liquid hydrocarbon is at least lower than containing conventional boiling range；

It can be capable of processing while processing the KMJ-TORU of material containing coal slurry in direct hydrogenation liquefaction of coal reaction process RU Its coal slurry material.

The present invention, in general, in direct hydrogenation liquefaction of coal reaction process RU, to participate in coming from for direct hydrogenation liquefaction of coal reaction On the basis of whole solvent oil ingredients of whole coal slurry materials, the weight ratio of conventional liquid hydrocarbon KC of the conventional boiling range lower than 200 DEG C It is 5~50%；1 kind or several in following of conventional liquid hydrocarbon KC:

1. the conventional liquid hydrocarbon that normal boiling point is 160~200 DEG C；

2. the conventional liquid hydrocarbon that normal boiling point is 120~160 DEG C；

3. the conventional liquid hydrocarbon that normal boiling point is 80~120 DEG C；

4. the conventional liquid hydrocarbon that normal boiling point is 40~80 DEG C.

The present invention, in general, the coal dust that material KMJ-TORU is carried carries out its coal in direct hydrogenation liquefaction of coal reaction process RU The whole volumes for the reactor for adding the reaction of hydrogen direct liquefaction to pass by are KRV；

Using the addition point P100 of material KMJ-TORU addition direct hydrogenation liquefaction of coal reaction process RU as starting point, material The coal dust that KMJ-TORU is carried flows through reactor, before 50% that the reactor volume flowed through reaches volume KRV, At least the 50% of the low boiling component KC that material KMJ-TORU is carried has been vaporized into gas phase.

The present invention, in general, recycling final hydrogenation reaction product RUP in separation and recovery process SYS300 and obtaining hydrogen rich gas gas Body RH, at least part hydrogen rich gas gas RH return to direct hydrogenation liquefaction of coal reaction process RU and are used as circulating hydrogen；

In general, separation and recovery process SYS300, the working method of hydrogen upgrading the process H2UPU, H2UPU of packet hydrogen material One of the following or several can be selected from:

1. using membrane separation process concentrate hydrogen；

2. using PSA pressure swing adsorption technique concentrate hydrogen；

3. using deep cooling process for separating concentrate hydrogen.

The present invention, in general, recycling final hydrogenation reaction product RUP in separation and recovery process SYS300 and obtaining containing low boiling point The hydrocarbon liquid KL-BASE of the hydrocarbon component KC, at least part hydrocarbon liquid KL-BASE return to coal slurry configuration process MIX10, are used as and contain low boiling point The hydrocarbon liquid KL of hydrocarbon, working method can be selected from one of the following or several:

1. thermal high separation process RUP-THPS, cold anticyclone separation process CHPS is arranged in separation and recovery process SYS300；

Hot high score gas RUP-THPS-V is separated into thermal high separation process RUP-THPS, final hydrogenation reaction product RUP With hot high score liquid material RUP-THPS-L；

Cold and hot high score gas CHPS-V and cold high score are separated into cold anticyclone separation process CHPS, hot high score gas RUP-THPS-V Liquid material CHPS-L；

Based on cold high score liquid material CHPS-L, hydrocarbon liquid KL-BASE is obtained；

2. in separation and recovery process SYS300, setting thermal high separation process RUP-THPS, warm high pressure separation process MHPS, Cold anticyclone separation process CHPS；

Warm high score gas MHPS-V and Wen Gaofen is separated into warm high pressure separation process MHPS, hot high score gas RUP-THPS-V Liquid material MHPS-L；

In cold anticyclone separation process CHPS, warms high score gas MHPS-V and be separated into cold and hot high score gas CHPS-V and cold high liquid separation Expect CHPS-L；

Based on warm high score liquid material MHPS-L and/or cold high score liquid material CHPS-L, hydrocarbon liquid KL-BASE is obtained；

3. the thermal high separation process RUP- with gas condensation collection step LCD is arranged in separation and recovery process SYS300 THPS, cold anticyclone separation process CHPS；

Hot high score gas RUP-THPS- is first separated into thermal high separation process RUP-THPS, final hydrogenation reaction product RUP V and hot high score liquid material RUP-THPS-L；Hot high score gas RUP-THPS-V is separated into cold in gas condensation collection step LCD cooling Lime set LCD-L and de- liquid gas LCD-V；

Cold and hot high score gas CHPS-V and cold high score liquid material are separated into cold anticyclone separation process CHPS, de- liquid gas LCD-V CHPS-L；

Based on condensate liquid LCD-L and/or cold high score liquid material CHPS-L, hydrocarbon liquid KL-BASE is obtained；

4. thermal high separation process RUP-THPS is arranged in separation and recovery process SYS300；

Heat of dissociation high score liquid material RUP-THPS-L, obtains hydrocarbon liquid KL-BASE.

The present invention, in general, in direct hydrogenation liquefaction of coal reaction process RU, while processing coal slurry material KMJ-TORU, Other coal slurry material NMJ are processed, working method is selected from one of the following:

1. the KMJ-TORU of material containing coal slurry, coal slurry material NMJ, into direct hydrogenation liquefaction of coal reaction process RU's after mixing In reactor；

2. the KMJ-TORU of material containing coal slurry, coal slurry material NMJ, into the same of direct hydrogenation liquefaction of coal reaction process RU The same reaction space of reactor；

3. positive, the coal of coal slurry material KMJ-TORU on the basis of crossing the main body flow direction in hydrogenation reaction space by coal slurry stream The intermediate reaction product for adding hydrogen direct liquefaction enters subsequent direct hydrogenation liquefaction of coal reaction process after mixing with coal slurry material NMJ In；

4. positive, the coal hydrogenation of coal slurry material NMJ on the basis of crossing the main body flow direction in hydrogenation reaction space by coal slurry stream The intermediate reaction product of direct liquefaction enters subsequent direct hydrogenation liquefaction of coal reaction process after mixing with coal slurry material KMJ-TORU In.

The present invention, in general, it is direct that coal slurry material KMJ-TORU enters coal hydrogenation in direct hydrogenation liquefaction of coal reaction process RU Liquefaction reaction process RU participates in direct hydrogenation liquefaction of coal reaction, and the other of first choice contact contain serum materials, and one in following Kind is several:

1. into the other coal slurry materials for participating in direct hydrogenation liquefaction of coal reaction of direct hydrogenation liquefaction of coal reaction process RU NMJ；

2. the recycle containing slurries for participating in direct hydrogenation liquefaction of coal reaction of direct hydrogenation liquefaction of coal reaction process RUU Material；

3. what direct hydrogenation liquefaction of coal reaction process RU was generated contains serum materials, intermediate from direct hydrogenation liquefaction of coal reaction Product；

4. what direct hydrogenation liquefaction of coal reaction process RU was generated contains serum materials, final from direct hydrogenation liquefaction of coal reaction Product.

The present invention, in general, in direct hydrogenation liquefaction of coal reaction process RU, at least two reaction of setting slurries serial operation Section, the hydrogen type of flow between each conversion zone is selected from one of the following or several:

1. hydrogen material flows to cocurrent in the same direction with the main body of serum materials, belong to liquid, gas cocurrent tandem reactor process；

2. gas-phase product does not enter the reaction process of other any conversion zones there are at least one conversion zone, gas is former Material do not use the hydrogen from other any conversion zones, belong to there are hydrogen material parallel operation reaction process；

3. reaction process receives the hydrogen product of downstream reaction section there are at least one conversion zone, belong in conversion zone Between there are the reaction process of hydrogen gas product counter-current operation.

The present invention, in general, in direct hydrogenation liquefaction of coal reaction process RU, at least two reaction of setting slurries serial operation Section, whole coal slurry raw materials, which enter in the reaction process of the first conversion zone, participates in direct hydrogenation liquefaction of coal reaction.

The present invention, in general, in direct hydrogenation liquefaction of coal reaction process RU, the direct hydrogenation liquefaction of coal reactor assembly that uses Working method and structure type, a kind or several in the following option:

Option 1, liquid material and gas material use the counter-current reactor of pure adverse current working method；

Option 2, reactor EA, forced circulation returns to reaction after the collection liquid that liquid collecting cup is arranged in top is pressurizeed by circulating pump The fluidized bed reactor of device EA material inlet；

Option 3, reactor EA, forced circulation returns to reaction after the collection liquid that liquid collecting cup is arranged in top is pressurizeed by circulating pump The suspended-bed reactor of device EA material inlet；

Option 4, reactor EA, forced circulation returns to reaction after the collection liquid that liquid collecting cup is arranged in top is pressurizeed by circulating pump The fluidized bed reactor of device EA material inlet, while circulating pump conveys circulation fluid, downstream transport liquid material product；

Option 5, reactor EA, forced circulation returns to reaction after the collection liquid that liquid collecting cup is arranged in top is pressurizeed by circulating pump The suspended-bed reactor of device EA material inlet, while circulating pump conveys circulation fluid, downstream transport liquid material product；

Option 6, reactor EA, forced circulation returns to reaction after the collection liquid that liquid collecting cup is arranged in top is pressurizeed by circulating pump The fluidized bed reactor of device EA material inlet, the other collection liquids for being collected simultaneously cup discharge pass through other dedicated feeding engines downstream Convey liquid material product；

Option 7, reactor EA, forced circulation returns to reaction after the collection liquid that liquid collecting cup is arranged in top is pressurizeed by circulating pump The suspended-bed reactor of device EA material inlet, the other collection liquids for being collected simultaneously cup discharge pass through other dedicated feeding engines downstream Convey liquid material product；

Option 8, reactor EA, top are arranged liquid collecting cup and liquid material product are discharged by dedicated feeding engine downstream transport liquid material Product is not provided with the fluidized bed reactor system of liquid material product forced circulation；

Option 9, reactor EA, top are arranged liquid collecting cup and liquid material product are discharged by dedicated feeding engine downstream transport liquid material Product is not provided with the suspended-bed reactor system of liquid material product forced circulation；

Option 10, reactor EA, forced circulation returns anti-after the collection liquid that liquid collecting cup is arranged in top is pressurizeed by circulating pump Answer the ebullated bed of device EA material inlet and the combination type reactor of ebullated bed；

Option 11, reactor EA, forced circulation returns anti-after the collection liquid that liquid collecting cup is arranged in top is pressurizeed by circulating pump The ebullated bed of device EA material inlet and the combination type reactor of ebullated bed are answered, it is downstream defeated while circulating pump conveys circulation fluid Liquor charging material product；

Option 12, reactor EA, forced circulation returns anti-after the collection liquid that liquid collecting cup is arranged in top is pressurizeed by circulating pump The ebullated bed of device EA material inlet and the combination type reactor of ebullated bed are answered, is collected simultaneously other collection liquids of cup discharge by it Its dedicated feeding engine downstream transport liquid material product；

The suspended-bed reactor system of flow pattern under the center upstream surrounding of internal guide cylinder is arranged in option 13；

The suspended-bed reactor system of flow pattern in the dirty surrounding in center of internal guide cylinder is arranged in option 14；

Option 15, empty cylinder bubbling bed suspended-bed reactor system；

Option 16 is formed reactor top reaction zone liquid phase and is flowed down under Returning reactor using the external circulation pipe of reactor The device outside circulation of portion's reaction zone.

The present invention, in general, in direct hydrogenation liquefaction of coal reaction process RU, the liquefied fraction of coal dust: typically larger than 85%, general It is 85~98%.

The present invention, in general, the non-coal base weight oil FD of refining can be mixed simultaneously in direct hydrogenation liquefaction of coal reaction process RU；

The cracking conversion rate of heavy oil FD, typically larger than 90%.

The present invention, in direct hydrogenation liquefaction of coal reaction process RU, operating condition is usual are as follows: reaction temperature is 400~485 DEG C, reactor pressure is 6~30MPa, and vapor phase hydrogen volumetric concentration 50~95%, gas-liquid volume ratio is 300~1500NL/kg, Deliquescence accelerant additive amount is 0.1~3 mass % of dry pulverized coal weight, and co-catalyst additive amount is S/ catalyst in co-catalyst The molar ratio of active metal is 1.0~2.0, and coal slurry solid concentration is 40~60 mass %, and reaction time TA is 0.5~4 Hour.

The present invention, in direct hydrogenation liquefaction of coal reaction process RU, the direct hydrogenation liquefaction of coal catalyst used can be one Kind composite hydrogenation catalyst, includes high-activity component and low activity component；The high-activity component metal and low activity component The weight ratio of metal is 1: 10 to 10: 1；The high-activity component is or mixtures thereof the water soluble salt compound of molybdenum；It is described Low activity group is divided into ferric oxide ore or iron sulfide ore, and wherein iron in ore content is not less than 40wt%, the direct liquid of coal hydrogenation Change catalyst water content and is lower than 2wt%；The powdered granule that direct hydrogenation liquefaction of coal catalyst particle diameter is 1~100 μm.

The present invention, in direct hydrogenation liquefaction of coal reaction process RU, direct hydrogenation liquefaction of coal catalyst can be ultra-fine for 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.

The present invention, in general, joining in direct hydrogenation liquefaction of coal reaction process RU into direct hydrogenation liquefaction of coal reaction process RU The hydrocarbon ils at least part reacted with direct hydrogenation liquefaction of coal is hydrogen supply dissolvent DS；

In general, at least part of hydrogen supply dissolvent DS is used as the solvent for preparing coal slurry；

In general, the ratio of the weight flow rate RUSF-W of the weight flow rate DS-W and coal dust RUSF of hydrogen supply dissolvent DS are agent coal ratio K100=(DS-W)/(RUSF-W), K100 are 0.5~2.0.

In general, hydrogen supply dissolvent DS is mainly that 250~530 DEG C of hydro carbons form by normal boiling point, part saturation aromatic hydrocarbons It is 0.35~0.70 that weight content, which is greater than 15%, aromatic carbon rate,；

Generally, hydrogen supply dissolvent DS is mainly that 250~530 DEG C of hydro carbons form by normal boiling point, part saturation aromatic hydrocarbons Weight content be greater than 25%, aromatic carbon rate be 0.45~0.60.

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 or heavy oil of the present invention refer 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.

Hydrogenation reaction space refers to the fluid circulation space that the hydrogenation reaction occurs, and can be the interior space of reaction such as Empty barrel reactor area, air lift hydrogen mixed zone, liquid collection cups upper space region etc., can be the reactor external space such as pipeline Space in interior space, valve, space in mixer, space etc. in pump.

Polycyclic aromatic hydrocarbon mentioned herein, aromatic ring number >=3.

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.

The present invention described in detail below.

Hydrogen supply hydrocarbon is described below.

Hydrogen supply hydrocarbon described herein refers to anti-in the high-temperature hydrogenation thermal cracking of low hydrogen content hydrocarbon ils such as residue oil fraction FD4 Should be in the process with the hydrocarbon component of hydrogen supply function, hydrogen supply hydrocarbon includes the polycyclic aromatic hydrocarbon of the double ring arene of fractional saturation, fractional saturation, It is same or similar with the type for the hydrogen supply hydrocarbon that coal liquefaction uses and function.In hydrogen supply hydrocarbon, the hydrogen supply speed of dihydro body is all larger than four Hydrogen body, the dihydro body of thrcylic aromatic hydrocarbon are compared with the dihydro body of double ring arene, and it is low that hydrogen supply speed has height to have；Test it has been proved that Although polycyclic aromatic hydrocarbon has the ability of transmitting hydrogen without hydrogen supply capacity.At 400 DEG C, the opposite hydrogen supply speed of following component is as follows:

DCL/Direct coal liquefaction process is described below.

DCL/Direct coal liquefaction process of the present invention, refers to the side under solvent naphtha existence condition by adding hydrogen to make coal liquefaction Method according to the difference of solvent naphtha and catalyst, pyrolysis way and adds the difference of hydrogen mode and the difference of process conditions, Ke Yifen For following several techniques:

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

6. 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.

In coal direct liquefaction method, majority belongs to direct hydrogenation liquefaction of coal liquefaction process, and no matter which kind of coal faces the direct liquid of hydrogen Change process, target are to obtain oil product, and the function of pursuit is " coal turns oil ", it is necessary to which existing chemical change is that " coal adds The common trait of hydrogen ", current such technology is using solvent naphtha and catalyst, and the conventional boiling range of solvent naphtha is generally 200~450 DEG C, it is most be 200~400 DEG C, solvent naphtha majority is distilled 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) or coal liquid that it is generated Carburetion modified oil can be used the method for the present invention and processed as long as its composition has raw material compositing characteristic of the present invention.

What patent CN100547055C stated clearly a kind of is pressed in lignite with the thermally dissolving and catalytic of lignite preparing liquid fuel is owned by France Add hydrogen direct liquefaction process, including Coal liquefaction process and liquefied coal coil hydrogenation modification process totally two processes.In order to improve The conversion ratio and realization coal feedstock of coal direct liquefaction enter reactor, and coal enters before reactor usually Coal dust is made, is made into coal with the solvent naphtha for having good hydrogen supply capacity, coal is pressurized, it is anti-to enter coal liquefaction after heating Answer device.

Coal liquefaction process of the present invention is referred to using coal and molecule hydrogen that may be present as raw material, with spy Fixed oil product (the usually hydrogenation modification oil of liquefied coal coil) is hydrogen supply dissolvent oil, certain operating condition (such as operation temperature, Operating pressure, solvent naphtha/coal weight ratio, hydrogen/solvent naphtha volume ratio and suitable hydrogenation catalyst) under, carbon directly occurs for coal The thermal cracking of carbon key, hydrogenation liquefaction reaction process.

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

After Coal liquefaction process works well, hydrogen supply dissolvent oil generallys use the self-produced coal liquid of Coal liquefaction process The hydrogenation modification oil of carburetion (usually conventional boiling range is higher than 165 DEG C of distillate), liquefied coal coil hydrogenation modification process it is main Target is production Coal liquefaction process solvent naphtha, is specifically exactly to improve in oil product " the group with good hydrogen supply function Point " content, for example improve naphthenic base benzene class, the content of bicyclic alkyl benzene class component, contained based on liquefied coal coil a large amount of bicyclic The fact that aromatic hydrocarbons and a large amount of thrcylic aromatic hydrocarbons, liquefied coal coil hydrogenation modification process be one " appropriate aromatic hydrocarbons saturation " plus hydrogen mistake Journey.

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.

Up flow type expanded bed hydrogenator of the present invention, the basic element of character usually have:

1. reactor shell；

2. the opening (or being adapter tube) in reactor shell；

3. the up flow type being arranged in reactor enclosure body adds hydrogen main reaction space, usually using catalyst when working condition, Usually using charging distributed component for being uniformly distributed charging；

4. being arranged in the feed distributor of bottom in reactor enclosure body；

5. being arranged in the liquid collection cups LD and liquid conduits LK of upper section or middle upper section in reactor enclosure body；

6. reactor intermediate feed distributor (or distributor), the mixer of catalyst bed interlayer, such as cold hydrogen box；

7. rectification part is exported, such as collector, liquid phase discharge vortex-proof device, mixed phase product fairlead.

8. the measuring instrumentss that may be installed: testing the temperature-measuring part such as thermocouple of reaction bed temperature, measure reactor The pressure gauge of system specific location pressure measures liquid level instrument such as glass plate, floating drum, the double flange difference gauges, guided wave of liquid level Radar, ray level-sensing device etc.；

Up-flow reactor of the present invention, accessory are external insulation material, supporting element (skirt or trunnion), base Plinth, ladder, operating platform and fire-fighting accessory that may be present such as steam smothering ring.According to the conditions such as construction ground geology, meteorology, knot The conditions such as weight of equipment, height are closed, up-flow reactor of the present invention needs to drive piles to control under its basis as needed The sinking speed on its basis.

Up-flow reactor of the present invention, working method can choose:

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. slight expanded-bed.

About direct hydrogenation liquefaction of coal reaction method, use can be reasonably selected to prior art or is used cooperatively, Through there are many method or schemes.

Characteristic of the invention is described below.

The present invention with the hydrocarbon liquid containing low boiling hydrocarbon match defeated coal slurry direct hydrogenation liquefaction of coal method, it is characterised in that comprising with Lower step:

(1) in coal slurry configuration process MIX10, with raw material coal dust KS, the KC containing low boiling hydrocarbon hydrocarbon liquid KL and may add Other materials make coal slurry KMJ；

Material KMJ-TORU is characterized in that by direct hydrogenation liquefaction of coal reaction process RU: from material KMJ-TORU's When low boiling hydrocarbon KC leaves reactor as final reacting product, vaporized with weight basis, at least 50% into gas phase In；

1. using membrane separation process concentrate hydrogen；

2. using PSA pressure swing adsorption technique concentrate hydrogen；

3. using deep cooling process for separating concentrate hydrogen.

Option 15, empty cylinder bubbling bed suspended-bed reactor system；

The cracking conversion rate of heavy oil FD, typically larger than 90%.

The general control principle of the gas-phase presulfiding hydrogen concentration of detailed description of the present invention hydrogenation process.

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~the part cold high score gas with exclude reaction generate methane, ethane.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 RU, 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.

Reference examples

Direct hydrogenation liquefaction of coal reaction process RU, using the suspension bed direct hydrogenation liquefaction of coal reactor of 3 serial operations, First direct hydrogenation liquefaction of coal reactor RUE01 product RUE01P enters the second direct hydrogenation liquefaction of coal reactor RUE02, and second Direct hydrogenation liquefaction of coal reactor RUE02 product RUE02P enters third direct hydrogenation liquefaction of coal reactor RUE03, and third coal adds Hydrogen direct liquefaction reactor RUE03 product RUE03P reacts final product RUP as direct hydrogenation liquefaction of coal, carries out oil gas point From the fractionation of, oil product.

Direct hydrogenation liquefaction of coal reaction process RU, the conventional feeding manner using a kind of coal concentration coal slurry are defeated to reaction process Slurry of delivering coal reacts after coal slurry pressurizes by force (forcing) pump, heats stove heating into the first direct hydrogenation liquefaction of coal of up flow type suspension bed The bottom of device RUE01；The circulation liquid material of liquid collecting cup outflow at the top of first direct hydrogenation liquefaction of coal reactor RUE01 is by circulation After pump pressurization, into the bottom of up flow type suspension bed the first direct hydrogenation liquefaction of coal reactor, with charging coal slurry, charging hot hydrogen The main reaction space of reactor RUE01 is flowed up into after mixing by the distributor of reactor RUE01 lower disposed, is carried out Direct hydrogenation liquefaction of coal reaction.

Be described below 200 tons/when raw material coal dust 96 tons of oil-producing/when direct hydrogenation liquefaction of coal process RUU operation Journey:

1. catalyst for coal liquefaction, hydrogen supply dissolvent RUDS, coal dust are made into quality of pc concentration in coal process for preparation AM For 45% coal LF, is pressurizeed with coal force (forcing) pump LF-PUMP and input coal heating furnace；After the pressurization of co-catalyst molten sulfur It is mixed with the coal LF of coal pressurization pump discharge；

Table 1 is the property of DCL/Direct coal liquefaction reaction process RU feed coal；

Table 2 is the property of DCL/Direct coal liquefaction reaction process RU solvent naphtha；

Table 3 is the catalyst property of DCL/Direct coal liquefaction reaction process RU；

Table 4 is the co-catalyst property of DCL/Direct coal liquefaction reaction process RU；

2. obtaining direct hydrogenation liquefaction of coal reaction product is RUP in direct hydrogenation liquefaction of coal reaction process RU；

Direct hydrogenation liquefaction of coal reaction process RU or its feed system will use hydrogen supply dissolvent oil and make flushing oil, cooling down Oil；

Table 5 is direct hydrogenation liquefaction of coal reaction condition summary sheet；

Using forced circulation suspended-bed reactor RUE01, RUE02, RUE03 of 3 serial operations, in every reactor Upper space arranges that built-in gas liquid-liquid separation unit, that is, liquid collection cups, Partial Liquid Phase product enter liquid collection cups, edge Catheter outflow reactor bottom returns to respective reactor inlet after circulating pump pressurizes and forms liquid circulation, liquid circulation Amount is 2.0~2.2 times of coal slurry total amount；Reactor head is discharged along diversion pipe in other mixed phase gas-liquid products；

Direct hydrogenation liquefaction of coal process RU final reacting product RUP temperature is 460 DEG C, and injecting cooling oil and cold hydrogen reduces temperature Degree is to entering high pressure hot separator ATHPS after 410 DEG C；

3., using high pressure hot separator ATHPS, being 410 in temperature in the separate section of Coal Liquefaction reaction product RUP DEG C, pressure be 18~20MPa under conditions of, separation Coal Liquefaction reaction product RUP obtain hot high score oil ATHPS-L and Re Gao Divide gas ATHPS-V；

The hydro carbons in hot high score oil ATHPS-L and hot high score gas ATHPS-V is collected, uses fractionation in fractionating section AFRAC Tower obtains narrow fraction oil product, is that 220~530 DEG C of fractions are sent into solvent oil hydrogenation stabilization process A-CRU by normal boiling point, is supplied Hydrogen solvent naphtha RUDS removes coal process for preparation AM and other uses a little；Obtain about 60 tons/when liquefied residue, go residue to form.

In separation process AF, direct hydrogenation liquefaction of coal reaction product RUP is recycled, obtaining hydrogen volume concentration is 85~88% Hydrogen-rich stream RUH, return to direct hydrogenation liquefaction of coal reaction process RU and be recycled, the concentrate mode of hydrogen mentions for UF membrane It is pure.

In separation process AF, recycle direct hydrogenation liquefaction of coal reaction product RUP, obtain mainly by conventional boiling range be 250~ The coal liquefaction of 530 DEG C of hydro carbons composition generates oil distillate oil AFD, and it is solid to obtain containing for the hydro carbons comprising normal boiling point higher than 530 DEG C Body dregs of fat AFK:

Part coal liquefaction generates oil distillate oil AFD as material flow A FD1, is used as hydrogen supply dissolvent predecessor hydrocarbon MFB；

Stabilized hydrogenation reaction, which is carried out, in stabilized hydrogenation reaction process MR, hydrogen supply dissolvent predecessor hydrocarbon MFB completes aromatic hydrocarbon molecule Part aromatic ring saturated reaction MRR is 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 direct hydrogenation liquefaction of coal reaction process RU as hydrogen supply dissolvent LF-DS, supplies Hydrogen solvent LF-DS and coal dust are formulated as coal slurry LF use；

Hydrogen supply dissolvent DS is the liquid phase stream containing hydrogen supply dissolvent, the hydro carbons group for being mainly 250~530 DEG C by conventional boiling range At.

Coal Liquefaction reaction process RU, liquefaction oil fractionating section AFRAC, liquefaction oil solvent oil hydrogenation stabilization process are made Liquefied coal coil yield for total system be i.e. 96 tons of 48% (to raw material coal dust)/when, be normal boiling point C₃~380 DEG C of hydrocarbon evaporates Point, wherein yield of liquefied gas be i.e. 8.0 tons of 4.0% (to raw material coal dust)/when, naphtha yield be 11.5% (to raw material coal dust) I.e. 23.0 tons/when, diesel yield be 65.0 tons of 32.5% (to raw material coal dust)/when.

In above-mentioned total system, hydrogen supply dissolvent amount be 1.22 times of coal dust i.e. 244.0 tons/when, solvent oil hydrogenation was stablized About 243.5 tons of the feed oil of journey production hydrogen supply dissolvent/when, it is the recycle oil being present in total system.

The coal of coal slurry: oily weight ratio is 45.05: 54.95, and the hydrogen supply dissolvent dosage of coal slurry thick in this way is coal blending 122.0%.

The property of 1 DCL/Direct coal liquefaction reaction process RU feed coal of table

The property of 2 DCL/Direct coal liquefaction reaction process RU solvent naphtha of table

The catalyst property of 3 DCL/Direct coal liquefaction reaction process RU of table

Serial number	Project	Data	Remarks
				1	Active component	Nanoscale FeOOH
2	Carrier	Part material coal
				3	Additive amount, (Fe/ dry coal), wt%	1.00
4	The Fe content of fine coal supported catalyst, wt%	5.6±0.5	Permanganimetric method
				5	The granularity of fine coal supported catalyst, wt%		Laser particle size method
	≤74μm	> 80
					74 μm of >	< 20
6	Catalyst is aqueous, wt%	≤4	Gravimetric method

The co-catalyst property of 4 DCL/Direct coal liquefaction reaction process RU of table

Serial number	Project	Data
			1	Co-catalyst	Molten sulfur
2	Molten sulfur sulfur content, wt%	100%
			3	Density, kg/m³	1726
4	Sulphur additive amount	Atomic ratio >=2 S/Fe
			5	Effect	The profile for guaranteeing iron is Fe₇S₈, and maintain gas phase H₂S partial pressure, prevents Fe₇S₈It is poly- It closes

5 direct hydrogenation liquefaction of coal reaction condition summary sheet of table

Project	Data
		React stagnation pressure, MPa	18~20
React hydrogen partial pressure, MPa	Minimum 13.0
		Average reaction temperature, DEG C	430~455
Hydrogen to oil volume ratio	600~800
		Catalyst for coal liquefaction	Nanoscale hydrated ferric oxide
Catalyst for coal liquefaction additive amount, (Fe/ dry coal), wt%	1.00
		Auxiliary agent	Liquid stream
Auxiliary dosage,	Atomic ratio >=2 S/Fe
		Reaction compartment hydrogen sulphide in the vapor phase volumetric concentration	Greater than 3000PPm
The coal of the liquefying reactor apparent residence time (to coal standard state volume)	140~145 minutes
		Moisture-and-ash-free basis lique faction of coal rate, weight %	Greater than 90

Embodiment

Embodiment one

The 10~20% of the hydrogen supply dissolvent oil of coal slurry will be configured, with low boiling hydrocarbon KC generation using the present invention based on reference examples It replaces；Configuration coal slurry is mixed with hydrogen supply dissolvent oil and low boiling hydrocarbon KC with coal slurry.

1 kind or several in following of low boiling hydrocarbon KC:

3. the conventional liquid hydrocarbon that normal boiling point is 80~120 DEG C.

Embodiment two

It is 197~280 by the conventional boiling range for accounting for hydrogen supply dissolvent oil total weight about 20% using the present invention based on reference examples DEG C fraction section, replaced with low boiling hydrocarbon KC；Configuration coal slurry is mixed with hydrogen supply dissolvent oil and low boiling hydrocarbon KC with coal slurry.

1 kind or several in following of low boiling hydrocarbon KC:

Embodiment three

1 kind or several in following of low boiling hydrocarbon KC:

Then by whole low boiling hydrocarbon KC, with etc. weight normal boiling point be 365~487 DEG C hydrogen supply dissolvent be mixed into the One coal blending slurry solvent oil KL accounts for about the 40% of overall solvent naphtha with slurry, according to coal: oily weight ratio is 45.05: 54.95 configurations Coal slurry KMJ.

The hydrogen supply dissolvent for being 280~365 DEG C using remaining normal boiling point accounts for about overall match as the second coal blending slurry solvent oil The 60% of slurry solvent oil, according to coal: oily weight ratio is 45.05: 54.95 configuration coal slurry NMJ.

Coal slurry KMJ, coal slurry NMJ are input to direct hydrogenation liquefaction of coal reaction process and participate in direct hydrogenation liquefaction of coal reaction.

Example IV

Based on embodiment one, the coal hydrogenation using the suspension bed direct hydrogenation liquefaction of coal reactor of 3 serial operations is direct Liquefaction reaction process RU changes flowage structure, using First reactor and a leading portion gas-liquid separator AD newly increasing as First conversion zone, using second reactor, third platform reactor, high pressure hot separator ATHPS serial operation as the second reaction Section.

The liquid material of first conversion zone, the liquid material be discharged by reactor liquid collecting cup and/or leading portion gas-liquid separator AD discharge, makees For the second conversion zone slurries raw material, second reactor, third platform reactor, high pressure hot separator ATHPS are passed sequentially through；

First conversion zone, gas-phase product do not enter the reaction process of the second conversion zone, and gas raw material is not used and come from The hydrogen of second conversion zone, such 2 conversion zones belong to there are hydrogen material parallel operation reaction process.

Second conversion zone, gas-phase product do not enter the reaction process of the first conversion zone, and gas raw material is not used and come from The hydrogen of first conversion zone；

Such 2 conversion zones belong to the reaction process of slurries serial operation, the parallel operation of hydrogen material.

Embodiment five

The hot high score gas of the high pressure hot separator discharge of second conversion zone, all as the raw material gas countercurrent of the first conversion zone Into secondary use in the reactor of the first conversion zone；

Such 2 conversion zones belong to the reaction process of slurries serial operation, hydrogen material counter-current operation.

Claims

1. matching the direct hydrogenation liquefaction of coal method of defeated coal slurry with the hydrocarbon liquid containing low boiling hydrocarbon, it is characterised in that comprise the steps of:

(1) in coal slurry configuration process MIX10, with raw material coal dust KS, the KC containing low boiling hydrocarbon hydrocarbon liquid KL and may add other Material makes coal slurry KMJ；

Solvent based on the material KMJ-TORU of coal slurry KMJ KS containing low boiling hydrocarbon by least part of coal powder KS and at least part Oily KL delivers into direct hydrogenation liquefaction of coal reaction process RU and participates in direct hydrogenation liquefaction of coal reaction RUR；

(2) in direct hydrogenation liquefaction of coal reaction process RU, 1 conversion zone is set or 2 reactions of liquid material serial operation are set Multiple conversion zones of section or setting liquid material serial operation；

One conversion zone refers to the gas-liquid separation step comprising slurry hyd reaction step and the step gas-liquid product Technical process；

In direct hydrogenation liquefaction of coal reaction process RU, there are hydrogen, hydrocarbon liquid phases simultaneously there may be under conditions of catalyst, into The direct hydrogenation liquefaction of coal of three phase materials of row gas, liquid, solid reacts RUR, material KMJ-TORU and that may be present other contains coal dust Material carries out at least part direct hydrogenation liquefaction of coal reaction RUR and is converted into direct hydrogenation liquefaction of coal final reacting product RUP；It returns Receive final hydrogenation reaction product RUP；Final hydrogenation reaction product RUP is 1 tunnel or 2 tunnels or multichannel material；

Material KMJ-TORU is characterized in that by direct hydrogenation liquefaction of coal reaction process RU: the low boiling from material KMJ-TORU When point hydrocarbon KC leaves reactor as final reacting product, vaporized with weight basis, at least 50% into gas phase；

Other coals can be capable of processing while processing the KMJ-TORU of material containing coal slurry in direct hydrogenation liquefaction of coal reaction process RU Starch material.

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

In direct hydrogenation liquefaction of coal reaction process RU, with participate in direct hydrogenation liquefaction of coal reaction from the complete of whole coal slurry materials On the basis of portion's solvent oil ingredient, the weight ratio of conventional liquid hydrocarbon KC of the conventional boiling range lower than 200 DEG C is 5~50%；

1 kind or several in following of conventional liquid hydrocarbon KC:

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

(2) in direct hydrogenation liquefaction of coal reaction process RU, the coal dust that material KMJ-TORU is carried carries out its direct hydrogenation liquefaction of coal The whole volumes for reacting the reactor passed by are KRV；

Using the addition point P100 of material KMJ-TORU addition direct hydrogenation liquefaction of coal reaction process RU as starting point, material KMJ- The coal dust that TORU is carried flows through reactor, before 50% that the reactor volume flowed through reaches volume KRV, material At least the 50% of the low boiling component KC that KMJ-TORU is carried has been vaporized into gas phase.

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

(3) it in separation and recovery process SYS300, recycles final hydrogenation reaction product RUP and obtains hydrogen rich gas gas RH, at least one Divide hydrogen rich gas gas RH to return to direct hydrogenation liquefaction of coal reaction process RU and is used as circulating hydrogen.

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

(3) it in separation and recovery process SYS300, recycles final hydrogenation reaction product RUP and obtains hydrogen rich gas gas RH, at least one Divide hydrogen rich gas gas RH to return to direct hydrogenation liquefaction of coal reaction process RU and be used as circulating hydrogen, separates and recovers process SYS300, packet The working method of hydrogen upgrading the process H2UPU, H2UPU of hydrogen material are selected from one of the following or several:

1. using membrane separation process concentrate hydrogen；

2. using PSA pressure swing adsorption technique concentrate hydrogen；

3. using deep cooling process for separating concentrate hydrogen.

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

(3) it in separation and recovery process SYS300, recycles final hydrogenation reaction product RUP and obtains the hydrocarbon liquid of the KC of component containing low boiling hydrocarbon KL-BASE, at least part hydrocarbon liquid KL-BASE return to coal slurry configuration process MIX10, as the hydrocarbon liquid KL containing low boiling hydrocarbon.

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

(3) it in separation and recovery process SYS300, recycles final hydrogenation reaction product RUP and obtains the hydrocarbon liquid of the KC of component containing low boiling hydrocarbon KL-BASE, at least part hydrocarbon liquid KL-BASE return to coal slurry configuration process MIX10, as the hydrocarbon liquid KL containing low boiling hydrocarbon, Working method is selected from one of the following or several:

Hot high score gas RUP-THPS-V and heat are separated into thermal high separation process RUP-THPS, final hydrogenation reaction product RUP High score liquid material RUP-THPS-L；

Cold and hot high score gas CHPS-V and cold high score liquid material are separated into cold anticyclone separation process CHPS, hot high score gas RUP-THPS-V CHPS-L；

2. in separation and recovery process SYS300, setting thermal high separation process RUP-THPS, warm high pressure separation process MHPS, cold height Press separation process CHPS；

Warm high score gas MHPS-V and warm high score liquid material are separated into warm high pressure separation process MHPS, hot high score gas RUP-THPS-V MHPS-L；

In cold anticyclone separation process CHPS, warms high score gas MHPS-V and be separated into cold and hot high score gas CHPS-V and cold high score liquid material CHPS-L；

3. in separation and recovery process SYS300, thermal high separation process RUP-THPS of the setting with gas condensation collection step LCD, Cold anticyclone separation process CHPS；

Thermal high separation process RUP-THPS, final hydrogenation reaction product RUP be first separated into hot high score gas RUP-THPS-V and Hot high score liquid material RUP-THPS-L；Hot high score gas RUP-THPS-V is separated into condensate liquid in gas condensation collection step LCD cooling LCD-L and de- liquid gas LCD-V；

Cold and hot high score gas CHPS-V and cold high score liquid material CHPS-L are separated into cold anticyclone separation process CHPS, de- liquid gas LCD-V；

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

Other coal slurry materials are processed while processing coal slurry material KMJ-TORU in direct hydrogenation liquefaction of coal reaction process RU NMJ, working method are selected from one of the following:

1. the KMJ-TORU of material containing coal slurry, coal slurry material NMJ enter the reaction of direct hydrogenation liquefaction of coal reaction process RU after mixing In device；

2. the KMJ-TORU of material containing coal slurry, coal slurry material NMJ, into the same reaction of direct hydrogenation liquefaction of coal reaction process RU The same reaction space of device；

3. positive, the coal hydrogenation of coal slurry material KMJ-TORU on the basis of crossing the main body flow direction in hydrogenation reaction space by coal slurry stream The intermediate reaction product of direct liquefaction enters in subsequent direct hydrogenation liquefaction of coal reaction process after mixing with coal slurry material NMJ；

4. positive on the basis of crossing the main body flow direction in hydrogenation reaction space by coal slurry stream, the coal hydrogenation of coal slurry material NMJ is direct Liquefied intermediate reaction product enters in subsequent direct hydrogenation liquefaction of coal reaction process after mixing with coal slurry material KMJ-TORU.

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

Enter direct hydrogenation liquefaction of coal reaction process RU ginseng in direct hydrogenation liquefaction of coal reaction process RU, coal slurry material KMJ-TORU It being reacted with direct hydrogenation liquefaction of coal, the other of first choice contact contain serum materials, it is selected from one of the following or several:

1. into the other coal slurry material NMJ for participating in direct hydrogenation liquefaction of coal reaction of direct hydrogenation liquefaction of coal reaction process RU；

2. the recycle stock containing slurries for participating in direct hydrogenation liquefaction of coal reaction of direct hydrogenation liquefaction of coal reaction process RUU；

3. what direct hydrogenation liquefaction of coal reaction process RU was generated contains serum materials, produced among direct hydrogenation liquefaction of coal reaction Object；

4. what direct hydrogenation liquefaction of coal reaction process RU was generated contains serum materials, finally produced from direct hydrogenation liquefaction of coal reaction Object.

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

In direct hydrogenation liquefaction of coal reaction process RU, at least two conversion zone of slurries serial operation, hydrogen between each conversion zone are set Air-flow flowing mode is selected from one of the following or several:

2. gas-phase product does not enter the reaction process of other any conversion zones, and gas raw material is not there are at least one conversion zone Using the hydrogen from other any conversion zones, belong to there are hydrogen material parallel operation reaction process；

3. reaction process receives the hydrogen product of downstream reaction section there are at least one conversion zone, belong between conversion zone There are the reaction process of hydrogen gas product counter-current operation.

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

In direct hydrogenation liquefaction of coal reaction process RU, at least two conversion zone of slurries serial operation is set, whole coal slurry raw materials into Enter to participate in direct hydrogenation liquefaction of coal reaction in the reaction process of the first conversion zone.

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

In direct hydrogenation liquefaction of coal reaction process RU, the working method and structure of the direct hydrogenation liquefaction of coal reactor assembly used Form, a kind or several in the following option:

Option 2, reactor EA, forced circulation Returning reactor EA after the collection liquid that liquid collecting cup is arranged in top is pressurizeed by circulating pump The fluidized bed reactor of material inlet；

Option 3, reactor EA, forced circulation Returning reactor EA after the collection liquid that liquid collecting cup is arranged in top is pressurizeed by circulating pump The suspended-bed reactor of material inlet；

Option 4, reactor EA, forced circulation Returning reactor EA after the collection liquid that liquid collecting cup is arranged in top is pressurizeed by circulating pump The fluidized bed reactor of material inlet, while circulating pump conveys circulation fluid, downstream transport liquid material product；

Option 5, reactor EA, forced circulation Returning reactor EA after the collection liquid that liquid collecting cup is arranged in top is pressurizeed by circulating pump The suspended-bed reactor of material inlet, while circulating pump conveys circulation fluid, downstream transport liquid material product；

Option 6, reactor EA, forced circulation Returning reactor EA after the collection liquid that liquid collecting cup is arranged in top is pressurizeed by circulating pump The fluidized bed reactor of material inlet is collected simultaneously other collection liquids of cup discharge by other dedicated feeding engine downstream transports Liquid material product；

Option 7, reactor EA, forced circulation Returning reactor EA after the collection liquid that liquid collecting cup is arranged in top is pressurizeed by circulating pump The suspended-bed reactor of material inlet is collected simultaneously other collection liquids of cup discharge by other dedicated feeding engine downstream transports Liquid material product；

Option 8, reactor EA, top are arranged liquid collecting cup and liquid material product are discharged by the production of dedicated feeding engine downstream transport liquid material Object is not provided with the fluidized bed reactor system of liquid material product forced circulation；

Option 9, reactor EA, top are arranged liquid collecting cup and liquid material product are discharged by the production of dedicated feeding engine downstream transport liquid material Object is not provided with the suspended-bed reactor system of liquid material product forced circulation；

Option 10, reactor EA, forced circulation Returning reactor after the collection liquid that liquid collecting cup is arranged in top is pressurizeed by circulating pump The ebullated bed of EA material inlet and the combination type reactor of ebullated bed；

Option 11, reactor EA, forced circulation Returning reactor after the collection liquid that liquid collecting cup is arranged in top is pressurizeed by circulating pump The ebullated bed of EA material inlet and the combination type reactor of ebullated bed, while circulating pump conveys circulation fluid, downstream transport liquid Expect product；

Option 12, reactor EA, forced circulation Returning reactor after the collection liquid that liquid collecting cup is arranged in top is pressurizeed by circulating pump The ebullated bed of EA material inlet and the combination type reactor of ebullated bed are collected simultaneously other collection liquids of cup discharge by other special With feeding engine downstream transport liquid material product；

Option 15, empty cylinder bubbling bed suspended-bed reactor system；

It is anti-to form the dirty Returning reactor lower part of reactor top reaction zone liquid phase using the external circulation pipe of reactor for option 16 Answer the device outside circulation in area.

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

It is greater than 85% in the liquefied fraction of direct hydrogenation liquefaction of coal reaction process RU, coal dust.

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

In direct hydrogenation liquefaction of coal reaction process RU, the liquefied fraction of coal dust is 85~98%.

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

In direct hydrogenation liquefaction of coal reaction process RU, while mixing the non-coal base weight oil FD of refining.

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

In direct hydrogenation liquefaction of coal reaction process RU, while mixing the non-coal base weight oil FD of refining；

The cracking conversion rate of heavy oil FD is greater than 90%.

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

In direct hydrogenation liquefaction of coal reaction process RU, operating condition are as follows: reaction temperature is 400~485 DEG C, reactor pressure 6 ~30MPa, vapor phase hydrogen volumetric concentration 50~95%, gas-liquid volume ratio are 300~1500NL/kg, deliquescence accelerant additive amount For 0.1~3 mass % of dry pulverized coal weight, co-catalyst additive amount is the molar ratio of S/ catalyst activity metal in co-catalyst It is 1.0~2.0, coal slurry solid concentration is 40~60 mass %, and reaction time TA is 0.5~4 hour.

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

In direct hydrogenation liquefaction of coal reaction process RU, the direct hydrogenation liquefaction of coal catalyst used is that a kind of composite hydrogenation is urged 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 direct hydrogenation liquefaction of coal catalyst water content is low In 2wt%；The powdered granule that direct hydrogenation liquefaction of coal catalyst particle diameter is 1~100 μm.

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

In direct hydrogenation liquefaction of coal reaction process RU, direct hydrogenation liquefaction of coal catalyst is that 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.

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

In direct hydrogenation liquefaction of coal reaction process RU, direct hydrogenation liquefaction of coal is participated in into direct hydrogenation liquefaction of coal reaction process RU Hydrocarbon ils at least part of reaction is hydrogen supply dissolvent DS.

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

In direct hydrogenation liquefaction of coal reaction process RU, direct hydrogenation liquefaction of coal is participated in into direct hydrogenation liquefaction of coal reaction process RU Hydrocarbon ils at least part of reaction is hydrogen supply dissolvent DS, and at least part of hydrogen supply dissolvent DS makes as the solvent for preparing coal slurry With；

The ratio of the weight flow rate RUSF-W of the weight flow rate DS-W and coal dust RUSF of hydrogen supply dissolvent DS are agent coal ratio K100= (DS-W)/(RUSF-W), K100 are 0.5~2.0.

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

Hydrogen supply dissolvent DS is mainly that 250~530 DEG C of hydro carbons form by normal boiling point, and the weight content of part saturation aromatic hydrocarbons is big In 15%, aromatic carbon rate be 0.35~0.70.

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

In direct hydrogenation liquefaction of coal reaction process RU, it is anti-that direct hydrogenation liquefaction of coal is participated in into direct hydrogenation liquefaction of coal reaction process The hydrocarbon ils at least part answered is hydrogen supply dissolvent DS, and at least part of hydrogen supply dissolvent DS is used as the solvent for preparing coal slurry；

Hydrogen supply dissolvent DS is mainly that 250~530 DEG C of hydro carbons form by normal boiling point, and the weight content of part saturation aromatic hydrocarbons is big In 25%, aromatic carbon rate be 0.45~0.60.