CN103074097A - Method and system for direct coal liquefaction - Google Patents
Method and system for direct coal liquefaction Download PDFInfo
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Abstract
The invention discloses a method for direct coal liquefaction, which comprises the following steps of coal slurry preparation, liquefaction reaction, gas-liquid separation of a coal liquefaction product, distillation separation, crude oil hydrogenation pretreatment, gas-liquid separation of a hydrogenation pretreatment product, and product fractionation. The liquefaction reaction comprises the steps that coal slurry and hydrogen are mixed, and sequentially filled in a first liquefaction reactor and a second liquefaction reactor that are connected with each other in series for liquefaction reaction; a liquefaction reaction product is obtained at an outlet of the second liquefaction reactor; and a part of liquefaction reaction product returns to an inlet of the first liquefaction reactor for recycling. With the method, effective use of heat energy can be achieved; reaction loads of the two coal liquefaction reactors are effectively balanced; deposition of solid particles in the reactors is avoided; and a direct coal liquefaction reaction system is low in operation difficulty, and can run stably for a long term.
Description
Technical field
The present invention relates to the Coal dressing technical field, more specifically relate to a kind of coal direct liquefaction method and system.
Background technology
Produced quantity constantly rises because prospective oil descends year by year, and it is soaring to cause oil price to continue in a high position, so worldwide oil shortage crisis will be inevitable.The rich coal of China is oil-poor, and the energy security situation is more serious.Coal direct liquefaction is exactly under High Temperature High Pressure, by means of hydrogen supply dissolvent and catalyzer, makes protium enter the molecular structure of coal and derivative thereof, thereby is the advanced clean coal technology of liquid fuel or industrial chemicals with coal conversion.The development of coal liquefaction technology, it is one of important channel of alleviating China's oil shortage of resources, petroleum products supply and demand pressure, simultaneously also be raising coal resources in China utilization ratio, alleviate coal burning pollution, promote the important measures of the energy, economy, harmonious development.
1913, the Bai Jiwusi (Bergius) of Germany invented direct coal liquefaction technology, and obtained in the world first DCL/Direct coal liquefaction patent.Nineteen twenty-seven, German I.G.Farbenindustrie(fuel corporation) set up in the world first DCL/Direct coal liquefaction factory at Leuna.During World War II Germany is once setting up 12 coal direct liquefaction factories in order to support war, and total industrial scale reaches 4,230,000 ton/years, after World War II finishes, and these factory's Close Alls.The liquefaction process of Germany adopted bubbling bed reactor at that time, solid-liquid separation adopts pressure filtration or centrifugal separation process, deliquescence accelerant is the iron content natural mineral, because circulating solvent contains the pitch of reaction in distress, and the natural mineral catalyst activity is low, so liquefaction condition is very harsh, reaction pressure is 70MPa, and temperature of reaction is 480 ℃.
After the early seventies oil crisis, the search for oil substitute has caused the great attention of each industrially developed country, and according to the difference of concrete technology flow process, various countries have researched and developed many coal direct liquefaction novel procesies in succession.
The U.S. will have developed H-COAL technique at the beginning of the end of the year 80 (patent No.: US4842719), this technique technical characteristics is the petroleum hydrogenation catalyst that adopts pump circulation suspended-bed reactor and nickel-molybdenum, cobalt-molybdenum, alumina supporter; Reaction pressure is 20MPa, and temperature of reaction is 455 ℃; Adopt spinning liquid to separate and underpressure distillation partitioning cycle solvent.Because adopt pump circulation suspended-bed reactor and petroleum catalyzer, temperature of reaction is controlled easily, product property is stable.But because petroleum hydrogenation catalyst inactivation in the Coal liquefaction system is serious, the catalyst updating cycle is short, and the liquefaction oil production cost is high.
Germany has developed IGOR+ technique, this process using bubbling bed reactor and red mud catalyzer at the end of the eighties; Adopt online fixed bed hydrogenation reactor that circulating solvent and product are carried out the hydrogenation of different depths, with vacuum distillation method partitioning cycle solvent.Owing to adopt the hydrogen supply circulating solvent behind the hydrogenation, character of coal slurry is stable and concentration is high, and preheating is easy, and can carry out heat exchange with the high-temperature separator gas phase, and heat utilization efficiency is high.But the red mud catalyst activity is low, severe reaction conditions, and typical operation conditions is: reaction pressure 30MPa, 470 ℃ of temperature of reaction; There is short risk of catalyzer coking and deactivation operational cycle in online fixed bed hydrogenation reactor; Bubbling bed reactor has the mineral deposit phenomenon to the high calcium coal.
Japan develops at the end of the nineties and has finished the NEDOL liquefaction process, and the Natural pyrite of this process using superfine grinding is done deliquescence accelerant, and adopts the fixed bed hydrogenation reactor of off-line that circulating solvent is carried out hydrogenation; Liquefying reactor is bubbling bed, with vacuum distillation method partitioning cycle solvent.The advantage of NEDOL technique and IGOR
+Technique is similar, and reaction conditions relaxes (17Mpa, 450 ℃).Shortcoming is that pyrite hardness is large, the superfine grinding difficulty, and cost is high; Bubbling bed reactor gas hold-up coefficient is large, and utilization ratio is low; Bubbling bed reactor liquid speed is low, and mineral deposit is arranged.
U.S. HTI company (predecessor is HRI company) has researched and developed out the HTI coal liquefaction craft (patent No.: US6190452B1) on the basis of H-COAL liquefaction process.The iron that the cyclic suspension bed reactor of two series connection of this process using and HTI have patent is gluey high activated catalyst; The online hydrogenation fixed-bed reactor of connecting in the high-temperature separator back; Solid-liquid separation adopts the method for critical solvent extraction, reclaims to greatest extent mink cell focus from liquefied residue.The shortcoming of this technique is that every reactor all needs to be equipped with the recycle pump that can move under high-temperature and high-pressure conditions, and the material solid content that recycle pump is carried is high, causes easily the pump serious wear, and the cost of keeping steady running is high, has a big risk; The space of the gas-liquid separation of providing must be provided reactor head, and the vapour-liquid ratio of reactor can not be too high, otherwise gas-liquid separation is incomplete, causes that recycle pump is found time easily and waits series of problems; Inner member in the reactor is complicated, has increased manufacturing and the maintenance cost of reactor.
China's Shenhua Group had been developed the Firing Shenhua Coal liquefaction process (patent No.: CN1257252C), adopt the efficient nano level aqua oxidation iron catalyst of China Coal Research Institute independent research with independent intellectual property right in recent years on the basis of HTI liquefaction process; Adopt the pump circulation suspended-bed reactor, and off-line boiling bed hydrogenation reactor carries out hydrogenation to circulating solvent, solid-liquid separation employing underpressure distillation.This technique need be equipped with the recycle system that two covers move under the severe condition, has reactor inner member complexity and the recycle pump problem such as find time easily.
Chinese direct coal liquefaction process (the China Direct Coal Liquefaction Process of China Coal Research Institute exploitation, referred to as CDCL technique), be the coal direct liquefaction method (patent No.: CN1243813C) of a kind of adverse current, circulation, online hydrogenator series connection.This process using increases separator in the middle of two reactors method solves the secondary resolution problem that generates oil, the lightweight liquiefied product that can satisfy simultaneously Coal liquefaction is shorter at reactor residence time, and difficult liquefaction and heavy Coal Liquefaction Products are long and with gas phase hydrogen higher rate of mass transfer is arranged and the requirement in reaction times of growing at reactor residence time.But facility investment increases greatly, is equivalent to increase a cover separation system, comprises one group of separator, wear-resisting high-pressure-difference pressure reducing valve, circulating hydrogen compressor etc.
Patent CN1869159A discloses a kind of coal direct liquefaction method, and the feature of this liquifying method is: the liquid phase material part that discharge the high-temperature separator bottom is discharged by reducing valve, and rest part turns back to the first reactor reaction feed(raw material)inlet and recycles; Wherein, recycle stock is 2-20 with the ratio of the weight rate of fresh material.The one way reaction times of this direct coal liquefaction process material in reactor is short, has avoided the deposition of solid materials in reactor, and the hydrogen consumption is low, and the gas productive rate is low.Because the high-temperature separator temperature of charge is lower than the reactor content temperature, the material of Returning reactor need to reheat, so the heat utilization efficiency of this liquifying method is low; The recycle ratio of recycle stock is larger in addition, has reduced the utilising efficiency of reactor.
Summary of the invention
The purpose of this invention is to provide a kind of new coal direct liquefaction method.The method may further comprise the steps: coal slurry preparation, liquefaction reaction, coal liquefaction products gas-liquid separation, fractionation by distillation, thick oil add hydrogen pretreatment, add the gas-liquid separation of hydrogen pretreatment product and product fractionation;
Described coal slurry preparation is that feed coal is broken for dry pulverized coal, then dry pulverized coal and catalyzer, promotor, circulating solvent or plus solvent is hybridly prepared into coal slurry;
Described liquefaction reaction is that described coal slurry is mixed then preheating with hydrogen, and the first liquefying reactor and the second liquefying reactor that pass into successively subsequently series connection carry out liquefaction reaction; Obtain the liquefaction reaction product in the outlet of the second liquefying reactor, wherein a part of liquefaction reaction product recycles through the entrance that recycle pump is transmitted back to the first liquefying reactor;
Described coal liquefaction products gas-liquid separation is that another part liquefaction reaction product that the second liquefying reactor exports is carried out gas-liquid separation, obtains gas phase part and liquid phase part;
Described fractionation by distillation is that the liquid phase part that the coal liquefaction products gas-liquid separation obtains is distilled, and thick oil and residue obtain liquefying;
Described thick oil adds hydrogen pretreatment, is the thick oil that liquefies is carried out hydrofining, removes sulphur, nitrogen, oxygen heteroatom, makes olefin saturated and polycyclic aromatic hydrocarbons fractional saturation, obtains thick oil and adds the hydrogen pretreatment product;
Describedly adding the gas-liquid separation of hydrogen pretreatment product, is thick oil to be added the hydrogen pretreatment product carry out gas-liquid separation, obtains gaseous phase materials and liquid phase material;
Described product fractionation is to add the liquid phase material that the gas-liquid separation of hydrogen pretreatment product obtains and separate described, obtains lightweight oil and mink cell focus, and wherein mink cell focus is as the circulating solvent of gelatin liquefaction process coal slurry preparation, and lightweight oil is as the product oil of gelatin liquefaction unit.
Further, coal direct liquefaction method of the present invention, described catalyzer are noble metal catalyst, metal halide catalyst, Fe-series catalyst or iron system, precious metal composite catalyst; Described promotor is vulcanizing agent; Catalyst loading is the 0.5-5% of dry pulverized coal weight, and the mol ratio of the sulphur that contains in the described promotor and catalyzer effective constituent is 0.5-3; The coal slurry solids concn is 20-55wt%; Described circulating solvent or plus solvent are aromatic hydrocarbons and hydrogenation of aromatics compounds or the oil products that contains the 2-4 ring, and boiling range is 220-650 ℃.
Further, coal direct liquefaction method of the present invention, described noble metal catalyst are cobalt, molybdenum, nickel; Described metal halide catalyst is ZnCl
2, SnCl
2Described Fe-series catalyst is the natural crystal of iron content, the industrial residue of iron content or the compound of pure state iron; Described iron system, precious metal composite catalyst are two or more natural crystal, artificial mixture or the artificial compound in iron content and nickel, tungsten, molybdenum or the cobalt.
Further, coal direct liquefaction method of the present invention, described Fe-series catalyst or iron system, precious metal composite catalyst are ultra-fine dispersed catalysts.
Further, coal direct liquefaction method of the present invention, in the described liquefaction reaction, the first liquefying reactor and the second liquefying reactor are the bubbling bed reactor that do not have inner member, paste state bed reactor or with the loop reactor of guide shell; The temperature of reaction of liquefaction reaction is 400-480 ℃, and reaction pressure is 10-30MPa; Vapour-liquid ratio is 600-2000NL/kg; The coal slurry air speed is 0.5-4.5h
-1
The a part of liquefaction reaction product that returns the first liquefying reactor from the second liquefying reactor outlet and the weight rate of coal slurry are than being 0.5-8.
Further, coal direct liquefaction method of the present invention, a part of liquefaction reaction product that returns the first liquefying reactor from the second liquefying reactor outlet and the weight rate of coal slurry are than being 1-3.
Further, to add the thick oily hydrogenation pretreatment reaction device in the hydrogen pretreatment be fixed-bed reactor or ebullated bed reactor for coal direct liquefaction method of the present invention, the thick oil of described step; Hydrogenation catalyst is loaded catalyst, carrier is one or more the combination in aluminum oxide, silicon oxide, magnesium oxide and the clay, its active metal component is one or more in VIB or the VIII family metal, and the group vib metal is preferably Mo and W, and VIII family metal is preferably Fe, Ni and Co.Temperature of reaction is 300-440 ℃; Reaction pressure is 5-25MPa; Vapour-liquid ratio is 400-2000; Air speed is 0.5-5h
-1
Further, coal direct liquefaction method of the present invention, the thick oil of described step add that temperature of reaction is 340-390 ℃ in the hydrogen pretreatment; Reaction pressure is 10-17Mpa; Vapour-liquid ratio is 800-1500; Air speed is 0.5-2.5h
-1
The present invention also provides a kind of DCL/Direct coal liquefaction system, and described system comprises:
Coal slurry preparation facilities, the first liquefying reactor, the second liquefying reactor, coal liquefaction products gas-liquid separation unit, distillation unit, thick oily hydrogenation pretreatment reaction device, add hydrogen pretreatment product gas-liquid separation unit, separation column;
Described coal slurry preparation facilities is used for feed coal and catalyzer, promotor, the circulating solvent of the dry coal-forming powder of fragmentation are hybridly prepared into coal slurry; Described the first liquefying reactor and described the second liquefying reactor are bubbling bed reactor, paste state bed reactor or loop reactor; Described the second liquefying reactor outlet is communicated with described the first liquefying reactor entrance and described coal liquefaction products gas-liquid separation unit entrance respectively; Described coal liquefaction products gas-liquid separation unit, the liquefaction reaction product separation that is used for the outlet of the second liquefying reactor is gas phase part and liquid phase part; Described distillation unit is used for distillation and separates the liquid phase part that obtains by described coal liquefaction products gas-liquid separation unit, and thick oil and residue obtain liquefying; Described thick oily hydrogenation pretreatment reaction device is fixed-bed reactor or ebullated bed reactor, be used for the thick oil of liquefaction that obtains by described distillation unit is carried out olefin saturated, the reaction of polycyclic aromatic hydrocarbons fractional saturation, removes sulphur, nitrogen, oxygen heteroatom, obtain thick oil and add the hydrogen pretreatment product; The described hydrogen pretreatment product gas-liquid separation unit that adds is used for that thick oil is added the hydrogen pretreatment product and carries out gas-liquid separation, obtains gaseous phase materials and liquid phase material; Described separation column is used for liquid phase material is carried out fractionation by distillation, isolates lightweight oil and mink cell focus, and wherein mink cell focus is as the circulating solvent of gelatin liquefaction process coal slurry preparation, and lightweight oil is as the product oil of gelatin liquefaction unit.
Coal direct liquefaction method of the present invention and system have following advantages:
1. in method and system provided by the present invention, employing does not have the bubbling bed, paste state bed reactor of inner member or with the loop reactor of guide shell, the reactor inner member is simple, and two reactor contents circulation recycle pumps of needs, therefore can reduce facility investment.
2. in method and system provided by the present invention, adopt the high-temperature material of the second reactor outlet and the low-temperature material of the first reactor inlet to mix, realized effective utilization of heat energy.
3. in method and system provided by the present invention, the material in the liquefying reactor is circulated between two reactors, but the reaction of two reactors of efficient balance load reduces the operation easier of DCL/Direct coal liquefaction reactive system.
4. in method and system provided by the present invention, material in the liquefying reactor is circulated between two reactors, can effectively increase liquid phase axial flow velocity in two reactors, avoid the deposition of solid particulate in reactor, guarantee liquefying plant running steady in a long-term.
Above-mentioned explanation only is the general introduction of technical solution of the present invention, for can clearer understanding technique means of the present invention, and can be implemented according to the content of specification sheets, below with preferred embodiment of the present invention and cooperate accompanying drawing to describe in detail.
Description of drawings
Fig. 1 is the schematic flow sheet of DCL/Direct coal liquefaction of the present invention system.
Among the figure:
The 1-fresh hydrogen, 2-circulating solvent, 3-feed coal, 4-catalyzer and auxiliary agent, 5-mixing hydrogen, 6-circulating hydrogen, 7-waste gas, 8-product oil, 9-residue;
V1-coal slurry preparation facilities, P1-coal slurry fresh feed pump, F1-process furnace, R1-the first liquefying reactor, R2-the second liquefying reactor, P2-Matter Transfer pump, V2-coal liquefaction products gas-liquid separation unit, F2-process furnace, T1-atmospheric distillation tower, the F3-process furnace, the T2-vacuum still, F4-process furnace, the thick oily hydrogenation pretreatment reaction device of R3-, V3-adds hydrogen pretreatment product gas-liquid separation unit, T3-separation column.
Embodiment
Reach technique means and the effect that predetermined goal of the invention is taked for further setting forth the present invention, below in conjunction with drawings and Examples explanation DCL/Direct coal liquefaction of the present invention system.
DCL/Direct coal liquefaction system as shown in Figure 1 comprises: coal slurry preparation facilities V1, coal slurry fresh feed pump P1, process furnace F1, the first liquefying reactor R1, the second liquefying reactor R2, Matter Transfer pump P2, coal liquefaction products gas-liquid separation unit V2, process furnace F2, distillation unit T, process furnace F4, thick oily hydrogenation pretreatment reaction device R3, add hydrogen pretreatment gas-liquid separation unit V3, separation column T3.Described distillation unit T comprises atmospheric distillation tower T1, process furnace F3, vacuum still T2.
Coal slurry preparation facilities V1 is used for feed coal and catalyzer, promotor, the circulating solvent of the dry coal-forming powder of fragmentation are hybridly prepared into coal slurry.The outlet of coal slurry preparation facilities V1 and the entrance of the first liquefying reactor R1 are disposed with coal slurry fresh feed pump P1 and process furnace F1, the pipeline communication hydrogen supply pipeline between coal slurry fresh feed pump P1 and the process furnace F1 by pipeline communication on the described pipeline.Technical process in this partial devices is: feed coal 3 is broken into coal dust through the pre-treatment drying, then join together coal slurry preparation facilities V1 with circulating solvent 2, catalyzer and promotor 4, in coal slurry preparation facilities V1, mix into the coal slurry that viscosity is lower than 500cp (60 ℃).Coal slurry after coal slurry fresh feed pump P1 supercharging with mix hydrogen 5 and mix, mixture is through the first process furnace F1 preheating, the mixture after the preheating enters the first liquefying reactor R1.
The entrance series connection of the outlet of the first liquefying reactor R1 and the second liquefying reactor R2, the outlet of the second liquefying reactor R2 arranges Matter Transfer pump P2 respectively by the entrance of pipeline communication coal liquefaction products gas-liquid separation unit V2 and the entrance of the first liquefying reactor R1 on the pipeline between the second liquefying reactor R2 outlet and the first liquefying reactor R1; The first liquefying reactor R1 of the present invention and the second liquefying reactor R2 are selected from bubbling bed reactor, paste state bed reactor or loop reactor.Technique and reaction in this partial devices are: the liquefaction reaction product that the first liquefying reactor R1 flows out enters the second liquefying reactor R2, proceeds liquefaction reaction; Obtain the liquefaction reaction product from the second liquefying reactor R2 outlet, a part wherein recycles by the entrance that Matter Transfer pump P2 is transmitted back to the first liquefying reactor R1.Another part of the liquefaction reaction product that the second liquefying reactor R2 flows out enters coal liquefaction products gas-liquid separation unit V2 and carries out gas-liquid separation.
The liquefaction reaction product separation that coal liquefaction products gas-liquid separation unit V2 is used for the outlet of the second liquefying reactor is gas phase part and liquid phase part.The upper port of coal liquefaction products gas-liquid separation unit V2 is by pipeline and hydrogen supply pipeline communication, and the lower port of coal liquefaction products gas-liquid separation unit V2 is by the opening for feed of pipeline communication atmospheric distillation tower T1; Process furnace F2 also is set between the opening for feed of V2 lower port pipeline and atmospheric distillation tower T1.Technical process in this partial devices is: a coal liquefaction products gas-liquid separation unit V2 gaseous phase materials part is used as circulating hydrogen 6, and another part is as waste gas 7 discharge systems.
Distillation unit T is used for distillation and separates the liquid phase part that obtains by described coal liquefaction products gas-liquid separation unit, and thick oil and residue obtain liquefying.The lower port of atmospheric distillation tower T1 is communicated with by the opening for feed of pipeline with vacuum still T2, and process furnace F3 is set on this pipeline; It is a pipeline that the upper port output channel of atmospheric distillation tower T1, the upper port output channel of vacuum still T2 and hydrogen supply pipeline can compile communicatively, the opening for feed of the thick oily hydrogenation pretreatment reaction device R3 of the pipeline communication after compiling; Between pipeline after compiling and the thick oily hydrogenation pretreatment reaction device R3 process furnace F4 is set.Technical process in this partial devices is: the liquid phase part that coal liquefaction products gas-liquid separation unit V2 obtains enters atmospheric distillation tower T1 after process furnace F2 heating, steam light phase oil product from atmospheric distillation tower T1 top, the heavy phase oil product that flows out from atmospheric distillation tower T1 bottom enters vacuum still T2 and further distills after the 3rd process furnace F3 heating; Oil product is separated into vacuum distillate and residue 9 in vacuum still T2, described light phase oil product and described vacuum distillate are mixed into the thick oil of liquefaction; The thick oil of this liquefaction after boosting with mixes the hydrogen mixing, carry out catalytic hydrogenation reaction through entering hydrogenator R3 after the process furnace F4 preheating after the mixing.
Thick oily hydrogenation pretreatment reaction device R3 is used for the thick oil that liquefies is added hydrogen pretreatment, and olefin saturated, polycyclic aromatic hydrocarbons fractional saturation and sulphur, nitrogen, oxygen heteroatom are removed, and obtains thick oily hydrogenation products.The discharge port of thick oily hydrogenation pretreatment reaction device R3 is communicated with the opening for feed that adds hydrogen pretreatment product gas-liquid separation unit V3, the upper port of gas-liquid separation unit V3 is communicated with the hydrogen supply pipeline, the lower port of gas-liquid separation unit V3 is communicated with the opening for feed of separation column T3, the upper port of separation column T3 connects the output of products pipeline, and the lower port of separation column T3 is communicated with coal slurry preparation facilities V1; Thick oily hydrogenation pretreatment reaction device R3 of the present invention is fixed-bed reactor or ebullated bed reactor.Technical process in this partial devices is: thick oil adds the hydrogen pretreatment product and carry out gas-liquid separation in gas-liquid separation unit V3, obtains gaseous phase materials and liquid phase material, and a gaseous phase materials part is as waste gas 7, and another part utilizes as circulating hydrogen 6; Liquid phase material enters separation column T3, obtains lightweight oil and mink cell focus through separating, and the cutting temperature point of lightweight oil and mink cell focus is between 220-370 ℃, and lightweight oil is Coal Liquefaction Products oil 8, and mink cell focus is used for the preparation coal slurry as circulating solvent 2.
The invention provides a kind of coal direct liquefaction method, step is:
1) coal slurry preparation is that feed coal is broken for dry pulverized coal, then dry pulverized coal and catalyzer, promotor, circulating solvent is hybridly prepared into coal slurry;
Feed coal is brown coal, sub-bituminous coal, bituminous coal or their mixture, and the granularity of coal dust is the 80-200 order, and water content is 0.5-4wt%.Catalyzer is noble metal catalyst, metal halide catalyst, Fe-series catalyst or iron system, precious metal composite catalyst.Noble metal catalyst such as cobalt, molybdenum, nickel; Metal halide catalyst such as ZnCl
2, SnCl
2The industrial residue (such as red mud) of the natural crystal of Fe-series catalyst such as iron content (such as pyrite), iron content or the compound of pure state iron (such as oxide compound, oxyhydroxide and the sulfide of iron).Catalyzer is ultra-fine dispersed catalysts preferably, such as ultra-fine pyrite, nano level hydrous iron oxide (FeOOH).Promotor is vulcanizing agent.
Catalyst loading is the 0.5-5% of dry pulverized coal weight, and the mol ratio of the sulphur that contains in the described promotor and catalyzer effective constituent is 0.5-3, and the coal slurry solids concn is 20-55wt%.
Circulating solvent or plus solvent are aromatic hydrocarbon and the hydrogenated aromatic hydrocarbon with 2-4 ring, and boiling range is 220-650 ℃, and aromatic carbon rate (fa) is 0.43-0.50.2) liquefaction reaction is described coal slurry to be mixed with hydrogen then be preheating to 350-410 ℃.The first liquefying reactor and the second liquefying reactor that pass into successively subsequently series connection carry out liquefaction reaction; Obtain the liquefaction reaction product in the second liquefying reactor outlet, wherein a part of liquefaction reaction product entrance of returning the first liquefying reactor through the Matter Transfer pump delivery recycles;
The first liquefying reactor and the second liquefying reactor are the bubbling bed reactor that do not have inner member, paste state bed reactor or with the loop reactor of guide shell; The temperature of reaction of liquefaction reaction is 400-480 ℃, and reaction pressure is 10-30MPa; Vapour-liquid ratio is 600-2000NL/kg; The coal slurry air speed is 0.5-4.5h
-1
The a part of liquefaction reaction product that returns the first liquefying reactor from the second liquefying reactor outlet and the weight rate of coal slurry are preferably 1-3 than being 0.5-8.In the implementation process of the method for the invention, can determine to return a part of liquefaction reaction product of the first liquefying reactor and the ratio of the weight rate of coal slurry from the outlet of the second liquefying reactor by the process calculation of routine according to unit scale, reactor void tower liquid speed.
3) coal liquefaction products gas-liquid separation is that another part liquefaction reaction product of the second liquefying reactor outlet enters the coal liquefaction products gas-liquid separation unit and carries out gas-liquid separation, obtains gas phase part and liquid phase part; The coal liquefaction products separating unit can be comprised of equipment such as a plurality of gas-liquid separators, condenser and reducing valve, and coal liquefaction products enters waste gas system through separating step by step a gas phase part part that obtains, and another part is as the circulating hydrogen utilization;
4) fractionation by distillation is above-mentioned steps 3) liquid phase part enter atmospheric distillation tower through after the process furnace heating, steam light phase oil product from atmospheric distillation tower top, the heavy phase oil product that flows out from the air distillation tower bottom enters vacuum still and further distills after heating; Oil product is separated into vacuum distillate and residue in vacuum still, the mixture of described light phase oil product and described vacuum distillate is the thick oil of liquefaction;
5) thick oil adds hydrogen pretreatment, is that the thick oil that liquefies is carried out hydrofining, removes sulphur, nitrogen, oxygen heteroatom, makes olefin saturated and polycyclic aromatic hydrocarbons fractional saturation, obtains thick oil and adds the hydrogen pretreatment product.
Thick oily hydrogenation pretreatment reaction device in the thick oily hydrogenation pre-treatment step is fixed-bed reactor or ebullated bed reactor; Hydrogenation catalyst is loaded catalyst, carrier is one or more the combination in aluminum oxide, silicon oxide, magnesium oxide and the clay, its active metal component is one or more in VIB or the VIII family metal, and the group vib metal is preferably Mo and W, and VIII family metal is preferably Fe, Ni and Co.The pretreated reaction conditions of thick oily hydrogenation is: temperature of reaction is 300-440 ℃, preferred 340-390 ℃; Reaction pressure is 5-25MPa, preferred 10-17Mpa; Vapour-liquid ratio is 400-2000, preferred 800-1500; Air speed is 0.5-5h
-1, preferred 0.5-2.5h
-1
6) add the gas-liquid separation of hydrogen pretreatment product, that thick oil adds the hydrogen pretreatment product carry out gas-liquid separation in adding hydrogen pretreatment product gas-liquid separation unit, gas-liquid separation unit can be comprised of equipment such as a plurality of separators, condenser and reducing valve, add the hydrogen pretreatment product and obtain gaseous phase materials and liquid phase material through separating step by step, a gaseous phase materials part enters waste gas system, and another part reuses as circulating hydrogen.
7) product fractionation, that the described hydrogen pretreatment product gas-liquid separation unit that adds enters separation column and obtains lightweight oil and mink cell focus through fractionation by distillation through separating the liquid phase material obtain, the cutting temperature point of lightweight oil and mink cell focus is between 220-370 ℃, lightweight oil is Coal Liquefaction Products oil, and mink cell focus is used for the preparation coal slurry as circulating solvent.
Adopt the Inner Mongol Shengli Brown to be the liquefaction feed coal, the coal analysis data see Table 1.At first Shengli Brown is pulverized, made granularity less than 180 purpose coal dusts, and be dried to water content less than 3%.Catalyzer is the iron-contained industrial waste red mud, and addition is: Fe/ dry coal=5wt%; Promotor is the technical grade SULPHUR POWDER, purity＞99%, S/Fe(mol ratio)=2.The coal slurry solids concn is 48wt%, and 40 ℃ of Coal Under slurry viscositys are 194.7cP.Fresh hydrogen purity is 99.9%, density of hydrogen in the recycle hydrogen＞90%.DCL/Direct coal liquefaction long run test unit scale is 0.1 ton/day, and DCL/Direct coal liquefaction method of the present invention is adopted in technical process.
The principal reaction condition of embodiment 1 sees Table 2; The liquefaction test of embodiment 1 the results are shown in Table 3, and the data in the table 3 are take the dry ash-free basis coal as calculating benchmark.
Comparative Examples 1
Adopt the feed coal identical with embodiment 1, the coal analysis data see Table 1; The continuous liquefaction test device of use and embodiment 1 same size, typical German IGOR+ technique is adopted in technical process, and the concrete technology condition is identical with embodiment 1, and concrete reaction conditions sees Table 2; The liquefaction test of Comparative Examples 1 the results are shown in Table 3, and data are take the dry ash-free basis coal as calculating benchmark in the table.
Adopt Tianzhu Area, Gansu bituminous coal to be the liquefaction feed coal, the coal analysis data see Table 1.Tianzhu Area, Gansu bituminous coal is pulverized, made granularity less than 190 purpose coal dust samples, and be dried to water content less than 2%.Catalyzer is ZnCl
2, addition is 3.0% of dry pulverized coal weight; Promotor is the technical grade SULPHUR POWDER, and purity is greater than 99%, and addition is the S/Zn(mol ratio)=0.5; The coal slurry solids concn is 40wt%, and 40 ℃ of Coal Under slurry viscositys are 187.8cP.Fresh hydrogen purity is 99.9%, density of hydrogen in the recycle hydrogen＞80%.DCL/Direct coal liquefaction long run test unit scale is 0.1t/d, and DCL/Direct coal liquefaction method of the present invention is adopted in technical process.
The technological condition of embodiment 2 sees Table 2; The liquefaction test of embodiment 2 the results are shown in Table 3, and the data in the table 3 are take the dry ash-free basis coal as calculating benchmark.
Comparative Examples 2
Adopt the feed coal identical with embodiment 2, the coal analysis data see Table 1; The continuous liquefaction test device of use and embodiment 2 same sizes, Japanese NEDOL technique is adopted in technical process, and the concrete technology condition is identical with embodiment 2, and the concrete technology condition sees Table 2; The liquefaction test of Comparative Examples 2 the results are shown in Table 3, and data are take the dry ash-free basis coal as calculating benchmark in the table.
Embodiment 3
Adopt Xinjiang Heishan bituminous coal to be the liquefaction feed coal, the coal analysis data see Table 1.At first Xinjiang Heishan bituminous coal is pulverized, made granularity less than 200 purpose coal dust samples, and be dried to water content less than 1%.Catalyzer is diameter 20-50 nanometer, length be the ultra-fine grain of 80-180 nanometer γ-hydrous iron oxide (the type high reactivity deliquescence accelerant of γ-FeOOH), addition is: Fe/ dry coal=0.5wt%; Promotor is dithiocarbonic anhydride or dimethyl thioether, and addition is the S/Fe(mol ratio)=3; The coal slurry solids concn is 45wt%, and 40 ℃ of Coal Under slurry viscositys are 214.5cP.Fresh hydrogen purity is 99.9%, density of hydrogen in the recycle hydrogen＞85%.DCL/Direct coal liquefaction long run test unit scale is 0.1t/d, and DCL/Direct coal liquefaction method of the present invention is adopted in technical process.
The technological condition of embodiment 3 sees Table 2; The liquefaction test of embodiment 3 the results are shown in Table 3, and the data in the table 3 are take the dry ash-free basis coal as calculating benchmark.
Comparative Examples 3
Adopt the feed coal identical with embodiment 3, the coal analysis data see Table 1; The continuous liquefaction test device of use and embodiment 3 same sizes, the Shenhua direct coal liquefaction process that is just turning round in commercialization is adopted in technical process, and the concrete technology condition is identical with embodiment 3, and the concrete technology condition sees Table 2; The liquefaction test of Comparative Examples 3 the results are shown in Table 3, and data are take the dry ash-free basis coal as calculating benchmark in the table.
Embodiment 4
Adopt Xinjiang Ai Ding brown coal to be the liquefaction feed coal, the coal analysis data see Table 1.At first feed coal is pulverized, made granularity less than 200 purpose coal dusts, and be dried to water content less than 4%.Catalyzer is the natural sulphur iron ore, and addition is: Fe/ dry coal=4.5wt%; Promotor is the technical grade SULPHUR POWDER, purity＞99%, S/Fe(mol ratio)=0.5.The coal slurry solids concn is 40wt%, and 40 ℃ of Coal Under slurry viscositys are 174.7cP.Fresh hydrogen purity is 99.9%, density of hydrogen in the recycle hydrogen＞90%.DCL/Direct coal liquefaction long run test unit scale is 0.1 ton/day, and DCL/Direct coal liquefaction method of the present invention is adopted in technical process.
The principal reaction condition of enforcement 4 sees Table 2; The liquefaction test of embodiment 4 the results are shown in Table 3, and the data in the table 3 are take the dry ash-free basis coal as calculating benchmark.
Comparative Examples 4
Adopt the feed coal identical with embodiment 4, the coal analysis data see Table 1; The continuous liquefaction test device of use and embodiment 4 same sizes, the Chinese direct coal liquefaction process (CDCL technique) of China Coal Research Institute exploitation is adopted in technical process, and the concrete technology condition is identical with embodiment 1, and concrete reaction conditions sees Table 2; The liquefaction test of Comparative Examples 4 the results are shown in Table 3, and data are take the dry ash-free basis coal as calculating benchmark in the table.
Adopt the young bituminous coal of Xinjiang Yili of China to be the liquefaction feed coal, the coal analysis data see Table 1.At first feed coal is pulverized, made granularity less than 120 purpose coal dusts, and be dried to water content less than 2%.Catalyzer is molybdenum-cobalt series catalyst, and addition is: Fe/ dry coal=1wt%; Promotor is the technical grade SULPHUR POWDER, purity＞99%, S/ molybdenum (mol ratio)=2.The coal slurry solids concn is 45wt%, and 40 ℃ of Coal Under slurry viscositys are 184.5cP.Fresh hydrogen purity is 99.9%, density of hydrogen in the recycle hydrogen＞90%.DCL/Direct coal liquefaction long run test unit scale is 0.1 ton/day, and DCL/Direct coal liquefaction method of the present invention is adopted in technical process.
The principal reaction condition of embodiment 5 sees Table 2; The liquefaction test of embodiment 5 the results are shown in Table 3, and the data in the table 3 are take the dry ash-free basis coal as calculating benchmark.
Comparative Examples 5
Adopt the feed coal identical with embodiment 5, the coal analysis data see Table 1; The continuous liquefaction test device of use and embodiment 5 same sizes, the H-COAL coal liquefaction craft of the U.S. is adopted in technical process, and the concrete technology condition is identical with embodiment 5, and concrete reaction conditions sees Table 2; The liquefaction test of Comparative Examples 5 the results are shown in Table 3, and data are take the dry ash-free basis coal as calculating benchmark in the table.
Table 1 embodiment 1-3 and Comparative Examples 1-3 liquefaction coal coal analysis data
The technological condition of table 2 embodiment 1-3 and Comparative Examples 1-3
The liquefaction test result of table 3 embodiment 1-3 and Comparative Examples 1-3 (wt%, daf coal)
| Case | Transformation efficiency | The oil yield | The gas productive rate | The aquatic products rate | Organic detritus | The hydrogen consumption |
| |
95.87 | 56.15 | 16.14 | 15.28 | 21.25 | 6.92 |
| Comparative Examples 1 | 96.25 | 56.78 | 17.32 | 16.13 | 20.15 | 7.28 |
| |
92.96 | 55.83 | 17.81 | 6.79 | 14.96 | 6.35 |
| Comparative Examples 2 | 94.01 | 57.22 | 15.64 | 6.52 | 13.69 | 6.22 |
| Embodiment 3 | 89.75 | 53.87 | 10.35 | 9.37 | 29.50 | 6.41 |
| Comparative Examples 3 | 89.78 | 53.54 | 9.42 | 9.88 | 28.58 | 6.62 |
| Embodiment 4 | 82.12 | 49.45 | 12.33 | 13.45 | 29.68 | 5.25 |
| Comparative Examples 4 | 84.21 | 49.92 | 12.10 | 12.26 | 28.97 | 5.36 |
| |
94.12 | 55.24 | 15.64. | 14.15 | 22.32 | 6.49 |
| Comparative Examples 5 | 93.22 | 54.81 | 16.71 | 14.18 | 23.16 | 6.05 |
Can find out that from the data of table 3 coal direct liquefaction method provided by the invention is compared with German IGOR coal liquefaction craft, Firing Shenhua Coal liquefaction process and U.S.'s H-COAL liquefaction process, under same reaction conditions, coal transformation efficiency and oily yield are substantially suitable; Compare with Chinese CDCL coal liquefaction craft, Japanese NEDOL coal liquefaction craft, under the equivalent responses condition, the coal transformation efficiency is suitable with oily yield; But but the reaction of two reactors of coal direct liquefaction method efficient balance provided by the invention load; Realize effective utilization of heat energy; Effectively increase liquid phase axial flow velocity in two reactors, avoid the deposition of solid particulate in reactor, system is long running period; Simplified reactor internal components, facility investment is few, and operation easier is low, thereby has significant economic benefit.
The above only is embodiments of the invention, is not the present invention is done any pro forma restriction, although the present invention is with the embodiment announcement as above, yet be not to limit the present invention.Any those skilled in the art, within not breaking away from the technical solution of the present invention scope, when the technology contents that can utilize above-mentioned announcement is made a little change or is modified to the equivalent embodiment of equivalent variations, in every case be the content that does not break away from technical solution of the present invention,, all still belong in the scope of technical solution of the present invention any simple modification, equivalent variations and modification that above embodiment does according to technical spirit of the present invention.
Claims (9)
1. a coal direct liquefaction method is characterized in that, may further comprise the steps: coal slurry preparation, liquefaction reaction, coal liquefaction products gas-liquid separation, fractionation by distillation, thick oil add hydrogen pretreatment, add the gas-liquid separation of hydrogen pretreatment product and product fractionation;
Described coal slurry preparation is that feed coal is broken for dry pulverized coal, then dry pulverized coal and catalyzer, promotor, circulating solvent or plus solvent is hybridly prepared into coal slurry;
Described liquefaction reaction is that described coal slurry is mixed then preheating with hydrogen, and the first liquefying reactor and the second liquefying reactor that pass into successively subsequently series connection carry out liquefaction reaction; Obtain the liquefaction reaction product in the outlet of the second liquefying reactor, wherein a part of liquefaction reaction product recycles through the entrance that recycle pump is transmitted back to the first liquefying reactor;
Described coal liquefaction products gas-liquid separation is that another part liquefaction reaction product that the second liquefying reactor exports is carried out gas-liquid separation, obtains gas phase part and liquid phase part;
Described fractionation by distillation is that the liquid phase part that the coal liquefaction products gas-liquid separation obtains is distilled, and thick oil and residue obtain liquefying;
Described thick oil adds hydrogen pretreatment, is the thick oil that liquefies is carried out hydrofining, removes sulphur, nitrogen, oxygen heteroatom, makes olefin saturated and polycyclic aromatic hydrocarbons fractional saturation, obtains thick oil and adds the hydrogen pretreatment product;
Describedly adding the gas-liquid separation of hydrogen pretreatment product, is thick oil to be added the hydrogen pretreatment product carry out gas-liquid separation, obtains gaseous phase materials and liquid phase material;
Described product fractionation is to add the liquid phase material that the gas-liquid separation of hydrogen pretreatment product obtains and separate described, obtains lightweight oil and mink cell focus, and wherein mink cell focus is as the circulating solvent of gelatin liquefaction process coal slurry preparation, and lightweight oil is as the product oil of gelatin liquefaction unit.
2. coal direct liquefaction method according to claim 1 is characterized in that, described catalyzer is noble metal catalyst, metal halide catalyst, Fe-series catalyst or iron system, precious metal composite catalyst; Described promotor is vulcanizing agent; Catalyst loading is the 0.5-5% of dry pulverized coal weight, and the mol ratio of the sulphur that contains in the described promotor and catalyzer effective constituent is 0.5-3; The coal slurry solids concn is 20-55wt%; Described circulating solvent or plus solvent are aromatic hydrocarbons and hydrogenation of aromatics compounds or the oil products that contains the 2-4 ring, and boiling range is 220-650 ℃.
3. coal direct liquefaction method according to claim 2 is characterized in that,
Described noble metal catalyst is cobalt, molybdenum, nickel;
Described metal halide catalyst is ZnCl
2, SnCl
2
Described Fe-series catalyst is the natural crystal of iron content, the industrial residue of iron content or the compound of pure state iron;
Described iron system, precious metal composite catalyst are two or more natural crystal, artificial mixture or the artificial compound in iron content and nickel, tungsten, molybdenum or the cobalt.
4. coal direct liquefaction method according to claim 2 is characterized in that, described Fe-series catalyst or iron system, precious metal composite catalyst are ultra-fine dispersed catalysts.
5. according to claim 1 to 5 each described coal direct liquefaction methods, it is characterized in that,
In the described liquefaction reaction, the first liquefying reactor and the second liquefying reactor are the bubbling bed reactor that do not have inner member, paste state bed reactor or with the loop reactor of guide shell; The temperature of reaction of liquefaction reaction is 400-480 ℃, and reaction pressure is 10-30MPa; Vapour-liquid ratio is 600-2000NL/kg; The coal slurry air speed is 0.5-4.5h
-1
The a part of liquefaction reaction product that returns the first liquefying reactor from the second liquefying reactor outlet and the weight rate of coal slurry are than being 0.5-8.
6. coal direct liquefaction method according to claim 5 is characterized in that, a part of liquefaction reaction product that returns the first liquefying reactor from the second liquefying reactor outlet and the weight rate of coal slurry are than being 1-3.
7. according to claim 1 to 4 each described coal direct liquefaction methods, it is characterized in that,
The thick oily hydrogenation pretreatment reaction device that the thick oil of described step adds in the hydrogen pretreatment is fixed-bed reactor or ebullated bed reactor; Hydrogenation catalyst is loaded catalyst, and its carrier is one or more the combination in aluminum oxide, silicon oxide, magnesium oxide and the clay, and its active metal component is one or more among Mo, W, Fe, Ni and the Co; Temperature of reaction is 300-440 ℃; Reaction pressure is 5-25MPa; Vapour-liquid ratio is 400-2000; Air speed is 0.5-5h
-1
8. coal direct liquefaction method according to claim 7 is characterized in that, the thick oil of described step adds that temperature of reaction is 340-390 ℃ in the hydrogen pretreatment; Reaction pressure is 10-17Mpa; Vapour-liquid ratio is 800-1500; Air speed is 0.5-2.5h
-1
9. a DCL/Direct coal liquefaction system is characterized in that, described system comprises:
Coal slurry preparation facilities, the first liquefying reactor, the second liquefying reactor, coal liquefaction products gas-liquid separation unit, distillation unit, thick oily hydrogenation pretreatment reaction device, add hydrogen pretreatment product gas-liquid separation unit, separation column;
Described coal slurry preparation facilities is used for feed coal and catalyzer, promotor, the circulating solvent of the dry coal-forming powder of fragmentation are hybridly prepared into coal slurry;
Described the first liquefying reactor and described the second liquefying reactor are bubbling bed reactor, paste state bed reactor or loop reactor;
Described the second liquefying reactor outlet is communicated with described the first liquefying reactor entrance and described coal liquefaction products gas-liquid separation unit entrance respectively;
Described coal liquefaction products gas-liquid separation unit, the liquefaction reaction product separation that is used for the outlet of the second liquefying reactor is gas phase part and liquid phase part;
Described distillation unit is used for distillation and separates the liquid phase part that obtains by described coal liquefaction products gas-liquid separation unit, and thick oil and residue obtain liquefying;
Described thick oily hydrogenation pretreatment reaction device is fixed-bed reactor or ebullated bed reactor, be used for the thick oil of liquefaction that obtains by described distillation unit is carried out olefin saturated, reaches the reaction of polycyclic aromatic hydrocarbons fractional saturation, removes sulphur, nitrogen, oxygen heteroatom, obtain thick oil and add the hydrogen pretreatment product;
The described hydrogen pretreatment product gas-liquid separation unit that adds is used for that thick oil is added the hydrogen pretreatment product and carries out gas-liquid separation, obtains gaseous phase materials and liquid phase material;
Described separation column, be used for separating the liquid phase material that obtains and carrying out fractionation by distillation adding hydrogen pretreatment product gas-liquid separation unit, isolate lightweight oil and mink cell focus, wherein mink cell focus is as the circulating solvent of gelatin liquefaction process coal slurry preparation, and lightweight oil is as the product oil of gelatin liquefaction unit.
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