CN106590712B

CN106590712B - A kind of coal hydrogenation catalysis gasification method and device

Info

Publication number: CN106590712B
Application number: CN201611270349.2A
Authority: CN
Inventors: 刘雷; 毛燕东; 李克忠
Original assignee: ENN Science and Technology Development Co Ltd
Current assignee: ENN Science and Technology Development Co Ltd
Priority date: 2016-12-30
Filing date: 2016-12-30
Publication date: 2019-08-02
Anticipated expiration: 2036-12-30
Also published as: CN106590712A

Abstract

The present invention provides a kind of coal hydrogenation catalysis gasification method and devices, are related to Coal Gasification Technology field, solve gasification furnace gas outlet CH in existing catalytic coal gasifaction technology₄The problem of content is low, complex process.Include the following steps: the coal dust that coal dust and catalyst are generated to supported catalyst；Under the effect of the catalyst, so that the coal dust and H of supported catalyst₂Hydrogenation catalyst gasification reaction occurs and generates CH₄, containing catalyst it is residual coke with CO₂With H₂Reaction generates CH₄；Under the effect of the catalyst, so that residual burnt and water vapour, O containing catalyst₂Mixed gas carry out the reaction of residual coke gasification and generate H₂、CO₂；The coal dust of supported catalyst and the H of generation₂Hydrogenation catalyst gasification reaction occurs and generates CH₄, residual coke containing catalyst, the CO of generation₂With H₂It reacts and generates CH₄；Repeat hydrogenation catalyst gasification reaction and the reaction of residual coke gasification and obtains CH until the residual coke containing catalyst is converted into the residue containing catalyst₄.The coal hydrogenation catalysis gasification method is applied to coal gasification field.

Description

A kind of coal hydrogenation catalysis gasification method and device

Technical field

The present invention relates to Coal Gasification Technology field more particularly to a kind of coal hydrogenation catalysis gasification methods and device.

Background technique

Currently, China's energy resources situation has the characteristics that " rich coal, few oil, deficency ", convert coal into fossil energy Top quality fuel-natural gas, i.e. coal gas technology are to be suitble to China's national situation, neutralizing energy crisis, the victory for guaranteeing energy security Diameter.

Catalytic coal gasifaction technology is one of most effective process routes in coal gas technology.Existing catalytic coal gasifaction technology It is to make coal react with water vapour at relatively low temperature using base metal catalysts to generate H₂, CO, the H of generation₂、CO Further occurrence conversion reaction, methanation reaction ultimately generate CH under the action of base metal catalysts₄.Base metal catalysts Addition occurs that multiple reactions in catalytic coal gasifaction technology in a device simultaneously, improves the energy thermal efficiency. But the CH in the gasification furnace gas outlet of such catalytic coal gasifaction technology₄Volume content is low (only 20% or so), moreover, after It is continuous to need H unreacted in gas₂, CO and CH₄Separation, then by unreacted H₂, CO conveying gasification furnace or methanation device CH is further synthesized again₄, above-mentioned separation the processes such as synthesizes again and certainly will will cause complex process.

Summary of the invention

The purpose of the present invention is to provide a kind of coal hydrogenation catalysis gasification method and devices, solve existing catalytic coal gasifaction skill Gasification furnace gas outlet CH in art₄The problem of content is low, complex process.

In order to achieve the above object, the invention provides the following technical scheme:

In a first aspect, this method comprises the following steps the present invention provides a kind of coal hydrogenation catalysis gasification method:

S1: coal dust and catalyst are carried out to the process of coal dust supported catalyst, generate the coal dust of supported catalyst；

S2: the coal dust of supported catalyst enters hydrogenation catalyst gasification portion, under the effect of the catalyst, so that supported catalyst Coal dust and hydrogenation catalyst gasification portion in existing H₂Hydrogenation catalyst gasification reaction occurs and generates CH₄, containing catalyst it is residual it is burnt with And aromatic series oil compounds, existing CO in hydrogenation catalyst gasification portion₂With H₂Reaction generates CH₄；

S3: residual burnt into residual coke gasification portion, water vapour and O containing catalyst₂Mixed gas be passed through the residual coke gasification Portion, under the effect of the catalyst, so that residual burnt and water vapour, O containing catalyst₂Mixed gas carry out the reaction life of residual coke gasification At H₂、CO₂；

S4: the H of generation₂、CO₂It is delivered to and adds hydrogen catalysis gasification portion, the coal dust of supported catalyst and the H of generation₂Occur Hydrogenation catalyst gasification reaction generates CH₄, residual burnt and aromatic series oil compounds containing catalyst, the CO of generation₂With H₂Occur anti- CH should be generated₄；

S5: repeating step S3~S4, until the residual coke containing catalyst is converted into the residue containing catalyst, obtains entrainment H₂、 CO₂, dust and aromatic series oil compounds CH₄。

Compared with prior art, coal hydrogenation catalysis gasification method provided by the invention, firstly, coal dust and catalyst are carried out The process of coal dust supported catalyst generates the coal dust of supported catalyst；Then, the coal dust of supported catalyst is delivered to plus hydrogen is urged Change gasification portion, under the effect of the catalyst, the coal dust and H of supported catalyst₂It can directly be converted under lower gasification temperature For CH₄, while the residual burnt and aromatic series oil compounds rich in catalyst are generated, being rich in for hydrogenation catalyst gasification portion generation is urged The residual coke of agent enters residual coke gasification portion and water vapour and O₂Reaction generates H₂And CO₂, the H of residual coke gasification portion generation₂And CO₂Energy again It is enough recycled into hydrogenation catalyst gasification portion, further generates CH with coal dust₄, residual burnt and aromatic series oils rich in catalyst Object is closed, both hydrogenation catalyst gasification portion and residual coke gasification portion form a circulating system, loop back and forth like this, when coal hydrogenation is catalyzed When reaction in gasification installation reaches or approaches the thermodynamical equilibrium limit, it will be able to generate a large amount of CH₄, improve CH₄Generation The CH of the gas vent of rate, efficiency of carbon con version and hydrogenation catalyst gasification portion₄Content, efficiency of carbon con version add hydrogen to urge up to 95% or more Change the CH of the gas vent in gasification portion₄Content reduces CO, CO up to 80%₂The generation of equal by-products, efficiently solves Existing catalysis gasification technique gasification furnace gas outlet CH₄Content is not high, need to separate CH again₄Change and existing hydropyrolysis efficiency of carbon con version is low The problem of.Meanwhile in coal dust and H₂Hydrogenation catalyst gasification reaction occurs and generates CH₄While, coal dust can also be with H₂Reaction generates Benzene-toluene mixture (BTX), phenol-cresol-diformazan phenol mixture (PCX), the naphthalene of high economic value are contour additional It is worth aromatic series oil compounds.

Second aspect, the present invention provides a kind of coal hydrogenation catalytic gasification devices, are used for above-mentioned coal hydrogenation catalytic gasification side Method, the coal hydrogenation catalytic gasification device include: catalyst-supported units and hydrogenation catalyst gasification reaction unit；The hydrogenation catalyst Gasification reaction unit includes mutually connected hydrogenation catalyst gasification portion and residual coke gasification portion；Wherein, the catalyst-supported units Coal powder entrance be connected with power transportation pipe, the coal of the discharges of the catalyst-supported units and hydrogenation catalyst gasification portion Powder entrance is connected；The catalyst inlet of the catalyst-supported units is connected with catalyst transport pipeline；The residual coke gasification portion Mixed gas entrance with for conveying water vapour and O₂Admission line be connected, the gas vent in hydrogenation catalyst gasification portion It is connected with methane collection device.

Compared with prior art, coal hydrogenation catalytic gasification device provided by the invention, by the coal dust of catalyst-supported units Entrance is connected with power transportation pipe, and the catalyst inlet of catalyst-supported units is connected with catalyst transport pipeline, coal dust Pass through power transportation pipe respectively with catalyst and catalyst transport pipeline is delivered to catalyst-supported units, is loaded in catalyst In unit, the process of coal dust and catalyst progress coal dust supported catalyst generates the coal dust of supported catalyst；By supported catalyst Coal dust be delivered to hydrogenation catalyst gasification reaction unit, hydrogenation catalyst gasification reaction dividing elements are hydrogenation catalyst gasification portion and residual Coke gasification portion, the two form a circulating system, under the effect of the catalyst, the coal dust and H of supported catalyst₂It can be lower Gasification temperature under be converted into CH₄, while the residual burnt and aromatic series oil compounds rich in catalyst are generated, add hydrogen to urge Change the residual coke rich in catalyst that gasification portion generates and enters residual coke gasification portion and water vapour and O₂Reaction generates H₂And CO₂, residual coke gas The H that change portion generates₂And CO₂It can be recycled into hydrogenation catalyst gasification portion again, further generate CH with coal dust₄, rich in catalyst Residual burnt and aromatic series oil compounds, loop back and forth like this, when the reaction in coal hydrogenation catalytic gasification device reaches or approaches When the thermodynamical equilibrium limit, it will be able to generate a large amount of CH₄, improve CH₄Generating rate, efficiency of carbon con version and hydrogenation catalyst The CH of the gas vent in gasification portion₄Content, efficiency of carbon con version is up to 95% or more, the CH of the gas vent in hydrogenation catalyst gasification portion₄Content Up to 80%, and reduce CO, CO₂The generation of equal by-products, efficiently solves existing catalysis gasification technique gasification furnace outlet Mouth CH₄Content is not high, need to separate CH again₄Change and the low problem of existing hydropyrolysis efficiency of carbon con version.Meanwhile in coal dust and H₂Occur Hydrogenation catalyst gasification reaction generates CH₄While, coal dust can also be with H₂Reaction generates the benzene-toluene of high economic value The high added values aromatic oil class compound such as mixture (BTX), phenol-cresol-diformazan phenol mixture (PCX), naphthalene.

Detailed description of the invention

The drawings described herein are used to provide a further understanding of the present invention, constitutes a part of the invention, this hair Bright illustrative embodiments and their description are used to explain the present invention, and are not constituted improper limitations of the present invention.In the accompanying drawings:

Fig. 1 is the structural schematic diagram of coal hydrogenation catalytic gasification device provided by the present invention, wherein hydrogenation catalyst gasification portion It is integral type device with residual coke gasification portion；

Fig. 2 is another structural schematic diagram of coal hydrogenation catalytic gasification device provided by the present invention, wherein hydrogenation catalyst Gasification portion and residual coke gasification portion are two part arrangement；

Fig. 3 is the flow chart of coal hydrogenation catalysis gasification method provided by the present invention.

Appended drawing reference:

1- catalyst-supported units；2- hydrogenation catalyst gasification reaction unit；

201- hydrogenation catalyst gasification portion；The residual coke gasification portion 202-；

3- deslagging unit；4- catalyst recovery unit；

5- gas solid separation unit；6- indirect condensing unit；

7- gas purification unit；8- hydrogen separation unit.

Specific embodiment

To keep the objects, features and advantages of technical solution proposed by the invention more obvious and easy to understand, state.Obviously, Described embodiment is only a part of the embodiment of proposed technical solution, instead of all the embodiments.Based on this Embodiment in invention, those of ordinary skill in the art are obtained all other without creative labor Embodiment belongs to the scope of protection of the invention.

Fig. 1~2 are please referred to, the present invention provides a kind of coal hydrogenation catalytic gasification devices, including 1 He of catalyst-supported units Hydrogenation catalyst gasification reaction unit 2, hydrogenation catalyst gasification reaction unit 2 include mutually connected 201 He of hydrogenation catalyst gasification portion Residual coke gasification portion 202, wherein the coal powder entrance of catalyst-supported units 1 is connected with power transportation pipe, catalyst-supported units 1 discharge is connected with the coal powder entrance in hydrogenation catalyst gasification portion 201；The catalyst inlet of catalyst-supported units 1 with urge Agent conveyance conduit is connected；The mixed gas entrance in residual coke gasification portion 202 with for conveying water vapour and O₂Admission line phase Even, the gas vent in hydrogenation catalyst gasification portion 201 is connected with methane collection device.

Catalyst-supported units 1 are used for coal dust supported catalyst process, and hydrogenation catalyst gasification portion 201 is used for coal dust and H₂Into Row hydrogenation catalyst gasification reaction, residual coke gasification portion 202 is for residual burnt and water vapour and O₂Carry out residual coke gasification reaction.

It is as follows to the course of work of coal hydrogenation catalytic gasification device provided by the invention with reference to the accompanying drawing:

Coal dust and catalyst: being carried out the process of coal dust supported catalyst by S1 in catalyst-supported units 1, is generated load and is urged The coal dust of agent.

S2: the coal dust of supported catalyst enters hydrogenation catalyst gasification portion 201, under the effect of the catalyst, so that load is urged Existing H in the coal dust of agent and hydrogen catalysis gasification portion 202₂Hydrogenation catalyst gasification reaction occurs and generates CH₄, be rich in catalyst Residual burnt and aromatic series oil compounds, existing CO in hydrogen catalysis gasification portion 202₂With H₂Reaction generates CH₄。

Specifically, due in hydrogenation catalyst gasification portion 201 feed stock for blast furnace be supported catalyst coal dust, under the action of catalyst The C-C key fracture of carbon particle generates the C atom with reactivity in coal dust, meanwhile, exist in hydrogenation catalyst gasification portion 201 H₂, the presence excitation H of catalyst₂Dissociation occurs and generates the H atom with reactivity, under the effect of the catalyst, the tool of generation There is the H atom of reactivity to spill into the C atomic surface with reactivity and hydrogenation catalyst gasification reaction occurs and generates CH₄。

S3: residual burnt into residual coke gasification portion 202, water vapour and O rich in catalyst₂Mixed gas pass through admission line It is passed through residual coke gasification portion 202, under the effect of the catalyst, so that residual burnt and water vapour, O rich in catalyst₂Mixed gas It carries out residual coke gasification reaction and generates H₂、CO₂。

S4: the H of generation₂、CO₂It is delivered to hydrogenation catalyst gasification portion 201, the coal dust of supported catalyst and the H of generation₂Occur Hydrogenation catalyst gasification reaction generates CH₄, residual burnt and aromatic series oil compounds rich in catalyst, the CO of generation₂With H₂Occur Reaction generates CH₄。

S5: repeating step S3~S4, until the residual coke rich in catalyst is converted into the residue rich in catalyst, (residue contains Carbon amounts < 10%), obtain entrainment H₂、CO₂, dust and aromatic series oil compounds CH₄。

Compared with prior art, coal hydrogenation catalytic gasification device provided by the invention, by the coal dust of catalyst-supported units 1 Entrance is connected with power transportation pipe, and the catalyst inlet of catalyst-supported units 1 is connected with catalyst transport pipeline, coal dust Pass through power transportation pipe respectively with catalyst and catalyst transport pipeline is delivered to catalyst-supported units 1, it is negative in catalyst In carrier unit 1, the process of coal dust and catalyst progress coal dust supported catalyst generates the coal dust of supported catalyst；Load is urged The coal dust of agent is delivered to hydrogenation catalyst gasification reaction unit 2, and hydrogenation catalyst gasification reaction unit 2 is divided into hydrogenation catalyst gasification Portion 201 and residual coke gasification portion 202, the two form a circulating system, under the effect of the catalyst, the coal dust of supported catalyst with H₂CH can be converted under lower gasification temperature₄, while generating the residual burnt and aromatic series oils rich in catalyst Object is closed, hydrogenation catalyst gasification portion 201 is generated residual burnt into residual coke gasification portion 202 and water vapour and O rich in catalyst₂Reaction Generate H₂And CO₂, the H of the residual generation of coke gasification portion 202₂And CO₂Hydrogenation catalyst gasification portion 201 can be recycled into again, further with Coal dust generates CH₄, residual burnt and aromatic series oil compounds rich in catalyst, loop back and forth like this, when coal hydrogenation is catalyzed gas Makeup set in reaction when reaching or approaching thermodynamical equilibrium limiting condition, it will be able to generate a large amount of CH₄, improve CH₄Life At the CH of the gas vent of rate, efficiency of carbon con version and hydrogenation catalyst gasification portion 201₄Content, efficiency of carbon con version add up to 95% or more The CH of the gas vent in hydrogen catalysis gasification portion 201₄Content reduces CO, CO up to 80%₂The generation of equal by-products, effectively Solves existing catalysis gasification technique gasification furnace gas outlet CH₄Content is not high, need to separate CH again₄Change and existing hydropyrolysis carbon turns The low problem of rate.Meanwhile in coal dust and H₂Hydrogenation catalyst gasification reaction occurs and generates CH₄While, coal dust can also be with H₂Instead Benzene-toluene mixture (BTX), phenol-cresol-diformazan phenol mixture (PCX), the naphthalene etc. of high economic value should be generated High added value aromatic series oil compounds.

Here, it should be noted that, although, the H in initial reaction stage, air₂And CO₂Content it is lower, and generate CH₄、 Residual coke rich in catalysis collection is less, still, due to the hydrogenation catalyst gasification portion of coal hydrogenation catalytic gasification device provided by the invention 201 and residual coke gasification portion 202 be a circulating system, when circulating system reaches dynamic equilibrium, it will be able to generate a large amount of H₂ And CO₂, to generate a large amount of CH₄。

Preferably, hydrogenation catalyst gasification portion 201 is higher than residual coke gasification portion 202 in gravity direction in the position of gravity direction Position；The CH generated in the hydrogenation catalyst gasification portion 201 being located above in this way₄It is discharged from the top in hydrogenation catalyst gasification portion 201, The residual coke rich in catalyst generated falls under gravity into underlying residual coke gasification portion 202 and water vapour and O₂Instead H should be generated₂And CO₂, the high temperature H that generates in residual coke gasification portion 202₂And CO₂Ascend into the hydrogenation catalyst gasification portion being located above 201 further participate in reaction.As it can be seen that above-mentioned residual burnt and various gases movement or flowing rich in catalyst is to utilize gravity Or the effect of air-flow, it is not necessarily to additional power device, hydrogenation catalyst gasification portion 201 is realized and the automatic of residual coke gasification portion 202 follows Ring.

Specifically, the hydrogenation catalyst gasification portion 201 in hydrogenation catalyst gasification reaction unit 2 and residual coke gasification portion 202 can be with For the device of integral type, or two part arrangement.

When hydrogenation catalyst gasification portion 201 and residual coke gasification portion 202 are integral type device, hydrogenation catalyst gasification reaction unit 2 be gasification furnace, and gasification furnace is divided into hydrogenation catalyst gasification portion 201 and residual coke gasification portion 202, hydrogenation catalyst gasification portion along gravity direction 201 and residual coke gasification portion 202 without specific boundary；It is integral type dress by hydrogenation catalyst gasification portion 201 and residual coke gasification portion 202 It sets, coal dust and H in hydrogenation catalyst gasification portion 201₂The residual coke rich in catalyst generate after hydrogenation catalyst gasification reaction exists Residual coke gasification portion 202 and water vapour and O are fallen directly under the action of gravity₂Reaction generates H₂And CO₂, raw in residual coke gasification portion 202 At high temperature H₂And CO₂Directly ascend into hydrogenation catalyst gasification portion 201, hydrogenation catalyst gasification portion 201 and residual coke gasification portion 202 Between circulation need not move through pipeline so that reaction is more abundant, and the internal structure of device can be simplified, after being conducive to The maintenance of phase.

When hydrogenation catalyst gasification portion 201 and residual coke gasification portion 202 are two part arrangement, 201 He of hydrogenation catalyst gasification portion Residual coke gasification portion 202 is gasification furnace, i.e., hydrogenation catalyst gasification portion 201 is hydrogenation catalyst gasification furnace, and residual coke gasification portion 202 is residual Coke gasification furnace.

It should be noted that hydrogenation catalyst gasification portion 201 can be fluidized bed, residual coke gasification portion 202 can be fluidized bed Or moving bed.Hydrogenation catalyst gasification portion 201 uses fluidized bed, and residual coke gasification portion 202 uses the specific original of thermopnore or moving bed Because being: the reaction occurred in hydrogenation catalyst gasification portion 201 is coal dust and H₂Between the hydrogenation catalyst gasification reaction that carries out, selection stream The operation format of dynamic bed makes coal dust and H₂It comes into full contact with, and the operating rate of thermopnore and hydrogenation catalyst gasification reaction rate are more Add matching；And for residual coke gasification portion 202, the reaction occurred in residual coke gasification portion 202 is that residual rich in catalyst burnt is steamed with water Vapour and O₂Between the residual coke gasification reaction that carries out, the residual coke rich in catalyst is made using the operation format of thermopnore or moving bed With water vapour and O₂Between come into full contact with, and the reaction rate that the operating rate of thermopnore or moving bed is reacted with residual coke gasification is more Add matching.Fluidized bed is used by hydrogenation catalyst gasification portion 201, residual coke gasification portion 202 uses thermopnore or moving bed, Neng Goujin One step improves CH₄Generating rate, efficiency of carbon con version and the gas vent in hydrogenation catalyst gasification portion 201 CH₄Content.

Normally, coal hydrogenation catalytic gasification device of the invention further includes post-processing unit, and post-processing unit includes successively Connected gas solid separation unit 5, indirect condensing unit 6, gas purification unit 7 and hydrogen separation unit 8, hydrogenation catalyst gasification portion 201 methane outlet pass sequentially through gas solid separation unit 5, indirect condensing unit 6, gas purification unit 7, for separating H₂And CH₄ Hydrogen separation unit 8 be connected with methane collection device.

When it is implemented, firstly, H will be carried secretly₂、CO₂, dust and aromatic series oil compounds CH₄Into gas solid separation Unit 5, by CH₄、H₂、CO₂, aromatic series oil compounds and dust carry out gas solid separation, after obtaining dust and removing dust Carry H secretly₂、CO₂And the CH of aromatic series oil compounds₄。

Then, H will be carried secretly₂、CO₂And the CH of aromatic series oil compounds₄Cool down into indirect condensing unit 6, recycling heat The water vapour is delivered in residual coke gasification portion 202, with O by volume production producing water vapor₂With the residual burnt residual burnt gas of generation rich in catalyst Change reaction and generates H₂And CO₂, naturally it is also possible to directly vapor is delivered in steam turbine and is generated electricity；Meanwhile according to boiling range Difference can to obtain benzene-toluene mixture (BTX), phenol-cresol-diformazan phenol mixture (PCX), naphthalene contour attached Value added aromatic series oil compounds, and the entrainment H of can be removed water vapour and aromatic series oil compounds₂And CO₂'s CH₄。

Secondly, H will be carried secretly₂And CO₂CH₄Depickling processing is carried out by gas purification unit 7, removes the CO in gas₂, Obtain entrainment H₂CH₄。

Finally, entrainment H₂CH₄By hydrogen separation unit 8, by H₂And CH₄It is separated, obtains CH₄。

In above-mentioned post-processing unit, gas solid separation unit 5 can be multi-cyclone, using multi-cyclone It, can be more effectively by CH as gas solid separation unit 5₄、H₂、CO₂, aromatic series oil compounds separated with dust, obtain The less CH of solid dust content₄、H₂、CO₂, aromatic series oil compounds；Indirect condensing unit 6 can be multistage indirect heat exchange Device can generate the water vapour of different qualities by recycling different heats；Hydrogen separation unit 8 can be preferably that transformation is inhaled Attached hydrogen separation device, low, separation is thorough, process flow is simple, automates journey with consuming energy for hydrogen psa separator The features such as degree is high, environmental benefit is good carries out H using hydrogen psa separator₂And CH₄Separation, can obtain purer CH₄, and it is more advantageous to the automation and environmental protection for realizing coal hydrogenation catalytic gasification device provided by the invention.

Preferably, the dust outlet of gas solid separation unit 5 is connected with the dust inlet in residual coke gasification portion 202, gas solid separation The gas vent of unit 5 is connected with the gas feed of indirect condensing unit 6, so that the dust isolated in gas solid separation unit 5 It is delivered to residual coke gasification portion 202 and water vapour and O₂Reaction generates H₂And CO₂, further increase CH₄Generating rate, carbon conversion The CH of the gas vent in rate and hydrogenation catalyst gasification portion 201₄Content.

The hydrogen outlet of hydrogen separation unit 8 is connected with the hydrogen inlet in hydrogenation catalyst gasification portion 201, the H isolated₂It is defeated It send to hydrogenation catalyst gasification portion 201 and coal dust and hydrogenation catalyst gasification reaction generation CH occurs₄。

Coal hydrogenation catalytic gasification device of the invention further includes deslagging unit 3 and catalyst recovery unit 4, residual coke gasification portion 202 solid discharge passes sequentially through deslagging unit 3, catalyst recovery unit 4 is connected with catalyst-supported units 1.

When it is implemented, when the reaction in coal hydrogenation catalytic gasification device reaches capacity state, after coal dust deep pyrolytic The residue rich in catalyst of obtained C content < 10% will be delivered to dreg removing system 3 from residual coke gasification portion 202 and catalyst returns It receives unit 4 and carries out catalyst recycling, catalyst transport to the catalyst-supported units 1 of recycling are recycled, and improve catalyst Utilization rate.

The present invention also provides a kind of coal hydrogenation catalysis gasification methods, and this method comprises the following steps:

S1: being 6mm or less, the coal dust of water content < 5% and catalyst in the progress coal dust of catalyst-supported units 1 by partial size The process of supported catalyst generates the coal dust of supported catalyst.

S2: the coal dust of supported catalyst enters hydrogenation catalyst gasification portion 201, under the effect of the catalyst, so that load is urged Existing H in the coal dust of agent and hydrogen catalysis gasification portion 202₂Hydrogenation catalyst gasification reaction occurs and generates CH₄(shown in formula I), Residual burnt and aromatic series oil compounds rich in catalyst, existing CO in hydrogen catalysis gasification portion 202₂With H₂Reaction generates CH₄(as shown in Formula II)；

C+2H₂→CH₄——(I)

4H₂+CO₂→CH₄+2H₂O——(II)

S3: residual burnt into residual coke gasification portion 202, water vapour and O rich in catalyst₂Mixed gas pass through admission line It is passed through residual coke gasification portion 202, under the effect of the catalyst, so that residual burnt and water vapour, O rich in catalyst₂Mixed gas It carries out residual coke gasification reaction and generates H₂、CO₂(as shown in formula III~VI).

2C+2H₂O→2H₂+2CO——(III)

CO+H₂O→CO₂+H₂——(IV)

2C+O₂→2CO——(V)

C+O₂→CO₂——(VI)

Compared with prior art, coal hydrogenation catalysis gasification method provided by the invention, firstly, coal dust and catalyst are carried out The process of coal dust supported catalyst generates the coal dust of supported catalyst；Then, the coal dust of supported catalyst is delivered to plus hydrogen is urged Change gasification portion 201, under the effect of the catalyst, the coal dust and H of supported catalyst₂Can directly it turn under lower gasification temperature Turn to CH₄, while the residual burnt and aromatic series oil compounds rich in catalyst are generated, what hydrogenation catalyst gasification portion 201 generated It is residual burnt into residual coke gasification portion 202 and water vapour and O rich in catalyst₂Reaction generates H₂And CO₂, residual coke gasification portion 202 generates H₂And CO₂It can be recycled into hydrogenation catalyst gasification portion 201 again, further generate CH with coal dust₄, residual coke rich in catalyst And aromatic series oil compounds, it loops back and forth like this, when the reaction in coal hydrogenation catalytic gasification device reaches or approaches heating power When learning reaching ability, it will be able to generate a large amount of CH₄, improve CH₄Generating rate, efficiency of carbon con version and hydrogenation catalyst gasification The CH of the gas vent in portion 201₄Content, efficiency of carbon con version is up to 95% or more, the CH of the gas vent in hydrogenation catalyst gasification portion 201₄Contain Amount reduces CO, CO up to 80%₂The generation of equal by-products, efficiently solves existing catalysis gasification technique gasification furnace and goes out Port CH₄Content is not high, need to separate CH again₄Change and the low problem of existing hydropyrolysis efficiency of carbon con version.Meanwhile in coal dust and H₂Hair Raw hydrogenation catalyst gasification reaction generates CH₄While, coal dust can also be with H₂Reaction generates benzene-toluene-diformazan of high economic value The high added values aromatic oil class compound such as benzol mixture (BTX), phenol-cresol-diformazan phenol mixture (PCX), naphthalene.

It should be noted that in coal hydrogenation catalysis gasification method of the invention, coal dust is chosen as brown coal powder, bituminous coal powder, secondary One of bituminous coal powder or anchracite duff or the mixing of a variety of arbitrary proportions, the preferably matter of brown coal powder, ub-bituminous coal powder or volatile matter High percentage is measured in 30% one of bituminous coal powder or the mixing of a variety of arbitrary proportions.This is because brown coal powder, ub-bituminous coal powder or The mass percent of volatile matter has the characteristics that low ash, low-sulfur, high volatile, activity are strong higher than 30% bituminous coal powder, can obtain Obtain more oil products and CH₄。

In addition, the mode of coal dust supported catalyst is chosen as dry-mixed, dipping and part is dry-mixed, in partial immersion mixing method It is a kind of.

Selection for catalyst, catalyst can be single catalyst or composite catalyst.

When catalyst is single catalyst, the single catalyst is transition metal salt, preferably Fe salt, Co salt, Ni One or more arbitrary proportions of salt mix.

In coal hydrogenation catalysis gasification method provided by the invention, catalyst is preferably composite catalyst, when catalyst is multiple When closing catalyst, major catalyst is preferably one or more arbitrary proportions mixing of Fe salt, Co salt, Ni salt in composite catalyst, Co-catalyst is preferably one of oxide of Ca salt, the oxide of Ca, Mg salt or Mg or the mixing of a variety of arbitrary proportions.

For composite catalyst, major catalyst is catalyzed C and H respectively₂、CO₂And H₂Generate CH₄Reaction, co-catalyst Mainly for increasing the dispersibility and catalytic activity of major catalyst, adsorption capacity of the major catalyst in active sites is improved, is formed More dynamics model inhibits inactivation, reduces inactivation probability, improves catalytic performance；It is rich in and urges after hydrogenation catalyst gasification reaction simultaneously When the residual coke gasification of the residual burnt further progress of agent, co-catalyst, i.e. alkaline-earth metal catalyst, be conducive to residual coke gasification react to Generate H₂And CO₂Direction carries out.

Further, in the coal dust of supported catalyst, the quality of major catalyst accounts for the 3% of quality of pc in composite catalyst ~8%, the quality of co-catalyst accounts for the 0.2%~2% of quality of pc；It is preferred that are as follows: in the coal dust of supported catalyst, composite catalyzing The quality of major catalyst accounts for the 4%~6% of quality of pc in agent, and the quality of co-catalyst accounts for the co-catalyst of quality of pc 0.4%~0.8%.Wherein, due to active sites limited amount on the particle of coal dust, the additive amount of major catalyst is too high, active sites Extra major catalyst can not play catalytic action after saturation, and being excessively added can be such that economic cost increases；But if main reminder The additive amount of agent is too low, and the active sites that can not be catalyzed completely on the particle of coal dust do not have expected catalytic effect, cause Hydrogenation catalyst gasification furnace gas outlet CH₄Content and efficiency of carbon con version reduce；The adding too much of co-catalyst then can same main catalytic Agent competes the active sites on the particle of coal dust, and active sites is caused to be covered by co-catalyst, and then reduces the same active sites of major catalyst Contact probability so that activity reduce, the additive amount of co-catalyst is too low, then can not effectively increase major catalyst dispersibility and Catalytic activity can not also effectively inhibit the inactivation of major catalyst, therefore, when catalyst is preferably composite catalyst, main reminder The additive amount of agent and co-catalyst is limited by catalytic performance and Technical Economy, compound to urge in the coal dust of supported catalyst The quality of major catalyst is limited to account for the 3%~8% of quality of pc in agent, and the quality of co-catalyst is limited to account for quality of pc 0.2%~2%；It is preferred that are as follows: in the coal dust of supported catalyst, the quality of major catalyst accounts for quality of pc in composite catalyst 4%~6%, the quality of co-catalyst accounts for the co-catalyst 0.4%~0.8% of quality of pc.

Preferably, the operating pressure of hydrogenation catalyst gasification reaction is 0.5MPa-8MPa, and preferably 1MPa-7MPa adds hydrogen to urge The reaction temperature for changing gasification reaction is 650 DEG C -900 DEG C, preferably 700 DEG C -800 DEG C.For the behaviour of hydrogenation catalyst gasification reaction The selection for making pressure, according to thermodynamical equilibrium, the operating pressure of hydrogenation catalyst gasification reaction more has within the scope of 0.5MPa-8MPa Conducive to hydrogenation catalyst gasification reaction to generate CH₄Direction carry out, can be improved hydrogenation catalyst gasification reaction rate, increase unit The operating pressure for the treatment of capacity in time, hydrogenation catalyst gasification reaction is higher than 8MPa, and hydrogenation catalyst gasification reaction rate is too fast, meeting Cause to react uncontrollable, increase operational hazards, and high pressure the high requirements on the equipment, increase equipment investment, and hydrogenation catalyst gasified reverse The operating pressure answered is lower than 0.5MPa, then is unfavorable for hydrogenation catalyst gasification reaction to generation CH₄Direction carry out, reaction rate mistake Slowly, unit time treating capacity reduces；Selection for the reaction temperature of hydrogenation catalyst gasification reaction, catalyst is at 650 DEG C -900 C-C key in coal can be more excited to be broken and promote H within the scope of DEG C₂Dissociation, H atom spills into the C Surface with reactivity On react and generate CH₄, the reaction temperature of hydrogenation catalyst gasification reaction, which is higher than 900 DEG C, will lead to sintering of catalyst inactivation, and Reaction temperature then will lead to that catalytic effect is bad, reaction rate is slow lower than 650 DEG C.

Preferably, the operating pressure of residual coke gasification reaction is 0.5MPa-8MPa, preferably 1MPa-7MPa, and residual coke gasification is anti- The reaction temperature answered is 800 DEG C -1000 DEG C.Selection for the operating pressure of residual coke gasification reaction, it is residual according to thermodynamical equilibrium The operating pressure of coke gasification reaction is more advantageous to residual coke gasification within the scope of 0.5MPa-8MPa and reacts to generation H₂、CO₂Direction It carries out, can be improved residual coke gasification reaction rate, the operating pressure of residual coke gasification reaction is higher than 8MPa, residual coke gasification reaction rate It is too fast, it will lead to and react uncontrollable, increase operational hazards, and high pressure the high requirements on the equipment, increase equipment investment, and residual coke gasification The operating pressure of reaction is lower than 0.5MPa, then is unfavorable for residual coke gasification and reacts to generation CH₄Direction carry out, reaction rate mistake Slowly, unit time treating capacity reduces, and further, the operating pressure of residual coke gasification reaction is equal to the behaviour of hydrogenation catalyst gasification reaction Make pressure, the system pressure of entire hydrogenation catalyst gasification reaction unit 2 keeps balance, is more advantageous to operation；For residual coke gasification The selection of the reaction temperature of reaction, catalyst can promote residual coke gasification to react to generation H at 800 DEG C -1000 DEG C₂、CO₂Direction It carries out, generates more H₂、CO₂For generating CH₄。

Coal hydrogenation catalysis gasification method provided by the invention further includes post-processing stages after step s 5, post-processes rank Section includes gas solid separation stage, indirect condensing stage, gas purification stage and Hydrogen Separation stage.

Specifically, the gas solid separation stage includes: that will carry H secretly₂、CO₂, dust and aromatic series oil compounds CH₄Into Gas solid separation unit 5, by CH₄、H₂、CO₂, aromatic series oil compounds and dust carry out gas solid separation, obtain dust and removing Entrainment H after dust₂、CO₂And the CH of aromatic series oil compounds₄。

The indirect condensing stage includes: that will carry H secretly₂、CO₂And the CH of aromatic series oil compounds₄Into indirect condensing unit 6 coolings, recycle heat, obtain benzene-toluene mixture (BTX), phenol-cresol-diformazan phenol mixture according to boiling range (PCX), the high added values such as naphthalene aromatic oil class compound, and the entrainment H of be removed water vapour and aromatic series oil compounds₂ And CO₂CH₄。

The gas purification stage includes: that will carry H secretly₂And CO₂CH₄Depickling processing, removal are carried out by gas purification unit 7 CO in gas₂, obtain entrainment H₂CH₄。

The Hydrogen Separation stage includes: entrainment H₂CH₄By hydrogen separation unit 8, by H₂And CH₄It is separated, is obtained most Finished product CH₄。

Further, the dust that the gas solid separation stage obtains be delivered to residual coke gasification portion 202 further with water vapour and O₂ Reaction generates H₂And CO₂, further increase CH₄Generating rate, efficiency of carbon con version and the gas in hydrogenation catalyst gasification portion 201 go out The CH of mouth₄Content.

Further, the H that the Hydrogen Separation stage obtains₂Hydrogenation catalyst gasification portion 201 is delivered to further to occur with coal dust Hydrogenation catalyst gasification reaction generates CH₄。

Coal hydrogenation catalysis gasification method provided by the invention is after step s 5, further includes: catalyst recovery stage.

Specifically, the residue rich in catalyst that catalyst recovery stage is C content < 10% by dreg removing system 3 and is urged Agent recovery unit 4 carries out catalyst recycling, and catalyst transport to the catalyst-supported units 1 of recycling are recycled, improve The utilization rate of catalyst.

It should be understood that the mode of catalyst recovery stage be washing, pickling, alkali cleaning, ammonia soak one or more of, It can specifically select according to the actual situation.

Several optional embodiments of coal hydrogenation catalysis gasification method provided by the invention are provided with reference to the accompanying drawing, only It indicates that, and does not lie in and limit the scope of protection of the present invention.

Embodiment one

A kind of coal hydrogenation catalysis gasification method is present embodiments provided, this method comprises the following steps:

S1: partial size is carried out for 6mm or less, the anchracite duff of water content < 5% and catalyst in catalyst-supported units 1 It is dry-mixed, the anchracite duff of load Fe salt is generated, catalyst is Fe salt.

S2: the anchracite duff of supported catalyst enters hydrogenation catalyst gasification portion 201, under the effect of the catalyst, so that negative Existing H in the anchracite duff of carried catalyst and hydrogen catalysis gasification portion 202₂Hydrogenation catalyst gasification reaction occurs and generates CH₄, it is rich Residual burnt and aromatic series oil compounds containing catalyst, existing CO in hydrogen catalysis gasification portion 202₂With H₂Reaction generates CH₄, wherein the operating pressure of hydrogenation catalyst gasification reaction is 0.5MPa, and the reaction temperature of hydrogenation catalyst gasification reaction is 900 ℃。

S3: residual burnt into residual coke gasification portion 202, water vapour and O rich in catalyst₂Mixed gas pass through admission line It is passed through residual coke gasification portion 202, under the effect of the catalyst, so that residual burnt and water vapour, O rich in catalyst₂Mixed gas It carries out residual coke gasification reaction and generates H₂、CO₂, wherein the operating pressure of residual coke gasification reaction is 0.5MPa, residual coke gasification reaction Reaction temperature is 1000 DEG C.

S4: the H of generation₂、CO₂It is delivered to hydrogenation catalyst gasification portion 201, the anchracite duff of supported catalyst and the H of generation₂ Hydrogenation catalyst gasification reaction occurs and generates CH₄, residual burnt and aromatic series oil compounds rich in catalyst, the CO of generation₂With H₂ It reacts and generates CH₄；

S6: H will be carried secretly₂、CO₂, dust and aromatic series oil compounds CH₄Carry out successively carry out the gas solid separation stage, Indirect condensing stage, gas purification stage and Hydrogen Separation stage, obtain final products CH₄；The powder that the gas solid separation stage obtains Dirt be delivered to residual coke gasification portion 202 further with water vapour and O₂Reaction generates H₂And CO₂；The H that the Hydrogen Separation stage obtains₂It is defeated It send and hydrogenation catalyst gasification reaction generation CH further occurs with anchracite duff to hydrogenation catalyst gasification portion 201₄；C content < 10% The residue rich in catalyst washed by dreg removing system 3 and catalyst recovery unit 4, the catalyst transport of recycling is to urging Agent load unit 1 is recycled.

It can be obtained by test, the efficiency of carbon con version of coal hydrogenation catalysis gasification method provided in this embodiment is 95% or more, is added The CH of the gas vent in hydrogen catalysis gasification portion 201₄Volume content be 80%.

Embodiment two

S1: by partial size be 6mm or less, the ub-bituminous coal powder of water content < 5%, catalyst are carried out in catalyst-supported units 1 Dipping and part are dry-mixed, generate the ub-bituminous coal powder of supported catalyst, and catalyst is the mixture of Co salt and Ni salt.

S2: the ub-bituminous coal powder of the mixture of supported catalyst enters hydrogenation catalyst gasification portion 201, in the effect of catalyst Under, so that H existing in the ub-bituminous coal powder of supported catalyst and hydrogen catalysis gasification portion 202₂Hydrogenation catalyst gasification reaction occurs Generate CH₄, residual burnt and aromatic series oil compounds rich in catalyst, existing CO in hydrogen catalysis gasification portion 202₂With H₂ Reaction generates CH₄, wherein the operating pressure of hydrogenation catalyst gasification reaction is 8MPa, the reaction temperature of hydrogenation catalyst gasification reaction It is 650 DEG C.

S3: residual burnt into residual coke gasification portion 202, water vapour and O rich in catalyst₂Mixed gas pass through admission line It is passed through residual coke gasification portion 202, under the effect of the catalyst, so that residual burnt and water vapour, O rich in catalyst₂Mixed gas It carries out residual coke gasification reaction and generates H₂、CO₂, wherein the operating pressure of residual coke gasification reaction is 8MPa, and residual coke gasification reacts anti- Answering temperature is 800 DEG C.

S4: the H of generation₂、CO₂It is delivered to hydrogenation catalyst gasification portion 201, the ub-bituminous coal powder of supported catalyst and the H of generation₂ Hydrogenation catalyst gasification reaction occurs and generates CH₄, residual burnt and aromatic series oil compounds rich in catalyst, the CO of generation₂With H₂ It reacts and generates CH₄；

S5: repeating step S3~S4, until the residual coke rich in catalyst is converted into the mixture rich in Co salt and Ni salt Residue (the phosphorus content < 10% of residue) obtains entrainment H₂、CO₂, dust and aromatic series oil compounds CH₄。

S6: H will be carried secretly₂、CO₂, dust and aromatic series oil compounds CH₄Carry out successively carry out the gas solid separation stage, Indirect condensing stage, gas purification stage and Hydrogen Separation stage, obtain final products CH₄；The powder that the gas solid separation stage obtains Dirt be delivered to residual coke gasification portion 202 further with water vapour and O₂Reaction generates H₂And CO₂；The H that the Hydrogen Separation stage obtains₂It is defeated It send and hydrogenation catalyst gasification reaction generation CH further occurs with ub-bituminous coal powder to hydrogenation catalyst gasification portion 201₄；C content < 10% The residue rich in catalyst carry out pickling by dreg removing system 3 and catalyst recovery unit 4, the catalyst transport of recycling is to urging Agent load unit 1 is recycled.

It can be obtained by test, the efficiency of carbon con version of coal hydrogenation catalysis gasification method provided in this embodiment is 96% or more, is added The CH of the gas vent in hydrogen catalysis gasification portion 201₄Volume content be 82%.

Embodiment three

S1: by partial size be 6mm or less, the coal dust intermixture of water content < 5%, catalyst catalyst-supported units 1 into Row dipping and part are dry-mixed, generate the coal dust intermixture of supported catalyst, and coal dust intermixture is the matter of ub-bituminous coal powder and volatile matter Measure high percentage in 30% bituminous coal powder mixture, catalyst is composite catalyst, and the major catalyst of composite catalyst is Fe Salt, co-catalyst are Mg salt, and the quality that the quality of Fe salt accounts for 3%, the Mg salt of the quality of coal dust accounts for the 0.2% of the quality of coal dust.

S2: the coal dust intermixture of supported catalyst enters hydrogenation catalyst gasification portion 201, under the effect of the catalyst, so that Existing H in the coal dust intermixture of supported catalyst and hydrogen catalysis gasification portion 202₂Hydrogenation catalyst gasification reaction occurs to generate CH₄, residual burnt and aromatic series oil compounds rich in catalyst, existing CO in hydrogen catalysis gasification portion 202₂With H₂Reaction Generate CH₄, wherein the operating pressure of hydrogenation catalyst gasification reaction is 1MPa, and the reaction temperature of hydrogenation catalyst gasification reaction is 800 ℃。

S3: residual burnt into residual coke gasification portion 202, water vapour and O rich in catalyst₂Mixed gas pass through admission line It is passed through residual coke gasification portion 202, under the action of catalyst, so that residual burnt and water vapour, O rich in catalyst₂Mixed gas into The residual coke gasification reaction of row generates H₂、CO₂, wherein the operating pressure of residual coke gasification reaction is 1MPa, the reaction of residual coke gasification reaction Temperature is 1000 DEG C.

S4: the H of generation₂、CO₂It is delivered to hydrogenation catalyst gasification portion 201, coal dust intermixture and the generation of supported catalyst H₂Hydrogenation catalyst gasification reaction occurs and generates CH₄, residual burnt and aromatic series oil compounds rich in catalyst, the CO of generation₂With H₂It reacts and generates CH₄；

S6: H will be carried secretly₂、CO₂, dust and aromatic series oil compounds CH₄Carry out successively carry out the gas solid separation stage, Indirect condensing stage, gas purification stage and Hydrogen Separation stage, obtain final products CH₄；The powder that the gas solid separation stage obtains Dirt be delivered to residual coke gasification portion 202 further with water vapour and O₂Reaction generates H₂And CO₂；The H that the Hydrogen Separation stage obtains₂It is defeated It send and hydrogenation catalyst gasification reaction generation CH further occurs with ub-bituminous coal powder to hydrogenation catalyst gasification portion 201₄；C content < 10% The residue of the mixture rich in Co salt and Ni salt carry out alkali cleaning by dreg removing system 3 and catalyst recovery unit 4, recycling is urged Agent is delivered to the recycling of catalyst-supported units 1.

It can be obtained by test, the efficiency of carbon con version of coal hydrogenation catalysis gasification method provided in this embodiment is 97% or more, is added The CH of the gas vent in hydrogen catalysis gasification portion 201₄Volume content be 85%.

Example IV

S1: by partial size be 6mm or less, the coal dust intermixture of water content < 5%, catalyst catalyst-supported units 1 into Row partial immersion mixing method, generates the coal dust intermixture of supported catalyst, and coal dust intermixture is the matter of ub-bituminous coal powder and volatile matter Measure high percentage in 30% bituminous coal powder mixture, catalyst is composite catalyst, and the major catalyst of composite catalyst is Co Salt, co-catalyst are the hopcalite of Ca salt and Mg, and the quality of Co salt accounts for 8%, the Ca salt and Mg of the quality of coal dust The quality of hopcalite accounts for the 2% of the quality of coal dust.

S2: the coal dust intermixture of supported catalyst enters hydrogenation catalyst gasification portion 201, under the effect of the catalyst, so that Existing H in the coal dust intermixture of supported catalyst and hydrogen catalysis gasification portion 202₂Hydrogenation catalyst gasification reaction occurs to generate CH₄, residual burnt and aromatic series oil compounds rich in catalyst, existing CO in hydrogen catalysis gasification portion 202₂With H₂Reaction Generate CH₄, wherein the operating pressure of hydrogenation catalyst gasification reaction is 7MPa, and the reaction temperature of hydrogenation catalyst gasification reaction is 700 ℃。

S3: residual burnt into residual coke gasification portion 202, water vapour and O rich in catalyst₂Mixed gas pass through admission line It is passed through residual coke gasification portion 202, under the action of catalyst, so that residual burnt and water vapour, O rich in catalyst₂Mixed gas into The residual coke gasification reaction of row generates H₂、CO₂, wherein the operating pressure of residual coke gasification reaction is 7MPa, the reaction of residual coke gasification reaction Temperature is 800 DEG C.

S6: H will be carried secretly₂、CO₂, dust and aromatic series oil compounds CH₄Carry out successively carry out the gas solid separation stage, Indirect condensing stage, gas purification stage and Hydrogen Separation stage, obtain final products CH₄；The powder that the gas solid separation stage obtains Dirt be delivered to residual coke gasification portion 202 further with water vapour and O₂Reaction generates H₂And CO₂；The H that the Hydrogen Separation stage obtains₂It is defeated It send and hydrogenation catalyst gasification reaction generation CH further occurs with ub-bituminous coal powder to hydrogenation catalyst gasification portion 201₄；C content < 10% The residue of the mixture rich in Co salt and Ni salt carry out ammonia leaching by dreg removing system 3 and catalyst recovery unit 4, recycling is urged Agent is delivered to the recycling of catalyst-supported units 1.

It can be obtained by test, the efficiency of carbon con version of coal hydrogenation catalysis gasification method provided in this embodiment is 97% or more, is added The CH of the gas vent in hydrogen catalysis gasification portion 201₄Volume content be 88%.

Embodiment five

S1: by partial size be 6mm or less, the coal dust intermixture of water content < 5%, catalyst catalyst-supported units 1 into Row partial immersion mixing method, generates the coal dust intermixture of supported catalyst, and coal dust intermixture is brown coal powder and ub-bituminous coal powder, catalysis Agent is composite catalyst, and the major catalyst of composite catalyst is Ni salt, and co-catalyst is the hopcalite of Ca salt and Ca, The quality that the quality of Ni salt accounts for 4%, the Ca salt of the quality of coal dust and the hopcalite of Ca accounts for the quality of coal dust 0.4%.

It can be obtained by test, the efficiency of carbon con version of coal hydrogenation catalysis gasification method provided in this embodiment is 97% or more, is added The CH of the gas vent in hydrogen catalysis gasification portion 201₄Volume content be 90%.

Embodiment six

S1: by partial size be 6mm or less, the coal dust intermixture of water content < 5%, catalyst catalyst-supported units 1 into Row partial immersion mixing method, generates the coal dust intermixture of supported catalyst, and coal dust intermixture is brown coal powder and ub-bituminous coal powder, catalysis Agent is composite catalyst, and the major catalyst of composite catalyst is Ni salt, and co-catalyst is the hopcalite of Ca salt and Ca, The quality that the quality of Ni salt accounts for 6%, the Ca salt of the quality of coal dust and the hopcalite of Ca accounts for the quality of coal dust 0.8%.

It can be obtained by test, the efficiency of carbon con version of coal hydrogenation catalysis gasification method provided in this embodiment is 97% or more, is added The CH of the gas vent in hydrogen catalysis gasification portion 201₄Volume content be 94%.

The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any Those familiar with the art in the technical scope disclosed by the present invention, can easily think of the change or the replacement, and should all contain Lid is within protection scope of the present invention.Therefore, protection scope of the present invention should be based on the protection scope of the described claims.

Claims

1. a kind of coal hydrogenation catalysis gasification method, which is characterized in that this method comprises the following steps:

S1: coal dust and catalyst are carried out to the process of coal dust supported catalyst, generate the coal dust of supported catalyst；Wherein, it is catalyzed Agent is single catalyst or composite catalyst；The single catalyst is transition metal salt；The composite catalyst includes main reminder Agent and co-catalyst, the major catalyst are transition metal salt；

S2: the coal dust of supported catalyst enters hydrogenation catalyst gasification portion, under the effect of the catalyst, so that the coal of supported catalyst Existing H in powder and hydrogenation catalyst gasification portion₂Hydrogenation catalyst gasification reaction occurs and generates CH₄, residual burnt and virtue containing catalyst Fragrant race's oil compounds, existing CO in hydrogenation catalyst gasification portion₂With H₂Reaction generates CH₄；

S3: residual burnt into residual coke gasification portion, water vapour and O containing catalyst₂Mixed gas be passed through the residual coke gasification portion, Under the action of catalyst, so that residual burnt and water vapour, O containing catalyst₂Mixed gas carry out the reaction of residual coke gasification and generate H₂、 CO₂；

S4: the H of generation₂、CO₂It is delivered to hydrogenation catalyst gasification portion, the coal dust of supported catalyst and the H of generation₂Occur to add hydrogen Catalytic gasification reaction generates CH₄, residual burnt and aromatic series oil compounds containing catalyst, the CO of generation₂With H₂React life At CH₄；

S5: repeating step S3~S4, until the residual coke containing catalyst is converted into the residue containing catalyst, obtains entrainment H₂、CO₂, powder The CH of dirt and aromatic series oil compounds₄。

2. coal hydrogenation catalysis gasification method according to claim 1, which is characterized in that the coal dust is brown coal powder, bituminous coal One of powder, ub-bituminous coal powder or anchracite duff or the mixing of a variety of arbitrary proportions.

3. coal hydrogenation catalysis gasification method according to claim 2, which is characterized in that in the S1, the grain of the coal dust Diameter is in 6mm hereinafter, the water content < 5% of coal dust.

4. coal hydrogenation catalysis gasification method according to claim 1, which is characterized in that when catalyst is single catalyst When, the single catalyst is one or more arbitrary proportions mixing of Fe salt, Co salt, Ni salt.

5. coal hydrogenation catalysis gasification method according to claim 1, which is characterized in that when catalyst is composite catalyst When, the major catalyst in the composite catalyst is one or more, the composite catalyst of Fe salt, Co salt, Ni salt In co-catalyst be one of oxide of Ca salt, the oxide of Ca, Mg salt or Mg or the mixing of a variety of arbitrary proportions.

6. coal hydrogenation catalysis gasification method according to claim 5, which is characterized in that the coal dust of the supported catalyst In, the quality of major catalyst accounts for the 3%~8% of quality of pc in composite catalyst；The quality of co-catalyst accounts for quality of pc 0.2%~2%.

7. coal hydrogenation catalysis gasification method according to claim 1, which is characterized in that the hydrogenation catalyst gasification reaction Operating pressure is 0.5MPa-8MPa, and the reaction temperature of the hydrogenation catalyst gasification reaction is 650 DEG C -900 DEG C；

The operating pressure of the residual coke gasification reaction is 0.5MPa-8MPa, the reaction temperature of residual coke gasification reaction is 800 DEG C- 1000℃。

8. coal hydrogenation catalysis gasification method according to claim 1, which is characterized in that further include gas after the S5 Gu separation phase, indirect condensing stage, gas purification stage and Hydrogen Separation stage, wherein

The gas solid separation stage includes: that will carry H secretly₂、CO₂, dust and aromatic series oil compounds CH₄Carry out gas-solid point From, obtain dust and remove dust after entrainment H₂、CO₂And the CH of aromatic series oil compounds₄；

The indirect condensing stage includes: that will carry H secretly₂、CO₂And the CH of aromatic series oil compounds₄Cool down, recycling heat Amount obtains aromatic series oil compounds and removes the entrainment H of water vapour and aromatic series oil compounds₂And CO₂CH₄；

The gas purification stage includes: that will carry H secretly₂And CO₂CH₄Depickling processing is carried out, the CO in gas is removed₂, pressed from both sides Band H₂CH₄；

The Hydrogen Separation stage includes: that will carry H secretly₂CH₄It is separated, obtains CH₄。

9. coal hydrogenation catalysis gasification method according to claim 8, which is characterized in that the gas solid separation stage also wraps It includes: dust is delivered to the residual coke gasification portion and water vapour and O₂Reaction generates H₂And CO₂；

The Hydrogen Separation stage further include: by H₂It is delivered to hydrogenation catalyst gasification portion and hydrogenation catalyst gasification reaction occurs for coal dust Generate CH₄。

10. coal hydrogenation catalysis gasification method according to claim 1, which is characterized in that after the S5, including catalysis Agent recovery stage；

The catalyst recovery stage includes: that the residue containing catalyst is carried out catalyst recycling, and the catalyst transport of recycling is extremely Catalyst-supported units are recycled.

11. a kind of coal hydrogenation catalytic gasification device, which is characterized in that add for the described in any item coals of such as claim 1~10 Hydrogen catalysis gasification process, the coal hydrogenation catalytic gasification device include: catalyst-supported units and hydrogenation catalyst gasification reaction list Member；The hydrogenation catalyst gasification reaction unit includes mutually connected hydrogenation catalyst gasification portion and residual coke gasification portion；Wherein,

The coal powder entrance of the catalyst-supported units is connected with power transportation pipe, and the coal dust of the catalyst-supported units goes out Mouth is connected with the coal powder entrance in hydrogenation catalyst gasification portion；The catalyst inlet and catalyst transport of the catalyst-supported units Road is connected；

The mixed gas entrance in the residual coke gasification portion with for conveying water vapour and O₂Admission line be connected, described plus hydrogen is urged The gas vent for changing gasification portion is connected with methane collection device.

12. coal hydrogenation catalytic gasification device according to claim 11, which is characterized in that hydrogenation catalyst gasification portion exists The position of gravity direction is higher than the residual coke gasification portion in the position of gravity direction.

13. coal hydrogenation catalytic gasification device according to claim 11, which is characterized in that the hydrogenation catalyst gasification reaction Unit is gasification furnace, and the gasification furnace is divided into hydrogenation catalyst gasification portion and the residual coke gasification portion along gravity direction；

Or, hydrogenation catalyst gasification portion and the residual coke gasification portion are gasification furnace.

14. 1~13 described in any item coal hydrogenation catalytic gasification devices according to claim 1, which is characterized in that described plus hydrogen is urged Change gasification portion gas vent pass sequentially through gas solid separation unit, indirect condensing unit, gas purification unit, for separating H₂With CH₄Hydrogen separation unit be connected with methane collection device.

15. coal hydrogenation catalytic gasification device according to claim 14, which is characterized in that the powder of the gas solid separation unit Dirt outlet is connected with the dust inlet in the residual coke gasification portion, the gas vent and the indirect condensing of the gas solid separation unit The gas feed of unit is connected；The hydrogen outlet of the hydrogen separation unit is connected with the hydrogen inlet in hydrogenation catalyst gasification portion.

16. 1~13 described in any item coal hydrogenation catalytic gasification devices according to claim 1, which is characterized in that the residual burnt gas The solid discharge in change portion passes sequentially through deslagging unit and catalyst recovery unit is connected with the catalyst-supported units.