CN106590712A

CN106590712A - Coal hydrogenation catalytic gasification method and device

Info

Publication number: CN106590712A
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: 2017-04-26
Anticipated expiration: 2036-12-30
Also published as: CN106590712B

Abstract

The invention provides a coal hydrogenation catalytic gasification method and device and relates to the technical field of coal gasification, aiming at the problems in an existing coal catalytic gasification technology that the content of CH4 at a gas outlet of a gasification furnace is low and a process is complicated. The coal hydrogenation catalytic gasification method comprises the following steps: processing coal powder and a catalyst to generate coal powder loaded with the catalyst; under the action of the catalyst, carrying out a hydrogenation catalytic gasification reaction on the coal powder loaded with the catalyst and H2 to generate CH4 and remained coke containing the catalyst; taking CO2 and H2 to react, so as to generate CH4; under the action of the catalyst, taking the remained coke containing the catalyst and mixed gas of water steam and O2 to be subjected to a remained coke gasification reaction, so as to generate H2 and CO2; taking the coal powder loaded with the catalyst and generated H2 to be subjected to the hydrogenation catalytic gasification reaction to generate CH4 and the remained coke containing the catalyst; taking generated CO2 and H2 to react, so as to generate CH4; and repeatedly carrying out the hydrogenation catalytic gasification reaction and the remained coke gasification reaction until the remained coke containing the catalyst is converted into residues containing the catalyst, so as to obtain CH4. The coal hydrogenation catalytic gasification method provided by the invention is applied to the field of coal gasification.

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 method and device.

Background technology

At present, the characteristics of China's energy resources situation has " rich coal, few oil, deficency ", converts coal in fossil energy Top quality fuel-natural gas, i.e. coal gas technology, are to be adapted to China's national situation, neutralizing energy crisis, the victory for ensureing energy security Footpath.

Catalytic coal gasifaction technology is one of maximally 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 there is transformationreation, methanation reaction in the presence of base metal catalysts and ultimately generate CH₄.Base metal catalysts Addition allows the multiple reactions in catalytic coal gasifaction technology while the generation in the device, improves the energy thermal efficiency. But, the CH in the gasification furnace gas outlet of this kind of catalytic coal gasifaction technology₄Volume content low (only 20% or so), and, after It is continuous to need unreacted H in gas₂, CO and CH₄Separate, then by unreacted H₂, CO conveying gasification furnaces or methanation device Further resynthesis CH₄, the operation such as above-mentioned separation, resynthesis will certainly cause complex process.

The content of the invention

It is an object of the invention to provide a kind of coal hydrogenation catalysis gasification method and device, solve existing catalytic coal gasifaction skill Gasification furnace gas outlet CH in art₄Content is low, the problem of complex process.

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

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

S1：Coal dust and catalyst are carried out into the process of coal dust supported catalyst, the coal dust of supported catalyst is generated；

S2：The coal dust of supported catalyst enters hydrogenation catalyst gasification portion, in the presence of catalyst so that supported catalyst Coal dust and hydrogenation catalyst gasification portion in existing H₂Generation hydrogenation catalyst gasification reaction generates CH₄, containing catalyst it is residual burnt with And aromatic series oil compounds, existing CO in hydrogenation catalyst gasification portion₂With H₂Reaction generates CH₄；

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

S4：The H of generation₂、CO₂It is delivered to the hydrogen catalysis gasification portion that adds, the coal dust of supported catalyst and the H for generating₂Occur Hydrogenation catalyst gasification reaction generates CH₄, the residual burnt and aromatic series oil compounds containing catalyst, the CO of generation₂With H₂Occur anti- CH should be generated₄；

S5：Repeat step S3～S4, until residual Jiao containing catalyst is converted into the residue containing catalyst, obtains carrying H secretly₂、 CO₂, dust and aromatic series oil compounds CH₄。

Compared with prior art, the coal hydrogenation catalysis gasification method that the present invention is provided, first, coal dust and catalyst is 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 hydrogenation to urge Activating QI portion, in the presence of catalyst, the coal dust and H of supported catalyst₂Can directly convert under relatively low gasification temperature For CH₄, while generate the residual burnt and aromatic series oil compounds rich in catalyst, hydrogenation catalyst gasification portion generate rich in urging The residual burnt of agent enters residual coke gasification portion with water vapour and O₂Reaction generates H₂And CO₂, the H that residual coke gasification portion generates₂And CO₂And energy Hydrogenation catalyst gasification portion is enough recycled into, and further CH is generated with coal dust₄, the residual burnt and aromatic series oils rich in catalyst Compound, both hydrogenation catalyst gasification portion and residual coke gasification portion constitute a circulating system, so move in circles, when coal hydrogenation is catalyzed When reaction in gasification installation reaches or is close to the thermodynamical equilibrium limit, it becomes possible to produce substantial amounts of CH₄, improve CH₄Generation The CH of the gas outlet of speed, efficiency of carbon con version and hydrogenation catalyst gasification portion₄Content, efficiency of carbon con version up to more than 95%, urge by hydrogenation The CH of the gas outlet in activating QI portion₄Content is up to 80%, and reduces CO, CO₂Deng the generation of by-product, efficiently solve 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 Problem.Meanwhile, in coal dust and H₂Generation hydrogenation catalyst gasification reaction generates CH₄While, coal dust can also be with H₂Reaction is generated The benzene-toluene mixture (BTX) of high economic worth, phenol-cresol-diformazan phenol mixture (PCX), naphthalene are contour additional Value aromatic series oil compounds.

Second aspect, the invention provides a kind of coal hydrogenation catalytic gasification device, 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 the hydrogenation catalyst gasification portion being mutually connected and residual coke gasification portion；Wherein, the catalyst-supported units Coal powder entrance be connected with power transportation pipe, the discharge of the catalyst-supported units and the coal in 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 outlet in the hydrogenation catalyst gasification portion It is connected with methane collection device.

Compared with prior art, the coal hydrogenation catalytic gasification device that the present invention is provided, 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 Catalyst-supported units are delivered to by power transportation pipe and catalyst transport pipeline respectively with catalyst, are loaded in catalyst In unit, coal dust and catalyst carry out the process of coal dust supported catalyst, generate 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, both one circulating systems of composition, in the presence of catalyst, the coal dust and H of supported catalyst₂Can be relatively low Gasification temperature under be converted into CH₄, while generating the residual burnt and aromatic series oil compounds rich in catalyst, hydrogenation is urged Residual Jiao rich in catalyst that activating QI portion generates enters residual coke gasification portion with water vapour and O₂Reaction generates H₂And CO₂, residual burnt gas The H that change portion generates₂And CO₂Hydrogenation catalyst gasification portion can be recycled into again, further generate CH with coal dust₄, rich in catalyst Residual burnt and aromatic series oil compounds, so move in circles, when the reaction in coal hydrogenation catalytic gasification device reaches or is close to During the thermodynamical equilibrium limit, it becomes possible to produce substantial amounts of CH₄, improve CH₄Generating rate, efficiency of carbon con version and hydrogenation catalyst The CH of the gas outlet in gasification portion₄Content, efficiency of carbon con version up to more than 95%, the CH of the gas outlet in hydrogenation catalyst gasification portion₄Content Up to 80%, and reduce CO, CO₂Deng the generation of by-product, existing catalysis gasification technique gasification furnace outlet is efficiently solved Mouth CH₄Content is not high, need to separate CH again₄The low problem of change and 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 worth The high added value aromatic oil class compound such as mixture (BTX), phenol-cresol-diformazan phenol mixture (PCX), naphthalene.

Description of the drawings

Accompanying drawing described herein is used for providing a further understanding of the present invention, constitutes the part of the present invention, this Bright schematic description and description does not constitute inappropriate limitation of the present invention for explaining the present invention.In the accompanying drawings：

Fig. 1 is the structural representation 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 kind of structural representation 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.

Reference：

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

201- hydrogenation catalyst gasifications portion；The residual coke gasification portions of 202-；

3- deslagging units；4- catalyst recovery units；

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

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

Specific embodiment

Objects, features and advantages to enable technical scheme proposed by the invention become apparent from understandable, state.Obviously, A part of embodiment of only the proposed technical scheme of described embodiment, rather than the embodiment of whole.Based on this Embodiment in invention, it is all other that those of ordinary skill in the art are obtained on the premise of creative work is not made Embodiment, belongs to the scope of protection of the invention.

Fig. 1～2 are referred to, the invention provides a kind of coal hydrogenation catalytic gasification device, including 1 He of catalyst-supported units Hydrogenation catalyst gasification reaction unit 2, hydrogenation catalyst gasification reaction unit 2 include 201 He of hydrogenation catalyst gasification portion being mutually connected 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 O₂9 phase of admission line Even, the gas outlet 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 H₂Enter Row hydrogenation catalyst gasification reaction, residual coke gasification portion 202 are used for residual burnt and water vapour and O₂Carry out residual coke gasification reaction.

The course of work of the coal hydrogenation catalytic gasification device for providing to the present invention below in conjunction with the accompanying drawings is as follows：

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

S2：The coal dust of supported catalyst enters hydrogenation catalyst gasification portion 201, in the presence of catalyst so that load is urged The coal dust of agent and H existing in hydrogen catalysis gasification portion 202₂Generation hydrogenation catalyst gasification reaction generates CH₄, 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 catalyst action The C-C bond fissions of carbon granule in coal dust generate the C atoms with reactivity, meanwhile, exist in hydrogenation catalyst gasification portion 201 H₂, the presence of catalyst excites H₂There is dissociation and generate the H atom with reactivity, in the presence of catalyst, the tool of generation The H atom for having reactivity spills into the C atomic surfaces with reactivity and hydrogenation catalyst gasification reaction occurs and generates CH₄。

S3：It is residual burnt into residual coke gasification portion 202, water vapour and O rich in catalyst₂Mixed gas pass through admission line 9 are passed through residual coke gasification portion 202, in the presence of catalyst so that residual burnt and water vapour, O rich in catalyst₂Mixed gas Carry out residual coke gasification reaction and generate 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 for generating₂Occur Hydrogenation catalyst gasification reaction generates CH₄, the residual burnt and aromatic series oil compounds rich in catalyst, the CO of generation₂With H₂Occur Reaction generates CH₄。

S5：Repeat step S3～S4, until residual Jiao rich in catalyst is converted into residue rich in catalyst, and (residue contains 10%) carbon amounts ＜, obtains carrying H secretly₂、CO₂, dust and aromatic series oil compounds CH₄。

Compared with prior art, the coal hydrogenation catalytic gasification device that the present invention is provided, 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 Catalyst-supported units 1 are delivered to by power transportation pipe and catalyst transport pipeline respectively with catalyst, it is negative in catalyst In carrier unit 1, coal dust and catalyst carry out the process of coal dust supported catalyst, generate 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, both composition one circulating system, in the presence of catalyst, the coal dust of supported catalyst with H₂CH can be converted under relatively low gasification temperature₄, while generating the residual burnt and aromatic series oils rich in catalyst Compound, the residual burnt residual coke gasification portion 202 that enters rich in catalyst that hydrogenation catalyst gasification portion 201 generates is with water vapour and O₂Reaction Generate H₂And CO₂, the H that residual coke gasification portion 202 generates₂And CO₂Hydrogenation catalyst gasification portion 201 can be recycled into again, further with Coal dust generates CH₄, the residual burnt and aromatic series oil compounds rich in catalyst, so move in circles, when coal hydrogenation is catalyzed gas Makeup put in reaction when reaching or be close to thermodynamical equilibrium limit state, it becomes possible to produce substantial amounts of CH₄, improve CH₄Life Into the CH of the gas outlet of speed, efficiency of carbon con version and hydrogenation catalyst gasification portion 201₄Content, efficiency of carbon con version up to more than 95%, plus The CH of the gas outlet in hydrogen catalysis gasification portion 201₄Content is up to 80%, and reduces CO, CO₂Deng the generation of by-product, effectively Solve 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 H₂Generation hydrogenation catalyst gasification reaction generates CH₄While, coal dust can also be with H₂Instead Benzene-toluene mixture (BTX), phenol-cresol-diformazan phenol mixture (PCX), naphthalene of high economic worth etc. 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 relatively low, and generate CH₄、 Residual Jiao rich in catalysis collection is less, but, due to the hydrogenation catalyst gasification portion of the coal hydrogenation catalytic gasification device that the present invention is provided 201 and residual coke gasification portion 202 be a circulating system, when circulating system reaches dynamic equilibrium, it becomes possible to produce substantial amounts of H₂ And CO₂, so as to generate substantial amounts of CH₄。

Preferably, hydrogenation catalyst gasification portion 201 the position of gravity direction higher than residual coke gasification portion 202 in gravity direction Position；The CH generated in hydrogenation catalyst gasification portion 201 so above₄Discharge from the top in hydrogenation catalyst gasification portion 201, Residual Jiao rich in catalyst for generating falls under gravity into underlying residual coke gasification portion 202 with water vapour and O₂Instead H should be generated₂And CO₂, the high temperature H generated in residual coke gasification portion 202₂And CO₂Ascend into hydrogenation catalyst gasification portion above 201 further participate in reaction.It can be seen that, the movement or flowing of the above-mentioned residual burnt and various gas rich in catalyst are to utilize gravity Or the effect of air-flow, without the need for additional power device, realize following automatically for hydrogenation catalyst gasification portion 201 and residual coke gasification portion 202 Ring.

Specifically, the hydrogenation catalyst gasification portion 201 and residual coke gasification portion 202 in hydrogenation catalyst gasification reaction unit 2 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 is 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 clear and definite boundary；Hydrogenation catalyst gasification portion 201 and residual coke gasification portion 202 are filled for integral type Put, coal dust and H in hydrogenation catalyst gasification portion 201₂Residual Jiao rich in catalyst generated after carrying out hydrogenation catalyst gasification reaction exists Residual coke gasification portion 202 is fallen directly in the presence of gravity with water vapour and O₂Reaction generates H₂And CO₂, it is raw in residual coke gasification portion 202 Into high temperature H₂And CO₂Hydrogenation catalyst gasification portion 201, hydrogenation catalyst gasification portion 201 and residual coke gasification portion 202 are ascended into directly Between circulation need not move through pipeline so that reaction more fully, and can simplify the internal structure of device, 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 It is hydrogenation catalyst gasification furnace that residual coke gasification portion 202 is gasification furnace, i.e. hydrogenation catalyst gasification portion 201, and residual coke gasification portion 202 is residual Coke gasification stove.

It should be noted that hydrogenation catalyst gasification portion 201 can be fluid bed, residual coke gasification portion 202 can be fluid bed Or moving bed.Hydrogenation catalyst gasification portion 201 adopts fluid bed, residual coke gasification portion 202 to adopt the concrete 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, select stream The operation format of dynamic bed causes coal dust and H₂It is fully contacted, and the operating rate of thermopnore is with hydrogenation catalyst gasification reaction speed more Plus matching；And for residual coke gasification portion 202, the reaction occurred in residual coke gasification portion 202 is the residual burnt and water steaming rich in catalyst Vapour and O₂Between the residual coke gasification reaction that carries out, residual Jiao rich in catalyst is caused using the operation format of thermopnore or moving bed With water vapour and O₂Between be fully contacted, and the reaction rate that the operating rate of thermopnore or moving bed is reacted with residual coke gasification is more Plus matching.Fluid bed, residual coke gasification portion 202 is adopted to adopt thermopnore or moving bed, Neng Goujin by hydrogenation catalyst gasification portion 201 One step improves CH₄Generating rate, efficiency of carbon con version and hydrogenation catalyst gasification portion 201 gas outlet CH₄Content.

Normally, coal hydrogenation catalytic gasification device of the invention also includes post-processing unit, and post-processing unit is included 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 being embodied as, first, 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 Entrainment H₂、CO₂And the CH of aromatic series oil compounds₄。

Then, H will be carried secretly₂、CO₂And the CH of aromatic series oil compounds₄Lower the temperature into indirect condensing unit 6, reclaim heat Volume production producing water vapor, the water vapour is delivered in residual coke gasification portion 202, with O₂With the residual burnt gas of residual burnt generation rich in catalyst Change reaction and generate 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 CO₂CH₄Deacidification process is carried out through gas purification unit 7, the CO in gas is removed₂, Obtain carrying H secretly₂CH₄。

Finally, carry H secretly₂CH₄Through hydrogen separation unit 8, by H₂And CH₄Separated, obtained CH₄。

In above-mentioned post-processing unit, gas solid separation unit 5 can be multi-cyclone, using multi-cyclone As gas solid separation unit 5, can more effectively by CH₄、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, by reclaiming different heats, can produce the water vapour of different qualities；Hydrogen separation unit 8 can be preferably transformation suction Attached hydrogen separation device, hydrogen psa segregation apparatuss have that power consumption is low, separate thoroughly, technological process is simple, automatization's journey The features such as degree is high, environmental benefit is good, carries out H using hydrogen psa segregation apparatuss₂And CH₄Separation, can obtain purer CH₄, and automatization and the environmental protection of the coal hydrogenation catalytic gasification device for being more beneficial for realizing present invention offer.

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 outlet 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 Residual coke gasification portion 202 is delivered to water vapour and O₂Reaction generates H₂And CO₂, further improve CH₄Generating rate, carbon conversion The CH of the gas outlet 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 for isolating₂It is defeated Deliver to hydrogenation catalyst gasification portion 201 and hydrogenation catalyst gasification reaction generation CH occurs with coal dust₄。

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

When being embodied as, when the reaction in coal hydrogenation catalytic gasification device reaches capacity state, after coal dust deep pyrolytic The residue rich in catalyst of the C content ＜ 10% for obtaining will be delivered to dreg removing system 3 from residual coke gasification portion 202 and catalyst is returned Receiving unit 4 carries out catalyst recovery, and the catalyst transport of recovery is recycled to catalyst-supported units 1, improves catalyst Utilization rate.

Present invention also offers a kind of coal hydrogenation catalysis gasification method, the method comprises the steps：

S1：Particle diameter is carried out into coal dust in catalyst-supported units 1 for below 6mm, the coal dust of water content ＜ 5% and catalyst 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, in the presence of catalyst so that load is urged The coal dust of agent and H existing in hydrogen catalysis gasification portion 202₂Generation hydrogenation catalyst gasification reaction 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 is generated CH₄(as shown in Formula II)；

C+2H₂→CH₄——(I)

4H₂+CO₂→CH₄+2H₂O——(II)

S3：It is residual burnt into residual coke gasification portion 202, water vapour and O rich in catalyst₂Mixed gas pass through admission line 9 are passed through residual coke gasification portion 202, in the presence of catalyst so that residual burnt and water vapour, O rich in catalyst₂Mixed gas Carry out residual coke gasification reaction and generate 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, the coal hydrogenation catalysis gasification method that the present invention is provided, first, coal dust and catalyst is 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 hydrogenation to urge Activating QI portion 201, in the presence of catalyst, the coal dust and H of supported catalyst₂Can directly turn under relatively low 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 The residual burnt residual coke gasification portion 202 that enters rich in catalyst is with water vapour and O₂Reaction generates H₂And CO₂, residual coke gasification portion 202 generates H₂And CO₂Hydrogenation catalyst gasification portion 201 can be recycled into again, further generate CH with coal dust₄, residual Jiao rich in catalyst And aromatic series oil compounds, so move in circles, when the reaction in coal hydrogenation catalytic gasification device reaches or is close to heating power When learning reaching ability, it becomes possible to produce substantial amounts of CH₄, improve CH₄Generating rate, efficiency of carbon con version and hydrogenation catalyst gasification The CH of the gas outlet in portion 201₄Content, efficiency of carbon con version up to more than 95%, the CH of the gas outlet in hydrogenation catalyst gasification portion 201₄Contain Amount is up to 80%, and reduces CO, CO₂Deng the generation of by-product, efficiently solve existing catalysis gasification technique gasification furnace and go out QI KOU CH₄Content is not high, need to separate CH again₄The low problem of change and existing hydropyrolysis efficiency of carbon con version.Meanwhile, in coal dust and H₂Send out Raw hydrogenation catalyst gasification reaction generates CH₄While, coal dust can also be with H₂Reaction generates the benzene-toluene-diformazan of high economic worth The high added value aromatic oil class compound such as benzol mixture (BTX), phenol-cresol-diformazan phenol mixture (PCX), naphthalene.

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

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

For the selection of 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 proportion mixing of salt.

In the coal hydrogenation catalysis gasification method that the present invention is provided, catalyst is preferably composite catalyst, when catalyst is multiple When closing catalyst, in composite catalyst, major catalyst is preferably one or more arbitrary proportion mixing of Fe salt, Co salt, Ni salt, Promoter is preferably one or more arbitrary proportion mixing in the oxide of Ca salt, the oxide of Ca, Mg salt or Mg.

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

Further, in the coal dust of supported catalyst, in composite catalyst, the quality of major catalyst accounts for the 3% of quality of pc ～8%, the quality of promoter accounts for the 0.2%～2% of quality of pc；Preferably：In the coal dust of supported catalyst, composite catalyzing In agent, the quality of major catalyst accounts for the 4%～6% of quality of pc, and the quality of promoter accounts for the promoter of quality of pc 0.4%～0.8%.Wherein, due to active sites limited amount on the granule of coal dust, the addition of major catalyst is too high, active sites After saturation, unnecessary major catalyst can not play catalytic action, and being excessively added increases can Financial cost；But, if sponsored The addition of agent is too low, the active sites that cannot be catalyzed completely on the granule of coal dust, does not have expected catalytic effect, causes Hydrogenation catalyst gasification furnace gas outlet CH₄Content and efficiency of carbon con version are reduced；The adding too much of promoter then can same main catalytic Active sites on the granule of agent competition coal dust, cause active sites to be covered by promoter, and then reduce the same active sites of major catalyst Contact probability so that activity is reduced, and the addition of promoter is too low, then effectively cannot increase major catalyst dispersibility and Catalysis activity, also cannot effectively suppress the inactivation of major catalyst, therefore, when catalyst is preferably composite catalyst, sponsor The addition of agent and promoter is limited by catalytic performance and Technical Economy, in the coal dust of supported catalyst, compound to urge In agent, the quality of major catalyst is defined to account for quality of pc 3%～8%, and the quality of promoter is defined to account for quality of pc 0.2%～2%；Preferably：In the coal dust of supported catalyst, in composite catalyst, the quality of major catalyst accounts for quality of pc 4%～6%, the quality of promoter accounts for the promoter 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, hydrogenation are urged 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 Make the selection of pressure, according to thermodynamical equilibrium, the operating pressure of hydrogenation catalyst gasification reaction more has in the range of 0.5MPa-8MPa Beneficial to hydrogenation catalyst gasification reaction to generate CH₄Direction carry out, it is possible to increase hydrogenation catalyst gasification reaction speed, increase unit Treating capacity in time, higher than 8MPa, hydrogenation catalyst gasification reaction speed is too fast, meeting for the operating pressure of hydrogenation catalyst gasification reaction Cause reaction uncontrollable, increase operational hazards, and high pressure is high to equipment requirements, increase equipment investment, and hydrogenation catalyst gasified reverse The operating pressure answered is less than 0.5MPa, then be unfavorable for hydrogenation catalyst gasification reaction to generation CH₄Direction carry out, reaction rate mistake Slowly, unit interval treating capacity is reduced；For the selection of the reaction temperature of hydrogenation catalyst gasification reaction, catalyst is at 650 DEG C -900 C-C bond fissions can be more excited in coal in the range of DEG C and promotes H₂Dissociation, H atom spills into the C Surface with reactivity On react generation CH₄, the reaction temperature of hydrogenation catalyst gasification reaction can cause sintering of catalyst to inactivate higher than 900 DEG C, and Reaction temperature can then cause less than 650 DEG C that catalytic effect is good, reaction rate is slow.

Preferably, the operating pressure of residual coke gasification reaction is 0.5MPa-8MPa, and preferably 1MPa-7MPa, residual coke gasification are anti- The reaction temperature answered is 800 DEG C -1000 DEG C.It is for the selection of the operating pressure of residual coke gasification reaction, according to thermodynamical equilibrium, residual The operating pressure of coke gasification reaction is more beneficial for residual coke gasification in the range of 0.5MPa-8MPa and reacts to generation H₂、CO₂Direction Carry out, it is possible to increase 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, reaction can be caused uncontrollable, increased operational hazards, and high pressure is high to equipment requirements, increase equipment investment, and residual coke gasification The operating pressure of reaction is less than 0.5MPa, then be unfavorable for that residual coke gasification is reacted to generation CH₄Direction carry out, reaction rate mistake Slowly, unit interval treating capacity is reduced, 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 whole hydrogenation catalyst gasification reaction unit 2 keeps balance, is more beneficial for 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 Carry out, generate more H₂、CO₂For generating CH₄。

The present invention provide coal hydrogenation catalysis gasification method after step s 5, also including post-processing stages, post processing rank Section includes gas solid separation stage, indirect condensing stage, gas purification stage and Hydrogen Separation stage.

Specifically, the gas solid separation stage include：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, obtain dust and removing Entrainment H after dust₂、CO₂And the CH of aromatic series oil compounds₄。

The indirect condensing stage includes：H will be carried secretly₂、CO₂And the CH of aromatic series oil compounds₄Into indirect condensing unit 6 coolings, reclaim heat, obtain benzene-toluene mixture (BTX), phenol-cresol-diformazan phenol mixture according to boiling range (PCX), the high added value 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：H will be carried secretly₂And CO₂CH₄Deacidification process is carried out through gas purification unit 7, is removed CO in gas₂, obtain carrying H secretly₂CH₄。

The Hydrogen Separation stage includes：Entrainment H₂CH₄Through hydrogen separation unit 8, by H₂And CH₄Separated, 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 improve CH₄The gas of generating rate, efficiency of carbon con version and hydrogenation catalyst gasification portion 201 go out The CH of mouth₄Content.

Further, the H that the Hydrogen Separation stage obtains₂It is delivered to hydrogenation catalyst gasification portion 201 further to occur with coal dust Hydrogenation catalyst gasification reaction generates CH₄。

The coal hydrogenation catalysis gasification method that the present invention is provided after step s 5, also includes：Catalyst recovery stage.

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

It should be noted that：The mode of catalyst recovery stage be washing, pickling, alkali cleaning, ammonia leaching in one or more, Specifically can be selected according to practical situation.

Several optional embodiments of the coal hydrogenation catalysis gasification method of present invention offer are given below in conjunction with the accompanying drawings, and which is only Indicate that, and do not lie in restriction protection scope of the present invention.

Embodiment one

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

S1：Particle diameter is carried out in catalyst-supported units 1 for below 6mm, the anchracite duff of water content ＜ 5% and catalyst 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, in the presence of catalyst so that negative The anchracite duff of carried catalyst and H existing in hydrogen catalysis gasification portion 202₂Generation hydrogenation catalyst gasification reaction generates CH₄, it is rich Residual burnt and aromatic series oil compounds containing catalyst, existing CO in hydrogen catalysis gasification portion 202₂With H₂Reaction is generated 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：It is residual burnt into residual coke gasification portion 202, water vapour and O rich in catalyst₂Mixed gas pass through admission line 9 are passed through residual coke gasification portion 202, in the presence of catalyst so that residual burnt and water vapour, O rich in catalyst₂Mixed gas Carry out residual coke gasification reaction and generate 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 for generating₂ Generation hydrogenation catalyst gasification reaction generates CH₄, the residual burnt and aromatic series oil compounds rich in catalyst, the CO of generation₂With H₂ React generation CH₄；

S6：H will be carried secretly₂、CO₂, dust and aromatic series oil compounds CH₄Carried out successively 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 Deliver to hydrogenation catalyst gasification portion 201 and hydrogenation catalyst gasification reaction generation CH further occurs with anchracite duff₄；C content ＜ 10% The residue rich in catalyst washed through dreg removing system 3 and catalyst recovery unit 4, the catalyst transport of recovery is to urging Agent load unit 1 is recycled.

Can be obtained by test, the efficiency of carbon con version of the coal hydrogenation catalysis gasification method that the present embodiment is provided is more than 95%, plus The CH of the gas outlet in hydrogen catalysis gasification portion 201₄Volume content be 80%.

Embodiment two

S1：It is that below 6mm, the ub-bituminous coal powder of water content ＜ 5%, catalyst are carried out in catalyst-supported units 1 by particle diameter 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 the ub-bituminous coal powder of supported catalyst and H existing in hydrogen catalysis gasification portion 202₂Generation hydrogenation catalyst gasification reaction Generate CH₄, the 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 For 650 DEG C.

S3：It is residual burnt into residual coke gasification portion 202, water vapour and O rich in catalyst₂Mixed gas pass through admission line 9 are passed through residual coke gasification portion 202, in the presence of catalyst so that residual burnt and water vapour, O rich in catalyst₂Mixed gas Carry out residual coke gasification reaction and generate H₂、CO₂, wherein, the operating pressure of residual coke gasification reaction is 8MPa, and it is anti-that residual coke gasification reacts Temperature is answered to be 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 for generating₂ Generation hydrogenation catalyst gasification reaction generates CH₄, the residual burnt and aromatic series oil compounds rich in catalyst, the CO of generation₂With H₂ React generation CH₄；

S5：Repeat step S3～S4, until residual Jiao rich in catalyst is converted into rich in Co salt and the mixture of Ni salt Residue (phosphorus content ＜ 10% of residue), obtains carrying H secretly₂、CO₂, dust and aromatic series oil compounds CH₄。

S6：H will be carried secretly₂、CO₂, dust and aromatic series oil compounds CH₄Carried out successively 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 Deliver to hydrogenation catalyst gasification portion 201 and hydrogenation catalyst gasification reaction generation CH further occurs with ub-bituminous coal powder₄；C content ＜ 10% The residue rich in catalyst carry out pickling through dreg removing system 3 and catalyst recovery unit 4, the catalyst transport of recovery is to urging Agent load unit 1 is recycled.

Can be obtained by test, the efficiency of carbon con version of the coal hydrogenation catalysis gasification method that the present embodiment is provided is more than 96%, plus The CH of the gas outlet in hydrogen catalysis gasification portion 201₄Volume content be 82%.

Embodiment three

S1：It is that below 6mm, the coal dust intermixture of water content ＜ 5%, catalyst enter in catalyst-supported units 1 by particle diameter 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 matters Mixture of the amount percentage ratio higher than 30% bituminous coal powder, catalyst are composite catalyst, and the major catalyst of composite catalyst is Fe Salt, promoter are Mg salt, and the quality of Fe salt accounts for 0.2% that the quality of 3%, the Mg salt of the quality of coal dust accounts for the quality of coal dust.

S2：The coal dust intermixture of supported catalyst enters hydrogenation catalyst gasification portion 201, in the presence of catalyst so that The coal dust intermixture of supported catalyst and H existing in hydrogen catalysis gasification portion 202₂Generation hydrogenation catalyst gasification reaction is generated CH₄, the 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：It is residual burnt into residual coke gasification portion 202, water vapour and O rich in catalyst₂Mixed gas pass through admission line 9 are passed through residual coke gasification portion 202, under catalyst action so that residual burnt and water vapour, O rich in catalyst₂Mixed gas enter 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 H₂Generation hydrogenation catalyst gasification reaction generates CH₄, the residual burnt and aromatic series oil compounds rich in catalyst, the CO of generation₂With H₂React generation CH₄；

S6：H will be carried secretly₂、CO₂, dust and aromatic series oil compounds CH₄Carried out successively 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 Deliver to hydrogenation catalyst gasification portion 201 and hydrogenation catalyst gasification reaction generation CH further occurs with ub-bituminous coal powder₄；C content ＜ 10% The residue rich in Co salt and the mixture of Ni salt carry out alkali cleaning through dreg removing system 3 and catalyst recovery unit 4, recovery is urged Agent is delivered to catalyst-supported units 1 and recycles.

Can be obtained by test, the efficiency of carbon con version of the coal hydrogenation catalysis gasification method that the present embodiment is provided is more than 97%, plus The CH of the gas outlet in hydrogen catalysis gasification portion 201₄Volume content be 85%.

Example IV

S1：It is that below 6mm, the coal dust intermixture of water content ＜ 5%, catalyst enter in catalyst-supported units 1 by particle diameter 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 matters Mixture of the amount percentage ratio higher than 30% bituminous coal powder, catalyst are composite catalyst, and the major catalyst of composite catalyst is Co Salt, promoter are Ca salt and the hopcalite of 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, in the presence of catalyst so that The coal dust intermixture of supported catalyst and H existing in hydrogen catalysis gasification portion 202₂Generation hydrogenation catalyst gasification reaction is generated CH₄, the 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：It is residual burnt into residual coke gasification portion 202, water vapour and O rich in catalyst₂Mixed gas pass through admission line 9 are passed through residual coke gasification portion 202, under catalyst action so that residual burnt and water vapour, O rich in catalyst₂Mixed gas enter 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 CH₄Carried out successively 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 Deliver to hydrogenation catalyst gasification portion 201 and hydrogenation catalyst gasification reaction generation CH further occurs with ub-bituminous coal powder₄；C content ＜ 10% The residue rich in Co salt and the mixture of Ni salt carry out ammonia leaching through dreg removing system 3 and catalyst recovery unit 4, recovery is urged Agent is delivered to catalyst-supported units 1 and recycles.

Can be obtained by test, the efficiency of carbon con version of the coal hydrogenation catalysis gasification method that the present embodiment is provided is more than 97%, plus The CH of the gas outlet in hydrogen catalysis gasification portion 201₄Volume content be 88%.

Embodiment five

S1：It is that below 6mm, the coal dust intermixture of water content ＜ 5%, catalyst enter in catalyst-supported units 1 by particle diameter 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, is catalyzed Agent is composite catalyst, and the major catalyst of composite catalyst is Ni salt, and promoter is the hopcalite of Ca salt and Ca, The quality of Ni salt accounts for the quality that the quality of the hopcalite of 4%, the Ca salt and Ca of the quality of coal dust accounts for coal dust 0.4%.

Can be obtained by test, the efficiency of carbon con version of the coal hydrogenation catalysis gasification method that the present embodiment is provided is more than 97%, plus The CH of the gas outlet in hydrogen catalysis gasification portion 201₄Volume content be 90%.

Embodiment six

S1：It is that below 6mm, the coal dust intermixture of water content ＜ 5%, catalyst enter in catalyst-supported units 1 by particle diameter 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, is catalyzed Agent is composite catalyst, and the major catalyst of composite catalyst is Ni salt, and promoter is the hopcalite of Ca salt and Ca, The quality of Ni salt accounts for the quality that the quality of the hopcalite of 6%, the Ca salt and Ca of the quality of coal dust accounts for coal dust 0.8%.

Can be obtained by test, the efficiency of carbon con version of the coal hydrogenation catalysis gasification method that the present embodiment is provided is more than 97%, plus The CH of the gas outlet in hydrogen catalysis gasification portion 201₄Volume content be 94%.

The above, the only specific embodiment of the present invention, but protection scope of the present invention is not limited thereto, any Those familiar with the art the invention discloses technical scope in, change or replacement can be readily occurred in, should all be contained Cover within protection scope of the present invention.Therefore, protection scope of the present invention should be defined by the scope of the claims.

Claims

1. a kind of coal hydrogenation catalysis gasification method, it is characterised in that the method comprises the steps：

S2：The coal dust of supported catalyst enters hydrogenation catalyst gasification portion, in the presence of catalyst so that the coal of supported catalyst Powder and H existing in hydrogenation catalyst gasification portion₂Generation hydrogenation catalyst gasification reaction generates CH₄, the residual burnt and virtue containing catalyst Fragrant race's oil compounds, existing CO in hydrogenation catalyst gasification portion₂With H₂Reaction generates CH₄；

S3：It is residual burnt into residual coke gasification portion, water vapour and O containing catalyst₂Mixed gas be passed through the residual coke gasification portion, In the presence 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 the hydrogen catalysis gasification portion that adds, the coal dust of supported catalyst and the H for generating₂Generation is hydrogenated with Catalytic gasification reaction generates CH₄, the residual burnt and aromatic series oil compounds containing catalyst, the CO of generation₂With H₂React life Into CH₄；

S5：Repeat step S3～S4, until residual Jiao containing catalyst is converted into the residue containing catalyst, obtains carrying H secretly₂、CO₂, powder The CH of dirt and aromatic series oil compounds₄。

2. coal hydrogenation catalysis gasification method according to claim 1, it is characterised in that the coal dust is brown coal powder, bituminous coal One or more arbitrary proportion mixing in powder, ub-bituminous coal powder or anchracite duff.

3. coal hydrogenation catalysis gasification method according to claim 2, it is characterised in that in the S1, the grain of the coal dust Footpath is in below 6mm, water content ＜ 5% of coal dust.

4. coal hydrogenation catalysis gasification method according to claim 1, it is characterised in that the catalyst is single catalyst Or composite catalyst；Wherein,

The single catalyst is transition metal salt；

The composite catalyst includes major catalyst and promoter, and the major catalyst is transition metal salt.

5. coal hydrogenation catalysis gasification method according to claim 4, it is characterised in that when catalyst is single catalyst When, the single catalyst is one or more arbitrary proportion mixing of Fe salt, Co salt, Ni salt.

6. coal hydrogenation catalysis gasification method according to claim 4, it is characterised in that when catalyst is composite catalyst When, the major catalyst in the composite catalyst be Fe salt, Co salt, one or more of Ni salt, the composite catalyst In promoter be the one or more arbitrary proportion mixing in the oxide of Ca salt, the oxide of Ca, Mg salt or Mg.

7. coal hydrogenation catalysis gasification method according to claim 6, it is characterised in that the coal dust of the supported catalyst In, in composite catalyst, the quality of major catalyst accounts for the 3%～8% of quality of pc；The quality of promoter accounts for quality of pc 0.2%～2%.

8. coal hydrogenation catalysis gasification method according to claim 1, it is characterised 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℃。

9. coal hydrogenation catalysis gasification method according to claim 1, it is characterised in that after the S5, also including gas Gu separation phase, indirect condensing stage, gas purification stage and Hydrogen Separation stage, wherein,

The gas solid separation stage includes：H will be carried 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：H will be carried secretly₂、CO₂And the CH of aromatic series oil compounds₄Lowered the temperature, reclaimed 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：H will be carried secretly₂And CO₂CH₄Deacidification process is carried out, the CO in gas is removed₂, pressed from both sides Band H₂CH₄；

The Hydrogen Separation stage includes：H will be carried secretly₂CH₄Separated, obtained CH₄。

10. coal hydrogenation catalysis gasification method according to claim 9, it is characterised in that the gas solid separation stage also wraps Include：Dust is delivered to into the residual coke gasification portion with water vapour and O₂Reaction generates H₂And CO₂；

The Hydrogen Separation stage also includes：By H₂It is delivered to hydrogenation catalyst gasification portion and hydrogenation catalyst gasification reaction occurs with coal dust Generate CH₄。

11. coal hydrogenation catalysis gasification methods according to claim 1, it is characterised in that after the S5, including catalysis Agent recovery stage；

The catalyst recovery stage includes：Residue containing catalyst is carried out into catalyst recovery, the catalyst transport of recovery is extremely Catalyst-supported units are recycled.

12. a kind of coal hydrogenation catalytic gasification devices, it is characterised in that add for the coal as described in any one of claim 1～11 Hydrogen catalysis gasification process, the coal hydrogenation catalytic gasification device include：Catalyst-supported units and hydrogenation catalyst gasification reaction list Unit；The hydrogenation catalyst gasification reaction unit includes the hydrogenation catalyst gasification portion being mutually connected 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, the hydrogenation is urged The gas outlet in activating QI portion is connected with methane collection device.

13. coal hydrogenation catalytic gasification devices according to claim 12, it is characterised in that the hydrogenation catalyst gasification portion exists The position of gravity direction is higher than the residual coke gasification portion in the position of gravity direction.

14. coal hydrogenation catalytic gasification devices according to claim 12, it is characterised 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, the hydrogenation catalyst gasification portion and the residual coke gasification portion are gasification furnace.

The 15. coal hydrogenation catalytic gasification devices according to any one of claim 12～14, it is characterised in that the hydrogenation is urged The gas outlet in activating QI portion 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.

16. coal hydrogenation catalytic gasification devices according to claim 15, it is characterised in that the powder of the gas solid separation unit Dirt outlet is connected with the dust inlet in the residual coke gasification portion, gas outlet 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.

The 17. coal hydrogenation catalytic gasification devices according to any one of claim 12～14, it is characterised 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.