CN106544060A - Carbonaceous material response system, method - Google Patents
Carbonaceous material response system, method Download PDFInfo
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- CN106544060A CN106544060A CN201510609694.3A CN201510609694A CN106544060A CN 106544060 A CN106544060 A CN 106544060A CN 201510609694 A CN201510609694 A CN 201510609694A CN 106544060 A CN106544060 A CN 106544060A
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Abstract
The invention discloses a kind of carbonaceous material response system, method, the reaction method includes：In use, wet body carries out middle warm solution to solid carbon-contg material；The gas in solution preocess is warmed in collecting this；Solid product after centering warm solution carries out Pintsch process gasification；The high-temperature gas product for producing that Pintsch process is gasified is cooled to middle wet body, and middle warm solution is carried out to solid carbon-contg material using wet body in this.The response system realizes the reaction method.So, the middle warm solution of carbonaceous material and Pintsch process gasification can form a circulation, after wherein middle warm solution, the higher solid product of phosphorus content can be used as the raw material of Pintsch process gasification, and the high-temperature gas product that Pintsch process gasification is produced can warm the thermal source of solution after the cooling period as in, therefore while carbonaceous material is fully pyrolyzed, the heat energy of system is made full use of, the energy consumption of system is relatively low, again because emission is less, the feature of environmental protection is good.
Description
Technical field
The present invention relates to the reaction field of carbonaceous material, in particular it relates to a kind of carbonaceous material response system,
Method, the carbonaceous material response system, method are used in particular for hydrogen manufacturing.
Background technology
Carbonaceous material can be used for preparing various products gas, such as hydrogen, carbon monoxide and acetylene etc..
Wherein, there are hydrogen energy source many merits can apply in various fields, but hydrogen energy source is a kind of secondary
The energy, needs to produce by certain method.The principle of production hydrogen molecule is divided hydrogen using chemical reaction
Son is separated from hydrogeneous compound, and this chemical reaction process is needed from extraneous input energy.
Ideally, the energy according to required for law of conservation of energy produces hydrogen should be with the hydrogen produced
Gas the released energy that burns completely is equal.But substantial amounts of energy loss is but there is in actual production,
So hydrogen gas production generally requires to expend the substantial amounts of energy.The main method for industrially preparing hydrogen at present has
Six kinds, it is respectively：
(1) steam conversion production hydrogen is carried out using fossil fuel；
(2) electrolysis water production hydrogen；
(3) biomass gasification reaction production hydrogen；
(4) Optical Electro-Chemistry reaction production hydrogen；
(5) optical-biological reaction production hydrogen；
(6) thermal decomposition production hydrogen.
The production of hydrogen necessarily involves both sides factor, and one is hydrogen feedstock, and one is hydrogen manufacturing way
Footpath.The hydrogen feedstock of different countries has very big difference, and this just determines different situations
Different process for making hydrogen must be adopted.World's hydrogen source has 90% at present is produced by fossil fuel.
In China, most of electric power generates electricity by coal-burning power plant and produces, and water power, wind-power electricity generation scale compare
Little, electricity price is larger by coal, the fluctuation of gas real estate impact, although water electrolysis hydrogen producing has absolutely in raw material resources
To advantage, but a large amount of electric energy need to be expended, the production cost of hydrogen is too high, only be sent out using water power, solar energy
Electricity or from the electric energy that regenerative resource is obtained when, water electrolysis hydrogen producing be possible to economically have it is real
Competitiveness.Additionally, China's natural gas reserves are relatively low, occupancy volume per person is seriously low, natural gas-steaming
Vapour reforming hydrogen producing technology only natural gas it is more plentiful and be difficult export area, for example Sichuan-chongqing Region or
Person's natural gas is more feasible as this method is adopted during a kind of process by-product gas, such as petroleum refining industry dry gas,
China's specific national conditions are not met using the method hydrogen manufacturing on a large scale.At present, most methanol itself
It is to be synthesized by hydrogen and carbon monoxide, goes the way for manufacturing hydrogen very aobvious using the methanol synthesized by hydrogen
It is so economically not to one's profit, while also wasting ample resources.
Additionally, the preparation of other product gas is also similar, the consuming of the course of reaction of carbonaceous material to the energy
It is higher, therefore a kind of low stain, the reaction process of the cleaning carbonaceous material of low emission are provided with actively meaning
Justice.
The content of the invention
It is an object of the present invention to provide a kind of carbonaceous material response system, the system is realizing carbon containing thing
While the high-efficiency thermal decomposition of material, energy consumption is low, the feature of environmental protection is good.
It is a further object to provide a kind of carbonaceous material reaction method, the method is realizing carbon containing
While the high-efficiency thermal decomposition of material, energy consumption is low, the feature of environmental protection is good.
To achieve these goals, according to an aspect of the present invention, there is provided a kind of carbonaceous material reaction system
System, the response system include middle temperature pyrolysis reactor and Pintsch process gasification reactor, the middle warm solution
Reactor has the first feed(raw material)inlet, gas outlet, solid outlet and middle temperature gas access, the high temperature
Cracking gasification reaction utensil has the second feed(raw material)inlet, high-temperature gas product exit and slag-drip opening, wherein, institute
State solid outlet to connect with second feed(raw material)inlet, so that solid carbon-contg material is in the middle warm solution
Entered in the Pintsch process gasification reactor by the solid product after middle wet body heat solution in reactor, and
And the high-temperature gas product exit is connected by chiller with the middle temperature reaction gas inlet, so that
The high-temperature gas product for obtaining the plasma reactor generation enters described in being cooled to after wet body
In middle temperature pyrolysis reactor.
According to a further aspect in the invention, there is provided a kind of carbonaceous material reaction method, the reaction method include：
In use, wet body carries out middle warm solution to solid carbon-contg material；The gas in solution preocess is warmed in collecting this
Body；Solid product after centering warm solution carries out Pintsch process gasification；Pintsch process is gasified the height for producing
Warm gaseous product is cooled to middle wet body, and carries out middle warm to solid carbon-contg material using wet body in this
Solution.
By above-mentioned technical proposal, the middle warm solution of carbonaceous material and Pintsch process gasification can be formed
One circulation, wherein the higher solid product of phosphorus content can be used as Pintsch process gasification after middle warm solution
Raw material, and the high-temperature gas product that Pintsch process gasification is produced can warm what is solved after the cooling period as in
Thermal source, therefore the heat energy of system while carbonaceous material is fully pyrolyzed, is made full use of, the energy consumption of system
It is relatively low, but because emission is less, the feature of environmental protection is good.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute the part of description, with
Detailed description below is used for explaining the present invention together, but is not construed as limiting the invention.
In accompanying drawing：
Fig. 2 is the cross section structure diagram of the device for producing hydrogen that first embodiment of the invention is provided；
Fig. 3 is the cross section structure diagram of the device for producing hydrogen that second embodiment of the invention is provided.
Description of reference numerals
1 reactor body, 2 plasma generator
3 first passage, 4 second channel
5 third channel, 6 fourth lane
7 Five-channels
11 second feed(raw material)inlet, 12 plasma inlet
13 high-temperature gas product exit, 21 negative electrode
22 anode, 23 insulating base
61 first inlet channel, 62 first water outlet
63 cooling water cavity, 71 second inlet channel
72 second water outlet, 73 cooling water channel
14 quenching liquid spouts
82 middle temperature pyrolysis reactor of oil reactor is received in 81 dedustings
83 solid-liquid material mixer, 85 chiller
84 Pintsch process gasification reactor, 91 first feed(raw material)inlet
92 gas outlet, 93 solid outlet
94 middle 95 cooling water inlets of temperature gas access
96 steam entry, 97 liquid carbon-containing material inlet
98 product gas outlets
Specific embodiment
The specific embodiment of the present invention is described in detail below in conjunction with accompanying drawing.It should be appreciated that
Specific embodiment described herein is merely to illustrate and explains the present invention, is not limited to this
It is bright.
In the present invention, in the case where contrary explanation is not made, the noun of locality for using as " it is upper and lower, left,
The right side " specifically refers to the page of Fig. 2 and Fig. 3, and " remote, near " refers to corresponding component profile
It is inner and outer.
In addition, the temperature range of " the middle temperature " that be related in the present invention is 600 DEG C -900 DEG C, " high temperature "
Temperature range is then the temperature range more than 900 DEG C.For example, in the present embodiment, to carbonaceous material
The temperature for carrying out the middle wet body of middle warm solution is 600 DEG C -900 DEG C, gasifies through Pintsch process and generates
High-temperature gas product temperature be 1300 DEG C -1600 DEG C.Under the temperature conditionss, in present embodiment
The carbonaceous material response system of offer and method are conveniently used for hydrogen manufacturing, i.e., the hydrogen in final product gas
Content is higher.Additionally, under present inventive concept, the carbonaceous material that other embodiment of the present invention is provided is anti-
System and method are answered to can be also used for preparing the product gas such as acetylene, carbon monoxide.
Wherein, it is to realize the object of the invention, the carbon material reaction side that illustrative embodiment of the present invention is provided
Method includes：In use, wet body carries out middle warm solution to solid carbon-contg material；Solution preocess is warmed in collecting this
In gas；Solid product after centering warm solution carries out Pintsch process gasification；Pintsch process gasification is produced
Raw high-temperature gas product is cooled to middle wet body, and solid carbon-contg material is carried out using wet body in this
Middle warm solution.
So, the middle warm solution and Pintsch process gasification of carbonaceous material can form a circulation, its
In, carbonaceous material such as coal liquefaction residue can deviate from the small molecules such as hydrogen other and its in middle warm solution
His fugitive constituent, now can obtain the solid product of high carbon containing, so while the gases such as hydrogen are obtained
The solid product can be directly as the raw material of Pintsch process gasification, so as to realize the abundant heat of carbonaceous material
Solution.And meanwhile, the high-temperature gas product that Pintsch process gasification is produced again can after the cooling period as middle temperature
The thermal source of pyrolysis, and middle warm solution is carried out to the continuous carbonaceous material for entering, solution preocess is warmed by centering
In gas be collected so as to the gas produced after obtaining in carbonaceous material warm solution and Pintsch process gasification
Body product.Therefore by such circulating pyrolysis way, can while carbonaceous material is fully pyrolyzed,
The heat energy of system is made full use of, the energy consumption of system is relatively low, and because emission is less, the feature of environmental protection is good.
In order to realize this reaction method, as shown in figure 1, the response system that embodiment of the present invention is provided
Including middle temperature pyrolysis reactor 82 and Pintsch process gasification reactor 84, middle temperature pyrolysis reactor 82 has
The gas that the first feed(raw material)inlet 91 entered for solid carbon-contg material, the gas collected in warm solution in are discharged
Body warms the solid outlet 93 of the high carbonaceous solids product discharge of solution and the wet body in exporting 92, confession
Entrance enter middle temperature gas access 94, Pintsch process gasification reactor 84 have the second feed(raw material)inlet 11,
High-temperature gas product exit 13 and slag-drip opening 15, wherein, solid outlet 93 and the second feed(raw material)inlet 11
Connection so that solid carbon-contg material in middle temperature pyrolysis reactor 82 by middle wet body heat solution after consolidate
Body product is entered in Pintsch process gasification reactor 84, and high-temperature gas product exit 13 is anti-with middle temperature
Gas access 94 is answered to connect by chiller 85, so that the height that plasma reactor 84 is produced
Warm gaseous product is entered in middle temperature pyrolysis reactor 82 after wet body in being cooled to.Other solid product
Lime-ash after Pintsch process gasification is discharged by slag-drip opening 15.
Wherein in the present embodiment, it is possible to use high-temperature plasma carries out Pintsch process to solid product
Gasification.The working gas of high-temperature plasma can include argon, vapor, oxygen, carbon dioxide,
One or more in air, wherein high-temperature plasma are carrying out the same of high-efficiency thermal decomposition to solid product
When, the hydrogen that contains in its working gas, oxygen composition further can be reacted with carbonaceous material, from
And the valuable gaseous product such as hydrogen and carbon monoxide is additionally obtained.Especially vapor effectively can be carried
The yield of hydrogen and carbon monoxide is risen, involved reaction is H2O+C=CO+H2.Accordingly, this reality
Pintsch process gasification reactor 84 in the carbonaceous material response system that the mode of applying is provided is that plasma is anti-
Device is answered, the plasma reactor has plasma inlet 12 to be input into the plasma of high temperature, high speed
Body.
Pyrolytic gasification is carried out to solid carbon-contg material using the plasma jet of high temperature, high speed and is efficiently made
Take hydrogen.The technique has that the response time is short, materials conversion rate is high, without CO2 emission, water consume it is few,
Unique advantage such as clean and effective hydrogen manufacturing, in energy consumption and environmental protection is respectively provided with wide market prospect, is one
Plant the new technique of the ultra-clean that can realize solid carbon-contg material.It is in other possible embodiments, high
The gasification of anneal crack solution can also be realized using the non-flammability such as microwave, laser thermal source.
It is in order to according to the heat energy for fully utilizing system, in the present embodiment, high using cooling water cooling
Warm gaseous product, and by the vapor produced in cooling procedure add plasma reactor 84 etc.
In gas ions working gas.So, by dexterously utilizing what the cooling of high-temperature gas product was produced simultaneously
As plasma working gas, vapor can either ensure that the cooling of high-temperature gas product is enabled to again
The heat energy of the absorption using cooling water in cooling procedure come produce the water in plasma working gas steaming
Gas, makes full use of system heat energy, achieves many things at one stroke.Accordingly, as shown in figure 1, present embodiment is provided
Response system in chiller 85 be gasification refrigerating mechanism, the gasification refrigerating mechanism have for cooling
The steam outlet that the cooling water inlet 95 and the vapor for producing during cooling that water is entered is discharged
96, steam outlet 96 is connected with plasma reactor 84, with to plasma reactor 84
The vapor for adding gasification refrigerating mechanism to produce in plasma working gas.
As shown in figure 1, plasma reactor 84 includes reactor body 1 and to the reactor body 1
The plasma generator 2 of high-temperature plasma, steam outlet 96 and plasma generator are passed through inside
2 connections think 2 feed vapor of plasma generator as working gas.In order to increase reaction effect,
Preferably, plasma generator 2 is for multiple, steam outlet 96 for it is multiple and with multiple plasmas
Body generator 2 is corresponded.Wherein for the concrete structure of plasma reactor, it can be this area
Interior various common various forms.As a kind of attainable embodiment, after a while will be with reference to Fig. 2 and Tu
3 introduce two kinds of embodiments therein.
In the present embodiment, in order to obtain reaction temperature and atmosphere needed for hydrogen manufacturing, it is possible to use water steams
Gas and argon are with 100-10：1 is mixed into plasma working gas for ratio, and the working gas flow is
50-200L/min, and high temperature etc. is generated by running the plasma generator 2 that power is 20-500kW
Gas ions.
In order to increase the Pintsch process gasification result of solid product, in the present embodiment, it is preferable that
Before solid product carries out Pintsch process gasification, it is passed through liquid carbonaceous material and mixes with solid product.So,
Mixed slurry can be entered in Pintsch process gasification reactor, so as to increase with the feeding manner of liquid
Charging rate, to improve gas-solid mixing efficiency.In addition, this liquid feedstock does not use carrier gas, improved
Journey energy efficiency and business efficiency.This charging is more smooth in addition and can further lift carbon containing
Amount, in addition liquid carbon-containing material can adopt coal tar or water-coal-slurry, wherein the hydrogen for containing, oxygen composition can
So that Pintsch process gasified it is middle produce more hydrogen and carbon monoxide, especially in water-coal-slurry
Water constituent is more utilized the generation of hydrogen and carbon monoxide.Accordingly, the carbon containing for providing in present embodiment
In material reaction system, between solid product outlet 93 and the second feed(raw material)inlet 11, solid-liquid raw material is provided with
Blender 83, the solid-liquid material mixer 83 have the liquid carbonaceous material of liquid carbon-containing material input altogether
Entrance 97, carries out solid-liquid with the solid product to being come by solid product outlet 93 and is mixed and delivered to the
Two feed(raw material)inlets 11.The structure of wherein solid-liquid material mixer is known to those skilled in the art, here
Do not do and excessively repeat.
Wherein, in order to increase the reaction efficiency and effect of the mixed serosity of solid-liquid, it is preferable that such as Fig. 3
Shown, the second feed(raw material)inlet 11 is multiple and is circumferentially opened in Pintsch process gasification reactor at equal intervals
On 84 side wall, and the opening direction of second feed(raw material)inlet 11 and Pintsch process gasification reactor
84 cross section of inboard wall is tangent.In such manner, it is possible to so that the slurry entered from the second feed(raw material)inlet 11 is entering
Can flow downward in eddy flow shape along sidewall of reactor after entering Pintsch process gasification reactor, it is anti-so as to increase
Area is answered, reaction efficiency and effect is lifted.Specifically can the second feed(raw material)inlet can be 4.
In addition, solid product and liquid carbon-containing material can be with 1：The ratio of 0.2-5 is mixed into slurry to make
For the raw material of Pintsch process gasification.In addition to above-mentioned eddy flow shape pan feeding, can also should by solid-liquid blender
Slurry is sprayed in Pintsch process gasification reactor in spray form, and this is more suitable for the plasma reaction in Fig. 2
Device, specifically, the spray particle diameter is 30-100 microns, can equally lift then reaction efficiency and effect
Really.
In addition, in the present embodiment, the gas of the collection in middle warm solution preocess can be removed
Dirt receives the oil finished product gas higher to obtain final purity.Specifically, carbonaceous material response system also include with
Oil reactor 81 is received in the dedusting of the connection of product gas outlet 92, and the dedusting is received oil reactor 81 and has product
Gas outlet 98.The finished product gas such as hydrogen, carbon monoxide, acetylene is obtained by products export 98 so.Its
The structure that oil reactor is received in middle dedusting is known to those skilled in the art, and here is not done and excessively repeated.
In the specific work process of present embodiment, can be started with centering warm solution and Pintsch process gasification
Order be adjusted, specifically, in a kind of mode, it is middle warm solution and Pintsch process gasification follow
In ring, middle wet body can be prepared in advance, such as during be incorporated as product gas
Wet body come so that it is middle warm solution prior to Pintsch process gasification carry out, so as in starting warm solution and high temperature
The circulation of cracking gasification.
Used as replacement, another kind of job order is, in the circulation of middle warm solution and Pintsch process gasification,
Prepare carbonaceous material for Pintsch process gasification in advance, so that Pintsch process gasification is entered prior to low temperature pyrogenation
OK.It is highly preferred that in the present embodiment, due to the mixing with liquid carbon-containing material and solid product
Step, therefore, it can pass first into the raw material that liquid carbonaceous material is used as Pintsch process gasification, so as to
From Pintsch process gasification proceed by the present invention reaction cycle, so without the need for additionally preparation carbonaceous material with
And middle wet body so that the reaction method that the present invention is provided is more easy to realize and operates.
The hydrogen higher in order to preferably obtain purity, the reaction method that the present invention is provided also are included using behaviour
Make temperature for 1300-1800 DEG C, operating pressure is that the Pintsch process gasification reactor 84 of 1～4MPa is carried out
Pintsch process gasifies, and slurry is with 20-100 degree Celsius of temperature, the speed of 0.2-5m/s, into high anneal crack
In solution gasification reactor, the time of staying of the slurry in Pintsch process gasification reactor is the 0.1-5 seconds, and
And using operation temperature to be 600-900 DEG C, operating pressure carries out institute for the middle temperature pyrolysis reactor 82 of normal pressure
State middle warm solution, time of middle position pyrolysis is 5-30 minutes, now resulting described middle wet body
Temperature be 600 DEG C -900 DEG C, the temperature of the high-temperature gas product is 1300 DEG C -1600 DEG C.This temperature
Degree scope is more using the preparation of hydrogen.
To sum up, the reaction method and response system that present embodiment of the present invention is provided is to cause solid-state
Carbonaceous material carries out middle temperature pyrolytic reaction and deviates from the micro-molecular gas such as hydrogen and other fugitive constituents, and generates
High carbonaceous solids product；And produced by plasma generator by hot plasma working gas high
Temperature, the plasma jet of high speed；High carbonaceous solids product in Pintsch process gasification reactor with it is oxygen-containing
There is pyrolytic gasification reaction after high temperature thermal plasma mixing；Can also be come by adjusting plasma atmosphere
Control whole course of reaction to reach highest hydrogen yield；And the high-temperature gas product for generating is after the cooling period
Can enter in middle temperature pyrolysis reactor and middle warm solution is carried out to solid carbon-contg material；The water for producing in addition
Steam not only makes full use of heat energy as plasma working gas, and further extracts the product of hydrogen
Amount, finally can obtain hydrogen or the product gas needed for other by segregation apparatuss, such as molecular sieve.
Further, since rich coal resources, especially China, coal resources account for the 75% of energy resources with
On, 94% is accounted in the fossil energy structure of China, and most of coal category is preferably used as the cigarette of gasified raw material
Coal, therefore, critical role of the coal in primary energy structure is determined and is being gasified by raw material of coal
Hydrogen producing technology has huge resources advantage.Therefore, solid carbon-contg material used in the present invention is preferably
Coal and its related derivative product.Therefore, realize that cleaning hydrogen manufacturing will be developed as source with coal.
Wherein, mesh of the present invention be using can produce substantial amounts of carbonaceous residues in Coal Chemical Industry, such as coal liquefaction residue,
Tar residue, heavy oil, Colophonium etc., the phosphorus content of these carbonaceous residues are high, but are harmful to and are difficult to straight
Connect utilization.And in the present invention, the circulation pyrolysis of gentle high temperature by, especially with heat plasma
The special performance of body, can be by high temperature, the plasma jet of Gao Han, by carbonaceous residues extremely short
It is converted into the very high gas products of hydrogen content in time, and obtains hydrogen again after separation.It is not only high
What is imitated achieves the product gas such as hydrogen, additionally it is possible to twice laid, and economy is high.Embodiment party wherein of the present invention
The particle diameter distribution of the coal liquefaction residue used by formula is 30-100 microns, so as to further lift reaction effect
Rate.
The structure of two kinds of plasma reactors is introduced with reference to Fig. 2 and Fig. 3.
As shown in Figures 2 and 3, the present invention provides a kind of device for producing hydrogen, including reactor body 1, is
The hydrogen production process that the application present invention is provided, have on reactor body 1 second feed(raw material)inlet 11, etc. from
Daughter entrance 12 and high-temperature gas product exit 13 so that from plasma inlet 12 enter grade from
Daughter jet can occur pyrolytic gasification reaction with the solid product from the second feed(raw material)inlet 11, and make
Obtain obtained high temperature hydrogen-containing gas product to discharge by high-temperature gas product exit 13.
First as shown in Fig. 2 introducing the device for producing hydrogen of first embodiment of the invention offer.This first
In embodiment, the second feed(raw material)inlet 11 and high-temperature gas product exit 13 are separately positioned on reactor sheet
The axial two ends of body 1, slag-drip opening 15 above-mentioned in addition can be identical with the high-temperature gas product exit 13
And ash and high-temperature gas product are separated by gas-solid separating device, not shown in Fig. 2.Plasma enters
Mouth 12 is arranged on the side wall of reactor body 1.So, operationally, by the wall of side with many
The mode of kind arranges the quantity of plasma inlet 12, direction etc., it is possible to achieve solid material is realized many
Plant distributed pyrolysis so that the rate of gasification of solid product is higher.
In the present embodiment, plasma inlet 12 is for multiple, wherein, at least part of plasma
Entrance 12 is arranged along the axially spaced-apart of reactor body 1, and so solid product can be carried out vertically
Distributed pyrolysis, the rate of gasification of solid product is higher.Additionally, at least two plasma inlets 12
Axes intersect, i.e., from corresponding plasma inlet 12 spray plasma jet mutually can disturb
Mixing such that it is able to pyrolytic gasification, hydrogen manufacturing effect are preferably carried out to the carbonaceous material in reactor body 1
It is really good.Wherein at least two plasma inlet 12 can be the plasma positioned at axially different position
Body entrance 12, or the plasma inlet 12 positioned at different circumferential positions.
As a kind of preferred embodiment, as shown in Fig. 2 plasma inlet 12 is four, and should
The axis of four plasma inlets 12 is conllinear two-by-two and intersects in X-type.So, from four grades from
The plasma jet that daughter entrance is entered mutually can be disturbed, and more preferably effectively mix with solid product,
So as to lift the pyrolytic gasification effect of solid product.In other possible embodiments, plasma inlet
12 number can be with more, and its axis can also be parallel to each other or intersecting with other structures.
In order to simplify the structure of the device for producing hydrogen of present invention offer, the present invention provides device for producing hydrogen using reaction
The side wall of device body 1 completes the generation of plasma jet.Specifically, as shown in Fig. 2 plasma
Entrance 12 is formed by the inner port of the first passage 3 of the side wall through reactor body 1, device for producing hydrogen
Also include plasma generator 2, the plasma generator 2 uses work gas in first passage 3
Body generates plasma jet.
Wherein, plasma generator 2 includes negative electrode 21 and anode 22, with by between negative and positive the two poles of the earth
Electronics movement realize the formation of plasma jet, in the present embodiment, anode 22 is at least formed
On the inwall of first passage 3, during negative electrode 21 is inserted into first passage 3 and with the first passage 3
Sidewall spacers are arranged.In such manner, it is possible to by the use of around negative electrode 21 reactor body 1 side wall as sun
Pole and complete the generating process of plasma jet, overall structure is simpler ingenious.
Specifically, in order to the inwall of the reactor body 1 for ensureing negative electrode 21 and being formed as anode 22 connects
Touch, plasma generator 2 also includes the insulating base 23 for fixing the negative electrode 22, the insulating base 23 is inserted
In first passage 3, and it is formed between the insulating base 23 and the side wall of the first passage 3 and supplies work
Gas is flowed into the second channel 4 between negative electrode 21 and anode 22.So as to ensure that entering for working gas
Enter.
Wherein, in the present embodiment, the negative electrode 21 that the present invention is provided is club shaped structure, and its material can
Think the cathode materials such as tungsten, anode 22 can be the anode materials such as copper, rustless steel.Insulating base 23 can be with
From politef Polymer material.For specific material is selected, as long as not affecting plasma
Pyrolytic gasification of the jet to carbonaceous material.Wherein, the material of negative electrode and anode can be solid material
Can also be to be coated to coating in corresponding matrix, for such deformation all should fall in protection scope of the present invention
In.
In order to cool down to negative electrode 21 during op plasma generator, it is preferable that such as
Shown in Fig. 2, the third channel 5 flowed by Cooling Water in insulating base 23, is formed.The third channel 5
With water inlet and outlet, so as to realize the flowing of cooling water.Equally, in order to carry out to anode 22
Cooling, should be provided with cooling-water duct accordingly, and this will be discussed in more detail below.
For the ease of forming anode, the side wall of reactor body 1 is integrally formed into anode 22, i.e., except first
Outside the inwall of passage, anode 22 is also formed in other regions of reactor body 1.So can be direct
Reactor body 1 is made using anode material, so as to easily manufactured, reduces cost.So, the anode
22 can include the multiple axially disposed anode segment that separated by first passage 3.
First anode section 221 that in the present embodiment, multiple anode segments include being sequentially arranged vertically,
Second plate section 222 and third anode section 223, i.e., be provided with first passage 3 on two axial locations,
Wherein, in the first passage 3 of the axial both sides of second plate section 223, it is respectively arranged with positioned at same
The negative electrode 21 of circumferential position, should be positioned at two negative electrodes 21 of same circumferential position along respective first passage 3
Axially inclined extension and place straight line intersection relative to reactor body 1.That is, realize positioned at not coaxial
Reaction can entered to the plasma jet generated by two negative electrodes 21 and respective anode 22 of position
Mutually disturb after in device body 1.In other words, should be same positioned at two first passages 3 of axially different position
Sample is inclined and is extended, so that the axes intersect of corresponding plasma inlet 12.
Further, as a kind of preferred embodiment, negative electrode 21 is all positioned at two respectively for one group two-by-two
To four on position, and the straight line that four negative electrodes are located is conllinear two-by-two and intersecting in X-type.That is,
As shown in Fig. 2 apart 180 ° of two circumferential positions that four negative electrodes 21 are located at.So that passing through
Four strands of plasma jets that corresponding plasma inlet 12 is entered fully can mix with solid product and
Reaction, hydrogen production efficiency are high.
Additionally, for the ease of the connection with working gas source, as shown in Fig. 2 the entrance of second channel 4
Along radially extending for reactor body 1, export and extension is inclined along negative electrode 21.That is, 4 shape of second channel
Become inflection structure.Wherein the inflection structure can be arc transition, it is also possible to be illustrated in figure 2 turning
Transition, wherein the advantage using turning transition is to be easy to insulating base 23 and snap fit onto first passage in 3.
The external port of first passage 3 is used to install insulating base 23 in addition, and inner port is used to form plasma inlet
12, therefore the sectional area of first passage 3 has the trend for tapering into from outside to inside, less plasma
Body entrance 12 can further increase the speed of plasma jet.
In a preferred embodiment of the invention, four first passages 4 are formed with reactor body 1, often
One negative electrode 21, i.e. first passage 4 are installed for four independent ducts in individual first passage 4.Pass through
This four two one group is located at the upper duct of two axial locations and forms above three anode segment.
For the ease of the cooling of anode 22, can be according to the different cooling of the structure setting of each anode segment
Passage.As shown in Fig. 2 the fourth lane 6 of Cooling Water flowing in second plate section 222, is formed with,
As 222 both sides of second plate section are provided with negative electrode 21, therefore caloric value is larger.It is therefore preferred that
Fourth lane 6 includes radially extending the first inlet channel 61 and the first water outlet 62 along reactor body 1,
And the cooling water cavity 63 that 222 profile of second plate section is formed is adapted to, due to the second plate section 222
The opposite inclination of the first passage of both sides so that the profile new city of second plate section 222 is general conical knot
Structure, inner space are larger, thus the internal capacity of the cooling water cavity 63 also it is larger can accommodate it is more
Cooling water, so as to ensure the cooling of second plate section 222.First inlet channel 61 and the first water outlet 62
The outside of cooling water cavity 63 is located at respectively to realize the flowing of cooling water.
In addition, being formed with Cooling Water in the third anode section 223 of high-temperature gas product exit 13
The Five-channel 7 of flowing, the Five-channel 7 include second water inlet for radially extending of reactor body 1
Road 71 and the second water outlet 72, and it is along the inwall around reactor body 1 and axially extending cold
But water channel 73, i.e. cooling water channel 73 in addition to cooling anode 22 can be also used for cooling down reactor body 1
Inside near the region of high-temperature gas product exit 13, can so assist product to be lowered the temperature.
Further, since only having side to have negative electrode 21 in third anode section 223, caloric value is less, positive to the 3rd
Pole section 223 also has sufficient cooling effect.In addition, cooling water channel 73 and the second inlet channel 71 and
Two water outlets, 72 orthogonal inflection structure also can adapt to the profile of third anode section 223, wherein
Second inlet channel and the second water outlet 72 are located at the outside of cooling water channel 73 respectively to realize the stream of cooling water
It is dynamic.
In addition, in order to carry out auxiliary temperature-reducing to the Pintsch process gasifying gas produced by reaction, with above-mentioned gas
Change unlike chiller 15, herein, be also provided with reactor body 1 near high-temperature gas
The quenching liquid spout 14 of product exit 13.Specifically the quenching liquid spout 14 can be quenched with being lifted for multiple
Cold effect.
The plasma reactor of first embodiment of the invention offer is be provided, as shown in figure 3,
In this second embodiment, from unlike first embodiment, plasma inlet 12 and High Temperature Gas
Body product exit 13 is arranged on the axial two ends of reactor body 1, and the second feed(raw material)inlet 11 is arranged on instead
Answer on the side wall of device body 1 and arrange near plasma inlet 12.As such, it is possible to increase from side
The solid product that wall is entered and the time of contact of plasma jet, increase pyrolytic reaction effect.Wherein,
In this second embodiment, various quantity and arrangement can be carried out to the second feed(raw material)inlet 11 as needed
Design in mode, such as it is above-mentioned in the structure for causing serosity eddy flow shape pan feeding that refers to.And plasma
Body entrance 12 can be with external plasma generator, it is also possible in the plasma inlet 12 assembling etc. from
Daughter generator, for its mode of texturing all should fall in protection scope of the present invention.
The present invention is further described with reference to embodiment.
Heat has been carried out using the reactor in Fig. 2 as the Pintsch process gasification reactor 84 in the present invention
Corona treatment coal directly-liquefied residue and the experiment of coal tar oil hydrogen making, liquefied residue and coal tar oil nature are such as
Shown in table 1.
Table 1
The coal liquefaction residue that particle diameter is 50 microns is fed and is pyrolyzed instead
Should, operation temperature is 700 degrees Celsius, and operating pressure is normal pressure, and coal liquefaction residue is in Pintsch process gasification
The time of staying 20 minutes in reactor, obtain gaseous pyrolysis product and solid-state thermal decomposition product (its component),
Product gas are obtained after gaseous pyrolysis product removing dust, density of hydrogen is 57% during Jing determines product gas, an oxygen
It is 27% to change concentration of carbon, and gas concentration lwevel is 11%, and remaining is the gases such as methane, acetylene, ethylene.
The solid product that temperature is 500 degrees Celsius is all fed in solid-liquid blender, and the coal in table 1
Tar compares 1 according to weight:2 are mixed to form slurry, and slurry is sent into 150 degree of temperature and 3MPa pressure
In hot plasma hydrogen-manufacturing reactor.
Raw material sample rate is 100g/min；Experiment is using vapor and the mixed gas (vapor of argon
3 are classified as with argon ratio:1) as plasma working gas, working gas flow be 40L/min, wait from
Electronic generator operation power is 30kW.The operation temperature of plasma reactor is 1700 degree, operation pressure
Power is 3Mpa, and Jing after 1 second time, the temperature by reaction gained is 1600 degree of Pintsch process gasification gas
Feed in middle temperature pyrolysis reactor all being sent into after gasification reactor apparatus are cooled to 900 degrees Celsius to connect liquefaction
Residue heating carries out pyrolytic reaction, as described above, final produce the product gas rich in hydrogen.
Embodiment two：
Heat has been carried out using the reactor in Fig. 2 as the Pintsch process gasification reactor 84 in the present invention
Corona treatment coal directly-liquefied residue and the experiment of coal tar oil hydrogen making, liquefied residue and coal tar oil nature are such as
Shown in table 2.
Table 2
The coal liquefaction residue that particle diameter is 50 microns is fed and is pyrolyzed instead
Should, operation temperature is 700 degrees Celsius, and operating pressure is normal pressure, and coal liquefaction residue is in Pintsch process gasification
The time of staying 20 minutes in reaction, obtain the solid-state thermal decomposition product of gaseous pyrolysis product sum, gaseous pyrolysis
Product gas are obtained after product removing dust.
The solid product that temperature is 500 degrees Celsius is all fed in solid-liquid blender, and the coal in table 2
Tar compares 1 according to weight:2 are mixed to form slurry, and slurry is sent into 150 degree of temperature and 3MPa pressure
In plasma reactor.
Raw material sample rate is 100g/min；Experiment is using vapor and the mixed gas (vapor of argon
3 are classified as with argon ratio:1) as plasma working gas, working gas flow be 40L/min, wait from
Electronic generator operation power is 30kW；The average reaction temperature of hydrogen production reaction be 1600 degree Celsius, it is high
Anneal crack vent one's spleen activating QI after gasification reactor apparatus are cooled to 900 degrees Celsius enter middle temperature pyrolysis reactor in
Liquefied residue heating will be connect carries out pyrolytic reaction, final to produce the product gas rich in hydrogen.As a result show to produce
In product gas, density of hydrogen is 49%, and carbonomonoxide concentration is 33%, and gas concentration lwevel is 12%, remaining
For gases such as methane, acetylene ethylene.
Embodiment three：
Heat has been carried out using the reactor in Fig. 2 as the Pintsch process gasification reactor 84 in the present invention
Corona treatment coal directly-liquefied residue and coal are mixed and made into the hydrogen manufacturing experiment after water-coal-slurry, liquefied residue
It is as shown in table 3 with coal property.
Table 3
The coal liquefaction residue that particle diameter is 50 microns is fed and is pyrolyzed instead
Should, operation temperature is 700 degrees Celsius, and operating pressure is normal pressure, and coal liquefaction residue is in Pintsch process gasification
The time of staying 20 minutes in reaction, obtain the solid-state thermal decomposition product of gaseous pyrolysis product sum, gaseous pyrolysis
Product gas are obtained after product removing dust.
The Shenmu Coal in solid product and table 3 after 700 degrees Celsius are pyrolyzed is according to weight 1:1 mixing is simultaneously
Water-coal-slurry is made, grain size distribution accounts for 55% for 25～200 mesh particle diameters, and the following particle diameter of 200 mesh is 45%.
It is 63.4% to make water coal slurry concentration, and apparent viscosity is 860mPas.Raw material sample rate is 100g/min；
Slurry is sent in Pintsch process gasification reactor with 25 degree of temperature and 3MPa pressure.
Test using the mixed gas of oxygen and argon that (oxygen is classified as 4 with argon ratio:1) as plasma
Body running gas, working gas flow are 40L/min, and plasma generator operation power is 30kW.
The average reaction temperature of hydrogen production reaction be 1600 degree Celsius, Pintsch process gasify gas through gasification reaction
Device in middle temperature pyrolysis reactor will connect liquefied residue after being cooled to 900 degrees Celsius and will be pyrolyzed
Reaction, it is final to produce the product gas rich in hydrogen.As a result in showing product gas, density of hydrogen is 44%, one
Oxidation concentration of carbon is 34%, and gas concentration lwevel is 21%, and remaining is the gases such as methane, acetylene ethylene.
The preferred embodiment of the present invention is described in detail above in association with accompanying drawing, but, the present invention is not limited
Detail in above-mentioned embodiment, in the range of the technology design of the present invention, can be to the present invention
Technical scheme carry out various simple variants, these simple variants belong to protection scope of the present invention.
It is further to note that each particular technique described in above-mentioned specific embodiment is special
Levy, in the case of reconcilable, can be combined by any suitable means, in order to avoid need not
The repetition wanted, the present invention are no longer separately illustrated to various possible compound modes.
Additionally, combination in any between a variety of embodiments of the present invention, can also be carried out, as long as its
Without prejudice to the thought of the present invention, which should equally be considered as content disclosed in this invention.
Claims (21)
1. a kind of carbonaceous material response system, it is characterised in that the response system includes that middle warm solution is anti-
Device (82) and Pintsch process gasification reactor (84), the middle temperature pyrolysis reactor (82) is answered to have
First feed(raw material)inlet (91), gas outlet (92), solid outlet (93) and middle temperature gas access (94),
The Pintsch process gasification reactor (84) goes out with the second feed(raw material)inlet (11), high-temperature gas product
Mouth (13) and slag-drip opening (15),
Wherein, the solid outlet (93) is connected with second feed(raw material)inlet (11), so that solid
State carbonaceous material is entered by the solid product after middle wet body heat solution in the middle temperature pyrolysis reactor (82)
Enter in the Pintsch process gasification reactor (84),
And the high-temperature gas product exit (13) is passed through with the middle temperature reaction gas inlet (94)
Chiller (85) is connected, so that the high-temperature gas that the plasma reactor (84) is produced is produced
Thing is entered in the middle temperature pyrolysis reactor (82) after wet body in being cooled to.
2. carbonaceous material response system according to claim 1, it is characterised in that the high temperature
Cracking gasification reactor (84) is plasma reactor, and the plasma reactor has plasma
Entrance (12).
3. carbonaceous material response system according to claim 2, it is characterised in that the cooling
Device (85) is gasification refrigerating mechanism, and there is the gasification refrigerating mechanism cooling water inlet (95) and water to steam
Gas exports (96), and the steam outlet (96) is connected with the plasma reactor (84),
So that the gasification cooling dress is added in the plasma working gas of the plasma reactor (84)
Put the vapor of generation.
4. carbonaceous material response system according to claim 3, it is characterised in that the grade from
Daughter reactor (84) is passed through high temperature including reactor body (1) and into the reactor body (1)
The plasma generator (2) of plasma, the steam outlet (96) are sent out with the plasma
Raw device (2) connection.
5. carbonaceous material response system according to claim 4, it is characterised in that the grade from
Daughter generator (2) be it is multiple, the steam outlet (96) for it is multiple and with it is multiple it is described etc. from
Daughter generator (2) is corresponded.
6. the carbonaceous material response system described in 1 is required as requested, it is characterised in that the solid
Solid-liquid material mixer (83) is provided between product exit (93) and second feed(raw material)inlet (11),
The solid-liquid material mixer (83) with liquid carbonaceous material entrance (97), with to being produced by the solid
Solid product and the liquid carbonaceous material that thing exports (93) and comes carries out solid-liquid and mixes and by mixed slurry
Liquid is transported to second feed(raw material)inlet (11).
7. carbonaceous material response system according to claim 1, it is characterised in that the carbon containing
Material reaction system also includes that oil reactor (81) is received in the dedusting connected with the product gas outlet (92),
The dedusting receives oil reactor (81) with product gas outlet (98).
8. carbonaceous material response system according to claim 1, it is characterised in that the carbon containing thing
Material response system is used for hydrogen manufacturing.
9. carbonaceous material response system according to claim 6, it is characterised in that the solid-state
Carbonaceous material is coal liquefaction residue or petroleum coke, and the liquid carbonaceous material is coal tar or water-coal-slurry.
10. the carbonaceous material response system according to claim 1 or 6, it is characterised in that described
Two feed(raw material)inlets (11) are multiple and be circumferentially opened in the Pintsch process gasification reactor at equal intervals
(84) on side wall, and the opening direction of second feed(raw material)inlet (11) and the Pintsch process
The cross section of inboard wall of gasification reactor (84) is tangent.
11. a kind of carbonaceous material reaction methods, it is characterised in that the reaction method includes：
In use, wet body carries out middle warm solution to solid carbon-contg material；
The gas in solution preocess is warmed in collecting this；
Solid product after centering warm solution carries out Pintsch process gasification；
The high-temperature gas product for producing that Pintsch process is gasified is cooled to middle wet body, and using wet in this
Body carries out middle warm solution to solid carbon-contg material.
12. carbonaceous material reaction methods according to claim 11, it is characterised in that using high
Isothermal plasma carries out Pintsch process gasification to the solid product.
13. carbonaceous material reaction methods according to claim 12, it is characterised in that using cold
But high-temperature gas product described in water cooling, and the vapor produced in cooling procedure is added into plasma
In working gas.
14. carbon containing thing reaction methods according to claim 13, it is characterised in that steamed using water
Gas and argon are with 100-10：1 is mixed into the plasma working gas for ratio, the working gas stream
Measure and give birth to for 50-200L/min, and the plasma generator (2) by operation power for 20-500kW
Into high-temperature plasma.
15. carbonaceous material reaction methods according to claim 11, it is characterised in that described
Before solid product carries out Pintsch process gasification, be passed through liquid carbonaceous material and oar be mixed into solid product
Material.
16. carbonaceous material reaction methods according to claim 15, it is characterised in that described solid
Body product and the liquid carbon-containing material are with 1：The ratio of 0.2-5 is mixed into slurry using as Pintsch process gas
The raw material of change.
17. carbonaceous material reaction methods according to claim 11, it is characterised in that in middle temperature
In the circulation of pyrolysis and Pintsch process gasification, middle wet body is prepared in advance, so that the middle warm solution is first
Carry out in Pintsch process gasification.
18. carbonaceous material reaction methods according to claim 15, it is characterised in that in middle temperature
In the circulation of pyrolysis and Pintsch process gasification, liquid carbonaceous material is passed through in advance, so that the high anneal crack
Solution gasification is carried out prior to the low temperature pyrogenation.
19. carbonaceous material reaction methods according to claim 11, it is characterised in that in institute
The gas for stating the collection in warm solution preocess carries out dedusting receipts oil.
20. carbonaceous material reaction methods according to claim 15, it is characterised in that described solid
State carbonaceous material is coal liquefaction residue or petroleum coke, and the liquid carbonaceous material is coal tar or water-coal-slurry.
21. carbonaceous material reaction methods according to claim 16, it is characterised in that described anti-
Induction method is used for hydrogen manufacturing, the use of operation temperature is 1300-1800 DEG C, and operating pressure is the height of 1～4MPa
Anneal crack solution gasification reactor (84) carries out the Pintsch process gasification, and the slurry is Celsius with 20-100
The temperature of degree, the speed of 0.2-5m/s, in the Pintsch process gasification reactor, the slurry exists
The time of staying in the Pintsch process gasification reactor is the 0.1-5 seconds, and using operation temperature is
600-900, operating pressure carry out the middle warm solution for the middle temperature pyrolysis reactor (82) of normal pressure, should
The time of middle position pyrolysis is 5-30 minutes, wherein the temperature of the middle wet body is 600 DEG C -900 DEG C, institute
The temperature for stating high-temperature gas product is 1300 DEG C -1600 DEG C.
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Citations (1)
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| CN101906325A (en) * | 2010-07-20 | 2010-12-08 | 武汉凯迪控股投资有限公司 | Process and apparatus thereof for low-temperature cracking and high-temperature gasification of biomass |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101906325A (en) * | 2010-07-20 | 2010-12-08 | 武汉凯迪控股投资有限公司 | Process and apparatus thereof for low-temperature cracking and high-temperature gasification of biomass |
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| Title |
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| 彭长琪: "《固体废物处理与处置技术》", 30 April 2009, 武汉理工大学出版社 * |
| 黄志方: "《学无止境》", 30 November 2015, 东华大学出版社 * |
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