CN105838449A - System and method for catalytic purification treatment on coal chemical industry crude synthesis gas - Google Patents
System and method for catalytic purification treatment on coal chemical industry crude synthesis gas Download PDFInfo
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- CN105838449A CN105838449A CN201610345582.6A CN201610345582A CN105838449A CN 105838449 A CN105838449 A CN 105838449A CN 201610345582 A CN201610345582 A CN 201610345582A CN 105838449 A CN105838449 A CN 105838449A
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- fuse salt
- synthesis gas
- crude synthesis
- gas
- catalytic
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
- C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
- C10K3/023—Reducing the tar content
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/46—Gasification of granular or pulverulent flues in suspension
- C10J3/48—Apparatus; Plants
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/32—Purifying combustible gases containing carbon monoxide with selectively adsorptive solids, e.g. active carbon
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
- C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
- C10K3/026—Increasing the carbon monoxide content, e.g. reverse water-gas shift [RWGS]
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0913—Carbonaceous raw material
- C10J2300/093—Coal
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0953—Gasifying agents
- C10J2300/0973—Water
- C10J2300/0976—Water as steam
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0983—Additives
- C10J2300/0986—Catalysts
Abstract
The invention discloses a system and a method for catalytic purification treatment on a coal chemical industry crude synthesis gas. The system comprises a molten salt catalysis reaction device and a secondary purification device, wherein the molten salt catalysis reaction device is filled with molten salt; the secondary purification device is filled with an adsorbent. When the system is used, the crude synthesis gas is fed into the molten salt catalysis reaction device; fine coal powder, semi-coke granules, tar and phenolic substances in the crude synthesis gas sufficiently contact the molten salt under the viscous capturing action of the molten salt, and are subjected to catalytic cracking, gasification and reforming reaction under the action of gasses such as H2, CO, CO2 and H2O(g) in the crude synthesis gas, and then the crude synthesis gas can be purified; the crude synthesis gas purified in the molten salt catalysis reaction device is fed into the secondary purification device, and the molten salt carried by the crude synthesis gas can be desorbed through the absorbent in the secondary purification device.
Description
Technical field
The present invention relates to technical field of energy utilization, particularly relate to a kind of catalytic purification process Coal Chemical Industry and slightly synthesize
The system and method for gas.
Background technology
Coal accounts for the 77% and about 70% of China's primary energy production and consumption total amount.In view of coal is in China
In energy resource structure, status highlights, acts on great, and this energy resource structure based on coal is predictable
Substantial change will not occur in a very long time from now on.So safe coal just becomes national energy war
The safest most important thing in research.Accordingly, it would be desirable to again examine the developmental pattern of coal field closely, change
The height consumption of consumption of coal field, heavily contaminated, the current situation of big greenhouse gas emissions, make low carbonization, clear
Clean utilizes the various aspects really implemented in coal industry development, to ensure that coal is supplied steadily in the long term,
Escort for national energy security and socio-economic development.Coal is the important component part of China's energy,
Realize Coal Clean and efficiently utilize the basic demand being to ensure that Chinese energy safety, environment, control atmosphere pollution
With greater need for solving clean coal utilization problem.Coal Gasification Technology has the market space widely in China, at coal
Gas processed and then system synthesis ammonia synthesis chemical fertilizer, coal town gas, and the coal sky that Present Domestic is fast-developing
So all there is relatively broad application in gas field.
Fixed bed gasification is a kind of important composition form of coal gasifying process.During fixed bed gasification, instead
There is dry section, pyrolysis zone, gasification zone and combustion zone in answering device the most simultaneously, although this form pair
Some process advan, if more reservation methane component etc..But, pyrolysis the tar that produces, phenol
Class material etc. is carried over the most in a large number.In order to cool down, washing, purifying crude synthesis gas, employ substantial amounts of cooling water,
Thus create a large amount of containing the multiple difficult degradation such as tar, phenols, the coal chemical industrial waste water of poisonous and harmful substances.
Additionally, in single coal coking or pyrolytic process, also there is the cooling procedure to pyrolysis gas, at this
During, substantial amounts of poisonous, harmful waste water can be produced equally.Aldehydes matter in these waste water, can be directly
Poison animal and plant cells, after strong aeration, generate quinone, increase water quality toxicity, add the difficulty that flood processes；Benzene,
The polycyclic aromatic hydrocarbons such as pyridine have stronger carcinogenecity.Waste water handling problem during Coal Chemical Industry, it has also become limit
Coal Chemical Industry processed, the especially fixed bed gasification technology a great problem of application in numerous areas.
Process to this kind of waste water at present, mainly uses pretreatment, biochemical process (activated sludge process), changes
The modes such as method sterilization, absorption, membrance separation carry out integrated treatment, but this processing mode is relatively costly.
According to statistics, the environmental protection facility direct investment of current Coal Chemical Engineering Project accounts for the ratio conservative estimation of gross investment and arrives
5～15%, and all need to pay huge cost every year.
How could solve this problem inexpensively, efficiently, except to new process for treating waste water, new technique
Exploitation, from source, if it is possible to reduce the content of the materials such as the tar in crude synthesis gas, phenols, then
Subsequent treatment pressure can be substantially reduced.To this, some researcheres are thought, improve crude synthesis gas outlet temperature,
Tar in the corresponding crude synthesis gas produced, the content of aldehydes matter reduce, then waste water just can be more disposable.
The fixed bed slag gasification furnace of the patent application publication of Publication No. CN102041098A is i.e. managed based on this
Read, improve reaction in furnace temperature, reduce tar content while improving treating capacity, reduce the amount of aldehydes matter,
But methane content reduces simultaneously.
When crude synthesis gas is taken out of from gasification furnace of the patent application publication of Publication No. CN104593079A
Carrying out reheating makes it at high temperature occur to crack reforming reaction, although can effectively remove in crude synthesis gas
Tar and aldehydes matter, but high temperature will cause methane cracking, thus the unfavorable and energy consumption to process for producing natural
Higher.
Summary of the invention
In order to solve at least one aspect of the above-mentioned problems in the prior art and defect, the present invention provides
A kind of system and method for catalytic purification Coal Chemical Industry crude synthesis gas.
According to an aspect of the invention, it is provided a kind of catalytic purification processes the system of Coal Chemical Industry crude synthesis gas,
Described system includes:
Fuse salt catalyst reaction device, is provided with fuse salt in described fuse salt catalyst reaction device；
Double purification device, is set to adsorbent in described double purification device；
The most in use, described crude synthesis gas enters in described fuse salt catalyst reaction device, described thick conjunction
Become the coal fine powder in gas, semicoke granule, tar, aldehydes matter in the viscous capture effect of described fuse salt
It is fully contacted with described fuse salt down, and the gas H in described crude synthesis gas2、CO、CO2And H2O(g)
Effect under there is catalytic pyrolysis, gasification, reforming reaction so that described crude synthesis gas is cleaned；
Crude synthesis gas after described fuse salt catalyst reaction device purifies enters described double purification device, with
Remove in the crude synthesis gas after described purification entrained by described adsorbent in described double purification device
Described fuse salt.
In one example, the crude synthesis gas before the described fuse salt catalyst reaction device of entrance is from coalification
The most cooled crude synthesis gas that work gasifying process is expelled directly out, the initial temperature of described crude synthesis gas exists
Between 400-600 DEG C.
In one example, any one or it during described fuse salt includes the alkali-metal salt of lithium, sodium, potassium
Combination in any.
In one example, the fusing point of described fuse salt is below 700 DEG C；
Described fuse salt also includes that promoter, described promoter include Ni, Al2O3And Fe2O3In appoint
A kind of or their combination in any.
In one example, described fuse salt catalyst reaction device includes: rustless steel is made and outer surface sets
Be equipped with the cylindrical reactor housing of heat-barrier material, crude synthesis gas import, gas distribution grid, crude synthesis gas go out
Mouthful, described crude synthesis gas import is positioned at the side in the lower bottom end up or down portion of described cylindrical reactor housing
On, described gas distribution grid has taper or plate pattern and is positioned under cylindrical reactor housing
Portion, the outlet of described crude synthesis gas is positioned at the top of described cylindrical reactor housing,
It is provided with described fuse salt on gas distribution grid in wherein said cylindrical reactor housing and is filled in
Stacking type filler between described fuse salt,
Crude synthesis gas enters into described cylinder through the crude synthesis gas inlet device being connected to crude synthesis gas import
In reactor enclosure body, and flow into described by the crude synthesis gas outlet device being connected with the outlet of described crude synthesis gas
Double purification device,
The bottom of described double purification device is provided with the import of the crude synthesis gas inflow after purifying and at it
Top is provided with the outlet that the crude synthesis gas after double purification flows out, the thick synthesis after described double purification
Gas flows out described by the crude synthesis gas outlet device after being connected to the double purification of the outlet of double purification device
Double purification device, wherein said adsorbent includes active carbocoal.
In one example, described system also includes fuse salt regenerating unit and the air intlet dress being connected to each other
Put,
In use, the fuse salt in described fuse salt catalyst reaction device is extracted to the regeneration of described fuse salt
In device, in described fuse salt regenerating unit, it is passed through air by described air intlet device afterwards, passes through
Air carries out combustion reaction to carry out institute to the not sufficiently reactive semicoke fine particle of remaining in described fuse salt
Stating the regeneration of fuse salt, the fuse salt after regeneration is drawn in described fuse salt catalyst reaction device again.
In one example, described fuse salt regenerating unit include being made of stainless steel and outer surface be provided with every
The cylindrical reactor housing of hot material, it is positioned at the gas distribution grid of the lower end of cylindrical reactor housing
And the fuse salt of the pending regenerative response being positioned on described gas distribution grid, described fuse salt regenerating unit
It is connected with described fuse salt catalyst reaction device by fuse salt discharge nozzle and fuse salt feed pipe,
In use, by described fuse salt discharge nozzle by means of pump by described fuse salt catalyst reaction device
Fuse salt be drawn in described fuse salt regenerating unit, and by described fuse salt feed pipe by means of separately
Fuse salt after regeneration is extracted back in described fuse salt catalyst reaction device by one pump, and described combustion reaction is produced
Raw waste gas is arranged by being positioned at the exhaust outlet on the top of the cylindrical reactor housing of described fuse salt regenerating unit
Go out.
In one example, after described crude synthesis gas inlet device, crude synthesis gas outlet device, double purification
Crude synthesis gas outlet device and air intlet device at least one on be provided with check (non-return) valve, described thick conjunction
Gas inlet device and described air intlet device is become to include multiple inlet channel respectively.
According to another aspect of the present invention, it is provided that a kind of utilize above-mentioned system catalytic purified treatment coalification
The method of work crude synthesis gas, comprises the following steps:
(1) catalytic cracking of tar in crude synthesis gas: the crude synthesis gas flowed out from Coal Chemical Industry gasifying process is straight
Tap into into fuse salt catalyst reaction device, rely on the temperature of described crude synthesis gas self to make described fuse salt melt,
After described crude synthesis gas enters in fuse salt, the tar in described crude synthesis gas is catalyzed in described fuse salt
Crack and obtain carbon residue and substantial amounts of mainly include CH4、H2With the gaseous product of CO, described carbon residue remains
With the CO in crude synthesis gas in described fuse salt2And H2O(g)Continue reaction generation and mainly include H2And CO
Forming gas；
(2) semicoke in crude synthesis gas and the gasification of fines granule: semicoke in described crude synthesis gas and thin
First pulverized coal particle is melted the capture of salt viscous, simultaneously under the catalytic action of fuse salt, in crude synthesis gas
CO2And H2O(g)React with the semicoke in crude synthesis gas and fines granule generating gasification, generate CO and H2；
(3) reformation of the composition of the forming gas in crude synthesis gas: under the catalytic action of fuse salt, described
There is reforming reaction in the gas composition in crude synthesis gas；
(4) purification of the forming gas after reforming: remove institute in described crude synthesis gas by double purification device
The fuse salt carried.
In one example, described method also includes: will urge from fuse salt containing the fuse salt of semicoke or carbon residue
Change in reaction unit and be drawn in fuse salt regenerating unit, make in fuse salt the half of residual by being passed through air
Jiao or fine powder generation combustion reaction, improve the temperature of fuse salt afterwards and carry out the regeneration of fuse salt；
Wherein, described reforming reaction includes water gas shift reaction and the cracking reaction of macromole gas, described
Macromole gas includes ethane and/or propane.
Technical scheme provides the benefit that: it is thick that catalytic purification provided by the present invention processes Coal Chemical Industry
The system and method for the synthesis gas method by fuse salt catalyzed conversion crude synthesis gas, the catalysis at fuse salt is made
Under with, make the materials such as the tar in crude synthesis gas, phenols again crack thus realize its lighting, innoxious,
And the available gas such as portion of methane can be produced again.By the viscous capture effect of fuse salt, get rid of thick conjunction
Become the semicoke in gas and fines granule, produce simultaneously as crude synthesis gas carries pyrolysis and gasify not
The CO reacted completely2And H2O(g), therefore can realize fuse salt catalytic gasification crude synthesis gas without adscititious gases
Middle semicoke or the purpose of fine breeze granule.And, under the catalytic action of fuse salt, it is possible to realize synthesis
The orientation reintegration of the component of gas, is finally reached purification crude synthesis gas, and realizes improving methane therein
Purpose etc. effective Gas content.Thus from source, reduce that crude synthesis gas is coal-tar middle oil, the amount of aldehydes matter, enter
And reduce the pressure of subsequent treatment operation.
Accompanying drawing explanation
These and/or other aspect of the present invention and advantage are from description of preferred embodiments below in conjunction with the accompanying drawings
Will be apparent from easy to understand, wherein:
Fig. 1 be according to an embodiment of the invention for catalytic purification process Coal Chemical Industry crude synthesis gas be
The structural representation of system；
Fig. 2 be according to another embodiment of the invention for catalytic purification process Coal Chemical Industry crude synthesis gas
The structural representation of system.
Detailed description of the invention
Below by embodiment, and combine accompanying drawing, technical scheme is described in further detail.
In the description, same or analogous drawing reference numeral indicates same or analogous parts.Following the most right
The explanation of embodiment of the present invention is intended to explain the present general inventive concept of the present invention, and is not to be understood that
For a kind of restriction to the present invention.
The inventive concept of the present invention is: by using the catalytic treatment technology of fuse salt, going out with gasification furnace
Under conditions of the crude synthesis gas temperature that mouth is discharged is close, is passed through the reactions such as catalytic cracking, reduced therein
Tar, phenols etc. harmful substance, this load that will be substantially reduced follow-up further purification, cooling processes,
The most greatly reduce coal chemical industrial waste water amount.
Therefore, the present invention uses the saline admixture with good heat conductive, accumulation of heat and catalytic performance as melted
Salt, under the conditions of close with crude synthesis gas temperature, all passes through fuse salt by crude synthesis gas.At fuse salt
Under catalytic action so that it is in tar, the material such as phenols again crack thus realize its lighting, innoxious,
And part methane gas can be produced again.Produce simultaneously as crude synthesis gas carries pyrolysis and gasify not
The CO reacted completely2And H2O(g), therefore can realize fuse salt catalytic gasification crude synthesis gas without adscititious gases
Middle semicoke or the purpose of fine breeze granule.It is finally reached purification crude synthesis gas, and realizes improving methane therein
Purpose etc. effective Gas content.
An embodiment provides a kind of catalytic purification and process the system of Coal Chemical Industry crude synthesis gas.As
Shown in Fig. 1, described system includes fuse salt catalyst reaction device 10 and double purification device 20, described melted
It is provided with fuse salt 11 in salt catalyst reaction device 10, in described double purification device 20, is provided with adsorbent
21, such as active carbocoal.Certainly, this adsorbent 21 can also select other any applicable adsorbents.
In use, described crude synthesis gas enters in fuse salt catalyst reaction device 10, in described crude synthesis gas
Coal fine powder, semicoke granule, tar, aldehydes matter under the viscous capture effect of fuse salt 11 with described
Fuse salt 11 is fully contacted, and the gas H in crude synthesis gas2、CO、CO2And H2O(g)Effect under
There is catalytic pyrolysis, gasification, reforming reaction so that described crude synthesis gas is cleaned；
Crude synthesis gas after fuse salt catalyst reaction device 10 purifies enters double purification device 20, with logical
Entrained by crossing in the crude synthesis gas after the adsorbent 21 in described double purification device 20 removes described purification
Fuse salt 11.
Specifically, fuse salt catalyst reaction device 10 includes cylindrical reactor housing 13, crude synthesis gas import
14, gas distribution grid 15 and crude synthesis gas outlet 16.Described cylindrical reactor housing 13 by corrosion-resistant,
Resistant to elevated temperatures stainless steel material is made, to realize the purpose of resistance to highly basic high temperature corrosion.It is, of course, preferable to ground, for
Prevent heat to scatter and disappear, it is also possible to arrange on the outer surface of described cylindrical reactor housing 13 one layer heat insulation
Material (not shown).The setting of all parts in described cylindrical reactor housing 13 need not be such as Fig. 1 institute
Showing, shown by Fig. 1 is only an example of the present invention, and those skilled in the art can be arranged as required to
The position of each parts.
In FIG, crude synthesis gas import 14 is positioned in the lower bottom end of described cylindrical reactor housing 13.
It addition, as in figure 2 it is shown, crude synthesis gas import 14 can also be arranged at the bottom of cylindrical reactor 13
On side, and the air inlet pipe of the crude synthesis gas inlet device 1 being attached thereto is inserted by this crude synthesis gas import 14
Enter at the bottom centre position of cylindrical reactor housing 13.Described gas distribution grid 15 have taper or
Plate pattern and be positioned at the bottom of cylindrical reactor housing 13, described crude synthesis gas exports 16
Top in described cylindrical reactor housing 13.So, in use, gas distribution grid 15 is put
Put fuse salt 11, and scatter to will go into crude synthesis gas therein, also at cylindrical reactor shell
The space above gas distribution grid 15 in body 13 is provided with different types of stacking type filler 12, to fill out
Fill between fuse salt 11.Crude synthesis gas is through being connected to the crude synthesis gas import dress of crude synthesis gas import 14
Put 1 to enter in cylindrical reactor housing 13.Afterwards, described crude synthesis gas first passes around gas distribution grid
15 redistribute, and the gas after distribution fills with fuse salt 11 in fuse salt catalyst reaction device 10
Divide reaction.Meanwhile, by arranging dissimilar stacking type filler 12 in this fuse salt catalyst reaction device 10
Come fully dispersed for described crude synthesis gas.Coal fine powder in crude synthesis gas, semicoke granule, tar, phenol
Class material is fully contacted with fuse salt under the viscous capture effect of fuse salt, and at crude synthetic gas H2、CO、
CO2And H2O(g)Under the effect of types of gases, there is catalytic pyrolysis, gasification, reforming reaction, so that slightly closing
Gas is become to be fully purified.
The bottom of double purification device 20 be provided with for purify after crude synthesis gas flow into import 22 and
Its top is provided with the outlet 23 that the crude synthesis gas after double purification flows out, thick after described double purification
Synthesis gas is by being connected to the crude synthesis gas outlet device 3 after the double purification of the outlet 23 of double purification device
Flowing out described double purification device 20, wherein said adsorbent 21 includes active carbocoal.
Through fuse salt catalyst reaction device 10 purified gas through crude synthesis gas outlet device 2 in import
Double purification device 20 is entered at 22；After the micro melting salt then carried in being stripped of crude synthesis gas,
Through outlet 23 discharge.It is of course also possible to through being connected to the crude synthesis gas exported after the double purification of 23
Outlet device 3 is discharged.Due to be stripped of in fuse salt catalyst reaction device 10 crude synthesis gas coal-tar middle oil,
The materials such as phenols, semicoke and fines, thus only need to remove i.e. the micro melting salt carried in crude synthesis gas
Can, therefore in this double purification device 20, be the most only filled with active carbocoal 21 carry out dry removal
Alkali metal class material.
As it can be seen, this double purification device 20 is the most substantially arranged to cylinder.
In the present invention, any one or it during described fuse salt 11 includes the alkali-metal salt of lithium, sodium, potassium
Combination in any.The fusing point of described fuse salt is below 700 DEG C.Described fuse salt 11 also includes co-catalysis
Agent, described promoter includes Ni, Al2O3And Fe2O3In the combination in any of any one or they.One
In individual example, can be by regulating the ratio of dissimilar alkali metal salt, so that control this fuse salt
Fusing point is below 700 DEG C, and such as can be arranged to mass ratio is Li2CO3∶Na2CO3∶K2CO3=1: 1: 1
Mixture, as described fuse salt 11.As mentioned above, it is also possible to according to the follow-up demand to product so that
This fuse salt 11 also includes above-mentioned auxiliary agent, to adjust the composition of forming gas, such as, can realize orientation and reform
And in gas the purpose of many producing natural gas.
At this it should be noted that fuse salt catalysis treatment method of the present invention is one relate to gas,
Liquid, solid phase reaction method, (i.e. the fuse salt of the present invention is urged to be characterized in being provided with the higher molten bath of a temperature
Change the space in reaction unit).Reactant for crude synthesis gas is directly entered molten bath, all processes of reaction
All complete in molten bath.Fuse salt 11 can be single alkali metal salt, it is possible to for composite catalyst, such as carbonic acid
Lithium, sodium carbonate, potassium carbonate mixtures etc..The fusing point of fuse salt is relevant with selected salt character.
In another example of the present invention, described system is except including above-mentioned fuse salt catalyst reaction device 10 He
Outside double purification device 20, also include fuse salt regenerating unit 30.By described fuse salt catalyst reaction device
In fuse salt 11 extraction extremely described fuse salt regenerating unit 30 in 20, afterwards by air intlet device 4
In described fuse salt regenerating unit 30, be passed through air, by air in fuse salt 11 remaining the most abundant
The semicoke fine particle of reaction carries out combustion reaction to carry out the regeneration of fuse salt 11, melted after described regeneration
Salt 11 is drawn in described fuse salt catalyst reaction device 10 again.
Described fuse salt regenerating unit 30 includes being made of stainless steel and outer surface is provided with the circle of heat-barrier material
Cylindricality reactor shell 31, the gas distribution grid 32 being positioned at the lower end of cylindrical reactor housing and position
The fuse salt 11 of the pending regenerative response on gas distribution grid 32, by fuse salt discharge nozzle 5 by means of
Fuse salt 11 in described fuse salt catalyst reaction device 10 is drawn into described fuse salt regenerating unit by pump 6
In 30, and the fuse salt after regeneration is extracted back described by fuse salt feed pipe 7 by means of another pump 8
In fuse salt catalyst reaction device 10, waste gas produced by described combustion reaction is by being positioned at fuse salt regeneration dress
The exhaust outlet 35 on the top putting the cylindrical reactor housing 31 of 30 is discharged.
As illustrated in fig. 1 and 2, air intlet device 4 is by being arranged at the bottom of cylindrical reactor housing 31
Import 33 be inserted in fuse salt regenerating unit 30, and one end of fuse salt feed pipe 7 by arrange
Outlet 34 on the top of cylindrical reactor housing 31 is inserted in fuse salt regenerating unit 30, and its
The other end is inserted in fuse salt catalyst reaction device 10.The two ends of fuse salt discharge nozzle 5 are inserted respectively into molten
Melt in salt catalyst reaction device 10 and fuse salt regenerating unit 30.
Certainly, stacking type filler can also be set in fuse salt regenerating unit 30, to realize disperseing gas
The purpose opened.
If use for reaction temperature as it has been described above, the type fuse salt of the present invention adds the mode of heat fusing and enter
When entering the Temperature Matching of crude synthesis gas in fuse salt catalyst reaction device 10, by what crude synthesis gas carried
Heat melts described fuse salt；If reaction conversion ratio is not enough under this condition, then at fuse salt regeneration dress
Put in 30 and be passed through air capacity by control, control coal-char combustion speed again to heat fuse salt and by this heating
After fuse salt be drawn in fuse salt catalyst reaction device 10, with have target improve fuse salt temperature.
It should be noted that the reason arranging fuse salt regenerating unit 30 is: fill in fuse salt catalytic reaction
In putting 10, due to the viscous capture effect of fuse salt, tar, aldehydes matter and fines and semicoke granule can
To be captured the most completely；Owing to tar, aldehydes matter are gaseous component, thus can be more
Sufficiently there is catalytic cracking reaction, and for amount of activated relatively low semicoke or carbon residue, will remain in melted
In salt, owing in fuse salt catalyst reaction device 10, temperature is relatively low, this kind of substance reaction speed is relatively slow,
So that this part is swept along the fuse salt of semicoke or carbon residue carry out in being delivered to fuse salt regenerating unit 30 again
Raw.Renovation process, for being passed through air, makes the semicoke of residual in fuse salt or fine powder that combustion reaction fully to occur,
By the combustion heat supplying of this kind of material, improve the temperature of fuse salt bed, and then improve reaction rate further,
Thus semicoke in fuse salt or fine powder are fully burnt completely, it is achieved the regeneration of fuse salt.For using one section
The fuse salt of time, it is also possible to by fuse salt regenerating unit 30, sampling is analyzed test, analyzes it anti-
Answer activity change, can realize supplementing new fuse salt to complete online updating simultaneously.
In an also example of the present invention, in order to the suck-back and fuse salt preventing crude synthesis gas enters to enter accordingly
In air-out apparatus, can be at described crude synthesis gas inlet device 1, crude synthesis gas outlet device 2, double purification
After crude synthesis gas outlet device 3 and air intlet device 4 on be respectively arranged with check (non-return) valve (sign)；
Can certainly select to arrange on which device check (non-return) valve rather than whole said apparatus as required all
Check (non-return) valve is set.In order to make in crude synthesis gas the most scattered entrance molten salt reaction device 10, described thick conjunction
Gas inlet device 1 is become to include multiple inlet channel.Certainly, in order to make air the most scattered entrance fuse salt
In regenerating unit 30, described air intlet device 4 also includes multiple inlet channel.
In another embodiment of the invention, it is provided that a kind of utilize above-mentioned system catalytic purified treatment coalification
The method of work crude synthesis gas.Said method comprising the steps of:
(1) catalytic cracking of tar in crude synthesis gas: the crude synthesis gas flowed out from Coal Chemical Industry gasifying process is not
Being directly entered molten salt reaction device 10 through supercooling, the temperature relying on described crude synthesis gas self is (the thickest
The initial temperature of synthesis gas is in the range of 400-600 DEG C, and this initial temperature is usually above the fusing temperature of fuse salt
Degree) make described fuse salt 11 melt, after described crude synthesis gas enters in fuse salt 11, described thick synthesis
Tar in gas catalytic pyrolysis obtain carbon residue and substantial amounts of mainly include CH in described fuse salt 114、H2
With the gaseous product of CO, described carbon residue remain in described fuse salt 11 with the CO in crude synthesis gas2With
H2O(g)Continue reaction generation and mainly include H2Forming gas with CO；
(2) semicoke in crude synthesis gas and the gasification of fines granule: the semicoke in described crude synthesis gas and fines
First granule is melted the capture of salt viscous, meanwhile, the CO under the catalytic action of fuse salt, in crude synthesis gas2
And H2O(g)React with the semicoke in crude synthesis gas and fines granule generating gasification, generate CO and synthesis gas；
(3) reformation of the composition of the forming gas in crude synthesis gas: under the catalytic action of fuse salt 11,
There is reforming reaction in the forming gas composition in described crude synthesis gas；
(4) purification of the forming gas after reforming: remove institute in described crude synthesis gas by double purification device
The fuse salt carried.
In step (1), fuse salt can be realized by the temperature of crude synthesis gas self melted and for phase
The reaction closed provides the purpose of energy.
In step (2), the Ash residue in semicoke, in fuse salt, thus for fuse salt, is using
After a period of time, need to change online, thus ensure the high activity of catalyst.
For some type of coal, its semicoke or fines gasification reactivity are poor, now, at this fuse salt
In catalyst reaction device 10, will mainly utilize the viscous capture effect of fuse salt, by the semicoke in crude synthesis gas
Or fines captures.Owing to the type semicoke activity is poor, in finite time, it can not be abundant
Gasification reaction, thus consider in this fuse salt catalyst reaction device 10, carry the fuse salt carrying semicoke in time
Go out, and in fuse salt regenerating unit 30, be passed through air burning, fully to realize the conversion of semicoke.Instead
Fuse salt temperature after should is necessarily promoted, and can be directly entered fuse salt catalyst reaction device as required
Fuse salt catalyst reaction device 10 is entered in 10 or after again purifying.
In step (3), due to the catalytic action of fuse salt, the gas composition in crude synthesis gas may be sent out
Raw certain reintegration, such as CO and H2O(g)Transformationreation etc..Described reforming reaction includes Water gas shift/WGS
Reaction and the cracking reaction of macromole gas, described macromole gas includes ethane and/or propane.Additionally, it is right
In some specific technique, such as synthesis gas process for producing natural, by fuse salt adds Ni, Fe etc.
Type catalyst, can realize orientation and reform, the purpose of many producing natural gas in gas.
In step (4), the fuse salt entrained by crude synthesis gas entered in double purification device 20 is micro-
Amount, directly can be removed by the active carbocoal 21 in double purification device 20.
In another example of the present invention, described method also includes: by the fuse salt containing semicoke or carbon residue from
It is drawn in fuse salt catalyst reaction device in fuse salt regenerating unit, makes in fuse salt by being passed through air
The semicoke of residual or fine powder generation combustion reaction, improve the temperature of fuse salt and carry out the regeneration of fuse salt.
In the regeneration step of described fuse salt, in fuse salt catalyst reaction device, due to gluing of fuse salt
Stagnant capture effect, tar, aldehydes matter and fines and semicoke granule can be captured the most completely.
Owing to tar, aldehydes matter are gaseous component, thus catalytic cracking reaction can the most sufficiently occur.
And for amount of activated relatively low semicoke or carbon residue, will remain in fuse salt.Due to fuse salt catalytic reaction
In device, temperature is relatively low, and this kind of substance reaction speed is relatively slow so that this part is swept along semicoke or
The fuse salt of carbon residue regenerates in being delivered to fuse salt regenerating unit.Renovation process, for being passed through air, makes to melt
Fully there is combustion reaction in the semicoke or the fine powder that melt residual in salt, by the combustion heat supplying of this kind of material, improves
The temperature of fuse salt bed, and then improve reaction rate further, thus semicoke in fuse salt or fine powder are filled
Divided combustion is complete, thus realizes the regeneration of fuse salt.For using the fuse salt of a period of time, it is also possible to logical
Crossing regenerating unit, sampling is analyzed test, analyzes its ACTIVITY CHANGE OF FT, can realize supplementing newly simultaneously
Fuse salt to complete online updating.
Compared with prior art, catalytic purification provided by the present invention process Coal Chemical Industry crude synthesis gas system and
Method, decreases a large amount of washing, cooling water, and then decreases the treating capacity of coal chemical industrial waste water.Additionally,
By fuse salt, the catalytic purification of crude synthesis gas is processed, more obtain available gas, and can basis
Subsequent technique needs synthesis gas is oriented reformation.The technique suitability provided by the present invention is relatively strong, and knot
Structure is simple, compact, and use is amplified in the industrialization being suitable for dissimilar scale.
Although some embodiments of this present general inventive concept are shown and explanation, those of ordinary skill in the art
It will be appreciated that in the case of without departing substantially from the principle of this present general inventive concept and spirit, these embodiments can be done
Going out to change, the scope of the present invention limits with claim and their equivalent.
Claims (10)
1. catalytic purification processes a system for Coal Chemical Industry crude synthesis gas, and described system includes:
Fuse salt catalyst reaction device, is provided with fuse salt in described fuse salt catalyst reaction device；
Double purification device, is provided with adsorbent in described double purification device；
The most in use, described crude synthesis gas enters in described fuse salt catalyst reaction device, described thick conjunction
Become the coal fine powder in gas, semicoke granule, tar, aldehydes matter in the viscous capture effect of described fuse salt
It is fully contacted with described fuse salt down, and the gas H in described crude synthesis gas2、CO、CO2And H2O(g)
Effect under there is catalytic pyrolysis, gasification, reforming reaction so that described crude synthesis gas is cleaned；
Crude synthesis gas after described fuse salt catalyst reaction device purifies enters described double purification device, with
Remove in the crude synthesis gas after described purification entrained by described adsorbent in described double purification device
Described fuse salt.
The system of catalytic purification the most according to claim 1 process Coal Chemical Industry crude synthesis gas, wherein,
Crude synthesis gas before entering described fuse salt catalyst reaction device is to be expelled directly out from Coal Chemical Industry gasifying process
The most cooled crude synthesis gas, the initial temperature of described crude synthesis gas is between 400-600 DEG C.
Catalytic purification the most according to claim 1 processes the system of Coal Chemical Industry crude synthesis gas, wherein, institute
State fuse salt and include any one in the alkali-metal salt of lithium, sodium, potassium or their combination in any.
Catalytic purification the most according to claim 3 processes the system of Coal Chemical Industry crude synthesis gas, wherein, institute
State the fusing point of fuse salt below 700 DEG C；
Described fuse salt also includes that promoter, described promoter include Ni, Al2O3And Fe2O3In appoint
A kind of or their combination in any.
5. the system of Coal Chemical Industry crude synthesis gas is processed according to the catalytic purification according to any one of claim 1-4,
Wherein, described fuse salt catalyst reaction device includes: rustless steel is made and outer surface is provided with heat-barrier material
Cylindrical reactor housing, crude synthesis gas import, gas distribution grid, crude synthesis gas outlet, described thick conjunction
Gas import is become to be positioned on the side in lower bottom end up or down portion of described cylindrical reactor housing, described gas
Distribution grid has taper or plate pattern and is positioned at the bottom of cylindrical reactor housing, described thick conjunction
Gas outlet is become to be positioned at the top of described cylindrical reactor housing,
It is provided with described fuse salt on gas distribution grid in wherein said cylindrical reactor housing and is filled in
Stacking type filler between described fuse salt,
Crude synthesis gas enters into described cylinder through the crude synthesis gas inlet device being connected to crude synthesis gas import
In reactor enclosure body, and flow into described by the crude synthesis gas outlet device being connected with the outlet of described crude synthesis gas
Double purification device,
The bottom of described double purification device is provided with the import of the crude synthesis gas inflow after purifying and at it
Top is provided with the outlet that the crude synthesis gas after double purification flows out, the thick synthesis after described double purification
Gas flows out described by the crude synthesis gas outlet device after being connected to the double purification of the outlet of double purification device
Double purification device, wherein said adsorbent includes active carbocoal.
Catalytic purification the most according to claim 5 processes the system of Coal Chemical Industry crude synthesis gas, wherein, institute
System of stating also includes fuse salt regenerating unit and the air intlet device being connected to each other,
In use, the fuse salt in described fuse salt catalyst reaction device is extracted to the regeneration of described fuse salt
In device, in described fuse salt regenerating unit, it is passed through air by described air intlet device afterwards, and leads to
Cross air and the not sufficiently reactive semicoke fine particle of remaining in described fuse salt is carried out combustion reaction to carry out
The regeneration of described fuse salt, the fuse salt after regeneration is drawn in described fuse salt catalyst reaction device again.
Catalytic purification the most according to claim 6 processes the system of Coal Chemical Industry crude synthesis gas, wherein, institute
State fuse salt regenerating unit to include being made of stainless steel and outer surface is provided with the cylindrical reactor of heat-barrier material
Housing, be positioned at the lower end of cylindrical reactor housing gas distribution grid and be positioned at described gas distribution
The fuse salt of the pending regenerative response on plate, described fuse salt regenerating unit is by fuse salt discharge nozzle and melts
Melt salt feed pipe to be connected with described fuse salt catalyst reaction device,
In use, by described fuse salt discharge nozzle by means of pump by described fuse salt catalyst reaction device
Fuse salt be drawn in described fuse salt regenerating unit, and by described fuse salt feed pipe by means of separately
Fuse salt after regeneration is extracted back in described fuse salt catalyst reaction device by one pump, and described combustion reaction is produced
Raw waste gas is arranged by being positioned at the exhaust outlet on the top of the cylindrical reactor housing of described fuse salt regenerating unit
Go out.
Catalytic purification the most according to claim 7 processes the system of Coal Chemical Industry crude synthesis gas, wherein, institute
State the crude synthesis gas outlet device after crude synthesis gas inlet device, crude synthesis gas outlet device, double purification and
Check (non-return) valve, described crude synthesis gas inlet device and described sky it is provided with at least one in air intlet device
Gas inlet device includes multiple inlet channel respectively.
9. a utilization is thick according to the system catalytic purified treatment Coal Chemical Industry according to any one of claim 1-8
The method of synthesis gas, comprises the following steps:
(1) catalytic cracking of tar in crude synthesis gas: the crude synthesis gas flowed out from Coal Chemical Industry gasifying process is straight
Tap into into fuse salt catalyst reaction device, rely on the temperature of described crude synthesis gas self to make described fuse salt melt,
After described crude synthesis gas enters in fuse salt, the tar in described crude synthesis gas is catalyzed in described fuse salt
Crack and obtain carbon residue and substantial amounts of mainly include CH4、H2With the gaseous product of CO, described carbon residue remains
With the CO in crude synthesis gas in described fuse salt2And H2O(g)Continue reaction generation and mainly include H2And CO
Forming gas；
(2) semicoke in crude synthesis gas and the gasification of fines granule: semicoke in described crude synthesis gas and thin
First pulverized coal particle is melted the capture of salt viscous, simultaneously under the catalytic action of fuse salt, in crude synthesis gas
CO2And H2O(g)React with the semicoke in crude synthesis gas and fines granule generating gasification, generate CO and H2；
(3) reformation of the composition of the forming gas in crude synthesis gas: under the catalytic action of fuse salt, described
There is part reforming reaction in the gas composition in crude synthesis gas；
(4) purification of the forming gas after reforming: remove institute in described crude synthesis gas by double purification device
The fuse salt carried.
Method the most according to claim 9, wherein, described method also includes: will containing semicoke or
The fuse salt of carbon residue is drawn in fuse salt regenerating unit in fuse salt catalyst reaction device, by being passed through sky
Gas makes semicoke or the fine powder generation combustion reaction of residual in fuse salt, and the temperature improving fuse salt afterwards is gone forward side by side
The regeneration of row fuse salt；
Wherein, described reforming reaction includes water gas shift reaction and the cracking reaction of macromole gas, described
Macromole gas includes ethane and/or propane.
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