CN109762606A - A kind of method of the reduction of low order coal gasification hydrogen and carbon monoxide - Google Patents
A kind of method of the reduction of low order coal gasification hydrogen and carbon monoxide Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 230
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- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 54
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 35
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 30
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The present invention provides a kind of method of low order coal gasification reduction hydrogen and carbon monoxide, low-order coal drying dried after low-order coal and exhaust gas, obtain coal dust after waste gas dedusting；Low order coal gasification after drying is restored to obtain gas mixture and upgraded coal, gasification reducing process is the chemical reaction process for heating the low-order coal after drying under anaerobic or micro-oxygen conditions；Mixed gas and waste water are obtained after gas mixture is purified；Synthesis gas is prepared by mixed gas is reforming；Waste water, coal dust and slurries additive agent are first prepared into water-coal-slurry and prepare synthesis gas again, using upgrading producing synthesis gas from coal, the reduction of fractions to a common denominator is from respectively obtaining products C O and H after three kinds of synthesis gas are mixed2.The present invention prepares CO and H2The approach of gas is more, and gas production is high, and purity is high is low in cost, and the recycling for a variety of wastes such as realize waste water, coal dust, saves resource.
Description
Technical field
The present invention relates to coal substance clean utilization technical fields more particularly to a kind of low order coal gasification to restore hydrogen and one
The method of carbonoxide.
Background technique
Modern Coal-based Chemical technology turns to technology faucet, valable starting materials CO needed for obtaining chemical industry synthesis by gasification with coal gas
And H2Deng, but Coal Gasification Technology is developed so far, and not yet forms mature large-scale commercial low order Coal Gasification Technology.The prior art
Middle that low order coal gasification usually will be obtained crude coal gas after low order pyrolysis of coal, general pyrolysis is that having a large amount of oxygen (or empty
Gas) under conditions of carry out, part of coal will react in oxygen and be used for heat supply and produce a large amount of CO when pyrolysis2, due to
CO2It cannot burn, belong to invalid gas, and because of oxy combustion, nitrogen content is excessively high in crude coal gas, reduces crude coal gas
Energy density, cannot function as the level-one raw material of chemical industry synthesis, other than return combustion, pyrolysis output mixed gas do not have it is other
Economic value.And because part of coal and oxygen combustion supply to be thermally generated CO2, cause the amount of upgraded coal less, finally use upgrading
The amount of water-gas made from coal approach is fewer and fewer, greatly wastes the efficient resource in low-order coal.
Drying is that low-order coal is former as boiler oil, gasified raw material, direct liquefaction raw material, pyrolysis feed or other deep processings
The first step of material.Drying is both the needs for meeting downstream processing requirement, and reduces entire project energy consumption and downstream unit
The needs of investment.What is generated in drying process is directly discharged into atmosphere comprising exhaust gas such as a large amount of vapor and coal dust etc., can aggravate
Environmental pollution, therefore the coal dust of the generation effectively in recycling drying process and moisture have important practical significance.In low-order coal
Moisture be generally divided into Free water and combine water, and it is dry be typically only capable to remove most Free water in low-order coal, be very difficult to
Except the combination water in low-order coal, most of Free water that usual drying process drying is removed is easy the recycling that is condensed.But
The Efficient Conversion Land use systems of usual low-order coal is are pyrolyzed after drying, still containing a large amount of in the high-temperature gas after pyrolysis
The content of vapor, this part water also should not be underestimated.However, it is contemplated that water content is higher in low-order coal, and low order is produced in richness
The regional water of coal is often of great rarity；If can be effectively recycled in water resource and drying course valuable in ground low-order coal simultaneously
Coal dust, to solving, the recycling of existing low order moisture in coal is insufficient and pollution environment has great importance.
Summary of the invention
In view of this, in view of the deficiencies of the prior art, it is an object of the present invention to provide a kind of reduction of low order coal gasification to make
The method of hydrogen and carbon monoxide prepares hydrogen and the approach of carbon monoxide is more in the present invention, low in cost, and realizes useless
The recycling of a variety of wastes such as water, coal dust saves resource.
In order to solve the above technical problems, the present invention provides the following technical scheme that
A kind of method of the reduction of low order coal gasification hydrogen and carbon monoxide, method includes the following steps:
(1) low-order coal and exhaust gas after low-order coal drying process is dried, the exhaust gas pass through the first dedusting
Technique obtains coal dust；
(2) by the low-order coal after being dried described in step (1) by the reducing process that gasifies handle to obtain gas mixture with
Upgraded coal, the gasification reducing process is the chemical reaction heated under anaerobic or micro-oxygen conditions to the low-order coal after drying
Technique；
(3) step (2) gas mixture is obtained by the first purification process comprising CO, H2With the gaseous mixture of hydro carbons
Body and waste water；
(4) mixed gas described in step (3) is obtained through the reforming process of some hydrocarbon comprising CO and H2's
First synthesis gas；
(5) water coal is obtained after mixing coal dust described in waste water described in step (3), step (1) with slurries additive agent
Slurry, by the water-coal-slurry and O2It handles to obtain comprising CO, CO by coal-water slurry gasification2And H2The second water-gas, it is described
Second water-gas obtains the second synthesis gas after handling by the second purification process；
(6) by upgraded coal described in step (2) by with H2O and O2Reaction preparation includes CO, CO2And H2Third water coal
Gas obtains third synthesis gas after handling the third water-gas by third purification process；
(7) third in the second synthesis gas in first synthesis gas, step (5) and step (6) will be synthesized in step (4)
Synthesis gas is obtained after gas mixing, the synthesis gas handles through separating technology and respectively obtains H2And CO.
Preferably using the low-order coal of powdery as raw material in the present invention, convenient for improving the efficiency of drying, drying generally can only
Most Free water in low-order coal is removed, and cannot generally remove the combination water in low-order coal, therefore, low-order coal passes through drying
Low-order coal and exhaust gas after being dried after process, the low-order coal after gained drying still contain a certain amount of moisture, this
The moisture of some residual can gasify in subsequent gasification reducing process and become vapor.Have one simultaneously during drying
The low-order coal of part small grain size is entered in exhaust gas in the form of fugitive dust, this part fugitive dust is mainly coal dust, raw material low-order coal
Granularity is smaller, and the coal dust in exhaust gas is more, and exhaust gas direct emission not only polluted environment, wastes coal resource, therefore pass through
The first coal dust in exhaust gas after first dust collecting process capture recycling stoving process has important economic value.It is general by the
95% or more coal dust in one dust collecting process exhaust gas recycling.
Low-order coal after drying enters gasification reducing process and reacts to obtain the gas mixture of high temperature.Wherein, gasify
Reducing process is the chemical reaction process heated under anaerobic or micro-oxygen conditions to the low-order coal after drying.It is low after drying
Rank coal enters gasification reducing process, under the heating of the heat mediums such as flue gas, in reaction process without be added additive etc. other
Substance, temperature are generally 350 DEG C -800 DEG C, and the process of complex chemical reaction occurs under pressure≤30Kpa, obtain solid carbon and
The gas mixture of high temperature, wherein solid carbon is upgraded coal, the volatile matter 8-15wt% in upgraded coal.The oil gas of high temperature
Mixture is to include CO, H2, hydro carbons, coal tar, dust and sulfur-containing compound etc. more foreign gases.
The source of oxygen is mainly in the following several ways in the anaerobic or micro- oxygen environment that reducing process uses that gasify: (1), raw material
Gap inside low-order coal, the air of the gap entrainment between material and material；(2) from gasification reducing process feed inlet, go out
Material mouth etc. reveals mixed a small amount of air；(3), coal is accounted for hereinafter, can slightly be passed through in gasification reducing process in explosion limit value
The O of charcoal mass percent 5%2Or (air), further preferably it is passed through the O for accounting for Coal Quality percentage 3%2Or (air),
Be conducive to improve temperature, the slagging prevention etc. of gasification reduction reaction, and ensure that entire gasification reducing process reaction simultaneously
Security and stability；It is preferred that the low-order coal after drying carries out gasification reduction reaction in oxygen-free environment, the low-order coal after avoiding drying
Combustion reaction occurs with oxygen in entering gasification reducing process reaction process, generates a large amount of aphlogistic CO2, to guarantee
CO in the gas mixture of obtained high temperature2Deng volume basis it is smaller, be conducive to it is subsequent prepare high-energy density first close
At gas, and processing step is few, simple to operation, so that reaction can carry out safely.
The gas mixture that gasification reducing process obtains enters the first purification process to remove a large amount of dust, coal tar
The impurity such as oil, vapor, sulphur and sulfide be purified after gas mixture.Gas mixture can be rich during purification
Producing coal tar and waste water, waste water can be used as the water resource of preparation water-coal-slurry, and coal tar can be used as the stored energy source of high value.
Mixed gas mainly includes CO, H2And hydro carbons, it is well known that CO and H2It can be directly as the level-one original of chemical industry synthesis
Material, hydro carbons then need reforming to generate CO and H2, therefore utilize reforming technique by some hydrocarbon in mixed gas
It is reforming to obtain comprising CO and H2The first synthesis gas, CO and H in the first synthesis gas2A part is original from mixed gas
CO and H2, another part obtains comprising CO and H from some hydrocarbon is reforming2, substantially increase CO in the first synthesis gas
And H2Total percent by volume.
Water-coal-slurry is a kind of environmental clean fuel of New type coal base flow body, burning of coal characteristic has both been remained, but also with class
It is the real clean coal technology in one, current China like the liquid-phase combustion application characteristic of heavy oil.Water-coal-slurry by 65-70% coal,
The water of 29-34% and chemical addition agent less than 1%, are made by certain processing technology, appearance picture oil, good fluidity,
Convenient transportation, high combustion efficiency, pollutant (SO2、NOX) discharge it is low, about 2t water-coal-slurry can substitute 1t fuel oil, can be in industrial pot
The generation oil such as furnace, station boiler and Industrial Stoves or coal, gas use.Water-coal-slurry crosses coal-water slurry gasification preparation and includes H2With CO's
Water-gas increases subsequent H2Gas production is also increased simultaneously with the approach of CO.Also using in drying course in the present invention
The waste water that generates during coal dust and the first purification process prepares water-coal-slurry.Water-coal-slurry passes through vaporizing system again for the second water coal
Dust, CO are removed in gas, the purification of the second water-gas2, sulphur and sulfide etc. fall impurity, obtain the second synthesis gas.
The upgraded coal and H that will be obtained after gasification reduction2O (vapor) prepares third water-gas, reaction equation C+H2O
=CO+H2, the upgraded coal obtained after gasification reducing process reaction is the upgraded coal with temperature, because upgraded coal contains certain temperature,
Temperature is generally 350 DEG C -800 DEG C, so its own has higher latent heat, low energy consumption for upgrading coal gasification, the third of preparation
Impurity in water-gas is few.By third purification process by dust, CO in third water-gas2, the impurity such as sulphur and sulfide remove,
Obtain third synthesis gas.
Finally synthesis gas will be obtained after the logical mixing of above-mentioned three kinds of synthesis gas, synthesis gas is in entering separating technology.To mixing
Gas separate generally using pressure swing adsorption method or low temperature process (or Deep Cooling Method), membrane separation process.CO boiling point is -19O DEG C, H2
Condensing temperature at -253 DEG C, be generally difficult to separate the two using pressure swing adsorption method, but pressurization cooling liquefaction so that
The temperature of synthesis gas is reduced to the boiling point of CO hereinafter, CO liquefies and H2It is still gaseous state, therefore present invention preferably employs Deep Cooling Methods, obtain
The CO of high high-purity H and high-purity are taken, the purity of two kinds of gases is up to 99% or more.
Preferably, the stoving process uses water vapour indirect drying, and the pressure of the water vapour is 0.3-1.5Mpa, institute
The temperature for stating water vapour is 105-250 DEG C, and the outlet material water ratio of the stoving process is no more than 7wt%, the drying work
The outlet mass temperatures of skill are 50-150 DEG C.If containing a large amount of moisture in low-order coal, will lead to during gasifying reduction reaction
Heat consumption is big.The drying medium of stoving process can be flue gas or vapor, and drying can be divided into directly drying and indirect drying.When
Using flue gas as when drying medium, although the efficiency for the drying that flue gas and low-order coal directly contact is highest, use
Flue gas wants the percent by volume of oxygen in strict control stoving process environment in explosion limit hereinafter, quick-fried to prevent when being dried
Combustion, the efficiency of flue gas indirect drying is also unsatisfactory, therefore for production safety and drying efficiency, preferably vapor is dried.Water
Steam directly dry be easy to be likely to result in vapor reacted with low-order coal consumption resource, therefore using vapor indirect drying it is low
The drying mode of rank coal, to prevent the moisture in water steam from entering in low-order coal.In addition, if water vapour pressure in drying course
Excessive, vapor bring temperature is excessively high to be easy to cause during the drying process, and part volatile matter can escape in low-order coal, and one
The evolution of aspect volatile matter can bring security risk, on the other hand will affect the gas production of subsequent gasification reducing process, therefore dry
Drying steam pressure is not easy excessive during dry, to guarantee not only to can guarantee drying effect, but also can guarantee the volatilization in low-order coal
Divide and is not gasified.
Preferably, first purification process includes the second dust collecting process, oil gas cooling technique and sulfur removal technology.High temperature
Contain dust, coal tar, vapor, CO in gas mixture2、H2S and COS etc.；First with the second dust collecting process dedusting, prevent
Since the temperature of gas mixture reduces in dust removal process, causes coal tar and vapor etc. to be condensed into liquid and adhere to a large amount of
Dust causes subsequent technique line clogging, and dust removing effects is caused to decline.Recycle oil gas cooling technique remove a large amount of tar and
The problems such as whose cooling vapor has prevented be attached in process pipe and has blocked pipeline, carbon distribution.It is further preferred that after cooling
Oil water mixture passes through water-oil separating again can be obtained byproduct coal tar.Finally by oil gas cooling technique, that treated is remaining again
Gas enter sulfur removal technology, prevent the catalyst poisoning in subsequent technique, also reduce foreign gas content.
Preferably, separating technology described in step (7) is Deep Cooling Method.
Preferably, the reaction temperature of gasification reducing process described in step (2) is 350-800 DEG C.At this temperature, it dries
The volatile matter in low-order coal afterwards is escaped from low-order coal, to obtain the gas mixture of high temperature, is remained after the reduction reaction that gasifies
Remaining solid residue is the upgraded coal with temperature, and the volatile matter content in upgraded coal is 8-15wt%.Wherein, gasify reducing process
It can be level-one, or multistage.When using level-one gasification reducing process, primarily to obtaining the oil of most of high temperature
Gas mixture, the height of temperature directly affect the temperature of subsequent gas production, the yield of upgraded coal and level-one upgraded coal；When using more
When grade gasification reducing process, multistage gasification reducing process main function is can not gasify in upper level gasification reducing process
Solid matter (including the fine coal after gasification, solid impurity etc.), a certain amount of, can not gasify within certain residence time, class
The higher boilings grease such as sapropelitic continue gasification and the residence time it is short have little time be precipitated or temperature phenolic compound, virtue is not achieved
The polycondensation reaction condition of fragrant hydrocarbon compound etc., gasification that the reaction was continued are conducive to the quality for improving gas yield and upgraded coal.Into one
Step is preferred, and the temperature for the reduction reaction that gasifies is 400-750 DEG C.
Preferably, mixed gas described in step (4) through the reforming technique of some hydrocarbon be will be each in mixed gas
It is CO and H that component gas is directly reforming by some hydrocarbon without isolation2Hydrocarbon reformation conversion process.Turn because reforming
The purpose of change is intended merely to the hydrocarbon conversion generating CO and H2, and itself contained some CO and H in mixed gas2, therefore nothing
Hydro carbons need to be separated from mixed gas and carry out the reforming of hydro carbons again, technique step is saved using such operation
Suddenly, high financial profit.Preferably, the reforming technique include Partial Oxidation, it is vapor catalyzed reforming and non-urge
Change reforming middle one or more.Partial Oxidation vapor catalyzed reforming is required to catalyst, reforming technique
Catalyst be mostly loaded catalyst, active component is mainly that Ni, Co, Fe, Cu etc. be nonmetallic and the noble metals such as Rh, Ru, Pt.
It is reforming to generally require heat supply, it can be by the way of direct heating or indirect heating.CO and H in reforming gas2's
Source is two parts, and a part is the CO and H that some hydrocarbon is obtained by catalyzed conversion in mixed gas2, another part is
Original H in mixed gas2And CO.
Partial Oxidation under the effect of the catalyst, is mixed using oxygen and a part of hydrocarbon fuel direct heating
It closes some hydrocarbon in gas and reacts generation CO and H with vapor2；Using extraneous heat supply when vapor catalyzed reforming, urging
It reacts some hydrocarbon and vapor in gaseous mixture and generates CO and H2；The key reaction machine of two methods
Reason are as follows:
(1)CmHn+mH2O=mCO+1/2 (n+2m) H2Main reaction, the endothermic reaction
(2)CO+H2O=CO2+H2Side reaction, the endothermic reaction
On-catalytic reforming conversion, which is reformed, does not need catalyst, key reaction mechanism are as follows: CH4+1/2O2→CO+2H2, remove methane
Other outer hydro carbons and methane and O2Reaction mechanism it is similar.
Preferably, the granularity of coal dust described in step (1) is less than 1mm.Water-coal-slurry preparation first has to carry out coal substance thin
Mill, the coal dust in exhaust gas generated during stoving process due to raw material of the present invention, can through the first dust collecting process
In exhaust gas 95% or more coal dust is recycled, coal powder size is generally less than 3mm, and coal dust of the preferred size less than 1mm is as subsequent system
The raw material for making water-coal-slurry mixes coal dust with waste water, additive, and without milled processed, water-coal-slurry can be obtained, and saves technique step
Suddenly, and the cost of coal pulverizer is greatly reduced, improves the service life of coal pulverizer.Still further preferably, fine coal partial size≤
50 μm of coal dust.
Preferably, water-coal-slurry and O described in step (5)2Before being handled by coal-water slurry gasification, the water-coal-slurry is first led to
Filter sizing process processing again with O2It is obtained by coal-water slurry gasification comprising CO, CO2And H2The second synthesis gas.Consider slurry purpose
It is the coarse granule occurred during removing water-coal-slurry processed and the certain sundries for being mixed into slurry, to prevent water coal slurry in storage and transportation and burning
Blocking pipeline and nozzle etc. in the process.
Based on above technical scheme, the present invention restores the low-order coal after drying in gasification under anaerobic or micro-oxygen conditions,
Hydrocarbon reformation in obtaining the volatile matter in low-order coal and will volatilize point is converted to CO and H2, improve CO and H2Energy density, then
Prepare the CO and H of high-purity respectively using separating technology2, to greatest extent by the volatile matter in low-order coal with CO and H2Shape
Formula remains；Can also obtain high added value upgraded coal approach and waste water preparation water-coal-slurry approach vaporizing system it is standby comprising CO and
H2Water-gas, prepare CO and H2Approach it is more, and a variety of refuse reclamations such as realize waste water, coal dust meet country energetically
The coal high-efficiency clean utilization of promotion；Therefore, the CO and H of preparation are separated2Yield it is high, purity is high can be used as the change of high value
Work synthesis material substantially increases the utilization rate of low-order coal.
Detailed description of the invention
It, below will be in embodiment in order to illustrate more clearly of embodiment in the present invention or technical solution in the prior art
Required attached drawing is briefly described, it should be apparent that, the accompanying drawings in the following description is only one recorded in the present invention
A little embodiments are also possible to obtain other drawings based on these drawings for those of ordinary skill in the art.
Fig. 1 is the flow diagram for a kind of method that low order coal gasification restores hydrogen and carbon monoxide.
Specific embodiment
Next combined with specific embodiments below invention is further explained, but does not limit the invention to these tools
Body embodiment.One skilled in the art would recognize that present invention encompasses may include in Claims scope
All alternatives, improvement project and equivalent scheme.
In the present invention, if not refering in particular to, used raw material and equipment etc. are commercially available or commonly used in the art.
Method in following embodiments is unless otherwise instructed the conventional method of this field.
As shown in Figure 1, this includes the invention discloses a kind of method of low order coal gasification reduction hydrogen and carbon monoxide
Following processing step；
(1) low-order coal and exhaust gas after low-order coal drying process is dried, the exhaust gas pass through the first dedusting
Technique obtains coal dust；
(2) by the low-order coal after being dried described in step (1) by the reducing process that gasifies handle to obtain gas mixture with
Upgraded coal, the gasification reducing process is the chemical reaction heated under anaerobic or micro-oxygen conditions to the low-order coal after drying
Technique；
(3) step (2) gas mixture is obtained by the first purification process comprising CO, H2With the gaseous mixture of hydro carbons
Body and waste water；
(4) mixed gas described in step (3) is obtained through the reforming process of some hydrocarbon comprising CO and H2's
First synthesis gas；
(5) water coal is obtained after mixing coal dust described in waste water described in step (3), step (1) with slurries additive agent
Slurry, by the water-coal-slurry and O2It handles to obtain comprising CO, CO by coal-water slurry gasification2And H2The second water-gas, it is described
Second water-gas obtains the second synthesis gas after handling by the second purification process；
(6) by upgraded coal described in step (2) by with H2O and O2Reaction preparation includes CO, CO2And H2Third water coal
Gas obtains third synthesis gas after handling the third water-gas by third purification process；
(7) third in the second synthesis gas in first synthesis gas, step (5) and step (6) will be synthesized in step (4)
Synthesis gas is obtained after gas mixing, the synthesis gas handles through separating technology and respectively obtains H2And CO.
Volatile matter content is generally 20%-55% in low-order coal, and the content of tar is 3%-15% or so, and fixed carbon contains
Amount is 30%-60%, the content of water is 10%-40%, remaining as dust and other impurities.The degree of coalification of low-order coal is low, but
Contain petroleum resources abundant, the volatile matter being rich in low-order coal is highly beneficial to synthesis gas is extracted.
Raw material low-order coal of the invention can be fine coal and be also possible to lump coal, when low-order coal uses lump coal, to bulk excessively
Coal can be by broken, screening process to obtain the lesser fine coal of granularity.It is preferred that using fine coal as raw material, be on the one hand because of
Fine coal is no longer needed to through broken, screening process, saves processing step, and heating surface area is big when drying, and drying efficiency is high, is on the other hand
Fine coal is cheap with respect to lump coal.It is preferred that being less than the fine coal of 20mm using granularity, still further preferably using granularity less than 6mm's
Fine coal.
Drying can only generally remove most Free water in low-order coal, and cannot remove the combination water in low-order coal, because
This, low-order coal by stoving process handle after dry after low-order coal and exhaust gas, gained dry after low-order coal still contain
There is a certain amount of moisture, the moisture of this some residual can gasify in subsequent gasification reducing process becomes vapor.If low order
Contain a large amount of moisture in coal, heat consumption is big during will lead to gasification reduction reaction, and therefore, technical solution of the present invention is preferred
The portion of water first removed in low-order coal is handled by stoving process to low-order coal.The drying medium of stoving process can be
Flue gas or vapor, drying can be divided into directly drying and indirect drying.When using flue gas as medium is dried, although flue gas
The efficiency of the drying directly contacted with low-order coal is highest, but while being dried using flue gas wants strict control stoving process
For the percent by volume of oxygen in explosion limit hereinafter, to prevent detonation, the efficiency of flue gas indirect drying is also unsatisfactory in environment,
Therefore for production safety and drying efficiency, preferably vapor is dried.Vapor directly dries and is easy to be likely to result in vapor
It is mixed into and is provided with the consumption in low-order coal, not only causing reaction coal resource, reduce drying efficiency, therefore using between vapor
The drying mode of drying low-order coal is connect, to prevent the moisture in water steam from entering in low-order coal.In addition, if water in drying course
Steam pressure is excessive, and vapor bring temperature is excessively high to be easy to cause during the drying process, and part volatile matter can be escaped in low-order coal
Evolution comes, and the evolution of one side volatile matter can bring security risk, on the other hand will affect the production gas of subsequent gasification reducing process
Amount, therefore dry steam pressure in drying course and be not easy excessive, to guarantee not only to can guarantee drying effect, but also it can guarantee low-order coal
In volatile matter do not gasified.It is preferred, therefore, that stoving process uses water vapour indirect drying, the pressure of water vapour is 0.3-
1.5Mpa, the temperature of water vapour are 105-250 DEG C, not only prevent the O in extraneous air2It is mixed into consumption coal substance, and
The moisture content in low-order coal can be maximumlly reduced under this process condition, it might even be possible to so that from the discharge port of stoving process
Water content in the low-order coal of discharge is reduced to 7wt% hereinafter, most moisture is along with fugitive dusts such as coal dusts from low order at this time
In the exhaust gas for escaping in coal, and generating as water vapor into after drying, the outlet mass temperatures of stoving process are 50-
150℃；Still further preferably, when the pressure of vapor is 0.6-1.2Mpa, and the temperature of vapor is 120-200 DEG C, drying
The moisture content of low-order coal will decrease to 6wt% hereinafter, the outlet mass temperatures of stoving process are 80 DEG C -130 DEG C afterwards.
Stoving process of the invention can be level-one, or it is multistage, because if low-order coal after level-one stoving process
Moisture content still reach to the requirement less than technique, can be continued using multistage dry such as second level drying, three-level stoving process into one
Drying is walked, until the moisture content of low-order coal meets process conditions after drying.In addition, multistage stoving process can be arranged in series
It can also be arranged in parallel, drying effect can be reinforced when connecting using multistage stoving process, stoving process can be increased when in parallel
Treating capacity therefore according to the demand of actual production technique be series connection to multistage stoving process or in parallel in parallel or in series
Design simultaneously, can be adjusted according to the actual situation, as long as identical technical effect can be reached, specifically, for example,
When the inlet amount of stoving process is in terms of the low-order coal of 20-30t/h, level-one steam drying technique can be used；When stoving process into
Second steam stoving process can be used in terms of the low order of 50-70t/h in doses, more economical reasonable in this way.
Exhaust gas in drying course mainly includes the low-order coal of small grain size and the vapor that drying is removed, raw material low-order coal
Granularity is smaller, and the coal dust in exhaust gas is more, and exhaust gas direct emission not only polluted environment, wastes coal resource, therefore pass through
The coal dust in exhaust gas after first dust collecting process recycling stoving process has important economic value.It can be returned through the first dust collecting process
In exhaust gas 95% or more coal dust, referred to herein as coal dust are received, coal powder size is generally less than 3mm, and preferred size is less than the coal dust of 1mm
Raw material as subsequent production water-coal-slurry improves grinder to reduce the grinding technics to large particulate matter in water-coal-slurry
Service life and efficiency.
Low-order coal after being dried by stoving process enters gasification reducing process and is reacted, in order to advanced optimize work
Skill, low-order coal after the drying can also add gasification feeding process before entering gasification reducing process, so as to low after drying
Rank coal rapidly enters gasification reducing process, increases the surface area of material, is conducive to accelerate gasification reduction reaction.
Wherein, gasification reducing process is that the chemistry that is heated under anaerobic or micro-oxygen conditions to the low-order coal after drying is anti-
Answer technique.Low-order coal after drying enters gasification reducing process, under the heating of the heat mediums such as flue gas, is not necessarily in reaction process
Other substances such as additive are added, temperature is generally 350 DEG C -800 DEG C, the mistake of complex chemical reaction occurs under pressure≤30Kpa
Journey obtains the gas mixture of solid carbon and high temperature, wherein solid carbon is upgraded coal, the volatile matter 8- in upgraded coal
15wt%.The gas mixture of high temperature is to include CO, H2, hydro carbons, coal tar, dust and sulfur-containing compound etc. more impurity gas
Body.
Wherein, the source of gasification reducing process uses anaerobic or micro- oxygen environment oxygen is mainly in the following several ways: (1),
Gap inside raw material low-order coal, the air of the gap entrainment between material and material, the O in the air of this part2Gasifying
It is reacted immediately with coal in the environment of reducing process high temperature and generates CO2Or CO；(2) from the feed inlet of gasification reducing process, discharging
The mixed a small amount of air of the leakage such as mouth, the oxygen of this partial air, the micro O in this part2In gasification reducing process high temperature
It is reacted immediately with coal under environment and generates CO2Or CO；(3), in explosion limit value hereinafter, can be slightly passed through in gasification reducing process
Account for the O of Coal Quality percentage 5%2Or (air), 1. this operation, which has the advantage that, can be improved in gasification reducing process
Temperature and capacity usage ratio；2. improving the conversion ratio of charcoal；3. preventing coal coking；4. a small amount of O2With low-order coal imperfect combustion
More CO are produced, bring more synthesis gas to be subsequent.Since gasification reducing process internal temperature is higher, what is be passed through lacks
Measure O2Moment can occur oxidation reaction (including combustion reaction), and the burning point of many combustibles is all in the reaction temperature of gasification reduction reaction
Below degree.Because CO mixes with air explosion limit 12%-74.2%；H2Explosion value is 4%-75%.O2Accounting for AIR Proportional is 21%.
The explosion limit upper value of pure oxygen is 6% or so after conversion.By theoretical calculation, the coal of 100kg can generate about 80Nm3CO and H2。
So being passed through the O for accounting for Coal Quality percentage 5%2It is safe；Still further preferably, it is passed through and accounts for Coal Quality percentage 3%
O2, with the security and stability for the reducing process reaction that ensures entirely to gasify.But when the temperature of gasification reduction reaction meets technique
It is required that when, it can not also be passed through oxygen, the low-order coal after preferably drying carries out gasification reduction reaction in oxygen-free environment, so that instead
It should be able to carry out safely.
Wherein, gasification reducing process can be level-one, or multistage.It is main when using level-one gasification reducing process
If the gas mixture of most of high temperature, the height of temperature directly affect subsequent gas production, the yield of upgraded coal in order to obtain
With the temperature of level-one upgraded coal, the reaction temperature for the reducing process that gasifies is 350 DEG C -800 DEG C, and the volatile matter content in upgraded coal is
8-15wt%, further preferably, the reaction temperature for the reducing process that gasifies are 400-750 DEG C；Still further preferably 450-700 DEG C.
When using multistage gasification reducing process, multistage gasification reducing process main function is the nothing in upper level gasification reducing process
The solid matter (including fine coal, the solid impurity etc. after gasification) of method gasification, it is a certain amount of, can not within certain residence time gas
The higher boilings grease such as pitch change, similar continue gasification and the residence time short has little time to be precipitated or phenol generalization is not achieved in temperature
The polycondensation reaction condition of object, arene compound etc. is closed, gasification that the reaction was continued is conducive to the product for improving gas yield and upgraded coal
Matter.
Other than the temperature of guarantee gasification reducing process is reasonable, while it must also guarantee certain in gasification reducing process stop
The time is stayed, the residence time is too short, and volatile matter also not evolution gasification completely while influencing gas yield, more influences upgrading
The quality of coal；Residence time is too long, although product is guaranteed, yield is not caught up with, so keeping a reasonable gasification
The reduction reaction residence time is most important to product yield and quality.It is general to gasify since the kind of raw material low-order coal is different
The residence time of material is 30min-4h in reducing process.
Preferably using two-stage gasification reducing process in the present invention, the material after stoving process drying is introduced into level-one gasification also
Original process enter back into second level gasification reducing process, and the low-order coal after drying is introduced into level-one gasification reducing process and obtains level-one gas
With level-one solid, level-one solid enter back into second level gasification reducing process continue gasification obtain secondary gas and second level solid, second level
Solid is upgraded coal；The feeding temperature of level-one gasification reducing process is 80 DEG C -120 DEG C, and air outlet temperature is 180 DEG C -550 DEG C,
Reaction temperature is 450 DEG C -650 DEG C, and drop temperature is 350 DEG C -600 DEG C；The feeding temperature of second level gasification reducing process is
350 DEG C -600 DEG C, drop temperature is 450 DEG C -750 DEG C, and reaction temperature is 550 DEG C -800 DEG C, and air outlet temperature is 450 DEG C -700
℃.When using two-stage gasification reducing process, primarily to most of volatile is made to be gasified totally, it can obtain a large amount of
Gas can obtain the lower upgraded coal of volatile matter again, and wherein the volatile matter content in upgraded coal is 3-8wt%.
Gasify reducing process preparation gas mixture can using a portion as fuel, for example, stoving process or
It is that subsequent reforming technique provides heat, realizes that heat supply oneself is self-sustaining, without using extraneous fuel heat supply.
The gas mixture of the high temperature obtained from gasification reducing process enters the first purification process to remove solid dirt, coke
Oil and sulfur-containing compound etc. are can be obtained mixed gas.
First purification process includes that the second dust collecting process, oil gas cooling technique and sulfur removal technology, gas mixture successively pass through
Second dust collecting process, oil gas cooling technique and sulfur removal technology handle to obtain comprising CO, H2With the mixed gas of hydro carbons.The oil of high temperature
Contain dust, coal tar, vapor, CO in gas mixture2、H2S and COS etc.；First with the second dust collecting process dedusting, such as adopt
With deduster dedusting, prevent from causing coal tar and vapor etc. cold since the temperature of gas mixture reduces in dust removal process
It congeals into liquid and adheres to a large amount of dusts and cause subsequent technique line clogging, dust removing effects is caused to decline.Recycle oil gas bosher
The problems such as skill removes a large amount of tar and vapor, has prevented whose cooling to be attached in process pipe and has blocked pipeline, carbon distribution.Decoking
Spray column can be used in oily technique, other devices can also be used, as long as can achieve the purpose that cooling tar removing.It is further excellent
Choosing, oil water mixture after cooling passes through water-oil separating again can be obtained byproduct coal tar, and the unit price of coal tar is
The value of 2000-2500 member/T, the coal tar that richness produces is higher.Finally by oil gas cooling technique, treated that remaining gas leads to again
Crossing sulfur removal technology makes the content of sulfide be reduced to 10ppm hereinafter, preventing sulfur-containing compound from causing subsequent reformation conversion process
In catalyst poisoning, such as dry desulfurization and wet desulphurization etc., as long as can achieve the effect that desulfurization.Using process above
Foreign gas and solid can be removed, so as to the mixed gas after being purified, mixed gas impurity is few, convenient at subsequent technique
Reason, ensure that the stability of follow-up equipment.
It, can also be if the volume fraction in gas mixture containing unsaturated hydrocarbons is excessively high in order to advanced optimize technique
The problems such as setting hydrogenation technique after first purification process and be translated into saturated hydrocarbons, preventing unsaturated hydrocarbons decarburization and cause carbon distribution；Into
One step, denitrating technique or dechlorination process can also be added to realize further purification gas mixture.
Preferably gasified reducing process using two-stage in the present invention, every grade of gasification reducing process distinguish successively with respective dedusting
The connection such as technique, oil gas cooling technique and sulfur removal technology；The amount of dust in high-temperature oil gas generated after every grade of gasification reduction is larger,
Therefore, in order to advanced optimize technique, every grade of gasification reducing process is first connect with respective dust collecting process, every grade of dust collecting process
It is sequentially connected again with same set of oil gas cooling technique and sulfur removal technology, to save process procedure.
It obtains mixed gas from the first purification process and is handled into reforming technique to obtain comprising CO and H2's
First synthesis gas.
In order to advanced optimize technique, mixed gas enters back into before reforming process and can first carry out compression processing and mention
The pressure of high mixed gas, convenient for the generation of reforming reaction.
Mixed gas is that each component gas in mixed gas is direct without isolation through the reforming technique of some hydrocarbon
Reforming by some hydrocarbon is CO and H2Hydrocarbon reformation conversion process.Because reforming purpose is intended merely to hydrocarbon
Class is converted into CO and H2, and itself contained some CO and H in mixed gas2, there is no need to by hydro carbons from mixed gas
It separates and carries out the reforming of hydro carbons again, processing step, high financial profit are saved using such operation.
It is reforming it is main including Partial Oxidation, one kind of vapor catalyzed reforming and on-catalytic reforming conversion or
Person is several.Partial Oxidation, it is vapor catalyzed it is reforming be required to catalyst, the catalyst of reforming technique is mostly to load
Type catalyst, active component are mainly that Ni, Co, Fe, Cu etc. be nonmetallic and the noble metals such as Rh, Ru, Pt.It is reforming to generally require
Heat supply, can be by the way of direct heating or indirect heating.CO and H in synthesis gas2Source be two parts, a part
The CO and H obtained for some hydrocarbon in mixed gas by catalyzed conversion2, another part is original H in mixed gas2And CO.
Partial Oxidation is to reach reaction temperature using oxygen (pure oxygen) and a part of hydrocarbon fuel direct heating
850-1300 DEG C, under the effect of the catalyst, some hydrocarbon in gaseous mixture is reacted with vapor generates CO and H2；Steam is urged
Using extraneous heat supply when changing reforming, so that temperature is reached 850-1200 DEG C, make in mixed gas under the effect of the catalyst
Some hydrocarbon reacted with vapor generate CO and H2；The key reaction mechanism of two methods are as follows:
(1)CmHn+mH2O=mCO+1/2 (n+2m) H2Main reaction, the endothermic reaction
(2)CO+H2O=CO2+H2Side reaction, the endothermic reaction
With CH4For, key reaction equation CH4+H2O→CO+3H2, the H of generation2Molar ratio with CO is 3:1, than
Example is larger, highly beneficial to the first synthesis gas of preparation.
On-catalytic reforming conversion, which is reformed, does not need catalyst, key reaction mechanism are as follows: CH4+1/2O2→CO+2H2, generation
H2Molar ratio with CO is 2:1, is conducive to prepare the first synthesis gas.Other hydro carbons and methane and O in addition to methane2Reaction mechanism
It is similar.
Table 1: the value range of each volume components percentage in reforming preceding mixed gas:
| Component | H2 | Include CH4Hydro carbons | CO | CO2 | Other |
| Content | 15-45% | 10-52% | 5-25% | 5-25% | 0.1-10% |
Other components are N2, vapor etc., the summation of the percent by volume of each component is in reforming preceding mixed gas
100%.
Table 2: the value range of each volume components percentage in reforming rear mixed gas:
| Component | H2 | Include CH4Hydro carbons | CO | CO2 | Other |
| Content | 30-70% | 1-5% | 10-30% | 3-35% | 0.1-10% |
Other components are N2With vapor etc., it is reforming after in mixed gas the summation of the percent by volume of each component be
100%.
By Tables 1 and 2 it is found that mixed gas is after reforming process, the volume ratio of the hydro carbons in mixed gas
Percentage is reduced to 1-5% by original 10-52%, it is reforming after mixed gas in be the first synthesis gas, first closes
At the H in gas2It is greatly improved with the volume ratio percentage of CO.
Water-coal-slurry is a kind of environmental clean fuel of New type coal base flow body, burning of coal characteristic has both been remained, but also with class
It is the real clean coal technology in one, current China like the liquid-phase combustion application characteristic of heavy oil.Water-coal-slurry by 65-70% coal,
The water of 29-34% and chemical addition agent less than 1%, are made by certain processing technology, appearance picture oil, good fluidity,
It stores general 3-6 months and does not precipitate, convenient transportation, high combustion efficiency, pollutant (SO2、NOX) discharge is low, about 2t water-coal-slurry can be with
1t fuel oil is substituted, it can be in industry for being used as preparation H2And CO.
From the point of view of the long term growth of water-coal-slurry industry, pulping raw material should be based on cheap jet coal, weakly caking coal, no
The high-orders coals such as low-order coals and anthracite, meager coal, poor Of-thin coal such as glutinous coal, lignite, or such as municipal sludge, industrial sludge, coal slurry flotation
Etc. various solid waste, the economy of water-coal-slurry not only can be improved, also comply with and national rationally utilize coal and waste resource
Policy.
Slurries additive agent mainly includes viscosity reduction dispersing agent and stabilizer.Wherein dispersing agent is mostly important, it is directly affected
The quality and preparation cost of water-coal-slurry.(1) dispersing agent: the surface of coal has strong hydrophobicity, cannot be intimately associated with water
As a kind of slurry, a kind of wet walk only will form in higher concentration.A small amount of dispersing agent is added in slurrying and changes coal
The surface nature of grain, making coal particle surface tightly is that additive molecule and hydration shell surround, and coal grain is allowed to be uniformly dispersed in water, and
The mobility of water-coal-slurry is improved, dosage is about the 1% of coal.In general, dispersing agent is a kind of surfactant.Common surface
Activating agent has sulfonate type segregant surfactant (such as lignosulfonates tea sulfonate, alkenyl sulfonate), polyoxy second
Alkene punishment is non-from surfactant, water soluble polymer f polymer and anion surface active column and non-ionic surface active
The compound of agent.(2) stabilizer: water-coal-slurry is one kind after all by solid, liquid two-phase coarse dispersion system, and coal grain is easy to spontaneously again
It coalesces each other.Under gravity or other outer plus mass force effects, precipitating occurs and is inevitable.To prevent to precipitate firmly,
A small amount of stabilizer must be added.Stabilizer acts on of both having, and the rheology on the one hand making water-coal-slurry have shear shinning is special
Property, i.e., there is higher viscosity when the static storage of water-coal-slurry, viscosity can lower rapidly again after starting flowing；On the other hand make to sink
Starch has soft structure, prevents expendable hard precipitating.
In the waste water obtained in the first purification process, still contain a small amount of coal tar, mainly in the form of oil-in-water
In the presence of COD (COD) is even higher between 5000mg/L~100000mg/L；Waste component is complicated, contains phenol
Class, oil and ammonia nitrogen etc..Wherein, phenols mainly contains methyl class phenol, catechol, the aromatic hydrocarbon substance of the complexity such as benzenediol.It is useless
The salinity of water is very high, and various ion concentrations are high, and the content of especially high price example is more prominent, this will give the performance band of water-coal-slurry
Carry out significant impact.Phenols has certain acidity mostly, with the waste water slurrying of high salinity, it is difficult to reach high-concentration coal-water slurry
Requirement can mitigate destruction of the high salinity to coal slurry mobility, therefore, containing phenols due to the presence of Phenol for Waste Water class
Waste water energy improves water-coal-slurry performance.It is on the one hand the middle impurity in waste water using waste water as the source of the water of production water-coal-slurry
More, processing discharge is difficult, is used as preparation water-coal-slurry, not only solves the problems, such as sewage discharge difficulty, and be effectively utilized
The original shortage of water resources of water resource, especially the Northwest；It compared with pure industrial water, is contained in waste water on the other hand
There are the substances such as a small amount of coal tar, phenols, lime-ash, the presence of the substances such as phenols is conducive to water-coal-slurry and is slurried, coal tar and ash
The presence of the substances such as slag increases the energy value of water-coal-slurry.
In the present invention, the main source for preparing the water of water-coal-slurry is waste water, and the source of coal substance is mainly coal dust.It will be upper
Waste water is stated, coal dust is mixed with slurries additive agent solution, and water-coal-slurry can be obtained, and the concentration of water-coal-slurry is greater than 64.1wt%；It is viscous
Degree be less than 1200mPas (at 20 DEG C of slurry temperature, shearing rate 100S-1When)；Calorific value is greater than 18.51MJ/kg.
In addition, the present invention, which can also be used in technical process, generates other coal substances and water resource as preparation water-coal-slurry
Raw material.Preferably, the exhaust gas that will be generated in drying course, remaining gas is again through condensing after first passing through the processing of the first dust collecting process
Process obtains waste water, and the source of water, inadequate to supplement waste water when this effluent part can also be used as preparation water-coal-slurry
When water resource shortage, while also improving the utilization rate of water resource in low-order coal.Preferably, gasification reducing process is handled
Arrive upgraded coal screening obtain granularity be less than 1mm coal dust, as preparation water-coal-slurry coal resource supplement, granularity less times greater than
The upgraded coal of 1mm directly can sell or do stored energy source.It preferably, is to prepare by the greasy filth generated during oil gas bosher
The source of the coal substance of water-coal-slurry, greasy filth are used as preparation water-coal-slurry, can make full use of the resource in greasy filth.As in the present invention
The further improvement of technique, in water-coal-slurry and O2Before being handled by coal-water slurry gasification, water-coal-slurry is first handled through filter pulp.Consider slurry
Purpose is to remove the coarse granule occurred during water-coal-slurry processed and the certain sundries for being mixed into slurry, to prevent water coal slurry in storage and transportation
With blocking pipeline in combustion process and nozzle etc..
Finally, again by the water-coal-slurry and O of above-mentioned preparation2It is obtained together by coal-water slurry gasification comprising CO and H2?
Two water-gas, the coal substance and O in key reaction water-coal-slurry in coal-water slurry gasification2Burnup heat release, coal substance and water coal
Water reaction in slurry generates CO and H2.Here O2It can be pure oxygen, be also possible to the oxygen rich gas of high-purity.Coal substance and H2O
The reaction of (vapor) is the endothermic reaction, reaction equation C+H2O=CO+H2, first it is passed through O2So that a part of a small amount of water coal
Coal substance combustion heat release in slurry so that environment temperature is rapidly achieved 800-1300 DEG C, then be passed through another part water-coal-slurry with
Vapor reacts at this temperature generates CO and H2, obtained gas is the second water-gas.In the actual production process, it generally adopts
With being continuously uninterruptedly passed through O2And vapor, so that coal substance and H in water-coal-slurry2O (vapor) reacts continual preparation
Second water-gas.Due to containing a certain amount of dust, CO in the second water-gas2、H2S, the impurity such as COS, the second water-gas pass through the
The second water-gas after the above impurity is purified is removed in the processing of two purification processes, and the second purification process includes dust collecting process, takes off
Sulphur technique and decarbonization process, dedusting mainly use deduster, such as cyclone dust removal, the CO in the second water-gas2、H2S, COS can be adopted
It is washed with low-temp methanol and is removed together.Low-temp methanol washing process is using cold methanol as lyosoption, using methanol at low temperature to acidity
Gas (CO2、H2S, COS etc.) the great good characteristic of solubility, the sour gas in the second water-gas is removed, is a kind of physics
Absorption process.Low-temp methanol washing process is recognized gas purification technique the most economic and high degree of purification domestic and international at present, tool
Selective absorption CO2、H2The characteristic of S and CO, solvent is cheap and easy to get, and low energy consumption, and running expense is low, and production run is stable, reliable
Deng.Second purification process is not limited to deduster and low-temp methanol is washed, as long as can achieve the effect that dedusting, decarburization, desulfurization.
Upgraded coal and H2The reaction of O (vapor) is the endothermic reaction, reaction equation C+H2O=CO+H2, also from gasification
Obtained upgraded coal is the warm upgraded coal of band after original process reaction, because upgraded coal contains certain temperature, temperature be generally 350 DEG C-
800 DEG C, so its own has higher latent heat, this technique is first passed through on the basis of making full use of upgraded coal itself latent heat
O2So that a part of a small amount of upgraded coal combustion heat release, so that environment temperature is rapidly achieved 800-1300 DEG C, then is passed through other one
Most of upgraded coal is reacted at this temperature with vapor generates CO and H2, obtained gas is third water-gas, in practical life
It is general to be uninterruptedly passed through O using continuous during production2And vapor, so that upgraded coal reacts continual system with vapor
Standby third water-gas.Because being removed by gasification in gasification reducing process stage most of volatile, tar etc., gained upgrading
The content of coal substance is higher in coal, therefore less using foreign gas in the resulting third water-gas of upgraded coal.In addition, from gasification
The upgraded coal that reducing process is handled, the upgraded coal granule size that gasification reducing process generates in the process is different, especially grain
Lesser upgraded coal is spent, moisture-free is easy to produce fugitive dust, it has not been convenient to transport, be easy to cause environmental pollution, therefore by upgraded coal
Screening obtains the coal dust that granularity is less than 1mm, the supplement of the coal resource as preparation water-coal-slurry, upgrading of the granularity less times greater than 1mm
Coal directly can sell or do stored energy source.Major impurity gas in third water-gas is CO2、H2S, the impurity such as COS, there are also few
The dust of amount, the third after being purified after being removed impurity in third coal gas by third purification process convert gas.Third is removed
Dirt technique and the second purification process that the second water-gas uses are substantially similar, mainly dedusting, decarburization and desulfurization, no longer heavy here
It is multiple to introduce.
Finally synthesis gas will be obtained after the logical mixing of above-mentioned three kinds of synthesis gas.It is further preferred that entering separation in synthesis gas
Before technique, the CO in synthesis gas can be first removed2With the foreign gases such as water vapour, to increase H in synthesis gas2With the volume basis of CO
Than convenient for the H of later separation purification high-purity2And CO.
Mixed gas separate generally using pressure swing adsorption method or Deep Cooling Method (or low temperature process), membrane separation process.It is low
Warm therapy be using each component boiling point in gas difference, by a series of technical process, by gas liquefaction, and by rectifying come
Reach the method for different component separation, the separation of these gases need to be just able to achieve under 100K low temperature environment below, so claiming
Be Deep Cooling Method (or low temperature process).Pressure-variable adsorption abbreviation PSA is frequently in and carries out under pressure environment, and pressure-variable adsorption proposes
The method that pressurization and decompression combine, it is usually by the absorption-desorption system of pressurized adsorbent, decompression recomposition.In isothermal
In the case of, adsorption operations cyclic process is combined into using pressurized adsorbent and decompression desorption.Adsorbent to the adsorbance of adsorbate with
The raising of pressure and increase, and reduced with the reduction of pressure, while during decompression (be down to normal pressure or vacuumize),
The gas being adsorbed is released, makes adsorbent reactivation, the external world, which does not need supply heat, can carry out the regeneration of adsorbent.CO boiling point
It is -19O DEG C, H2Condensing temperature at -253 DEG C, be generally difficult to separate the two using pressure swing adsorption method, but pressurization drop
Temperature liquefaction is so that the temperature of synthesis gas is reduced to the boiling point of CO hereinafter, CO liquefies and H2It is still gaseous state, so that the two separates,
Therefore present invention preferably employs Deep Cooling Method separation, obtain high-purity H299% is up to the purity of the CO of high-purity, two kinds of gases
More than.
In conclusion the present invention restores the low-order coal after drying in gasification under anaerobic or micro-oxygen conditions, low order is obtained
Volatile matter in the coal and hydrocarbon reformation in will volatilize point is converted to CO and H2, improve CO and H2Energy density recycles separation
Technique prepares the CO and H of high-purity respectively2, to greatest extent by the volatile matter in low-order coal with CO and H2Form retain
Come；Upgraded coal approach and the waste water preparation water-coal-slurry approach vaporizing system that can also obtain high added value are standby comprising CO and H2Water coal
Gas prepares CO and H2Approach it is more, and a variety of refuse reclamations such as realize waste water, coal dust meet what country advocated energetically
Coal high-efficiency clean utilization；Therefore, the CO and H of preparation are separated2Yield it is high, purity is high can be used as the chemical industry synthesis of high value
Raw material substantially increases the utilization rate of low-order coal.
The above, the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although referring to before
Stating embodiment, invention is explained in detail, those skilled in the art should understand that: it still can be to preceding
Technical solution documented by each embodiment is stated to modify or equivalent replacement of some of the technical features；And these
It modifies or replaces, the spirit and scope for technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution.
Claims (10)
1. a kind of method of the reduction of low order coal gasification hydrogen and carbon monoxide, which is characterized in that method includes the following steps:
(1) low-order coal and exhaust gas after low-order coal drying process is dried, the exhaust gas pass through the first dust collecting process
Obtain coal dust；
(2) low-order coal after drying described in step (1) is handled to obtain gas mixture and upgrading by the reducing process that gasifies
Coal, the gasification reducing process is the chemical reaction work heated under anaerobic or micro-oxygen conditions to the low-order coal after drying
Skill；
(3) step (2) gas mixture is obtained by the first purification process comprising CO, H2With the mixed gas of hydro carbons and
Waste water；
(4) mixed gas described in step (3) is obtained through the reforming process of some hydrocarbon comprising CO and H2First close
At gas；
(5) water-coal-slurry is obtained after mixing coal dust described in waste water described in step (3), step (1) with slurries additive agent, it will
The water-coal-slurry and O2It handles to obtain comprising CO, CO by coal-water slurry gasification2And H2The second water-gas, described second
Water-gas obtains the second synthesis gas after handling by the second purification process；
(6) by upgraded coal described in step (2) by with H2O and O2Reaction preparation includes CO, CO2And H2Third water-gas, will
The third water-gas obtains third synthesis gas after handling by third purification process；
It (7) will be mixed by third synthesis gas in the second synthesis gas in first synthesis gas, step (5) and step (6) in step (4)
Synthesis gas is obtained after conjunction, the synthesis gas handles through separating technology and respectively obtains H2And CO.
2. the method for a kind of reduction of low order coal gasification hydrogen and carbon monoxide as described in claim 1, which is characterized in that institute
Stoving process is stated using water vapour indirect drying, the pressure of the water vapour is 0.3-1.5Mpa, and the temperature of the water vapour is
105-250 DEG C, the outlet material water ratio of the stoving process is no more than 7wt%, the outlet mass temperatures of the stoving process
It is 50-150 DEG C.
3. the method for a kind of reduction of low order coal gasification hydrogen and carbon monoxide as described in claim 1, which is characterized in that institute
Stating the first purification process includes the second dust collecting process, oil gas cooling technique and sulfur removal technology.
4. the method for a kind of reduction of low order coal gasification hydrogen and carbon monoxide as described in claim 1, it is characterised in that: step
Suddenly separating technology described in (7) is Deep Cooling Method.
5. the method for a kind of reduction of low order coal gasification hydrogen and carbon monoxide as described in claim 1, which is characterized in that step
Suddenly the reaction temperature of gasification reducing process described in (2) is 350-800 DEG C.
6. the method for a kind of reduction of low order coal gasification hydrogen and carbon monoxide as claimed in claim 5, which is characterized in that institute
The temperature for stating gasification reduction reaction is 400-750 DEG C.
7. the method for a kind of reduction of low order coal gasification hydrogen and carbon monoxide as described in claim 1, which is characterized in that step
Suddenly mixed gas described in (4) is that each component gas in mixed gas is straight without isolation through the reforming technique of some hydrocarbon
It is reforming for CO and H to connect some hydrocarbon2Hydrocarbon reformation conversion process.
8. the method for a kind of reduction of low order coal gasification hydrogen and carbon monoxide as claimed in claim 7, which is characterized in that institute
State reforming technique include Partial Oxidation, it is one or more of in the conversion of vapor catalyzed reforming and on-catalytic reforming.
9. the method for a kind of reduction of low order coal gasification hydrogen and carbon monoxide as described in claim 1, which is characterized in that step
Suddenly the granularity of coal dust described in (1) is less than 1mm.
10. the method for a kind of reduction of low order coal gasification hydrogen and carbon monoxide as described in claim 1, which is characterized in that
Water-coal-slurry and O described in step (5)2Before being handled by coal-water slurry gasification, the water-coal-slurry first passes through filter pulp process
Again with O2It is obtained by coal-water slurry gasification comprising CO, CO2And H2The second synthesis gas.
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