CN103484180B - A kind of fire coal is from the technique of the catalytic gasification preparing natural gas of heat supply and system - Google Patents
A kind of fire coal is from the technique of the catalytic gasification preparing natural gas of heat supply and system Download PDFInfo
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Abstract
The present invention provides technique and the system of a kind of fire coal catalytic gasification preparing natural gas from heat supply, coal, catalyst and gasifying agent are supplied in gasification installation, wherein disperse to be supplied to gasification installation from the diverse location of gasification installation by gasifying agent, and in described gasification installation, introduce oxygen.According to the technique from the catalytic coal gasifaction preparing natural gas of heat supply of the fire coal disclosed in the present invention, coal-fired can provide institute's calorific requirement for catalytic gasification reaction from heat-supplying mode, it is not necessary to add firing equipment, technique is simple, Technical Economy is good, and single stove realizes heat coupling, and system effectiveness is higher；Additionally, by providing gasifying agent to gasification installation dispersion, can while reaction institute calorific requirement be provided, by controlling the proportioning of the distribution of full bed oxygen and the steam regulated in distribution grid and bed and oxygen, oxygen concentration is controlled within the specific limits, can avoid bed that district of localized hyperthermia occurs, thus being prevented effectively from slagging scorification.
Description
Technical field
The present invention relates to catalytic coal gasifaction technical field, and more particularly, to the fire coal technique from the catalytic coal gasifaction preparing natural gas of heat supply and system.
Background technology
Develop rapidly and the increasingly stringent of environmental regulations along with economical, the following more than ten years, the demand of this clean energy resource of natural gas be explosive growth by China, though and gas production has increase but far below the growth trend of demand, imbalance between supply and demand becomes increasingly conspicuous, and supply breach strengthens year by year.Feature in view of China's energy resources situation " rich coal, few oil, deficency "; the long term maintenance energy consumption structure based on coal will not change in a short time; orientation direction according to clean coal technology and the development trend of world's low-carbon economy; coal is changed into top quality fuel natural gas in fossil energy, is applicable China's national situation, dissolves energy crisis and ensure a shortcut of energy security.
Common Coal Gasification Technology, namely coal at high temperature with oxygen (or air) and/or water vapour (H2O) gasifying agent formed carries out gasification reaction, generates containing a small amount of methane (CH4) synthesis gas (mainly hydrogen, carbon monoxide and carbon dioxide), carry out hydrosphere transformation and methanation operation afterwards, adopt two-step method to prepare methane.This Coal Gasification Technology has that temperature needed for gasification reaction is high, energy consumption is big, equipment requirements is high, and need the shortcomings such as three reaction units, technique are more complicated.
Catalytic coal gasifaction technology is the clean a kind of important way efficiently utilized of coal, adopts catalytic coal gasifaction technology, coal at relatively low temperature with water vapour (H2O), hydrogen (H2), the gasifying agent that forms of carbon monoxide (CO) under the catalytic action of catalyst, carry out gasification reaction, generate the methane (CH of high concentration4).Catalytic coal gasifaction technology compared with other Coal Gasification Technology, the advantage such as temperature needed for having methane content height, gasification reaction is low.
Coal one-step method methane technology has been carried out substantial amounts of experimentation by Exxon company of the U.S..US Patent No. 4318712 discloses the whole technological process of a kind of coal direct methanation, after wherein coal being mixed with catalyst in advance, entering gasification furnace, the superheated steam passed into serves not only as gasifying agent, simultaneously as thermal source, maintain reaction in furnace temperature, control in-furnace temperature at about 700 DEG C, superheat steam temperature 850 DEG C, gasification furnace reaction pressure 3.5MPa, coal reacts with superheated steam under the effect of catalyst, directly obtains product methane-rich gas.Cryogenic separation is adopted the methane in aerogenesis and carbon monoxide, hydrogen to be easily separated, by the hydrogen in reacting gas and carbon monoxide cycle to gasification furnace, so as to carry out methanation reaction in gasification furnace to be converted into methane, thus improving the yield of system methane.This coal technology has the shortcomings such as gasification reaction speed is low, response time length, efficiency of carbon con version are relatively low, gas separation system investment is high, steam superheating system and heat-exchange system load are higher, and catalyst recovery system is complicated, and method is expensive, to sum up causing technique macroeconomic not good, aggregate efficiency is relatively low.
GPE company of the U.S. makes further research on the basis of EXXON Technology, is widened by raw material as petroleum coke and biomass, and has carried out perfect to portion of techniques.Owing to catalytic gasification process temperature is relatively low, the efficiency of carbon con version reaching more than 90% needs the longer time of staying, is difficulty with the heat gasified with methanation and couples, it is necessary to providing system institute calorific requirement with a large amount of superheated steams, the energy consumption of technique is bigger.Additionally eliminate cryogenic separation, change partial oxidation gasification furnace gas product into provide carbon monoxide needed for superheated steam and methanation reaction and hydrogen, or provide superheated steam and CO, H for catalytic gasification reactor by setting up the gasification stove of combustion2, the carbon raw material of employing is that the catalytic gasification fire grate after reclaiming catalyst goes out semicoke, gas solid separation gained flying dust and standby coal workshop section salvage stores etc..Above content refers to patent US20090246120A1, US20090165376A1.This investment in machinery and equipment is high, and technological process is complicated, and energy consumption is relatively big, and technique macroeconomic is poor, and aggregate efficiency is relatively low.
Existing catalysis gasification technique all adopts outer heat-supplying mode, namely need with a large amount of superheated steams and cyclic part gas product carbon monoxide, hydrogen enters gasification furnace generation methanation reaction heat release provides system institute calorific requirement, adopts cryogenic separation, gas product partial oxidation or sets up the gasification stove of combustion to provide superheated steam and CO, H2, the energy consumption of technique is all relatively big, and equipment investment is high, and technological process is complicated, and steam superheating system and heat-exchange system load are higher, to sum up cause technique macroeconomic not good, and aggregate efficiency is relatively low.
The addition of catalyst can catalyst combustion reaction, improve coal dust firing thermal discharge, the base metal catalysts simultaneously added be likely under certain process conditions, reaction atmosphere same coal mineral formed low temperature fused matter, the ash fusion point of coal can be reduced；And catalysis gasification technique requires higher gas-solid contact time, bed is of a relatively high, the uniform flash heat transfer relative difficulty in full bed region, in bed, the too high coal ash particle that may result in of local temperature bonds slagging scorification mutually, cause fluidized state bad, time serious, deslagging difficulty, even defluidization etc., cause reactor to be difficult to continuous and steady operation.
Therefore, catalytic gasification reaction can be provided institute's calorific requirement without additional miscellaneous equipment with fire coal from heat-supplying mode by current exploitation one, and catalytic coal gasifaction process for producing natural and the system tool that can be prevented effectively from slagging scorification in equipment have very great significance simultaneously.
Summary of the invention
In order to solve above technical problem, present inventor has performed intensive research, thus providing technique and the system of a kind of fire coal catalytic coal gasifaction preparing natural gas from heat supply, it is for simply and efficiently producing natural gas.
Specifically, according to an aspect of the present invention, the technique that the invention provides a kind of fire coal catalytic gasification preparing natural gas from heat supply, including coal, catalyst and gasifying agent are supplied in gasification installation, wherein disperse to be supplied to gasification installation from the diverse location of gasification installation by gasifying agent, and in gasification installation, introduce oxygen.
According to another aspect of the present invention, the invention provides the system of a kind of fire coal catalytic gasification preparing natural gas from heat supply, including the gasification installation for making coal, catalyst and the reaction of gasifying agent generating gasification, to produce to comprise mixture after the gasification of described natural gas.
According to the technique from the catalytic coal gasifaction preparing natural gas of heat supply of the fire coal disclosed in the present invention, by gasifying agent dispersion being supplied in gasification installation to the diverse location of gasification installation, by controlling the proportioning of oxygen distribution and the steam regulated in distribution grid and bed and oxygen in gasification installation, oxygen concentration can be controlled within the specific limits, can avoid bed that district of localized hyperthermia occurs, thus being prevented effectively from slagging scorification.Additionally, owing to gasification installation there being oxygen exist, make coal aoxidize (heat release) reaction, and then the catalytic gasification reaction occurred under catalyst action for coal provides heat, without additional firing equipment, technique is simple, Technical Economy is good, and single stove realizes heat coupling, and system effectiveness is high, and technique provided by the present invention industrially easily realizes, industrialization is amplified simple.
Accompanying drawing explanation
Fig. 1 shows the technical process schematic diagram of an embodiment of the technique confessing hot coal catalytic gasification preparing natural gas for the fire coal according to the present invention.
Fig. 2 shows and gasifying agent (comprising steam and oxygen) is incorporated into the schematic diagram according to the technique in the gasification installation of the present invention.
Detailed description of the invention
In the present invention, unless specifically indicated otherwise, term " gasifying agent " refers to necessary gas medium in coal gasification processes, preferably comprises the gas of steam in the present invention, and it can also comprise oxygen according to practical situation.Term " natural gas " refers to the gas rich in methane.
According to an aspect of the present invention, the present invention provides the technique of a kind of fire coal catalytic gasification preparing natural gas from heat supply, and it is for simply and efficiently producing natural gas.
Specifically, the technique that the present invention provides a kind of fire coal catalytic gasification preparing natural gas from heat supply, including being supplied in gasification installation by coal, catalyst and gasifying agent, wherein disperse to be supplied to gasification installation from the diverse location of gasification installation by gasifying agent, and in gasification installation, introduce oxygen.Wherein, described gasification installation is for making coal device of generating gasification reaction in comprising the environment of catalyst and gasifying agent, to produce to comprise mixture after the gasification of described natural gas, described gasification installation is axial specific diameter to long regular or irregular 3 D stereo device, has the space for generating gasification reaction inside it.The diverse location of gasification installation, according to the conventional understanding of those skilled in the art, i.e. multiple positions of gasification installation, gasifying agent enters into gasification installation from multiple diverse locations of gasification installation, reaches the purpose that gasifying agent is dispersed into.
Some preferred embodiment according to the present invention, at the fire coal according to the present invention in the technique of the catalytic gasification preparing natural gas of heat supply, described gasifying agent comprises concentration and is 0 to 30mol%, is preferably greater than 0 to 20mol%, more preferably the oxygen of 5 to 15mol%, and comprises steam.The catalytic gasification reaction occurred in the presence of a catalyst because of coal is the endothermic reaction, it is necessary to heat, and the catalytic gasification reaction that the present invention preferably occurs for the coal in gasification installation in the presence of a catalyst with steam provides heat.
At the fire coal according to the present invention in the catalytic gasification process for producing natural of heat supply, the fire coal in order to realize catalytic coal gasifaction process for producing natural introduces oxygen from heat supply in described gasification installation.But, in order to avoid the coal combustion in gasification installation acutely so that produce instability, introducing of described oxygen not carries out with the form of pure oxygen, but the form to comprise the gasifying agent of steam and oxygen simultaneously introduces.
Some preferred embodiment according to the present invention, at the fire coal according to the present invention in the technique of the catalytic coal gasifaction preparing natural gas of heat supply, make described gasifying agent by disperseing to be supplied in described gasification installation at the one or more distribution devices axially arranged of described gasification installation.
Some preferred embodiment according to the present invention, at the fire coal according to the present invention in the technique of the catalytic coal gasifaction preparing natural gas of heat supply, described gasifying agent is made to be supplied in described gasification installation by the one or more distribution devices dispersion arranged in the same level in described gasification installation.Described distribution device be for gasifying agent from which by and the device that enters in gasification installation, for instance nozzle, straight tube, bend pipe, jet pipe or there is gathering tube and the device of multiple branched pipes connected with gathering tube, the effect being dispersed into oxygen can be played.
Some preferred embodiment according to the present invention, at the fire coal according to the present invention in the technique of the catalytic coal gasifaction preparing natural gas of heat supply, the temperature of described gasifying agent is 300-600 DEG C, it is preferable that 300-550 DEG C, more preferably 350-500 DEG C.
Some preferred embodiment according to the present invention, at the fire coal according to the present invention in the technique of the catalytic coal gasifaction preparing natural gas of heat supply, described gasifying agent comprises the mixture of superheated steam and oxygen.
Some preferred embodiment according to the present invention, at the fire coal according to the present invention in the technique of the catalytic coal gasifaction preparing natural gas of heat supply, be linked in sequence successively gas-solid separating device, gas cleaning plant, gas fractionation unit or methanation device in described gasification installation downstream.
Some preferred embodiment according to the present invention, at the fire coal according to the present invention in the technique of the catalytic coal gasifaction preparing natural gas of heat supply, also include the steam raising plant being connected with described gasification installation being positioned at described gasification installation upstream, described steam raising plant produces steam, and described steam is carried out heat exchange with the process gas from described gas-solid separating device together with oxygen between described gas-solid separating device and described gas cleaning plant, to produce the gasifying agent comprising superheated steam and oxygen.The temperature of described process gas is higher than the temperature after the steam of steam raising plant and oxygen mix, described superheated steam is the steam exceeding saturation temperature, after steam and the oxygen mix of steam raising plant again with process gas heat exchange, described steam will exceed saturation temperature, be superheated steam.
Some preferred embodiment according to the present invention, at the fire coal according to the present invention in the technique of the catalytic coal gasifaction preparing natural gas of heat supply, described distribution device is nozzle.
Some preferred embodiment according to the present invention, at the fire coal according to the present invention in the technique of the catalytic coal gasifaction preparing natural gas of heat supply, described gasification installation is gasification furnace.
Some preferred embodiment according to the present invention, at the fire coal according to the present invention in the technique of the catalytic coal gasifaction preparing natural gas of heat supply, described steam raising plant is boiler.
Some preferred embodiment according to the present invention, at the fire coal according to the present invention in the technique of the catalytic coal gasifaction preparing natural gas of heat supply, described catalyst is alkali-metal carbonate, or the carbonate of alkaline-earth metal, or alkali-metal hydroxide, or the hydroxide of alkaline-earth metal, or papermaking wastewater, or industrial alkali waste, or plant ash, or the mixture of they at least two, or they at least one mixture with transition metal.
Some preferred embodiment according to the present invention, for the technique optimizing the described fire coal catalytic coal gasifaction preparing natural gas from heat supply further, described gasification installation includes being positioned at the distribution grid bottom described gasification installation and is positioned at the one or more distribution devices above described distribution grid, and introduce steam from described distribution grid to described gasification installation, introduce described gasifying agent from the one or more distribution device to described gasification installation.Described gasifying agent is the mixture of steam and oxygen, and wherein the concentration of oxygen is more than 0 to 30mol%.
Some preferred embodiment according to the present invention, for the technique optimizing the described fire coal catalytic coal gasifaction preparing natural gas from heat supply further, described gasification installation includes being positioned at the distribution grid bottom described gasification installation and is positioned at the one or more distribution devices above described distribution grid, and to described gasification installation, introduce described gasifying agent from described distribution grid and the one or more distribution device, wherein the concentration of the oxygen in the gasifying agent that described distribution grid place introduces is 0 to 20mol%, it is preferably 0 to 10mol%, and the concentration of the oxygen in the gasifying agent that the one or more distribution device place introduces is more than 0 to 30mol%, it is preferably greater than 5 to 15mol%.
Some preferred embodiment according to the present invention, at the fire coal according to the present invention in the technique of the catalytic gasification preparing natural gas of heat supply, the operation temperature of described gasification installation is 600-800 DEG C, it is preferable that 650-800 DEG C, and more preferably 650-750 DEG C；Pressure is 0-4MPa, it is preferable that 1-4MPa, more preferably 3-4MPa.
Some preferred embodiment according to the present invention, at the fire coal according to the present invention in the technique of the catalytic gasification preparing natural gas of heat supply, in described gasification installation, the mol ratio of water and carbon is 1: 1 to 3: 1, it is preferable that 1.1: 1 to 2.5: 1, more preferably 1.5: 1 to 2: 1.
According to another aspect of the present invention, the present invention provides the system of a kind of fire coal catalytic gasification preparing natural gas from heat supply, including the gasification installation for making coal, catalyst and the reaction of gasifying agent generating gasification, to produce to comprise mixture after the gasification of described natural gas.Wherein, described gasification installation is for making coal device of generating gasification reaction in comprising the environment of catalyst and gasifying agent, to produce to comprise mixture after the gasification of described natural gas, described gasification installation is axial specific diameter to long regular or irregular 3 D stereo device, has the space for generating gasification reaction inside it.
Some preferred embodiment according to the present invention, at the fire coal according to the present invention in the system of the catalytic gasification preparing natural gas of heat supply, is provided with one or more distribution device in described gasification installation, is used for passing into described gasifying agent.
Some preferred embodiment according to the present invention, at the fire coal according to the present invention in the system of the catalytic gasification preparing natural gas of heat supply, described distribution device is arranged in the same level in described gasification installation in the way of equal or unequal.
Some preferred embodiment according to the present invention, at the fire coal according to the present invention in the system of the catalytic gasification preparing natural gas of heat supply, described distribution device axially arranging in the way of equal or unequal in described gasification installation.
Some preferred embodiment according to the present invention, at the fire coal according to the present invention in the system of the catalytic gasification preparing natural gas of heat supply, also include steam raising plant, gas-solid separating device and gas cleaning plant, the order of connection is followed successively by steam raising plant, gasification installation, gas-solid separating device and gas cleaning plant, wherein
Steam raising plant, is used for producing at least some of described gasifying agent；
Gas-solid separating device, for separating mixture after described gasification, to obtain process gas；
Gas cleaning plant, is used for purifying described process gas, to obtain the gas rich in methane.
In described process gas, except containing except the fuel gas such as methane, possibly together with other gases or impurity, described purification refers to the process removed by composition in addition to natural gas.
Below by way of reference Fig. 1, the fire coal of the present invention is described in more detail from the technique of the catalytic coal gasifaction preparing natural gas of heat supply.
Coal is broken to suitable particle diameter scope, joins in gasification installation 20.The steam that steam raising plant 37 produces carries out heat exchange with the process gas of gas-solid separating device outlet together with after oxygen mix in heat exchanger 34, produce superheated steam and oxygen, from the distribution grid of gasification installation 20 bottom and be arranged in distribution device above distribution grid and enter gasification installation 20, react with coal generating gasification under the effect of catalyst.Described distribution device 10 is arranged in the same level in gasification installation 20 in the way of equal or unequal, or axially arranging in the way of equal or unequal in gasification installation 20, preferably in axially arranging in the way of equal or unequal in gasification installation 20, so, oxygen is from multiple positions of gasification installation 20 and distribution grid, distribution device enters gasification installation 20, wherein the concentration of the oxygen in the gasifying agent that distribution grid place introduces is 0 to 20mol%, it is preferably 0 to 10mol%, and the concentration of the oxygen in the gasifying agent introduced by distribution device place is for more than 0 to 30mol%, it is preferably greater than 5 to 15mol%.By regulating oxygen and the concentration of oxygen in overheated steam burden control gasification installation 20, in described gasification installation, water is 1: 1 to 3: 1 with the mol ratio of carbon, preferably 1.1: 1 to 2.5: 1, more preferably make oxygen at bed dispersed at 1.5: 1 to 2: 1, it is avoided that district of localized hyperthermia occurs, thus realizing avoiding the effect of slagging scorification.Meanwhile, the heat put by means of coal partial oxidation (burning) in oxygen atmosphere is that the gasification reaction that coal occurs under catalyst and oxygen exist provides required heat.Gasification installation 20 is maintained at 600-800 DEG C, it is preferable that 650-800 DEG C by controlling the flow of oxygen.When certain temperature, pressure, coal dust generating gasification, conversion, methanation etc. under the effect of catalyst and gasifying agent are reacted, and generate available gas composition and carbon dioxide, a small amount of hydrogen sulfide and the ammonia etc. such as methane, carbon monoxide, hydrogen.Residue after gasification is discharged from gasification installation 20 bottom.The dust-filtering carried secretly is got off and returns it to gasification installation 20 to carry out gasification reaction by the exit gas of gasification installation 20 through gas-solid separating device 21, gas after separating from gas-solid separating device 21 enters gas cleaning plant 22 with the sour gas such as carbon dioxide removal and hydrogen sulfide, thus obtaining the gas rich in methane.Gas rich in methane can carry out gas separation in gas fractionation unit 23, or occurs methanation reaction to obtain the natural gas of pipeline grade in methanation device 23.
Specifically, above following part is mainly included for the fire coal according to the present invention from the equipment of an embodiment of the technique of the catalytic coal gasifaction preparing natural gas of heat supply.
Gasification installation 20, it is connected with gas-solid separating device 21, for issuing the gasification reaction of soft coal and gasifying agent in the effect of catalyst and gasifying agent, and afterwards the mixture after gasification reaction is sent into gas-solid separating device 21.In described gasification installation 20, catalyst can adopt alkali-metal carbonate, or the carbonate of alkaline-earth metal, or alkali-metal hydroxide, or the hydroxide of alkaline-earth metal, or papermaking wastewater, or industrial alkali waste, or plant ash, or the mixture of they at least two, or they at least one mixture with transition metal.Catalyst is preferably potassium carbonate in a preferred embodiment.Gasifying agent includes steam and oxygen, can pass into from the different parts such as distribution grid or bed of gasification installation 20 by different ratio.Mixture after gasification reaction generally comprises: methane, hydrogen, carbon monoxide, carbon dioxide, hydrogen sulfide, ammonia, coal dust, coal ash, catalyst etc..Described gasification installation 20 can be fluidized-bed gasification furnace, and operation temperature is 600-800 DEG C, it is preferable that 650-800 DEG C, and more preferably 650-750 DEG C.Under the effect of catalyst, there is the reaction such as catalytic gasification, methanation, generate CH4, CO, H2Deng available gas composition.Due to the addition of oxygen, making coal that oxidation or combustion reaction to occur, release heat, the catalytic gasification for coal reacts the heat providing required, to maintain reaction temperature in required interval range.The pressure of gasification installation 20 can between 0-4 MPa (MPa), it is preferable that 1-4MPa, more preferably 3-4MPa.
Gas-solid separating device 21, it is connected with gasification installation 20 and gas cleaning plant 22.Gas-solid separating device 21 can be cyclone separator, it is preferable that multi-cyclone, for mixture after gasification installation 20 gasification reaction is carried out gas solid separation, is back in gasification installation 20 by isolated solid in a preferred embodiment.
Gas cleaning plant 22, it is connected with gas-solid separating device 21, for the gas separated from gas-solid separating device 21 carries out purification separation, removes sour gas, obtains the gas rich in methane.
Gas fractionation unit or methanation device 23, it is connected with gas cleaning plant 22, gas fractionation unit carries out gas separation for gas cleaning plant 22 is exported the gas rich in methane, or, methanation device carries out methanation reaction for gas cleaning plant 22 is exported the gas rich in methane, to obtain the natural gas of pipeline grade.
Coal of the present invention can be bituminous coal, anthracite or brown coal, it is preferable that coal is pulverized, and being more preferably crushed to particle diameter is 10-500 micron, it is most preferred that particle diameter is 10-200 micron.
Heat exchanger 34, it is connected with gasification installation 20, oxygen feedway, steam raising plant 37, for carrying out heat exchange by oxygen with from outlet process gas with described gas-solid separating device after the steam of steam raising plant 37, the temperature of the gaseous mixture after preferred heat exchange is between 300-500 DEG C, being sent into by gaseous mixture after heat exchange in gasification installation 20, in gasification installation 20, coal carries out gasification reaction under the existence of catalyst and this gas.Steam raising plant 37 is preferably boiler, and this boiler is for being heated as steam by water.
Below, it is described in detail according to the technique in the gasification installation of the present invention gasifying agent (comprising steam and oxygen) is incorporated in conjunction with Fig. 2.
Coal and the mixture entrance gasification installation 20 of catalyst, react with gasifying agent generating gasification under the effect of catalyst.Reaction temperature in gasification installation 20 is 600～800 DEG C, and pressure is 0～4MPa, and in described gasification installation, water is 1: 1 to 3: 1 with the mol ratio of carbon, it is preferable that 1.1: 1 to 2.5: 1, and more preferably 1.5: 1 to 2: 1 at O2CH is generated with under the effect of water vapour4, CO, H2Deng available gas composition and CO2, a small amount of H2S and NH3Deng.Dominant response is as follows:
2C+2H2O→2H2+2CO(1)
CO+H2O→CO2+H2(2)
3H2+CO→CH4+H2O(3)
C+2H2→CH4(4)
2C+O2→2CO(5)
C+O2→CO2(6)
Gasifying agent comprises steam, and comprising concentration is the oxygen more than 0 to 30mol%, preferably 0 to 20mol%, more preferably the oxygen of 5 to 15mol%, temperature is 300～600 DEG C, gasification installation can be entered through distribution grid, it is possible to be dispersed into from the different parts of gasification installation 20 by distribution device bottom gasification installation.Distribution device arrangement form in bed can adopt whole bed to be equidistantly distributed or not determining deviation distribution.It can be one or more that same level gas passes into mouthful number.Also can in bed axially arranged distribution device, it is ensured that overall bed oxygen is uniformly dispersed.Water carbon mol ratio controls 1～3.Oxygen total flow is adjusted according to the temperature requirement of gasification installation.Partial oxidation is strong exothermal reaction, provides required heat for catalytic gasification.Control operation temperature at 600～800 DEG C.
According to currently preferred specific embodiments, it is possible to realize the fire coal of catalytic coal gasifaction process for producing natural from heat supply by introducing oxygen at the local location of gasification installation.For example, it is possible to introduce the gasifying agent containing only steam in the distribution grid position of gasification installation, and introduce the gasifying agent simultaneously containing steam and oxygen in other position (such as, bed) except distribution grid, thus reaching coal-fired from the purpose of heat supply.
There is provided the following example to describe the present invention, but the invention is not restricted to described embodiment.
Embodiment
The fire coal being used for according to the present invention is assembled from the equipment of the technique of the catalytic coal gasifaction preparing natural gas of heat supply according to the embodiment in Fig. 1 and Fig. 2.
The technique as described in detailed description of the invention part is adopted to carry out coal-fired confession hot coal catalytic gasification preparing natural gas.Wherein, the temperature of gasifying agent is 500 DEG C.
In the gasifying agent introduced to described gasification installation 20, distribution grid the oxygen concentration of the gasifying agent entering gasification installation 20 is 5mol%, bed distribution device the oxygen concentration of the gasifying agent entering gasification installation 20 is 10mol%.
In the above equipment for fire coal confession hot coal catalytic gasification preparing natural gas, about the concrete structure supplying gasifying agent with a scattered manner it is: gasification installation 20 has gas distribution grid, it is used for passing into oxygen and superheated steam mixing gas, and the concentration of oxygen is 5mol%；In bed, above distribution grid, 150mm horizontal level arranges two jet pipes, jet pipe has nozzle arrangements, jet hole installation direction is axially in parallel with gasification installation 20, towards the feedstock direction of coal (as gasification installation 20 is vertically placed, then jet hole is vertically upward), described nozzle passes into oxygen and superheated steam mixing gas, and the concentration of oxygen is 10mol%.
In described gasification installation 20, water is 1.5: 1 with the mol ratio of carbon, and the operation temperature of described gasification installation 20 is 700 DEG C, and pressure is 3.5MPa.Employing raw material is bituminous coal, and it is impregnated with the potassium carbonate catalyst of 15 mass % (benchmark is bituminous coal gross mass).
The analysis result of raw material is shown in following table:
The table 1 analysis result to raw material
Wherein, Mad: air-dried moisture；Aad: air-dried basis ash；Vad: air-dried basis volatile matter；St, ad: air-dried basis total sulphur content；Cad: air-dried basis carbon content: Had: air-dried basis hydrogen content；Nad: air-dried basis nitrogen content；Oad: air-dried basis oxygen content；Numerical value is weight/mass percentage composition.
From above experiment it can be seen that pass through to disperse oxygen supply, it is provided that reaction institute calorific requirement, it is possible to maintain gasification installation reaction temperature at 700 DEG C, it is achieved that from the purpose of heat supply；By controlling full bed oxygen, to be distributed-regulate distribution grid oxygen concentration be 5mol%, bed distribution device jet pipe nozzle place oxygen concentration be 10mol%, efficiently avoid the appearance in district of bed localized hyperthermia, overall bed temperature is comparatively uniform, run non-slagging scorification in 24 hours continuously, efficiency of carbon con version is 90 mass %, and lime-ash carbon residue is about 9 mass %.Purified gas component is shown in following table:
| Component | Wet basis content (mol%) | Contents on dry basis (mol%) |
| CO | 7.3 | 11.4 |
| H2 | 19.8 | 31.1 |
| CO2 | 21 | 33.0 |
| CH4 | 15.6 | 24.5 |
| H2O | 35.7 | - |
Although describe the design of the present invention in detail above with reference to accompanying drawing and preferred embodiment, it should be noted that, the invention is not restricted to described drawings and Examples, embodiment be only present inventive concept preferred embodiment, in the scope without departing substantially from the spirit of the present invention, it is possible to the preferred technical solution of the present invention is changed or changes.Such as, the position of each building block non-essential, order etc. are adjusted；Technological parameter is changed.
Claims (5)
1. a fire coal is from the technique of the catalytic gasification preparing natural gas of heat supply, including coal, catalyst and gasifying agent are supplied in gasification installation, wherein disperse to be supplied to gasification installation from the diverse location of gasification installation by gasifying agent, and in gasification installation, introduce oxygen, described oxygen makes coal generation oxidation reaction, the catalytic gasification reaction occurred under catalyst action for coal provides heat, without additional firing equipment；
The operation temperature of described gasification installation is 600-750 DEG C, and pressure is 0-4MPa, and the mol ratio of water and carbon is 1: 1 to 3: 1；
Wherein said gasification installation includes being positioned at the distribution grid bottom described gasification installation and is positioned at the one or more distribution devices above described distribution grid, and introduce steam from described distribution grid to described gasification installation, introduce described gasifying agent from the one or more distribution device to described gasification installation or to described gasification installation, introduce described gasifying agent from described distribution grid and the one or more distribution device；
Wherein the concentration of the oxygen in the gasifying agent that described distribution grid place introduces is 0 to 20mol%, and the concentration of the oxygen in the gasifying agent that the one or more distribution device place introduces is more than 0 to 30mol%.
2. technique according to claim 1, wherein make described gasifying agent by disperseing to be supplied in described gasification installation at the one or more distribution devices axially arranged of described gasification installation, or make described gasifying agent be supplied in described gasification installation by the one or more distribution devices dispersion arranged in the same level in described gasification installation.
3. technique according to claim 1, be wherein linked in sequence successively gas-solid separating device, gas cleaning plant and be linked in sequence gas fractionation unit and/or methanation device in described gasification installation downstream.
4. technique according to claim 3, wherein also include the steam raising plant being connected with described gasification installation being positioned at described gasification installation upstream, described steam raising plant produces steam, and described steam is carried out heat exchange with the process gas separated from described gas-solid separating device together with oxygen between described gas-solid separating device and described gas cleaning plant, to produce the gasifying agent comprising superheated steam and oxygen.
5. technique according to claim 1, wherein said catalyst is alkali-metal carbonate, or the carbonate of alkaline-earth metal, or alkali-metal hydroxide, or the hydroxide of alkaline-earth metal, or papermaking wastewater, or industrial alkali waste, or plant ash, or the mixture of they at least two, or they at least one mixture with transition metal.
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| CN102234545A (en) * | 2010-04-28 | 2011-11-09 | 中国石油化工股份有限公司 | Preparation method of synthesis gas by gasifying carbonaceous materials |
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| CN102234545A (en) * | 2010-04-28 | 2011-11-09 | 中国石油化工股份有限公司 | Preparation method of synthesis gas by gasifying carbonaceous materials |
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