CN105000534B - Method for combined preparation of synthetic gas based on slurry gasification and natural gas conversion - Google Patents
Method for combined preparation of synthetic gas based on slurry gasification and natural gas conversion Download PDFInfo
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- CN105000534B CN105000534B CN201510381146.XA CN201510381146A CN105000534B CN 105000534 B CN105000534 B CN 105000534B CN 201510381146 A CN201510381146 A CN 201510381146A CN 105000534 B CN105000534 B CN 105000534B
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Abstract
The invention relates to a method for combined preparation of synthetic gas based on slurry gasification and natural gas conversion. The method comprises the following steps: slurry gasification, natural gas conversion, synthetic gas preparation, etc. The method has the advantages of wide raw material source, high integrated utilization efficiency of raw materials, reasonable energy utilization, low refuse discharge amount, mature unit assemblytechnology, easily adjustable synthetic gas H/C ratio, high added value of product, distinctive scale merit, etc. By means of gas preparation, the synthetic gas H/C ratio can be adjusted in the range of 1.0-2.0. After the gas preparation, the synthetic gas obtained in the step A and the step B does not needed to be converted or a little of gas is convertedtotally or mostly, and the synthetic gas can be directlyused as raw material formethanol synthesisandFischer-Tropsch synthesis of oil. By adopting the method provided by the invention, conversion of 40-600 Nm3 of synthetic gas is saved after gasification of each ton of coal and emission of CO2 is reduced by 20-300 Nm3 per ton of coal.
Description
【Technical field】
The invention belongs to technical field of coal chemical industry.More particularly it relates to one kind is turned with slip gasification and natural gas
Turn to the method that based Joint prepares synthesis gas.
【Background technology】
It is well known that in world's fossil energy reserves, natural gas and coal account for sizable ratio, realize above two certainly
So resource cleaning, efficient utilization have great reality and strategic importance.
Coal resources be in fossil class resource reserves at most, while be also exploitation at most, usage amount it is maximum, using approach most
A kind of many resources.In the various ways of coal resources conversion, gasification mode is that to realize that resource clean and effective is utilized optimal
Approach, it is to avoid heat utilization rate that coal directly burns is not high, produce the shortcoming of substantial amounts of greenhouse gases and solid dust, can subtract
Few pollution and destruction to ecological environment.Because coal build-in attribute and wet method gasify itself operational characteristic, wet method pressurized gasification
, than relatively low, in order to arrange in pairs or groups with subsequent technique, synthesis gas need to be through Partial Transformation or total transform, by gas for H/C in the synthesis gas for obtaining
Body component ratio is adjusted to suitable H/C.
Wet method pressurized gasification temperature is higher, and high-temperature synthesis gas are typically lowered the temperature using direct Quench, and its sensible heat is not reclaimed
Utilize, energy utilization is not quite reasonable.The synthesis gas of generation is high due to C/Hratio, and the carbon dioxide produced after methanol is washed is past
Toward emptying, aggravate greenhouse effect.
Natural gas is a kind of cleaning, natural resourcess easy to use.Two sections of conversions of natural gas are main to include that one section of steam turns
Change and two-stage nitration pure oxygen reformation.After desulfurization, its sulfur content is down to 0.1ppm to natural gas, and the unstripped gas Jing saturators after purification are satisfied
With, process steam is added by certain steam/hydrocarbons ratio, one-stage converter is entered Jing after the preheating of two-stage nitration heating furnace convection section, turn with two-stage nitration
After changing the heat exchange of stove high-temperature synthesis gas, one-stage converter to be worked off one's feeling vent one's spleen and carry out conversion reaction into secondary reformer and oxygen, steam, raw
Into synthesis gas.
Perfect with natural gas resource large-scale development and infrastructure, part chemical enterprise is using natural gas as change
Work raw material, for products such as production synthesis ammonia, methanol.During with natural gas as raw material production methanol, H/C ratios in the synthesis gas of production
It is higher, H in synthesis purge gas2Content is high, and discharge capacity is larger, causes resource, power waste more serious.
The present invention, with natural gas and coal as raw material, is led to for above two resources characteristic and corresponding transformation technology present situation
Cross natural gas conversion process, Multiplex Stuff Slurry Gasification Process combination, the polynary slurry according to H/C in natural gas processing product is higher
In gasifying gas composition H/C than it is relatively low the characteristics of, rationally using the sensible heat preheating natural gas of high-temperature synthesis gas, produce cleaning
Synthesis gas, reasonable distribution adjusts synthesis gas H/C ratios, for the synthesis material of downstream section.
The present invention carries out distribution using to the synthesis gas that coal gasification and natural gas conversion are produced, and reduces carbon dioxide row
Put, increased synthesis gas yield, reduce greenhouse effect.By said process, achievable raw material abundant profit in process
With, by H/C in adjustment synthesis gas, the hydrocarbon adjustment amplitude of gas is simplified, the consumable goodss such as the energy and catalyst have been saved, increase
The production capacity of end product is added.
【The content of the invention】
[technical problem to be solved]
It is an object of the invention to provide a kind of be converted into the side that based Joint prepares synthesis gas with slip gasification with natural gas
Method.
[technical scheme]
The present invention is achieved through the following technical solutions.
The present invention relates to a kind of be converted into the method that based Joint prepares synthesis gas with slip gasification with natural gas.
The step of the method, is as follows：
A, slip gasification
To contain first hydrocarbon raw material of substance, additive and solvent make a kind of concentration be 50 in terms of dry carbon hydrogen substance weight～
70% slip；Then, allow described slip by slip pipeline 14 and allow oxygen to pass through the Jing nozzles 8 simultaneously of oxygen pipeline 15
In being sprayed onto gasification furnace 1；Described slip and oxygen enter under conditions of 1200～1400 DEG C of 1.0～10.0MPa of pressure and temperature
Row Some redox reacts, and generates and contains CO, H2、CO2、CH4、H2The crude synthesis gas and molten ash of O main components；It is described
Molten ash successively by two-stage nitration heating furnace 2 with one section of heating furnace 3 when lowered the temperature, discharge out-of-bounds from lock hopper 4 in solid form；
Described crude synthesis gas are successively by two-stage nitration heating furnace 2 and one section of heating furnace 3 and the day from gas pipeline 24
So gas heat exchange；The crude synthesis gas of heat exchange enter steam superheater 5 by the pipeline of synthesis gas containing solid particle 16, will be from water vapour
The steam heating of pipeline 22, then passes through solid particle separator feeding pipe 17 and enters solid particle separator 6, wherein
It is separated off the fine ash of the crude synthesis gas entrainment；Described fine ash is discharged out-of-bounds by solid particle separator bottom conduit 20；Remove
The synthesis gas of fine ash is gone to be sent to 1# heat exchangers 7 by solid particle separator top pipeline 18, and from water vapour intake line 21
Water vapour heat exchange, cooled synthesis gas closed by synthesis gas discharge line 19 with the synthesis gas obtained by natural gas conversion
And, follow-up processing system is sent to Jing after distribution；
B, natural gas conversion
Natural gas enters one section of heating furnace 3 by gas pipeline 24, indirect with the crude synthesis gas from two-stage nitration heating furnace 2
Heat exchange, the natural gas of preheating enters desulfurizing tower 9 by preheating gas pipeline 25, removes the sulfide in the natural gas；It is de-
The natural gas of sulfur is sent to two-stage nitration heating by desulphurised natural gas pipeline 26 together with the water vapour sent by superheated steam pipeline 23
Stove 2, they exchange heat here with the crude synthesis gas from gasification furnace 1；The natural gas of heating passes through one-stage converter with water vapour
Feeding pipe 27 is sent to one-stage converter 10, and the natural gas for heating wherein carries out catalytic conversion reaction with water vapour, obtains
One section of conversion gas passes through overheated steam pipe by one-stage converter discharging pipeline 28, oxygen by oxygen pipeline 29 and water vapour
Road 34 is sent to the top of secondary reformer 11 simultaneously, and one section of described conversion gas, oxygen and water vapour enters in secondary reformer 11
Row gas by partial oxidation of natural reacts and vapor catalyzed conversion reaction, obtains containing CO, CO2、H2Synthesis gas；
It is natural gas that described synthesis gas is returned in one-stage converter 10 by secondary reformer furnace bottom discharge line 30
The heat needed for providing is reacted with Steam Reforming；The synthesis gas of heat exchange is sent to by one-stage converter synthesis gas discharge line 31
Steam superheater 12, it reclaims the heat of synthesis gas with the water vapour heat exchange sent by 2# heat-exchanging water vapour-discharge tubes road 35；
Described synthesis gas is sent to 2# heat exchangers 13 by the 2# synthesis gas feeding pipes 32 that exchange heat, it with from water vapour intake line 36
Water vapour heat exchange, realize further cooling, the synthesis gas of cooling is by 2# heat exchange synthesis gas discharge line 33 and above-mentioned slip
The synthesis gas that gasification is obtained merges, and aftertreatment systems process is sent to after distribution.
A preferred embodiment of the invention, it is described containing hydrocarbon raw material of substance be one or more selected from coal,
Biomass, the dregs of fat and other raw materials；Described solvent is one or more selected from water, organic wastewater, carbon monodixe conversion condensation
Liquid and other solvents.
A preferred embodiment of the invention, described additive is one or more selected from lignin sulfonic acid
The additive of sodium, calcium lignosulfonate, polycondensation sodium naphthalene sulfonate, high polymerization sodium naphthalene sulfonate or non-gluey high phosphorus china clay.
Another kind of preferred implementation of the invention, two-stage nitration heating furnace 2 and one section of heating furnace 3 are all hyperthermia radiation pots
Stove.
Another kind of preferred implementation of the invention, described hyperthermia radiation boiler is a kind of in its bottom configuration cloth
Trachea 41, top configuration discharge 42, in the middle of it on the basis of the axis of one section of heating furnace 3 and two-stage nitration heating furnace 2, by high temperature resistant
High-grade alloy steel pipe makes the boiler of tubulation or the composition of coiling coil pipe 40.
Another kind of preferred implementation of the invention, the desulfurizing agent loaded in desulfurizing tower 9 is cobalt molybdenum hydrogen desulfurization agent
And/or Zinc oxide desulfurizer.
Another kind of preferred implementation of the invention, the structure of one-stage converter 10 is tubular type reburner, in pipe
A section of conversion catalyst that filling is sold by Li- ling city Xie Hua Scientific and Technical Industry Co., Ltd of Hunan Province with trade name FZ-3.
Another kind of preferred implementation of the invention, the structure of secondary reformer 11 is material filling type reburner, in stove
The secondary reforming catalyst that filling is sold by Sichuan Tianyi Science ＆ Technology Co., Ltd with trade name Z204.
Another kind of preferred implementation of the invention, the synthesis gas that slip gasification step is obtained and natural gas conversion step
The H/C of the synthesis gas that the synthesis gas for obtaining suddenly is obtained after distribution is 1.0～2.0, its butt composition be by volume 30～
60%CO, 30～60%H2, 10～25%CO2And the N of surplus2、CH4And H2S。
The present invention is described in more detail below.
The present invention relates to a kind of be converted into the method that based Joint prepares synthesis gas with slip gasification with natural gas.
The step of the method, is as follows：
A, slip gasification
To contain first hydrocarbon raw material of substance, additive and solvent make a kind of concentration be 50 in terms of dry carbon hydrogen substance weight～
70% slip；Described is one or more selected from coal, biomass, the dregs of fat and other raw materials containing hydrocarbon raw material of substance；It is described
Solvent be one or more selected from water, organic wastewater, carbon monodixe conversion condensed fluid and other solvents；Described additive is
One or more selected from sodium lignin sulfonate, calcium lignosulfonate, polycondensation sodium naphthalene sulfonate, high polymerization sodium naphthalene sulfonate or non-gluey high
The additive of phosphorus china clay.Then, allow described slip by slip pipeline 14 and allow oxygen to pass through the Jing simultaneously of oxygen pipeline 15
Nozzle 8 is sprayed onto in gasification furnace 1；Described slip is with oxygen in 1.0～10.0MPa of pressure and the condition of 1200～1400 DEG C of temperature
Under carry out Some redox reaction, generate and contain CO, H2、CO2、CH4、H2The crude synthesis gas and molten ash of O main components.
The temperature of the crude synthesis gas discharged from gasification furnace 1 is 1200～1400 DEG C, pressure is 1.0～10.0MPa, vapour content be with
Crude synthesis gas volume is calculated as 10～30%.Dropped when described molten ash is successively by two-stage nitration heating furnace 2 with one section of heating furnace 3
Temperature, discharges out-of-bounds in solid form from lock hopper 4.
Described crude synthesis gas are successively by two-stage nitration heating furnace 2 and one section of heating furnace 3 and the day from gas pipeline 24
So gas heat exchange, reclaims the sensible heat of crude synthesis gas；The crude synthesis gas of heat exchange enter steam by the pipeline of synthesis gas containing solid particle 16
Superheater 5, by from the steam heating on steam pipe road 22, reclaims the heat of crude synthesis gas.Described crude synthesis gas are then
Solid particle separator 6 is entered by solid particle separator feeding pipe 17, the crude synthesis gas entrainment is separated off wherein
Fine ash；Described fine ash is discharged out-of-bounds by solid particle separator bottom conduit 20；The synthesis gas of fine ash is removed by solid
Grain separator top pipeline 18 is sent to 1# heat exchangers 7, exchanges heat with the water vapour from water vapour intake line 21, cooled conjunction
Merged with the synthesis gas obtained by natural gas conversion by synthesis gas discharge line 19 into gas, follow-up process is sent to Jing after distribution
System.
Described two-stage nitration heating furnace 2 and one section of heating furnace 3 is hyperthermia radiation boiler.
Described hyperthermia radiation boiler is that a kind of steel of included heat exchanger tube is pressure with heatproof equipment, generally heats two-stage nitration
Stove 2 and one section of heating furnace 3 and the being made of one equipment of gasification furnace 1.In such a device, described heat exchanger tube is gas distribution by bottom
Pipe 41, top is discharge 42, on the basis of two-stage nitration heating furnace 2 and one section of axis of heating furnace 3, by high temperature resistant high-grade alloy steel pipe
Make tubulation or coiling coil pipe 40 is constituted, the resistant to elevated temperatures Incoly600 that the senior alloy is e.g. sold in the market is closed
Golden material, concrete structure is referring to accompanying drawing 2.High temperature resistant nonmetallic materials are applied in the coil surface contacted with high-temperature gas, for example
Resistant to elevated temperatures SiC coatings.Described heat exchanger tube can also be the middle high temperature resistant high-grade alloy steel pipe for straight tube, the alloy pipe
The resistant to elevated temperatures Incoly600 alloy pipes e.g. sold in the market.In the heat exchange pipe surface contacted with high-temperature gas
High temperature resistant nonmetallic materials are scribbled, such as resistant to elevated temperatures SiC coatings.
Solid particle separator 6 is the product sold in the market, such as Fushun Ende Machinery Co., Ltd.'s production
Cyclone separator, the cyclone separator of Nanjing Zhong Jian chemical machineries Manufacturing Co., Ltd production.
Steam superheater 5 and 1# heat exchangers 7 are the products sold in the market, and for example boiler Limited Liability in Harbin is public
The shell-and-tube heat exchanger of department's production, the shell-and-tube heat exchanger of east boiler Co., Ltd production, wherein passing through cold flow in pipe
Body or hot fluid.The hot fluid that the present invention is used is synthesis gas, and in heat exchanger, hot synthesis gas carry out heat exchange with water vapour,
Synthesis gas be cooled, water vapour be heated/it is overheated.
According to the present invention, the polynary slurry gasification system partial picture such as described nozzle 8, gasification furnace 1, lock hopper 4 specifically may be used
With referring to ZL 200810132975.4.
In this step, CO, H in described synthesis gas2、CO2、CH4Analysis method be all to adopt GB/T27885-
2011 and GB/T10410-2008 standard analysiss.
The chemical composition of synthesis gas is 38～48%CO, 30～40%H by volume obtained by the step2, 15～
25%CO2, the N of surplus2、CH4And H2S。
B, natural gas conversion
Gas pressure is promoted to into 3.0～3.5MPa, allows natural gas to enter one section of heating furnace by gas pipeline 24
3, with the crude synthesis gas indirect heat exchange from two-stage nitration heating furnace 2, natural gas is heated to 320～340 DEG C from room temperature；The day of preheating
So gas enters desulfurizing tower 9 by preheating gas pipeline 25, removes the sulfide in the natural gas, contains the sulfur in unstripped gas
Amount is down to below 0.1ppm.
The natural gas of desulfurization is sent by desulphurised natural gas pipeline 26 together with the water vapour sent by superheated steam pipeline 23
To two-stage nitration heating furnace 2, they exchange heat here with the crude synthesis gas from gasification furnace 1；The natural gas of heating passes through with water vapour
One-stage converter feeding pipe 27 is sent to one-stage converter 10, described one-stage converter 10 manage in be filled with one section of conversion catalyst
Agent, the natural gas for heating wherein carries out catalytic conversion reaction with water vapour, from one section of conversion gas that one-stage converter 10 is discharged
In, methane content is about by volume 30%, about 660～690 DEG C of temperature.
The one section of conversion gas for obtaining discharges pipeline 28, oxygen by oxygen pipeline 29 and water vapour by one-stage converter
The top of secondary reformer 11 is sent to by superheated steam pipeline 34 simultaneously, one section of described conversion gas, oxygen and water vapour is two
Gas by partial oxidation of natural reaction and vapor catalyzed conversion reaction, remaining natural gas in one section of conversion gas are carried out in section reburner 11
Basic conversion is complete, obtains containing CO, CO2、H2Synthesis gas；Described secondary reformer 11 is filled with secondary reforming catalyst,
About 960～1000 DEG C of the synthesis gas temperature of generation.
It is natural gas that described synthesis gas is returned in one-stage converter 10 by secondary reformer furnace bottom discharge line 30
The heat needed for providing is reacted with Steam Reforming；The synthesis gas of heat exchange is sent to by one-stage converter synthesis gas discharge line 31
Steam superheater 12, it reclaims the heat of synthesis gas with the water vapour heat exchange sent by 2# heat-exchanging water vapour-discharge tubes road 35.
Described synthesis gas is sent to 2# heat exchangers 13 by the 2# synthesis gas feeding pipes 32 that exchange heat, it with from water vapour intake line 36
Water vapour heat exchange, realize further cooling, the synthesis gas of cooling is by 2# heat exchange synthesis gas discharge line 33 and above-mentioned slip
The synthesis gas that gasification is obtained merges, and aftertreatment systems process is sent to after distribution.
The cobalt molybdenum hydrogen desulfurization agent and/or Zinc oxide desulfurizer that desulfurizing tower 9 is used in the present invention is all in the market
The product of sale.The cobalt molybdenum hydrogen desulfurization agent for example sold with trade name T201 by Xibei Chemical Inst；By the polycyclic of Beijing three
Protect the cobalt molybdenum hydrogen desulfurization agent that new material limited company is sold with trade name T201.By Xibei Chemical Inst with trade name
The Zinc oxide desulfurizer of T305 sale；The Zinc oxide desulfurizer sold with trade name EZ-2 up to environmentally friendly company limited by Hunan ring；
By the fast Zinc oxide desulfurizer sold with trade name Z919 up to Chemical Co., Ltd. in Shandong.
In the present invention, described natural gas conversion is converted using segmented mode.The structure of one-stage converter 10 turns for tubular type
Change stove, a section of conversion catalyst is filled with pipe, natural gas and water vapour are by the way that wherein, conversion institute calorific requirement is by secondary reformer
11 synthesis gas for producing are provided.The structure of secondary reformer 11 is material filling type reburner, is filled with secondary reforming catalyst in stove, one
There is conversion reaction in section conversion gas, oxygen and water vapour, generate synthesis gas in stove.
Described one section of natural gas, secondary reformer are a kind of product sold in the market, such as Nanjing chemical industry machine
Pressure, the high temperature resistant natural gas reformer of tool Manufacturing Co., Ltd production, the natural gas conversion of the factory of nuclear industry Xi'an 524 production
Stove.
A section of conversion catalyst, secondary reforming catalyst are all the products sold in the market in described natural gas conversion
Product.The a section of conversion catalyst for example sold with trade name FZ-3 by Li- ling city Xie Hua Scientific and Technical Industry Co., Ltd of Hunan Province；By
The secondary reforming catalyst that Sichuan Tianyi Science ＆ Technology Co., Ltd is sold with trade name Z204.
Synthesis gas composition after natural gas conversion is 25-35%CO, 55-65%H by volume2, 3-20%CO2、0.2-
1.1%CH4, the N of surplus2And H2S。
In this step, CO, H in described synthesis gas2、CO2、CH4Analysis method be all to adopt GB/T27885-
2011 and GB/T10410-2008 standard analysiss.
Described steam superheater 12 and 2# heat exchangers 13 is all a kind of product sold in the market, such as Harbin
The shell-and-tube heat exchanger of boiler Co., Ltd production, the shell-and-tube heat exchanger of east boiler Co., Ltd production.
The H/C of gas is about 1.0～2.0 after the synthesis gas ECDC reason distribution that step A of the present invention is obtained with step B, the conjunction
Butt composition into gas is by volume:30～60%CO, 30～60%H2, 10～25%CO2, the N of surplus2、CH4And H2S。
The synthesis gas that step A of the present invention and step B are obtained after distribution gas can without or a small amount of conversion, can be direct
For methanol-fueled CLC and/or the raw material of oil from Fischer-Tropsch synthesis.The synthesis gas that the coal per ton that gasifies is produced converts less 40～600Nm3/ ton
Coal, CO2Reduce discharging 20～300Nm3/ ton coal.
The present invention is converted into based Joint and prepares synthetic gas method with slip gasification with natural gas has following features：
1st, in slip gasification synthesis gas H/C than 0.5～0.9, natural gas convert H/C than 1.8～3.0.The inventive method is adopted
The method for combining is converted with slip gasification, two sections of natural gas, the synthesis gas that slip gasification and natural gas conversion are obtained is carried out
Rationally distribution, H/C ratios are adjusted to 0.8～2.0, it is to avoid using H/C in single slip gasification synthesis gas than too low, and adopt single
One natural gas converts H/C than too high problem, reduces the waste of carbon, hydrogen resource and power.
2nd, two kinds of synthesis gas are carried out into reasonable distribution, just can reduces slip gasification conversion degree.The coal per ton that gasifies is produced
Raw synthesis gas converts less 40～600Nm3/ ton coal, CO2Reduce discharging 20～300Nm3/ ton coal, reduces conversion process medium temperature chamber gas
Body CO2Discharge, while converting the enough carbon of supplement for natural gas, improve the yield of chemical industry synthesis product.
3rd, the synthesis gas temperature that slip gasification is produced is high, and sensible heat is big, can be used to preheat natural gas, is rationally closed using high temperature
Into the high level heat of gas, natural gas is reduced as the consumption of fuel.Both techniques are combined, and energy consumption decreasing value is natural gas and slip
The heat exchange amount of the synthesis gas of gasification, is converted into natural gas volume about 200～2000Nm3/h。
4th, the slip gasification process and natural gas conversion process that the present invention is adopted is maturation process, and technical process is easy to real
It is existing, two kinds of techniques are carried out into reasonable combination, the arrangement of device is more becoming tight and gathers, the utilization rate of lifting device.
5th, the present invention converts joint and prepares synthesis device of air, the process stream kind that device needs for slip gasification, natural gas
Class is less, the inner loop of the achievable logistics of the present invention, realizes the inside supply of water, steam, part material, realizes resource most
The purpose that bigization is utilized.
[beneficial effect]
The present invention has following good effects：
1st, it is 0.5～0.9 using the H/C ratios of synthesis gas obtained by slip evaporating method, obtained by natural gas conversion method
The H/C ratios of synthesis gas are 1.8～3.0.The method of the present invention is the method that slip gasifies in combination with natural gas converts two sections, will
The synthesis gas that they are obtained carries out reasonable distribution, and H/C ratios can reach 0.8～2.0, in can be to avoid the gasification of single slip from closing
H/C is than too low in gas, and single natural gas conversion H/C reduces the waste of carbon, hydrogen resource and power than too high problem.
2nd, two kinds of synthesis gas are carried out into reasonable distribution, just can reduces slip gasification conversion degree.The coal per ton that gasifies is produced
Raw synthesis gas converts less 40～600Nm3/ ton coal, CO2Reduce discharging 20～300Nm3/ ton coal, reduces conversion process medium temperature chamber gas
Body CO2Discharge, while converting the enough carbon of supplement for natural gas, improve the yield of chemical industry synthesis product.
3rd, the synthesis gas temperature that slip gasification is produced is high, and sensible heat is big, can be used to preheat natural gas, is rationally closed using high temperature
Into the high level heat of gas, natural gas is reduced as the consumption of fuel.Both techniques are combined, fuel reduction be natural gas with
The heat exchange amount of slip gasification synthesis gas, is converted into natural gas volume about 200～2000Nm3/ h, its reducing energy consumption is clearly.
4th, the slip gasification process and natural gas conversion process that the present invention is adopted is maturation process, and technical process is easy to real
It is existing, two kinds of techniques are carried out into reasonable combination, the arrangement of device is more becoming tight and gathers, the utilization rate of lifting device.
5th, the present invention converts joint and prepares synthesis device of air, the process stream kind that device needs for slip gasification, natural gas
Class is less, the inner loop of the achievable logistics of the present invention, realizes the inside supply of water, steam, part material, realizes resource most
The purpose that bigization is utilized.
The present invention is converted into based Joint and is prepared synthesis gas process with slip gasification, natural gas, with former containing hydrocarbon substance
Material, natural gas, oxygen are primary raw material, while comprehensively utilizing waste water, the waste gas of periphery, reduce waste processing cost, are reduced
Production cost, improves environment, improves resource utilization, has saved resource, expands product category and production scale, accords with
The circular economy policy that country implements is closed, the requirement built a resource-conserving and environment-friendly society of country's proposition is also complied with.
In a word, the method for the present invention using hydrocarbon substance, natural gas be raw material, by way of optimum organization with it is relatively low into
Originally and environmentally friendly the synthesis gas with high added value is produced, is China's non-renewable resources high value added utilization, chemical industry
Industry development, environmental conservation task make significant contribution.
【Description of the drawings】
Fig. 1 is that the present invention is converted into the flow chart that based Joint prepares synthetic gas method with slip gasification with natural gas.
In figure：
1- gasification furnaces, 2- two-stage nitration heating furnaces, mono- section of heating furnace of 3-, 4- lock hoppers, 5- steam superheaters, 6- solid particles are separated
Device, 7-1# heat exchangers, 8- nozzles, 9- desulfurizing towers, 10- one-stage converters, 11- secondary reformers, 12- steam superheaters, 13-2#
Heat exchanger, 14- slip pipelines, 15- oxygen pipelines, 16- synthesis gas containing solid particle pipeline, the charging of 17- solid particle separators
Pipeline, 18- solid particle separators top pipeline, 19- synthesis gas discharge lines, 20- solid particle separator bottom conduits,
21- water vapour intake lines, 22- water vapour pipelines, 23- superheated steam pipelines, 24- gas pipelines, 25- preheating natural gas tubes
Road, 26- desulphurised natural gas pipelines, 27- one-stage converter feeding pipes, 28- one-stage converters discharging pipeline, 29- oxygen pipelines,
30- secondary reformer furnace bottom discharge lines, 31- one-stage converter synthesis gas discharge lines, 32-2# heat exchange synthesis gas feed pipes
Road, 33-2# heat exchange synthesis gas discharge lines, 34- superheated steam pipelines, 35-2# heat-exchanging water vapour-discharge tubes road, 36- water vapour
Intake line.
Fig. 2 is one section of heating furnace 3 and the heat exchange tube structure schematic diagram of two-stage nitration heating furnace 2；
In figure：
A- gas distribution pipe profiles；B- heat exchanger tubes arrange side view；C- discharge profiles.
40- coil pipes, 41- gas distribution pipes, 42- discharges.
【Specific embodiment】
The present invention is will be better understood that by following embodiments.
Embodiment 1：The present invention is converted into based Joint and prepares synthesis gas with slip gasification with natural gas
The embodiment is listed in Table 1 below using the composition of coal, and the composition (with butt stereometer) of natural gas is listed in Table 2 below.
Table 1：The composition of feed coal
Table 2：Natural gas butt is constituted, with total volume meter
The embodiment is implemented according to the technological process that this specification accompanying drawing 1 is described.
Specific implementation step is as follows：
The feed coal of moisture content 10% about 25010.66kg/h, makes with water and a small amount of additive (the high sodium naphthalene sulfonate that is polymerized)
A kind of slip of concentration in terms of dry coal weight 60%, slip flow about 37515.98kg/h, slip is sent by slip pipeline 14
It is 15463.54Nm to nozzle 8, Jing nozzles 8 and from the flow of oxygen pipeline 153The oxygen of/h sprays into together gasification furnace 1.
Described slip, oxygen carry out Some redox reaction under conditions of 1350 DEG C of pressure 6.5MPa and temperature,
Generate and contain CO, H2、CO2、CH4、H2O is the high-temperature crude synthesis gas of main component and the mixture of melting warm sludge.High-temperature synthesis gas
Total tolerance is about 52391.91Nm3/ h, containing H2O about 22%, its butt composition is as follows by volume：CO～46%, H2～34%,
CO2～19%, other N2、CH4、H2S≤1%, about 1350 DEG C of gas temperature, pressure 6.4MPa.The molten ash flow of generation
4437.36kg/h, after lowering the temperature in two-stage nitration heating furnace 2 and one section of heating furnace 3, discharges out-of-bounds in solid form from lock hopper 4.
Described crude synthesis gas Jing two-stage nitration heating furnace 2 and one section of heating furnace 3 is changed with the natural gas from gas pipeline 24
Heat, reclaims the sensible heat of synthesis gas.One section of heating furnace 3 and two-stage nitration heating furnace 2 are hyperthermia radiation boilers, and synthesis gas is by 1350 DEG C of temperature
550 DEG C of temperature is reduced to, natural gas is heated to 480 DEG C of temperature from room temperature.
The crude synthesis gas ECDC of heat exchange enters steam superheater 5 into air pipe 16, what heating was sent by water vapour pipeline 22
Flow is 118267.62Nm3The water vapour of/h, crude synthesis gas are reduced to 350 DEG C of temperature for 550 DEG C by temperature, and water vapour is from temperature
310 DEG C are heated to 340 DEG C of temperature, reclaim the heat of crude synthesis gas.Described crude synthesis gas are entered by solid particle separator
Expects pipe road 17 is sent to solid particle separator 6, is separated off the fine ash carried secretly in synthesis gas, and described fine ash is by solid particle
Separator bottom pipeline 20 is discharged out-of-bounds.
The synthesis gas for removing fine ash is sent to 1# heat exchangers 7 by solid particle separator top pipeline 18, with water vapour input
The water vapour heat exchange of pipeline 21, cooled synthesis gas is reduced to 200 DEG C of temperature by 350 DEG C of temperature, and water vapour is from 160 DEG C of temperature
It is heated to 270 DEG C of temperature.The synthesis gas that synthesis gas ECDC after cooling is obtained into after gas discharge line 19 and natural gas conversion
Merge, carry out reasonable distribution.
The flow of natural gas is 20740.39Nm3/ h, boost in pressure to 3.2MPa, Jing gas pipelines 24 add into one section
Hot stove 3, with the synthesis gas indirect heat exchange from two-stage nitration heating furnace 2, about 340 DEG C of the natural gas temperature of preheating, preheated natural gas
Pipeline 25 enters the desulfurizing tower 9 for being filled with cobalt molybdenum hydrogen desulfurization agent, removes the sulfide in natural gas, contains the sulfur in unstripped gas
Amount is down to below 0.1ppm.
320 DEG C of desulphurised natural gas temperature, it is by desulphurised natural gas pipeline 26 and the temperature sent by superheated steam pipeline 23
The water vapour of 340 DEG C of degree is sent to together two-stage nitration heating furnace 2, and they exchange heat here with the crude synthesis gas from gasification furnace 1, natural
Gas and water vapour are heated to 480 DEG C of temperature for 340 DEG C from temperature.Natural gas exchanges heat with the synthesis gas of slip gasification, and energy consumption is reduced
It is worth the heat exchange amount for both, is converted into natural gas volume about 1155.67Nm3/h。
The natural gas of heating is sent to one-stage converter 10 with water vapour by one-stage converter feeding pipe 27.One section of conversion
Stove 10 is filled with a section of conversion catalyst in managing, and one section of conversion reaction is carried out when natural gas and water vapour are by pipe, and conversion is anti-
Heat that should be required is provided by the synthesis gas that secondary reformer 11 is obtained.In the one section of conversion gas discharged from one-stage converter 10
Middle methane content is by volume 30%, and its temperature is 690 DEG C.
The one section of conversion gas for obtaining discharges pipeline 28, oxygen with flow 15401.69Nm by one-stage converter3/ h passes through
Oxygen pipeline 29 and water vapour are with flow 2000.42Nm3/ h is sent to secondary reformer 11 simultaneously by superheated steam pipeline 34
Top.One section of described conversion gas, oxygen and water vapour carries out gas by partial oxidation of natural reaction in secondary reformer 11 and steams
Vapour catalytic conversion reaction, remaining natural gas is substantially completely converted in one section of conversion gas, is obtained containing CO, CO2、H2Synthesis gas,
Its butt composition is as follows：31%CO, 64%H by volume2, 3.0%CO2、CH4<0.5%, other O2、H2S<1.5%, its temperature
Degree about 980 DEG C, flow about 69862.13Nm3/h。
Described synthesis gas Jing secondary reformer furnace bottoms discharge line 30 returned to and exchanged heat between the pipe of one-stage converter 10, is
Natural gas and Steam Reforming reaction provide required heat, and the temperature of the synthesis gas is down to 600 DEG C.Heat exchange synthesis gas passes through one
Section reburner synthesis gas discharge line 31 enters steam superheater 12 and further lowers the temperature, and heats by 2# heat-exchanging water vapour-discharge tubes road
35 water vapour sent, reclaim its synthesis gas heat, and steam temperature reaches 270 DEG C by 160 DEG C of heating/overheated.Described conjunction
2# heat exchangers 13 are sent to into gas Jing 2# heat exchange synthesis gas feeding pipe 32, are changed with the water vapour from water vapour intake line 36
Heat, realizes further cooling, and the temperature of synthesis gas of lowering the temperature is further reduced to 200 DEG C, and the steam for obtaining can be supplied in addition or itself
Use；The synthesis gas of cooling is merged by the synthesis gas that 2# heat exchange synthesis gas discharge line 33 is obtained with the gasification of above-mentioned slip, is matched somebody with somebody
Aftertreatment systems process is sent to after gas.
Whole slip gasification synthesis gas and the gas flow 122250.66Nm of all natural gas transformation of synthetic gas distribution3/ h,
Its butt composition is by volume:30%CO, 57%H2, 12%CO2, the N of surplus2、CH4And H2S.H/C ratios are 1.94, and gasification is every
Ton coal can reduce the synthesis gas about 422.16Nm of conversion3/ ton coal, CO2Reduce discharging 191.66Nm3/ ton coal.
Embodiment 2：The present invention is converted into based Joint and prepares synthesis gas with slip gasification with natural gas
Implement the present invention by primary raw material of somewhere coal, feed coal analytical data is listed in Table 3 below, natural gas butt composition row
In table 4.
Table 3：The composition of feed coal
Table 4：Natural gas butt is constituted, with total volume meter
| Composition | CH4 | C2H6 | C3H8 | N2 | H2S |
| Volume vol% | 95.0% | 1.0% | 0.9% | 3.0% | It is micro |
The specific implementation step of the embodiment is identical with embodiment 1, simply somewhere feed coal 13291.9kg/h, with water
And a small amount of additive (height polymerization sodium naphthalene sulfonate) makes concentration 56%, the slip of flow 20623.8kg/h, oxygen flow
12237.2Nm3/ h, slip and oxygen Jing nozzles 8 spray into gasification furnace 1,1320 DEG C of gasification reaction pressure 4.5MPa, temperature.Reaction
The lime-ash flow discharged from lock hopper 4 afterwards is 1460.1kg/h, and high warm and humid synthesis gas flow is 15805.3Nm3/ h, containing H2O is measured
30%, its butt composition volume ratio is as follows：CO 39.2%, H235.4%th, CO224.6%, other N2、CH4And H2S etc. is less than
1%, 1320 DEG C and pressure 4.5MPa of the temperature of synthesis gas.
Described synthesis gas Jing two-stage nitration heating furnace 2 and one section of heating furnace 3 and heat exchange gas.The synthesis gas of heat exchange is entered and steamed
Vapour superheater 5, by flow 4313.18Nm3The steam heating of/h, crude synthesis gas temperature is reduced to 350 DEG C.Described thick synthesis
Gas enters solid particle separator 6, and the fine ash carried secretly in separating synthetic gas, fine ash is discharged out-of-bounds.The synthesis gas for removing fine ash enters
Enter 1# heat exchangers 7, with water vapour heat exchange, the synthesis gas temperature is reduced to 200 DEG C.Obtain after the synthesis gas of cooling and natural gas conversion
The synthesis gas for arriving merges, and carries out distribution.
The flow of natural gas is about 12823.78Nm3/ h, boost in pressure to 3.0MPa, into one section of heating furnace 3, with from
The synthesis gas indirect heat exchange of two-stage nitration heating furnace 2, into desulfurizing tower 9, removes the sulfide in natural gas.Desulphurised natural gas are steamed with water
Vapour is mixed into two-stage nitration heating furnace 2, and the synthesis gas obtained with gasification furnace 1 exchanges heat.Natural gas exchanges heat with the synthesis gas of slip gasification,
Energy consumption decreasing value is both heat exchange amounts, is converted into natural gas volume about 362.53Nm3/h.Natural gas and water vapour after heating
Into one-stage converter 10, one section of conversion reaction is carried out, generate one section of conversion gas.
Described one section converts gas and 7630.18Nm3/ h oxygen, 2124.85Nm3/ h water vapour enters two process transform simultaneously
, there is gas by partial oxidation of natural reaction and vapor catalyzed conversion reaction in the top of stove 11, generate and contain CO, CO2、H2Synthesis gas.Should
Synthesis gas butt composition is as follows：28.0%CO, 57.0%H by volume2, 13.0%CO2、CH4<1%, other<1%, flow is about
32447.24Nm3/h.Described synthesis gas is returned between the pipe of one-stage converter 10, there is provided the heat needed for one section of conversion reaction
Amount.The synthesis gas of heat exchange is lowered the temperature into steam superheater 12, is entered back into 2# heat exchangers 13 and is further lowered the temperature.The synthesis gas of cooling with
The synthesis gas obtained after slip gasification merges, and carries out reasonable distribution.
Whole slip gasification synthesis gas and portion of natural gas transformation of synthetic gas distribution, gas flow about 17427.64Nm3/ h,
Its butt composition is by volume:～37.8%CO ,～38.2%H2,～23.0%CO2, the N of surplus2、CH4And H2S.H/C is about
1.01, the coal per ton that gasifies can reduce the synthesis gas about 92.01Nm of conversion3/ ton coal, CO2Reduce discharging 36.04Nm3/ ton coal.
Embodiment 3：The present invention is converted into based Joint and prepares synthesis gas with slip gasification with natural gas
Implement the present invention by primary raw material of somewhere coal, feed coal analytical data is listed in Table 5 below, natural gas butt composition row
In table 6.
Table 5：The composition of feed coal
Table 6：Natural gas butt is constituted, with total volume meter
The specific implementation step of the embodiment is identical with embodiment 1, from somewhere feed coal about 14503.07kg/h, with
Water and a small amount of additive (height polymerization sodium naphthalene sulfonate) make the concentration about 57%, slip of flow 25443.99kg/h, oxygen flow
8628.82Nm3/ h, slip and oxygen Jing nozzles 8 are sprayed in gasification furnace 1,1300 DEG C of gasification reaction pressure 4.2MPa, temperature.Instead
The lime-ash flow discharged from lock hopper 4 after answering is 1663.13kg/h, and high warm and humid synthesis gas flow is 23063.20Nm3/ h, containing H2O is measured
For 29%, its butt composition is as follows：By volume, CO 44.2%, H233.6%th, CO221.5%, other N2、CH4And H2S etc.
Less than 1%, 1300 DEG C and pressure 4.2MPa of the temperature of crude synthesis gas.
Described crude synthesis gas Jing two-stage nitration heating furnace 2 and one section of heating furnace 3 and heat exchange gas.The synthesis gas of heat exchange is entered
Steam superheater 5, is 7863.50Nm by flow3The steam heating of/h, synthesis gas temperature is reduced to～350 DEG C.Described is thick
Synthesis gas enters solid particle separator 6, and the fine ash carried secretly in separating synthetic gas, fine ash is discharged out-of-bounds.Remove the synthesis of fine ash
Gas enters 1# heat exchangers 7, and with water vapour heat exchange, synthesis gas temperature is reduced to 200 DEG C.After the synthesis gas of cooling is converted with natural gas
The synthesis gas for obtaining merges, and carries out reasonable distribution.
The flow of natural gas is about 18883.79Nm3/ h, boost in pressure to 3.1MPa, into one section of heating furnace 3, with from
The synthesis gas indirect heat exchange of two-stage nitration heating furnace 2, enters back into desulfurizing tower 9, removes the sulfide in natural gas.The natural gas of desulfurization with
Water vapour is mixed into two-stage nitration heating furnace 2, and the synthesis gas obtained with gasification furnace 1 exchanges heat.The natural gas of desulfurization with by slip gasify
The synthesis gas heat exchange for obtaining, energy consumption decreasing value is heat exchange amount, is converted into natural gas volume about 522.06Nm3/h.The day of heating
So gas and water vapour enter one-stage converter 10, carry out one section of conversion reaction, obtain one section of conversion gas.
One section of described conversion gas, 11669.35Nm3/ h oxygen and 3546.40Nm3/ h water vapour is sent to two process transform simultaneously
The top of stove 11, carries out gas by partial oxidation of natural reaction and vapor catalyzed conversion reaction, obtains containing CO, CO2、H2Wet synthesis gas,
Its flow is 51310.7Nm3/ h, the butt composition of the synthesis gas is as follows：28.6%CO, 58.9%H by volume2, 10.7%
CO2、CH4<1%, other components<1%.Described synthesis gas is returned between the pipe of one-stage converter 10, is that one section of conversion reaction is carried
For required heat.The synthesis gas of heat exchange is sent to steam superheater 12 and lowers the temperature, and enters back into 2# heat exchangers 13 and further lowers the temperature.Cooling
The gasification of synthesis gas and slip after the synthesis gas that obtains merges, aftertreatment systems are sent to after distribution and are processed.
Whole slip gasification synthesis gas and portion of natural gas transformation of synthetic gas distribution, its gas flow about 38456.41Nm3/
H, its butt is constituted is:37.0%CO, 45.2%H by volume2, 16.5%CO2, the N of surplus2、CH4And H2S.Its H/C ratios
It is 1.22, the coal per ton that gasifies can reduce the synthesis gas about 182.06Nm of conversion3/ ton coal, CO2Reduce discharging 118.9Nm3/ ton coal.
Claims (9)
1. it is a kind of that the method that based Joint prepares synthesis gas is converted into natural gas with slip gasification, it is characterised in that the method
Step is as follows：
A, slip gasification
It is containing in terms of hydrocarbon raw material of substance weight 50 by dry that hydrocarbon raw material of substance, additive and solvent will be contained first to make a kind of concentration
~ 70% slip；Then, described slip is allowed to pass through slip pipeline（14）And allow oxygen to pass through the first oxygen pipeline（15）Together
When Jing nozzles（8）It is sprayed onto gasification furnace（1）In；Described slip is with oxygen in 1200 ~ 1400 DEG C of 1.0 ~ 10.0MPa of pressure and temperature
Under conditions of carry out Some redox reaction, generate and contain CO, H2、CO2、CH4、H2The crude synthesis gas of O main components and melting
Lime-ash；Described molten ash successively passes through two-stage nitration heating furnace（2）With one section of heating furnace（3）When lowered the temperature, in solid form from
Lock hopper（4）Discharge out-of-bounds；
Described crude synthesis gas successively pass through two-stage nitration heating furnace（2）With one section of heating furnace（3）With from gas pipeline（24）'s
Heat exchange gas；The crude synthesis gas of heat exchange are by the pipeline of synthesis gas containing solid particle（16）Into the first steam superheater（5）, will
From water vapour pipeline（22）Steam heating, then pass through solid particle separator feeding pipe（17）Into solid particle
Separator（6）, the fine ash of the crude synthesis gas entrainment is separated off wherein；Described fine ash is by solid particle separator lower tube
Road（20）Discharge out-of-bounds；The synthesis gas of fine ash is removed by solid particle separator top pipeline（18）It is sent to 1# heat exchangers（7）, with
From the first water vapour intake line（21）Water vapour heat exchange, cooled synthesis gas passes through synthesis gas discharge line（19）With
The synthesis gas obtained by natural gas conversion merges, and follow-up processing system is sent to Jing after distribution；
B, natural gas conversion
Natural gas passes through gas pipeline（24）Into one section of heating furnace（3）, and from two-stage nitration heating furnace（2）Crude synthesis gas between
Heat exchange is connect, the natural gas of preheating is by preheating gas pipeline（25）Into desulfurizing tower（9）, remove the sulfuration in the natural gas
Thing；The natural gas of desulfurization passes through desulphurised natural gas pipeline（26）With by the first superheated steam pipeline（23）The water vapour sent is together
It is sent to two-stage nitration heating furnace（2）, they here with from gasification furnace（1）Crude synthesis gas heat exchange；The natural gas of heating steams with water
Vapour passes through one-stage converter feeding pipe（27）It is sent to one-stage converter（10）, the natural gas for heating wherein carries out with water vapour
Catalytic conversion reaction, for obtaining section is converted gas and is discharged pipeline by one-stage converter（28）, oxygen pass through the second oxygen pipeline
（29）And water vapour passes through the second superheated steam pipeline（34）It is sent to secondary reformer simultaneously（11）Top, described one section turns
Activating QI, oxygen and water vapour are in secondary reformer（11）In carry out gas by partial oxidation of natural reaction and vapor catalyzed conversion reaction,
Obtain containing CO, CO2、H2Synthesis gas；
Described synthesis gas passes through secondary reformer furnace bottom discharge line（30）Return to one-stage converter（10）In be natural gas
The heat needed for providing is reacted with Steam Reforming；The synthesis gas of heat exchange passes through one-stage converter synthesis gas discharge line（31）Send
To the second steam superheater（12）, it with pass through 2# heat-exchanging water vapour-discharge tubes road（35）Synthesis is reclaimed in the water vapour heat exchange sent
The heat of gas；Described synthesis gas is by 2# heat exchange synthesis gas feeding pipes（32）It is sent to 2# heat exchangers（13）, it with from the
Two water vapour intake lines（36）Water vapour heat exchange, realize further cooling, the synthesis gas of cooling is exchanged heat synthesis gas by 2#
Discharge line（33）The synthesis gas obtained with the gasification of above-mentioned slip merges, and aftertreatment systems process is sent to after distribution.
2. method according to claim 1, it is characterised in that described is to be selected from for one or more containing hydrocarbon raw material of substance
Coal, biomass, the dregs of fat and other raw materials；Described solvent is one or more cold selected from water, organic wastewater, carbon monodixe conversion
Lime set and other solvents.
3. method according to claim 1, it is characterised in that described additive is one or more selected from sulfomethylated lignin
The additive of sour sodium, calcium lignosulfonate, polycondensation sodium naphthalene sulfonate, high polymerization sodium naphthalene sulfonate or non-gluey high phosphorus china clay.
4. method according to claim 1, it is characterised in that two-stage nitration heating furnace（2）With one section of heating furnace（3）All it is high temperature
Radiant boiler.
5. method according to claim 4, it is characterised in that described hyperthermia radiation boiler is a kind of in its bottom configuration
Gas distribution pipe（41）, top configuration discharge（42）, in the middle of it with one section of heating furnace（3）With two-stage nitration heating furnace（2）Axis be base
Standard, by high temperature resistant high-grade alloy steel pipe tubulation or coiling coil pipe are made（40）The boiler of composition.
6. method according to claim 1, it is characterised in that desulfurizing tower（9）The desulfurizing agent of middle filling is cobalt molybdenum hydrodesulfurization
Agent and/or Zinc oxide desulfurizer.
7. method according to claim 1, it is characterised in that one-stage converter（10）Structure be tubular type reburner, pipe
It is interior to load a section of conversion catalyst sold with trade name FZ-3 by Li- ling city Xie Hua Scientific and Technical Industry Co., Ltd of Hunan Province.
8. method according to claim 1, it is characterised in that secondary reformer（11）Structure be material filling type reburner, stove
It is interior to load the secondary reforming catalyst sold with trade name Z204 by Sichuan Tianyi Science ＆ Technology Co., Ltd.
9. method according to claim 1, it is characterised in that（A）Synthesis gas that slip gasification step is obtained with（B）It is natural
The H/C of the synthesis gas that the synthesis gas that gas step of converting is obtained is obtained after distribution is 1.0 ~ 2.0, and its butt composition is with volume
30 ~ 60%CO of meter, 30 ~ 60%H2、10~25%CO2And the N of surplus2、CH4And H2S。
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| US20110284800A1 (en) * | 2008-11-21 | 2011-11-24 | Robert Millner | Method and device for producing a raw synthesis gas |
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| CN103896209A (en) * | 2014-03-07 | 2014-07-02 | 陕西延长石油（集团）有限责任公司 | Method for producing synthesis gas by catalytically reforming coal, natural gas and carbon dioxide |
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| CN101407313A (en) * | 2008-07-04 | 2009-04-15 | 西北化工研究院 | Method for producing synthesis gas from hydrocarbon substance-containing slurry |
| US20110284800A1 (en) * | 2008-11-21 | 2011-11-24 | Robert Millner | Method and device for producing a raw synthesis gas |
| CN102660339A (en) * | 2012-04-27 | 2012-09-12 | 阳光凯迪新能源集团有限公司 | Gas-steam efficient cogeneration process and system based on biomass gasification and methanation |
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