CN110003961A - A kind of method of subcritical water depolymerization hydrocarbon preparing natural gas - Google Patents
A kind of method of subcritical water depolymerization hydrocarbon preparing natural gas Download PDFInfo
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- CN110003961A CN110003961A CN201910339795.1A CN201910339795A CN110003961A CN 110003961 A CN110003961 A CN 110003961A CN 201910339795 A CN201910339795 A CN 201910339795A CN 110003961 A CN110003961 A CN 110003961A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/08—Production of synthetic natural gas
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
- C10L3/102—Removal of contaminants of acid contaminants
- C10L3/103—Sulfur containing contaminants
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of methods of subcritical water depolymerization hydrocarbon preparing natural gas, this method comprises: subcritical water and dry pulverized coal or water-coal-slurry being carried out heat exchange gasification in closed reactor, and then methanation reaction occurs, methane gas being made.Method of the invention carries out heat exchange gasification by subcritical water and dry pulverized coal or water-coal-slurry using subcritical water as reactant and heat source agent, without adding catalyst, avoids addition catalyst bring environmental pollution, and reduce the cost of natural gas from coal.
Description
Technical field
The invention belongs to natural gas from coal technical fields, more particularly, to a kind of subcritical water depolymerization hydrocarbon
The method of preparing natural gas.
Background technique
Synthetic natural gas be it is a kind of according to methanation reaction principle using corresponding equipment by carbon containing resource conversion be methane
Technology.The energy resources feature in China is few oil, lean gas, rich coal.Efficiently, the cheap coal resources of clean utilization are to solve me
The important channel of state's natural gas imbalance between supply and demand.
Early in the last century 70's, natural gas from coal technology is just to become global scientific research field advanced subject.China is certainly
Since this century, in the extensive investment construction coal methanation (natural gas from coal) in the ground such as Inner Mongol, Xinjiang, Shaanxi, Shanxi
Project.Although above-mentioned project alleviates natural gas resource in short supply, but also bring seriously polluted and soil significant wastage and at
The problems such as this is high.Its reason is entangled, mainly: traditional natural gas from coal technology, heavy dependence are simultaneously largely high using price
Expensive catalyst and complicated technique.
Summary of the invention
The purpose of the present invention is overcoming the deficiencies of existing technologies, it is natural to provide a kind of subcritical water depolymerization hydrocarbon system
The method of gas, this method are reacted by subcritical water with dry pulverized coal or water-coal-slurry, and methane gas is prepared；Reaction is without adding catalysis
Agent overcomes and largely uses " generating the catalyst of serious pollution to environment " as natural gas from coal core technology in the prior art
Defect；Greatly reduce the cost of natural gas from coal.
To achieve the goals above, the present invention provides a kind of sides of subcritical water depolymerization hydrocarbon preparing natural gas
Method, this method comprises: subcritical water and dry pulverized coal or water-coal-slurry are carried out heat exchange gasification, Jin Erfa in closed reactor
Raw methanation reaction, is made methane gas.
Preferably, the mixed gas containing methane obtained in the closed reactor enters backend reactors, described
Methane gas is made in further occurrence methanation reaction in backend reactors.
Preferably, it is 0.2-15MPa that the subcritical water, which is in pressure, and the Asia under conditions of temperature is 200-1050 DEG C is faced
Boundary's water；
The average grain diameter of the dry pulverized coal is 30-300 mesh；
The water-coal-slurry includes: dry pulverized coal, water and surfactant, the quality of the dry pulverized coal, water and surfactant
Than for 1:(0.6-1): (0.001-0.003).
Preferably, the dry pulverized coal is atomization dry pulverized coal, and the water-coal-slurry is atomization coal water slurry；
Preferably, the subcritical water carries out adverse current with the atomization dry pulverized coal or the atomization coal water slurry or cross-flow connects
Touching.
Preferably, controlling the reaction temperature in the closed reactor is 200-1050 DEG C, preferably 700-900 DEG C；Instead
Answering pressure is 0.2-15Mpa, preferably 8-12Mpa；
The mass ratio of the dry pulverized coal and subcritical water is 1:1-4, preferably 1:2-4；The water-coal-slurry and subcritical water
Mass ratio be 1:1-4, preferably 1:2-4.
Preferably, controlling the reaction temperature in the backend reactors is 200-1050 DEG C, preferably 700-900 DEG C；Instead
Answering pressure is 0.2-15Mpa, preferably 8-12Mpa.
Preferably, cooling removal of impurities separating treatment is carried out to the mixed gas containing methane in the backend reactors.
Preferably, the cooling removal of impurities separating treatment successively includes: water Quench dedirt desulfurization process, optional washing cooling
Dedirt desulfurization process, centrifugal dehydration treatment and optional desulfurization process.
Preferably, the gas temperature after the water Quench dedirt desulfurization process and optional washing cooling dedirt desulfurization process
100 DEG C are down to hereinafter, preferably 30-80 DEG C；
The dehydrating speed of centrifugal dehydration treatment is 200-1500rpm/min, preferably 800-1200rpm/min.
Preferably, the product gas after the cooling removal of impurities separating treatment is delivered to natural gas line；
The waste that the cooling removal of impurities separating treatment generates carries out gas, solid and liquid separation processing.
Technical solution of the present invention has the following beneficial effects:
(1) method of the invention passes through subcritical water and dry pulverized coal or water using subcritical water as reactant and heat source agent
Coal slurry carries out heat exchange gasification, without adding catalyst, avoids addition catalyst bring environmental pollution, and reduce coal system
The cost of natural gas.
(2) by water Quench dedirt desulfurization process, it can be realized a step and complete cooling, dedusting and desulfurization process；Pass through water
Quench dedirt desulfurization process can prevent methane gas back reaction, stablize the yield of methane, and can be achieved at the same time washing dedusting
And sulfur removal technology.
(3) method of the invention, reaction raw materials are easily obtained, and reaction process is simple, are transferred flexible.
Other features and advantages of the present invention will then part of the detailed description can be specified.
Detailed description of the invention
Exemplary embodiment of the invention is described in more detail in conjunction with the accompanying drawings, it is of the invention above-mentioned and its
Its purpose, feature and advantage will be apparent, wherein in exemplary embodiment of the invention, identical reference label
Typically represent same parts.
Fig. 1 shows a kind of subcritical water depolymerization hydrocarbon preparing natural gas according to an embodiment of the invention
Method flow diagram.
Fig. 2 shows water Quench dedirt desulfurization process according to an embodiment of the invention gas Quench washing filterings
The structural schematic diagram of device.
Specific embodiment
The preferred embodiment of the present invention is described in more detail below.Although the following describe preferred implementations of the invention
Mode, however, it is to be appreciated that may be realized in various forms the present invention without that should be limited by the embodiments set forth herein.Phase
Instead, these embodiments are provided so that the present invention is more thorough and complete, and can be by the scope of the present invention completely
It is communicated to those skilled in the art.
The present invention provides a kind of method of subcritical water depolymerization hydrocarbon preparing natural gas, belongs to and a kind of faced using Asia
The method that boundary's water prepares methane gas, this method comprises: carrying out subcritical water and dry pulverized coal or water-coal-slurry in closed reactor
Heat exchange gasification, and then methanation reaction occurs, methane gas is made.
Method of the invention, using subcritical water as reactant and heat source agent, so that subcritical water and dry pulverized coal or water coal
Slurry carries out heat exchange gasification, and gasification product includes CO, CO2、H2And CH4, and then utilize CO, CO2And H2Further occurrence methanation
Methane gas is made in reaction.Meanwhile the heat that methanation reaction is released can further promote subcritical water and dry pulverized coal or water coal again
The heat exchange of slurry is gasified.By means of the present invention, the production rate of methane gas is not less than 75% in closed reactor.
In the present invention, it is preferable that carry out gas, solid and liquid separation processing to the waste generated in closed reactor.
In accordance with the present invention it is preferred that enter back segment anti-for the mixed gas obtained in the closed reactor containing methane
Device is answered, methane gas is made in the further occurrence methanation reaction in the backend reactors.
In the present invention, CO, CO of methanation does not occur in leading portion closed reactor2And H2It is further in backend reactors
Methanation reaction occurs and generates methane gas.By the way that after this segment process, total production rate of methane gas is not less than 80%.
In accordance with the present invention it is preferred that it is 0.2-15MPa that the subcritical water, which is in pressure, temperature is 200-1050 DEG C
Under the conditions of subcritical water；
The average grain diameter of the dry pulverized coal is 30-300 mesh；
The water-coal-slurry includes: dry pulverized coal, water and surfactant, the quality of the dry pulverized coal, water and surfactant
Than for 1:(0.6-1): (0.001-0.003).
The preparation method of water-coal-slurry of the invention is the conventional method of this field, such as by dry pulverized coal, water and surface-active
Agent is uniformly mixed to get water-coal-slurry.The average grain diameter for preparing the dry pulverized coal of water-coal-slurry is preferably 30-300 mesh.
In the present invention, surfactant used is to facilitate water and the wet surfactant for forming slurry of dry pulverized coal, institute
Stating surfactant can be the surfactant for having aforementioned wettability of any preparation water-coal-slurry in this field；Such as it is wooden
Plain sulfonate, alkenyl sulfonate etc..
In accordance with the present invention it is preferred that the dry pulverized coal is atomization dry pulverized coal, the water-coal-slurry is atomization coal water slurry；
In the present invention, it is atomized dry pulverized coal and atomization coal water slurry and realizes atomization using gas as delivery vehicles；It is gases used
Preferably methane, CO, CO2Or H2；Preferably, the atomization condition of dry pulverized coal are as follows: the solid-gas ratio of dry pulverized coal and gas is 1:(2-4)
Kg/nl, atomizing pressure 0.2-15MPa；The atomization condition of water-coal-slurry are as follows: the liquid-gas ratio of water-coal-slurry and gas is 1:(2-4) kg/
Nl, atomizing pressure 0.2-15Mpa.
In the present invention, using methane, CO, CO2Or H2The purity of the methane gas of generation is capable of providing as delivery vehicles.
In the present invention, by atomization dry pulverized coal or atomization coal water slurry to increase connecing for dry pulverized coal or water-coal-slurry and subcritical water
Contacting surface product, and then can be carried out the two and more fully react.
In accordance with the present invention it is preferred that the subcritical water and the atomization dry pulverized coal or atomization coal water slurry progress are inverse
Stream or cross-flow contact.Subcritical water and the atomization dry pulverized coal or atomization coal water slurry are both preferably counter current contacting.Counter current contacting energy
Enough more fully reacted.
In accordance with the present invention it is preferred that controlling the reaction temperature in the closed reactor is 200-1050 DEG C, preferably
700-900℃；Reaction pressure is 0.2-15Mpa, preferably 8-12Mpa；
The mass ratio of the dry pulverized coal and subcritical water is 1:1-4, preferably 1:2-4；The water-coal-slurry and subcritical water
Mass ratio be 1:1-4, preferably 1:2-4.
In accordance with the present invention it is preferred that controlling the reaction temperature in the backend reactors is 200-1050 DEG C, preferably
700-900℃；Reaction pressure is 0.2-15Mpa, preferably 8-12Mpa.
In accordance with the present invention it is preferred that carrying out cooling removal of impurities to the mixed gas containing methane in the backend reactors
Separating treatment.
Can there are the foreign gases such as some sulfur dioxide and solid in the mixed gas containing methane in backend reactors
Granule foreign etc..
In accordance with the present invention it is preferred that the cooling removal of impurities separating treatment successively includes: water Quench dedirt desulfurization process, appoint
The washing cooling dedirt desulfurization process of choosing, centrifugal dehydration treatment and optional desulfurization process.
In the present invention, by water Quench dedirt desulfurization process, it can be realized a step and complete cooling, dedusting and desulfurization process；
Methane gas back reaction can be prevented by water Quench dedirt desulfurization process, stablizes the yield of methane, and can be achieved at the same time water
Remove dirt and sulfur removal technology；In water Quench dedirt desulfurization process, the ammonia, sulfur dioxide and this section generated in front process is utilized
Water reaction in technique, realizes the ammonia process of desulfurization, does not have to another introducing desulfurizing agent.Passed through in water using gas, realizes washing dedusting.
In the present invention, when the dry pulverized coal in dry pulverized coal or water-coal-slurry used is sulphur coal, it will usually de- in centrifugation
Desulfurization process is carried out after water process again.In the present invention, the desulfurization process is the desulfurization process mode of this field routine, is made
Desulfurizing agent is the desulfurizing agent of this field routine, such as metal oxide base desulfurizer, specific such as CaO, FeO；Desulfurization process
Temperature is preferably 30-250 DEG C.
In accordance with the present invention it is preferred that the water Quench dedirt desulfurization process and optional washing cooling dedirt desulfurization process
Gas temperature afterwards is down to 100 DEG C hereinafter, preferably 30-80 DEG C；
The dehydrating speed of centrifugal dehydration treatment is 200-1500rpm/min, preferably 800-1200rpm/min.
In accordance with the present invention it is preferred that the product gas after the cooling removal of impurities separating treatment is delivered to natural gas line；
The waste that the cooling removal of impurities separating treatment generates carries out gas, solid and liquid separation processing.
In the present invention, temperature be 30-50 DEG C, pressure be 0.2-0.8MPa under, it is described cold with the total volume meter of product gas
But contain in the product gas after the separating treatment that cleans: methane gas is not less than 80%, H2It is not more than 6%, CO no more than 6%, CO2No
Greater than 6%.
In the present invention, gas, solid and liquid separation treated processing water energy be enough in preparation water-coal-slurry；Preferably, processing water is logical
It crosses circulation line and is delivered to water-coal-slurry preparation unit；
The gas that gas, solid and liquid separation processing are isolated is preferably as atomization dry pulverized coal or the delivery vehicles of atomization coal water slurry；
For being atomized dry pulverized coal or water-coal-slurry.
The solid residue that gas, solid and liquid separation processing are isolated, discharge is collected, for the raw material as building materials.
The present invention is further illustrated by the following examples:
Water-coal-slurry used in following embodiment the preparation method comprises the following steps: the dry pulverized coal, surfactant and water of metering are mixed
It closes uniformly, obtains water-coal-slurry；
Atomization coal water slurry used in following embodiment or atomization dry pulverized coal realize mist using methane gas as delivery vehicles
Change, wherein the atomization condition of dry pulverized coal are as follows: dry pulverized coal and the solid-gas ratio of methane gas are 1:3kg/nl, atomizing pressure 8MPa；Water
The atomization condition of coal slurry are as follows: the liquid-gas ratio of water-coal-slurry and methane gas is 1:3kg/nl, atomizing pressure 8Mpa；
Water Quench dedirt desulfurization process in following embodiment is using the gas Quench washing filtering specially designed and developed
Device is implemented:
The gas Quench Water filtration device for filtering includes: as shown in Figure 1:
Unit 1 is washed, washing unit 1 includes inlet tube 2 and washing pipe 3, and the top of inlet tube 2 is connected to washing pipe 3
One end is provided with water filling port 4 and gas injection port 5 on inlet tube 2；
Gas filtration decompressing unit 6, gas filtration decompressing unit 6 include three-stage filtration relief pipe 8, first order filtering decompression
Pipe 8 is connected to the other end of washing pipe 3, has been located at gas outlet 7 on afterbody filtering relief pipe 8；
Gas-guide tube 9, adjacent head relief pipe 8 are sequentially communicated by gas-guide tube 9, gas-guide tube 9 be it is T-shaped, air guide 9 is located at
It filters in relief pipe 8, top of the T-shaped horizontal edge far from filtering relief pipe 8, T-shaped vertical edge is connected to adjacent head decompression
The top of pipe 8；
Denoising device is depressurized, decompression denoising device setting is in washing pipe 3 and/or gas filtration decompressing unit 6；
Liquidometer 10, the setting of liquidometer 10 is in gas filtration decompressing unit 6 and gas filtration decompressing unit 6 and washing pipe 3
Connectivity part.
Tapping valve 11, blowdown valve 12 and relief valve 13, the setting of tapping valve 11 is in washing unit 1 and gas filtration decompressing unit
On 6, the lowest part of washing 3 vertical position of pipe is arranged in blowdown valve 12, and relief valve 13 is arranged in gas filtration decompressing unit 6.
Wherein, washing unit 1 includes two washing pipes 3, and two washing pipes 3 are sequentially communicated, and two washing pipes 3 are u-shaped.
Specifically, it is contemplated that integration of equipments, the quantity and washing 3 cooperating number of pipe for filtering relief pipe 8 are closed, managed in washing
Connecting flange is arranged in 3 tops and filtering relief pipe 8, and gas filtration decompressing unit 6 is arranged by connecting flange pushes up in washing unit 1
Portion, further, the height for washing unit 1 and gas filtration decompressing unit 6 are matched with container height, when needing transfer gas
When body Quench Water filtration device for filtering, washing unit 1 and gas filtration decompressing unit 6 can be dismounted by connecting flange, be dispensed,
It assembles again when it is desired to be used.
Wherein, decompression denoising device includes at least one pressure relief assembly and fixing piece, and one end of pressure relief assembly passes through fixation
Part is connected to the tube wall of washing pipe 3 and gas filtration decompressing unit 6.
Further, fixing piece is fixed disk 15 or fixed link 14, and setting is depressurized in gas filtration, and the fixing piece in 6 is
One end of each pressure relief assembly is arranged in fixed disk 15, fixed disk 15, and for annular shape, interior edge is fixedly connected on pressure relief assembly, outside
Edge is fixedly connected on tube wall；The fixing piece being arranged in washing unit 1 is fixed link 14, and fixed link 14 includes end socket limit and bar
Body, pressure relief assembly are set between the body of rod, are located between two end socket limits.
Wherein, pressure relief assembly includes strainer 16 and reset spring 17, and strainer 16 is two, is separately positioned on reset spring 17
Both ends.
Specifically, the mixed gas containing methane when use in backend reactors enters inlet tube 2 via gas injection port 5,
Liquid water enters inlet tube 2 via water filling port 4, and gaseous product is contacted with water carries out Quench washing cooling, then into U-shaped
Pipe 3 is washed, liquid water can be deposited in the washing pipe 3 of U-shaped, and gaseous product is by water and depressurizes the filtering of denoising device, removes
Enter gas filtration decompressing unit 6 after dirt and sulphur removal, gaseous product is conveyed and subtracted by turning back in three-stage filtration relief pipe 8
It is discharged after pressing the buffering step by step of denoising device, decompression by gas outlet 7.
In following embodiment, the production rate of the methane gas obtains after the cooling removal of impurities separating treatment
The volumn concentration of methane gas in product gas.
Embodiment 1
As shown in Figure 1, the present embodiment provides a kind of method of subcritical water depolymerization hydrocarbon preparing natural gas, this method
Include:
(1) in closed reactor, subcritical water and atomization coal water slurry are subjected to heat exchange gasification, and then methanation occurs
Methane gas is made in reaction；The subcritical water and the atomization coal water slurry carry out counter current contacting；It controls in the closed reactor
Reaction temperature be 600 DEG C, reaction pressure 3Mpa；Gas is carried out, at solid and liquid separation to the waste generated in closed reactor
Reason；
(2) mixed gas containing methane obtained in the closed reactor enters backend reactors, in the back segment
Methane gas is made in further occurrence methanation reaction in reactor；Controlling the reaction temperature in the backend reactors is 600
DEG C, reaction pressure 3Mpa；
(3) cooling removal of impurities separating treatment is carried out to the mixed gas containing methane in the backend reactors, it is described cold
But removal of impurities separating treatment successively includes: water Quench dedirt desulfurization process, washing cooling dedirt desulfurization process and centrifugal dehydration treatment；
Wherein, the gas temperature after the water Quench dedirt desulfurization process and washing cooling dedirt desulfurization process is down to 50 DEG C；Centrifugation is de-
The dehydrating speed of water process is 1000rpm/min.
(4) product gas after the cooling removal of impurities separating treatment is delivered to natural gas line；At the cooling removal of impurities separation
The waste that each processing step of reason generates carries out gas, solid and liquid separation processing.
Wherein, it is 3MPa that the subcritical water, which is in pressure, and temperature is the subcritical water under conditions of 600 DEG C；Water-coal-slurry
It include: dry pulverized coal, water and surfactant, the mass ratio of the dry pulverized coal, water and surfactant is 1:0.8:0.002, table
Face activating agent is sodium lignin sulfonate, and the average grain diameter of dry pulverized coal used is 200 mesh；The mass ratio of water-coal-slurry and subcritical water is
1:3。
Using the method methane gas of the present embodiment, detected using gas chromatograph: the production rate of methane gas is 85%.
Embodiment 2
As shown in Figure 1, the present embodiment provides a kind of method of subcritical water depolymerization hydrocarbon preparing natural gas, this method
Include:
(1) in closed reactor, subcritical water and atomization coal water slurry are subjected to heat exchange gasification, and then methanation occurs
Methane gas is made in reaction；The subcritical water and the atomization coal water slurry carry out counter current contacting；It controls in the closed reactor
Reaction temperature be 750 DEG C, reaction pressure 9Mpa；Gas is carried out, at solid and liquid separation to the waste generated in closed reactor
Reason；
(2) mixed gas containing methane obtained in the closed reactor enters backend reactors, in the back segment
Methane gas is made in further occurrence methanation reaction in reactor；Controlling the reaction temperature in the backend reactors is 750
DEG C, reaction pressure 9Mpa；
(3) cooling removal of impurities separating treatment is carried out to the mixed gas containing methane in the backend reactors, it is described cold
But removal of impurities separating treatment successively includes: water Quench dedirt desulfurization process, washing cooling dedirt desulfurization process and centrifugal dehydration treatment；
Wherein, the gas temperature after the water Quench dedirt desulfurization process and washing cooling dedirt desulfurization process is down to 50 DEG C；Centrifugation is de-
The dehydrating speed of water process is 1000rpm/min.
(4) product gas after the cooling removal of impurities separating treatment is delivered to natural gas line；At the cooling removal of impurities separation
The waste that each processing step of reason generates carries out gas, solid and liquid separation processing.
Wherein, it is 9MPa that the subcritical water, which is in pressure, and temperature is the subcritical water under conditions of 750 DEG C；Water-coal-slurry
It include: dry pulverized coal, water and surfactant, the mass ratio of the dry pulverized coal, water and surfactant is 1:0.8:0.002, table
Face activating agent is sodium lignin sulfonate, and the average grain diameter of dry pulverized coal used is 200 mesh；The mass ratio of water-coal-slurry and subcritical water is
1:3。
Using the method methane gas of the present embodiment, detected using gas chromatograph: the production rate of methane gas is 86%.
Embodiment 3
As shown in Figure 1, the present embodiment provides a kind of method of subcritical water depolymerization hydrocarbon preparing natural gas, this method
Include:
(1) in closed reactor, subcritical water and atomization coal water slurry are subjected to heat exchange gasification, and then methanation occurs
Methane gas is made in reaction；The subcritical water and the atomization coal water slurry carry out counter current contacting；It controls in the closed reactor
Reaction temperature be 850 DEG C, reaction pressure 11Mpa；Gas, solid and liquid separation are carried out to the waste generated in closed reactor
Processing；
(2) mixed gas containing methane obtained in the closed reactor enters backend reactors, in the back segment
Methane gas is made in further occurrence methanation reaction in reactor；Controlling the reaction temperature in the backend reactors is 850
DEG C, reaction pressure 11Mpa；
(3) cooling removal of impurities separating treatment is carried out to the mixed gas containing methane in the backend reactors, it is described cold
But removal of impurities separating treatment successively includes: water Quench dedirt desulfurization process, washing cooling dedirt desulfurization process and centrifugal dehydration treatment；
Wherein, the gas temperature after the water Quench dedirt desulfurization process and washing cooling dedirt desulfurization process is down to 50 DEG C；Centrifugation is de-
The dehydrating speed of water process is 1000rpm/min.
(4) product gas after the cooling removal of impurities separating treatment is delivered to natural gas line；At the cooling removal of impurities separation
The waste that each processing step of reason generates carries out gas, solid and liquid separation processing.
Wherein, it is 11MPa that the subcritical water, which is in pressure, and temperature is the subcritical water under conditions of 850 DEG C；Water-coal-slurry
It include: dry pulverized coal, water and surfactant, the mass ratio of the dry pulverized coal, water and surfactant is 1:0.8:0.002, table
Face activating agent is sodium lignin sulfonate, and the average grain diameter of dry pulverized coal used is 200 mesh；The mass ratio of water-coal-slurry and subcritical water is
1:3。
Using the present embodiment method methane its, detected using gas chromatograph: the production rate of methane gas be 87%.
Embodiment 4
The present embodiment provides a kind of methods of subcritical water depolymerization hydrocarbon preparing natural gas, this method comprises:
(1) in closed reactor, subcritical water and atomization dry pulverized coal are subjected to heat exchange gasification, and then methanation occurs
Methane gas is made in reaction；The subcritical water and the atomization dry pulverized coal carry out counter current contacting；It controls in the closed reactor
Reaction temperature be 600 DEG C, reaction pressure 3Mpa；Gas is carried out, at solid and liquid separation to the waste generated in closed reactor
Reason；
(2) mixed gas containing methane obtained in the closed reactor enters backend reactors, in the back segment
Methane gas is made in further occurrence methanation reaction in reactor；Controlling the reaction temperature in the backend reactors is 600
DEG C, reaction pressure 3Mpa；
(3) cooling removal of impurities separating treatment is carried out to the mixed gas containing methane in the backend reactors, it is described cold
But removal of impurities separating treatment successively includes: water Quench dedirt desulfurization process, washing cooling dedirt desulfurization process and centrifugal dehydration treatment；
Wherein, the gas temperature after the water Quench dedirt desulfurization process and washing cooling dedirt desulfurization process is down to 50 DEG C；Centrifugation is de-
The dehydrating speed of water process is 1000rpm/min.
(4) product gas after the cooling removal of impurities separating treatment is delivered to natural gas line；At the cooling removal of impurities separation
The waste that each processing step of reason generates carries out gas, solid and liquid separation processing.
Wherein, it is 3MPa that the subcritical water, which is in pressure, and temperature is the subcritical water under conditions of 600 DEG C；It is described dry
The average grain diameter of coal dust is 200 mesh；The mass ratio of dry pulverized coal and subcritical water is 1:3.
Using the method methane gas of the present embodiment, detected using gas chromatograph: the production rate of methane gas is 84%.
Embodiment 5
The present embodiment provides a kind of methods of subcritical water depolymerization hydrocarbon preparing natural gas, this method comprises:
(1) in closed reactor, subcritical water and atomization coal water slurry are subjected to heat exchange gasification, and then methanation occurs
Methane gas is made in reaction；The subcritical water and the atomization coal water slurry carry out counter current contacting；It controls in the closed reactor
Reaction temperature be 600 DEG C, reaction pressure 3Mpa；Gas is carried out, at solid and liquid separation to the waste generated in closed reactor
Reason；
(2) mixed gas containing methane obtained in the closed reactor enters backend reactors, in the back segment
Methane gas is made in further occurrence methanation reaction in reactor；Controlling the reaction temperature in the backend reactors is 600
DEG C, reaction pressure 3Mpa；
(3) cooling removal of impurities separating treatment is carried out to the mixed gas containing methane in the backend reactors, it is described cold
But removal of impurities separating treatment successively includes: water Quench dedirt desulfurization process and centrifugal dehydration treatment；Wherein, the water Quench dedirt is de-
Gas temperature after sulphuring treatment is down to 50 DEG C；The dehydrating speed of centrifugal dehydration treatment is 1000rpm/min.
(4) product gas after the cooling removal of impurities separating treatment is delivered to natural gas line；At the cooling removal of impurities separation
The waste that each processing step of reason generates carries out gas, solid and liquid separation processing.
Wherein, it is 3MPa that the subcritical water, which is in pressure, and temperature is the subcritical water under conditions of 600 DEG C；Water-coal-slurry
It include: dry pulverized coal, water and surfactant, the mass ratio of the dry pulverized coal, water and surfactant is 1:0.8:0.002, table
Face activating agent is sodium lignin sulfonate, and the average grain diameter of dry pulverized coal used is 200 mesh；The mass ratio of water-coal-slurry and subcritical water is
1:3。
Using the method methane gas of the present embodiment, detected using gas chromatograph: the production rate of methane gas is 85%.
Embodiment 6
The present embodiment provides a kind of methods of subcritical water depolymerization hydrocarbon preparing natural gas, this method comprises:
(1) in closed reactor, subcritical water and atomization coal water slurry are subjected to heat exchange gasification, and then methanation occurs
Methane gas is made in reaction；The subcritical water and the atomization coal water slurry carry out counter current contacting；It controls in the closed reactor
Reaction temperature be 600 DEG C, reaction pressure 3Mpa；Gas is carried out, at solid and liquid separation to the waste generated in closed reactor
Reason；
(2) cooling removal of impurities separating treatment is carried out to the mixed gas containing methane in the closed reactor, it is described cold
But removal of impurities separating treatment successively includes: water Quench dedirt desulfurization process, washing cooling dedirt desulfurization process and centrifugal dehydration treatment；
Wherein, the gas temperature after the water Quench dedirt desulfurization process and washing cooling dedirt desulfurization process is down to 50 DEG C；Centrifugation is de-
The dehydrating speed of water process is 1000rpm/min.
(4) product gas after the cooling removal of impurities separating treatment is delivered to natural gas line；At the cooling removal of impurities separation
The waste that each processing step of reason generates carries out gas, solid and liquid separation processing.
Wherein, it is 3MPa that the subcritical water, which is in pressure, and temperature is the subcritical water under conditions of 600 DEG C；Water-coal-slurry
It include: dry pulverized coal, water and surfactant, the mass ratio of the dry pulverized coal, water and surfactant is 1:0.8:0.002, table
Face activating agent is sodium lignin sulfonate, and the average grain diameter of dry pulverized coal used is 200 mesh；The mass ratio of water-coal-slurry and subcritical water is
1:3。
Using the method methane gas of the present embodiment, detected using gas chromatograph: the production rate of methane gas is 80%.
Embodiment 7
The present embodiment provides a kind of methods of subcritical water depolymerization hydrocarbon preparing natural gas, this method comprises:
(1) in closed reactor, subcritical water and water-coal-slurry are subjected to heat exchange gasification, and then it is anti-that methanation occurs
It answers, methane gas is made；The subcritical water and the water-coal-slurry carry out counter current contacting；Control the reaction in the closed reactor
Temperature is 600 DEG C, reaction pressure 3Mpa；Gas, solid and liquid separation processing are carried out to the waste generated in closed reactor；
(2) mixed gas containing methane obtained in the closed reactor enters backend reactors, in the back segment
Methane gas is made in further occurrence methanation reaction in reactor；Controlling the reaction temperature in the backend reactors is 600
DEG C, reaction pressure 3Mpa；
(3) cooling removal of impurities separating treatment is carried out to the mixed gas containing methane in the backend reactors, it is described cold
But removal of impurities separating treatment successively includes: water Quench dedirt desulfurization process, washing cooling dedirt desulfurization process and centrifugal dehydration treatment；
Wherein, the gas temperature after the water Quench dedirt desulfurization process and washing cooling dedirt desulfurization process is down to 50 DEG C；Centrifugation is de-
The dehydrating speed of water process is 1000rpm/min.
(4) product gas after the cooling removal of impurities separating treatment is delivered to natural gas line；At the cooling removal of impurities separation
The waste that each processing step of reason generates carries out gas, solid and liquid separation processing.
Wherein, it is 3MPa that the subcritical water, which is in pressure, and temperature is the subcritical water under conditions of 600 DEG C；Water-coal-slurry
It include: dry pulverized coal, water and surfactant, the mass ratio of the dry pulverized coal, water and surfactant is 1:0.8:0.002, table
Face activating agent is sodium lignin sulfonate, and the average grain diameter of dry pulverized coal used is 200 mesh；The mass ratio of water-coal-slurry and subcritical water is
1:3。
Using the method methane gas of the present embodiment, detected using gas chromatograph: the production rate of methane gas is 83%.
Various embodiments of the present invention are described above, above description is exemplary, and non-exclusive, and
It is not limited to disclosed each embodiment.Without departing from the scope and spirit of illustrated each embodiment, for this skill
Many modifications and changes are obvious for the those of ordinary skill in art field.
Claims (10)
1. a kind of method of subcritical water depolymerization hydrocarbon preparing natural gas, which is characterized in that this method comprises: closed anti-
It answers in device, subcritical water and dry pulverized coal or water-coal-slurry is subjected to heat exchange gasification, and then methanation reaction occurs, methane is made
Gas.
2. according to the method described in claim 1, wherein, mixed gas obtained in the closed reactor containing methane into
Enter backend reactors, methane gas is made in the further occurrence methanation reaction in the backend reactors.
3. method according to claim 1 or 2, wherein it is 0.2-15MPa that the subcritical water, which is in pressure, and temperature is
Subcritical water under conditions of 200-1050 DEG C；
The average grain diameter of the dry pulverized coal is 30-300 mesh；
The water-coal-slurry includes: dry pulverized coal, water and surfactant, and the mass ratio of the dry pulverized coal, water and surfactant is
1:(0.6-1): (0.001-0.003).
4. method according to claim 1 or 2, wherein the dry pulverized coal is atomization dry pulverized coal, and the water-coal-slurry is atomization
Water-coal-slurry；
Preferably, the subcritical water carries out adverse current with the atomization dry pulverized coal or the atomization coal water slurry or cross-flow contacts.
5. method according to claim 1 or 2, wherein controlling the reaction temperature in the closed reactor is 200-
1050 DEG C, preferably 700-900 DEG C；Reaction pressure is 0.2-15Mpa, preferably 8-12Mpa；
The mass ratio of the dry pulverized coal and subcritical water is 1:1-4, preferably 1:2-4；The matter of the water-coal-slurry and subcritical water
Amount is than being 1:1-4, preferably 1:2-4.
6. according to the method described in claim 2, wherein, controlling the reaction temperature in the backend reactors is 200-1050
DEG C, preferably 700-900 DEG C；Reaction pressure is 0.2-15Mpa, preferably 8-12Mpa.
7. according to the method described in claim 2, wherein, being carried out to the mixed gas containing methane in the backend reactors
Cooling removal of impurities separating treatment.
8. according to the method described in claim 7, wherein, the cooling removal of impurities separating treatment successively includes: that water Quench dedirt is de-
Sulphuring treatment, optional washing cooling dedirt desulfurization process, centrifugal dehydration treatment and optional desulfurization process.
9. according to the method described in claim 8, wherein, the water Quench dedirt desulfurization process and optional washing cooling dedirt
Gas temperature after desulfurization process is down to 100 DEG C hereinafter, preferably 30-80 DEG C；
The dehydrating speed of centrifugal dehydration treatment is 200-1500rpm/min, preferably 800-1200rpm/min.
10. according to the method described in claim 7, wherein, the product gas after the cooling removal of impurities separating treatment is delivered to naturally
Feed channel；
The waste that the cooling removal of impurities separating treatment generates carries out gas, solid and liquid separation processing.
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| CN101892085A (en) * | 2009-05-19 | 2010-11-24 | 新奥科技发展有限公司 | Novel coal gasification method |
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| Title |
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| 关清卿: "《亚/超临界水技术与原理》", 31 December 2014, 冶金工业出版社 * |
| 马宝岐: "《半焦的利用》", 30 June 2014, 《冶金工业出版社》 * |
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