CN1920251A - Method and device for natural gas hydrate exploitation with in-situ catalytic oxidation thermochemistry method - Google Patents
Method and device for natural gas hydrate exploitation with in-situ catalytic oxidation thermochemistry method Download PDFInfo
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- CN1920251A CN1920251A CNA2006100375826A CN200610037582A CN1920251A CN 1920251 A CN1920251 A CN 1920251A CN A2006100375826 A CNA2006100375826 A CN A2006100375826A CN 200610037582 A CN200610037582 A CN 200610037582A CN 1920251 A CN1920251 A CN 1920251A
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- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 40
- NMJORVOYSJLJGU-UHFFFAOYSA-N methane clathrate Chemical compound C.C.C.C.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O NMJORVOYSJLJGU-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 230000003647 oxidation Effects 0.000 title claims description 85
- 230000003197 catalytic effect Effects 0.000 title claims description 84
- 238000011065 in-situ storage Methods 0.000 title claims description 18
- 239000007789 gas Substances 0.000 claims abstract description 78
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 77
- 239000000446 fuel Substances 0.000 claims abstract description 26
- 230000001590 oxidative effect Effects 0.000 claims abstract description 19
- 239000007800 oxidant agent Substances 0.000 claims abstract description 18
- 238000003860 storage Methods 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 238000002485 combustion reaction Methods 0.000 claims description 64
- 150000004677 hydrates Chemical class 0.000 claims description 52
- 239000012530 fluid Substances 0.000 claims description 37
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 36
- 238000011084 recovery Methods 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 23
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 239000003345 natural gas Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 9
- 239000012266 salt solution Substances 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000007084 catalytic combustion reaction Methods 0.000 claims description 7
- 239000002828 fuel tank Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 4
- 150000005846 sugar alcohols Polymers 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 15
- 239000007788 liquid Substances 0.000 abstract 2
- 238000010297 mechanical methods and process Methods 0.000 abstract 1
- 238000005086 pumping Methods 0.000 abstract 1
- 238000005065 mining Methods 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
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- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
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- MXRGSJAOLKBZLU-UHFFFAOYSA-N 3-ethenylazepan-2-one Chemical compound C=CC1CCCCNC1=O MXRGSJAOLKBZLU-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 230000000202 analgesic effect Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
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- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- PZNOBXVHZYGUEX-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine;hydrochloride Chemical compound Cl.C=CCNCC=C PZNOBXVHZYGUEX-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
- E21B43/24—Enhanced recovery methods for obtaining hydrocarbons using heat, e.g. steam injection
- E21B43/243—Combustion in situ
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B41/00—Equipment or details not covered by groups E21B15/00 - E21B40/00
- E21B41/0099—Equipment or details not covered by groups E21B15/00 - E21B40/00 specially adapted for drilling for or production of natural hydrate or clathrate gas reservoirs; Drilling through or monitoring of formations containing gas hydrates or clathrates
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Geology (AREA)
- Mining & Mineral Resources (AREA)
- Physics & Mathematics (AREA)
- Environmental & Geological Engineering (AREA)
- Fluid Mechanics (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a method for using original catalyst oxidization thermal chemical method to product natural gas hydrate, and a relative device, wherein said method is characterized in that: pouring hydrate decompose accelerant into the hydrate storage layer to decompose the natural hydrate; using oxidant to catalyze and oxidize the fuel to heat the heat liquid in the catalyst oxidization burner; then pumping the liquid into storage layer to support the heat needed in the decomposition of natural gas hydrate; then pouring the CO<SUB>2</SUB> gas generated by burning into hydrate storage layer; and the inventive device comprises: catalyze oxidize burner 14, as one coaxial sleeve reactor, while the tube is the catalyze oxidize burning area and the frame is divided into preheating section and heat exchanging section. The invention can combine the mechanical method and the CO<SUB>2</SUB> exchange method, to improve the producing speed and confirm the stability of seabed.
Description
Technical field
The present invention relates to the production technique of gas hydrates, especially a kind of method of natural gas hydrate exploitation with in-situ catalytic oxidation thermochemistry and device.
Technical background
Gas hydrates (Natural Gas Hydrate, be called for short Gas Hydrate) are a kind of non-stoichiometry type, class ice shape, the cage modle crystalline compounds that low-molecular-weight hydrocarbon compound forms in water and the natural gas under low temperature, condition of high voltage.Gas hydrates have master-guest materials feature, hydrone (main body) by hydrogen bond in conjunction with forming the space lattice structure, gas molecule (object) by and hydrone between Van der Waals force be filled in the interlattice hole of hydrone.The gas hydrates that nature exists are based on methane hydrate, and wherein most the tax is stored in the seabed, have advantages such as reserves are big, distribution is wide, it is shallow to bury, energy density is high, the back of burning is pollution-free and residual.The methane hydrate of unit volume decomposes the methane gas that can produce the 150-180 normal volume.Exist gas hydrates formation condition widely under seabed and the land permafrost soil layer, according to estimates, organic carbon with gas hydrates form storage on the earth accounts for 53% of global total organic carbon, is coal, oil, three kinds of fossil fuel total carbons of natural gas 2 times.Therefore, gas hydrates are considered to the ideal cleaning alternative energy source of 21 century.
Gas hydrates are composed with solid form and are stored in the flusch layer in shale seabed, and inversion of phases takes place in recovery process, compare with oil, gas extraction, have very big exploitation difficulty.The exploitation of gas hydrates, particularly ocean gas hydrate still is in the experimental exploring stage, and up to now, people do not find technical feasible as yet, economically the exploitation method of rational ocean gas hydrate.According to the place difference of decomposition of hydrate in the recovery process, the exploitation of gas hydrates can be divided into underground mining and exploit two big classes on the ground.Wherein underground mining research report at most, mainly be with reference to oil, gas extraction technology, at first in the stratum, seabed, construct pit shaft, take measures to destroy the thermodynamic condition such as temperature, pressure of hydrate stable existence, promote that hydrate is decomposed into water and natural gas in tax with depositing, adopt the natural gas after natural gas extraction technology will be decomposed to collect, be delivered to ground then.The key of gas hydrates underground mining is how to take cost-effective measure to promote the decomposition of hydrate, keeps the shaft bottom stable simultaneously, does not make methane leak, not cause greenhouse effect.At present the method that proposes mainly comprises three kinds of temperature activation method, voltage drop method and chemical methods.
Temperature activation method mainly is that thermophores such as steam, hot water, hot salt brine are injected the hydrate reservoir, and temperature is reached more than the decomposition of hydrate temperature.U.S. Pat 6994159B2 and Japan Patent JP09158662 propose to inject hot fluids such as hot water, steam to the hydrate reservoir by recovery well respectively and promote decomposition of hydrate, but the major defect of temperature activation method is that heat transport fluid is delivered to the seabed from the sea, big along the journey heat waste, the heat energy utilization rate is low.Chinese patent CN1609409A has proposed a kind of method and device that utilizes the heating using microwave exploitation of gas hydrate, U.S. Pat 6148911 proposes to adopt down-hole electrical heating exploitation natural gas hydrate, but these methods all need adopt the electric energy heating, and efficiency of energy utilization is low, simultaneously the quarrying apparatus complexity.
Chemical method mainly is to inject chemical substances such as salt solution, methyl alcohol, ethanol, ethylene glycol to the hydrate reservoir, change the activity of water, thereby change the phase balance condition that hydrate forms, reduce the hydrate equilibrium temperature, promote the decomposition of gas hydrates, the shortcoming of chemical method is that dosing is big, and the cost height uses chemical agent also can cause problem of environmental pollution in a large number.In recovery process, must guarantee the drug concentration of hydrate reservoir, because decomposition of hydrate discharges mass crystallization water, cause drug concentration constantly to reduce, simultaneously, because decomposition of hydrate is the endothermic reaction, the temperature of hydrate layer can constantly reduce along with the carrying out of recovery process, thereby cause production efficiency to reduce, the concentration of required chemical agent also constantly raises.
U.S. Pat 2005/0121200A1 discloses a kind of employing CO
2Displacement method exploitation methane hydrate is realized simultaneously to greenhouse gases CO
2The safety and stability landfill.Because CO
2The temperature that hydrate forms is higher than methane, and pressure is lower than methane, therefore, as long as the temperature and pressure condition of control gas hydrates reservoir is in CO
2Stable region and CH that hydrate forms
4CO just can be realized in the range of instability of hydrate
2To CH
4The automatic replacement exploitation of hydrate.CO
2It is 57.98KJ/mol that hydrate generates heat, and the branch of methane hydrate is analgesic to be 54.49KJ/mol, and methane hydrate decomposes required heat fully can be by CO
2Hydrate generates institute's liberated heat and provides, simultaneously, and CO
2The timely backfill of hydrate helps keeping the shaft bottom geological conditions stable, prevents to subside and come down.But CO
2The problem that displacement method exists is the CO that forms
2Hydrate solids tends to be wrapped in the external surface of methane hydrate, thereby causes gas hydrates are decomposed not thorough, and replacement reaction speed is extremely slow.
Voltage drop method is by reducing the pressure of hydrate reservoir, causes that gas hydrates move to the range of instability and decompose, and this method often is difficult to reach the temperature and pressure condition of decomposition of hydrate because the seabottom geology condition varies, and exploitation rate is slow simultaneously, and efficient is low.
Chinese patent CN1294648A proposes to adopt high pressure draught to impact the hydrate reservoir, and carries the conveying solid substance gas hydrates secretly to the sea by air-flow.Chinese patent CN1587642A proposes to adopt the solid gas hydrate of the mechanical exploitation of automatic mining under water, adopts silt to separate then with reference to land mining branch lectotype, technology exploitation of gas hydrate such as decomposition of hydrate, these disassemble mining method on the ground and all exist limit of mining little, automatic under water mining equipment technical requirements height, serious to the seabottom geology structure destruction, cause problems such as the shaft bottom subsides, landslide easily.
Up to now, also there is not a kind of economy and effective method can be used for realizing the heavy industrialization exploitation of gas hydrates.Various hydrate exploitation methods respectively have pluses and minuses, the simple economical and effective exploitation of adopting the very difficult realization of a certain exploitation method to gas hydrates, the advantage of necessary comprehensive the whole bag of tricks, learning from other's strong points to offset one's weaknesses just to reach the economy to gas hydrates, efficient, safe working.
Summary of the invention
The object of the present invention is to provide the method and the device of a kind of economy, efficient, safe natural gas hydrate exploitation with in-situ catalytic oxidation thermochemistry, realize that ocean gas hydrate is extensive, the industrialization exploitation, the present invention simultaneously also can be applicable to the exploitation of ever frozen soil area, land gas hydrates.
For achieving the above object, the present invention has taked following technical scheme:
1) constructs recovery well and gas collection well.At first adopt the prior art of deepwater drilling technical field to construct recovery well and gas collection well in the hydrate metallogenic province, and construct the interface channel between recovery well and the gas collection well; Recovery well and gas collection well are through to hydrate reservoir bottom.
2) gas hydrates decompose.Inject decomposition of hydrate accelerator to the hydrate reservoir, gas hydrates are decomposed into natural G﹠W, adopt oxidant in-situ catalytic oxidation combustion fuel heating heat transport fluid simultaneously in the catalytic oxidation combustion device under being installed on recovery well, then heat transport fluid is pumped into the hydrate reservoir and supply with the required heat energy of gas hydrates decomposition, with the CO that catalytic oxidation combustion produced
2Gas injects the hydrate reservoir, makes it form CO
2Hydrate is filled the space that stays after the methane hydrate exploitation, CO
2Hydrate generates the heat transferred decomposition of hydrate accelerator that is discharged, and is used for the decomposition of gas hydrates, CO
2Hydrate forms the moisture content that absorbs in the decomposition accelerating agent, has improved the concentration of decomposition of hydrate accelerator.
3) natural gas after the decomposition is derived.Derive natural gas after pipeline will decompose by natural gas and be collected into separation, caisson on the sea.
In the inventive method, described step (1) and step (3) all adopt prior art, and step (2) gas hydrates are decomposed into innovative point of the present invention.
Described step (2) gas hydrates decompose can specifically be refined as following steps:
(1) the catalytic oxidation combustion device adopts the electrical heating combustion preheater;
(2) catalytic oxidation combustion device transfer the fuel and the oxidant in being installed on recovery well, the preheating in preheater of fuel and oxidant;
(3) under catalyst action, fuel is oxidized dose of catalytic oxidation in the catalytic oxidation combustion device of down-hole, emits heat heating heat transport fluid;
(4) inject decomposition of hydrate accelerator to the gas hydrates reservoir, gas hydrates are decomposed into natural G﹠W;
(5) heat transport fluid is delivered to hydrate reservoir heating decomposition of hydrate accelerator and gas hydrates reservoir, promotes the decomposition of gas hydrates;
(6) the catalytic oxidation combustion product is delivered to the hydrate reservoir, control hydrate reservoir temperature is lower than CO
2The hydrate equilibrium temperature is higher than CH
4The hydrate equilibrium temperature;
(7) CO in the catalytic oxidation combustion product
2Form CO at the hydrate reservoir
2Hydrate is emitted hydrate and is generated heat heating decomposition of hydrate accelerator;
(8) CO
2Hydrate forms the moisture content that absorbs in the decomposition of hydrate accelerator, and the decomposition of hydrate promoter concentration raises, and the decomposition rate of gas hydrates is accelerated.
Described decomposition of hydrate accelerator is low-carbon alcohols or polyalcohol or salt solution or its mixed solution;
Described decomposition of hydrate accelerator is contained the surfactant of 0.1-2% simultaneously;
Described low-carbon alcohols is methyl alcohol or ethanol or isopropyl alcohol or its mixed solution; Polyalcohol is ethylene glycol or diethylene glycol (DEG) or triethylene glycol or glycerine or its mixture; The concentration of described alcoholic solution is 20-60%.
The cation of described salt solution is K
+, Na
+, Ca
2+, Mg
2+, NH
4 +, anion is F
-, Cl
-, Br
-, PO
4 3-, oxalate, acetate; The concentration of described salt solution is 10-60%.
Described surfactant is straight chain, side chain or interlinkage organic high molecular polymer or its mixture, contains one or more N, P, the heteroatomic hydrophilic polar of O, S functional group in the polymer at least; Described surfactant preferably contains the heteroatomic PVP of N, Vinylcaprolactam homopolymer, polyetheramine, poly-many alkyl polyamines, polyacrylamide, poly dialkyl diallyl ammonium chloride, high carbon chain quaternary amine.
Described heat transport fluid is water or salt solution or decomposition of hydrate accelerator or its mixture;
Described decomposition of hydrate accelerator and heat transport fluid can be respectively through different line transportation to hydrate reservoir and catalytic oxidation combustion device, decomposition accelerating agent and heat transport fluid also can mixed after same line transportation is delivered to the hydrate reservoir after the catalytic oxidation combustion device is heated to 40-90 ℃ on the mobile platform of sea earlier.
The device of natural gas hydrate exploitation with in-situ catalytic oxidation thermochemistry of the present invention, comprise the horizontal interface channel between recovery well 13 and gas collection well 6 and recovery well 13 and the gas collection well 6, and gasholder 7 and natural-gas transfer pipeline, it is characterized in that: also comprise catalytic oxidation combustion device 14, catalytic oxidation combustion device 14 is installed in the recovery well 13, fuel tank 8, decomposition accelerating agent storage tank 9, thermophore storage tank 10 connects catalytic oxidation combustion device 14 through pipeline respectively, be provided with igniter 22 in the catalytic oxidation combustion device 14, the catalytic combustion product outlet 27 of catalytic oxidation combustion device 14 is connected to the bottom of horizontal interface channel, is provided with decomposition accelerating agent and heat transport fluid outlet 19 on the catalytic oxidation combustion device 14 in addition.
Described catalytic oxidation combustion device 14 is a coaxial sleeve reactor, interior pipe 18 tube sides are the catalytic oxidation combustion district, shell side between interior pipe 18 and the outer layer sleeve is divided into two sections separate portions, wherein one section is burner preheating section 24, the The pre-heat treatment that is used for fuel and oxidant, another section is a burner heat exchanging segment 26, is used for the heating of heat transport fluid.Described fuel tank 8 is connected to burner preheating section 24 by fuel and oxidant inlet pipe 21, decomposition accelerating agent storage tank 9 and thermophore storage tank 10 are connected to burner heat exchanging segment 26 by decomposition accelerating agent and heat transport fluid inlet tube 25, and catalytic oxidation combustion device inlet tube 23 connects pipe 18 in burner preheating section 24 and the catalytic oxidation combustion device; Pipe 18 is fixed on by many interior pipes and forms shell and tube reactor on the tube sheet in the described catalytic oxidation combustion device, and catalyst cupport is on the reactor inner tubal wall; Pipe 18 in catalytic combustion product outlet 27 is communicated with, decomposition accelerating agent and heat transport fluid outlet 19 are communicated with outer tube.
Pipe 18 also can be fixed on the shell and tube reactor of forming on the tube sheet by many interior pipes in the described reactor, and catalyst cupport is on the reactor inner tubal wall.For strengthening the load area of rate of heat transfer and catalyzer, increase the contact area of catalyzer and reactant, dwindle the volume of catalytic reactor, the interior pipe of reactor can adopt finned tube.
Adopt the electrical heating igniter to be preheated to 500-900 ℃ before the catalytic oxidation combustion device is started working earlier, close igniter then, feed fuel and oxidant;
Described fuel is lower carbon number hydrocarbons class A fuel As such as methane, natural gas, oil gas, oxidant is air or oxygen-enriched air, fuel and oxidant through different line transportation to the catalytic oxidation combustion device, after also fuel and oxidant can being mixed earlier across the sea, be transported to preheater again and be preheated to 400-600 ℃, gas after the preheating enters the catalytic oxidation combustion device and under the effect of catalyzer oxidation reaction takes place, emit reaction heat, the line transportation of the product after the burning by having backstop is to the hydrate reservoir;
The reaction heat that catalytic oxidation is emitted is in heat exchanger section heating heat transport fluid, and heat transport fluid heats decomposition of hydrate accelerator by line transportation to hydrate reservoir;
HC fuel and oxidant also can pass through separately independently, and line transportation mixes to preheater;
The temperature of controlling in the catalytic oxidation combustion device by flow, proportioning and the heat transport fluid flow of control HC fuel and oxidant is 600-1000 ℃, and the too high meeting of temperature makes catalysqt deactivation, and temperature is low excessively, and oxidized is insufficient;
By control HC fuel and the flow of oxidant and the temperature that proportioning is controlled heat transport fluid, the temperature of controlling the hydrate reservoir by the temperature of adjusting heat transport fluid is in more than the equilibrium temperature of methane hydrate CO
2Below the equilibrium temperature of hydrate;
CO in the oxidation product behind the catalytic combustion
2Generate CO at the hydrate reservoir
2Hydrate, liberated heat are used to heat decomposition of hydrate accelerator, simultaneously CO
2The hydrate generative process absorbs the moisture content in the decomposition of hydrate accelerator, improves the concentration of decomposition of hydrate accelerator, has avoided promoter concentration to reduce and has caused decomposition of hydrate speed to reduce.
The CO that is generated
2The density of hydrate is greater than the density of heat transport fluid and decomposition of hydrate accelerator, the CO of generation
2Hydrate is deposited on bottom automatically, fills because of the left space of exploitation of gas hydrates, helps keeping the seabottom geology construction of stable, avoids geological disasters such as the seabed subsides, landslide to take place;
CO
2Hydrate and gas hydrates are separated by heat transport fluid and decomposition of hydrate accelerator because of density variation, have avoided because of CO well
2Hydrate is in the coating of gas hydrates appearance and cause the gas hydrates decomposition rate to slow down, and the phenomenon that decomposition temperature raises, production efficiency reduces takes place.
Described catalyzer is that the metal of one of Pt, Rh, La, Mn, Ni, Cr etc. and metal oxide or its mixture support in α-Al
2O
3Particle or γ-Al
2O
3Particle surface and making, then with catalyst cupport on burner inner tubal wall or fin.
Described catalytic oxidation combustion device can vertically be installed in the bottom of vertical recovery well, also can horizontally be installed in the horizon mining well; The catalytic oxidation combustion device can move up in pit shaft along with the rising on exploitation plane.
The present invention has overcome the problem that the prior art gas hydrate mining methods exists, and it is big to adopt the in-situ catalytic oxidation heating to solve traditional temperature activation method thermal loss, and the shortcoming that production efficiency is low adopts chemical method and CO simultaneously
2Displacement combines, and has accelerated exploitation rate, has reduced the consumption of chemical injecting greatly, has guaranteed the stable of seabottom geology simultaneously effectively, has avoided the generation of geology and environmental hazard.
Description of drawings
Accompanying drawing 1 is production practice of the present invention and device sketch;
Accompanying drawing 2 is that the B-B of embodiment of the invention catalytic oxidation combustion device 14 is to view;
Accompanying drawing 3 is that the A-A of embodiment of the invention catalytic oxidation combustion device 14 is to view;
Description of reference numerals: 1, marine rock layer, 2, CO
2Hydrate, 3, the gas hydrates reservoir, 4, the bottom sediment layer, 5, sea water layer, 6, the gas collection well, 7, gasholder, 8, fuel tank, 9, the decomposition accelerating agent storage tank, 10, the thermophore storage tank, 11, marine mobile platform, 12, control system, 13, recovery well, 14, the catalytic oxidation combustion device, 15, chemical breakdown accelerator and heat transport fluid layer, 16, check device, 17, catalyzer, 18, interior pipe, 19, decomposition accelerating agent and heat transport fluid outlet, 20, outer tube, 21, fuel and oxidant inlet pipe, 22, igniter, 23, catalytic oxidation combustion device inlet tube, 24, the burner preheating section, 25, decomposition accelerating agent and heat transport fluid inlet tube, 26, the burner heat exchanging segment, 27, catalytic combustion product outlet, 28, fin.
The specific embodiment
Describe the specific embodiment of the present invention in detail below in conjunction with accompanying drawing:
As shown in Figure 1, 2, 3, at first adopt the deepwater drilling technology to construct recovery well 13 and gas collection well 6 in the seabed, get through the horizontal interface channel between recovery well and the gas collection well simultaneously, recovery well 13 and gas collection well 6 pass sea water layer 5 and bottom sediment layer 4 is through to gas hydrates reservoir 3 bottoms.Catalytic oxidation combustion device 14 is installed in the recovery well.In the recovery process, with volume ratio earlier 1: 10 CH
4Mix in fuel tank 8 with air, fuel combination gas enters burner preheating section 24 through fuel and oxidant inlet pipe 21, is preheated to 400-600 ℃, enters in the catalytic oxidation combustion device through catalytic oxidation combustion device inlet tube 23 then and manages 18.Pipe 18 is fixed on by the interior pipe that is provided with fin 28 in many and forms shell and tube reactor on the tube sheet in the catalytic oxidation combustion device, catalyzer 17 is carried on reactor inner tubal wall and the fin 28, and catalyzer is that the metal of one of Pt, Rh, La, Mn, Ni, Cr etc. and metal oxide or its mixture support in α-Al
2O
3Particle or γ-Al
2O
3Particle surface and making.Catalytic oxidation takes place on catalyzer 17 surfaces in the fuel combination gas of preheating.Decomposition accelerating agent storage tank 9 and thermophore storage tank 10 are connected to burner heat exchanging segment 26 by decomposition accelerating agent and heat transport fluid inlet tube 25, and decomposition of hydrate accelerator is low-carbon alcohols or polyalcohol or salt solution or its mixed solution; Decomposition of hydrate accelerator is contained the surfactant of 0.1-2% simultaneously, and heat transport fluid is water or salt solution or decomposition of hydrate accelerator or its mixture.Temperature in the catalytic oxidation combustion in the pipe 18 is 600-1000 ℃, a reaction liberated heat part is used for burner preheating section 24 preheating fuel combination gas, another part is used at burner heat exchanging segment 26 heating heat transport fluids and decomposition accelerating agent to 60-90 ℃, decomposition accelerating agent after the heating and heat transport fluid are delivered to gas hydrates reservoir 3 gas hydrates are decomposed into natural G﹠W along the horizontal channel, natural gas via gas collection well 6 is collected into marine mobile platform 11, is stored in gasholder 7; A large amount of moisture content discharge and cause the promoter concentration in chemical breakdown accelerator and the heat transport fluid layer 15 constantly to reduce in the gas hydrates decomposable process, and decomposition of hydrate speed reduces; Oxidation product after the catalytic oxidation combustion device burning is delivered to the bottom of horizontal interface channel, the CO in the oxidation product through outlet 27 and check device 16
2Generate CO at this
2 Hydrate 2, and the space that stays after the exploitation of filled natural gas hydrate; CO
2Liberated heat passes to chemical breakdown accelerator and heat transport fluid layer 15 in the hydrate formation, simultaneously CO
2Hydrate forms and has absorbed a large amount of moisture content from chemical breakdown accelerator and heat transport fluid layer, cause the concentration of chemical breakdown accelerator to rise, chemical promoter increases the decomposition rate of gas hydrates, therefore in hydrate recovery process of the present invention, the concentration of chemical breakdown accelerator can maintain more than the operate as normal concentration always.
At hydrate exploitation initial period, pipe 18 temperature are low in the catalytic oxidation combustion device, catalytic oxidation is difficult to carry out, before carrying out catalytic oxidation combustion, adopt earlier in the electrical heating igniter 22 heatable catalytic oxidizing fire organ pipes temperature to 500-900 ℃, close electrical heating igniter 22 then, feed fuel combination, enter the normal exploitation operation phase.
Claims (10)
1, a kind of method of natural gas hydrate exploitation with in-situ catalytic oxidation thermochemistry comprises that step (1) constructs recovery well and gas collection well; (2) gas hydrates decompose; (3) natural gas after the decomposition is derived, and it is characterized in that described step (2) gas hydrates decompose the following method of taking: inject decomposition of hydrate accelerator to the hydrate reservoir, gas hydrates are decomposed into natural G﹠W; Adopt oxidant in-situ catalytic oxidation combustion fuel heating heat transport fluid simultaneously in the catalytic oxidation combustion device under being installed on recovery well, then heat transport fluid is pumped into the hydrate reservoir and supply with the required heat energy of gas hydrates decomposition; With the CO that catalytic oxidation combustion produced
2Gas injects the hydrate reservoir, makes it form CO
2Hydrate is filled the space that stays after the methane hydrate exploitation; CO
2Hydrate generates the heat transferred decomposition of hydrate accelerator that is discharged, and is used for the decomposition of gas hydrates, CO
2Hydrate forms the moisture content that absorbs in the decomposition accelerating agent, has improved the concentration of decomposition of hydrate accelerator.
2, the method for natural gas hydrate exploitation with in-situ catalytic oxidation thermochemistry as claimed in claim 1 is characterized in that the decomposition of described step (2) gas hydrates may further comprise the steps:
(1) the catalytic oxidation combustion device adopts the electrical heating combustion preheater;
(2) catalytic oxidation combustion device transfer the fuel and the oxidant in being installed on recovery well, the preheating in preheater of fuel and oxidant;
(3) under catalyst action, fuel is oxidized dose of catalytic oxidation in the catalytic oxidation combustion device of down-hole, emits heat heating heat transport fluid;
(4) inject decomposition of hydrate accelerator to the gas hydrates reservoir, gas hydrates are decomposed into natural G﹠W;
(5) heat transport fluid is delivered to hydrate reservoir heating decomposition of hydrate accelerator and gas hydrates reservoir, promotes the decomposition of gas hydrates;
(6) the catalytic oxidation combustion product is delivered to the hydrate reservoir, control hydrate reservoir temperature is lower than CO
2The hydrate equilibrium temperature is higher than CH
4The hydrate equilibrium temperature;
(7) CO in the catalytic oxidation combustion product
2Form CO at the hydrate reservoir
2Hydrate is emitted hydrate and is generated heat heating decomposition of hydrate accelerator;
(8) CO
2Hydrate forms the moisture content that absorbs in the decomposition of hydrate accelerator, and the decomposition of hydrate promoter concentration raises, and the decomposition rate of gas hydrates is accelerated.
3, the method for natural gas hydrate exploitation with in-situ catalytic oxidation thermochemistry as claimed in claim 1 or 2 is characterized in that described decomposition of hydrate accelerator is low-carbon alcohols or polyalcohol or salt solution or its mixed solution; Described decomposition of hydrate accelerator is contained the surfactant of 0.1-2% simultaneously.
4, the method for natural gas hydrate exploitation with in-situ catalytic oxidation thermochemistry as claimed in claim 1 or 2 is characterized in that: described heat transport fluid is water or salt solution or decomposition of hydrate accelerator or its mixture.
5, the method for natural gas hydrate exploitation with in-situ catalytic oxidation thermochemistry as claimed in claim 1 or 2, it is characterized in that: supported catalyst in the described catalytic oxidation combustion device, described catalyzer are that the metal of one of Pt, Rh, La, Mn, Ni, Cr and metal oxide or its mixture support in α-Al
2O
3Particle or γ-Al
2O
3Particle surface and making.
6, the method for natural gas hydrate exploitation with in-situ catalytic oxidation thermochemistry as claimed in claim 2, it is characterized in that: described catalytic oxidation combustion device electrical heating combustion preheater temperature is 500-900 ℃, the preheating of fuel temperature is 400-600 ℃, and the catalytic oxidation combustion temperature is 600-1000 ℃.
7, a kind of device of natural gas hydrate exploitation with in-situ catalytic oxidation thermochemistry, comprise the horizontal interface channel between recovery well (13) and gas collection well (6) and recovery well (13) and the gas collection well (6), and gasholder (7) and natural-gas transfer pipeline, it is characterized in that: also comprise catalytic oxidation combustion device (14), catalytic oxidation combustion device (14) is installed in (13) in the recovery well, fuel tank (8), decomposition accelerating agent storage tank (9), thermophore storage tank (10) connects catalytic oxidation combustion device (14) through pipeline respectively, be provided with igniter (22) in the catalytic oxidation combustion device (14), the catalytic combustion product outlet (27) of catalytic oxidation combustion device (14) is connected to the bottom of horizontal interface channel, is provided with decomposition accelerating agent and heat transport fluid outlet (19) on the catalytic oxidation combustion device (14) in addition.
8, the device of natural gas hydrate exploitation with in-situ catalytic oxidation thermochemistry as claimed in claim 7, it is characterized in that: described catalytic oxidation combustion device (14) is a coaxial sleeve reactor, interior pipe (18) tube side is the catalytic oxidation combustion district, shell side between interior pipe (18) and the outer layer sleeve is divided into two sections separate portions, wherein one section is burner preheating section (24), another section is burner heat exchanging segment (26), described fuel tank (8) is connected to burner preheating section (24) by pipeline, decomposition accelerating agent storage tank (9) and thermophore storage tank (10) are connected to burner heat exchanging segment (26) by pipeline, and catalytic oxidation combustion device inlet tube (23) connects pipe (18) in burner preheating section (24) and the catalytic oxidation combustion device; Pipe (18) is fixed on by many interior pipes and forms shell and tube reactor on the tube sheet in the described catalytic oxidation combustion device, and catalyst cupport is on the reactor inner tubal wall; Pipe (18) in catalytic combustion product outlet (27) is communicated with, decomposition accelerating agent and heat transport fluid outlet (19) are communicated with outer tube.
9, as the device of claim 7 or 8 described natural gas hydrate exploitation with in-situ catalytic oxidation thermochemistry, it is characterized in that: pipe (18) is finned tube in described.
10, as the device of claim 7 or 8 described natural gas hydrate exploitation with in-situ catalytic oxidation thermochemistry, it is characterized in that: described catalytic combustion product outlet (27) is provided with check device (16).
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