CN110013797A - A method of improving carbon dioxide replacement methane hydrate replacement rate - Google Patents

A method of improving carbon dioxide replacement methane hydrate replacement rate Download PDF

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Publication number
CN110013797A
CN110013797A CN201910298855.XA CN201910298855A CN110013797A CN 110013797 A CN110013797 A CN 110013797A CN 201910298855 A CN201910298855 A CN 201910298855A CN 110013797 A CN110013797 A CN 110013797A
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hydrate
gas
replacement
displacement
carbon dioxide
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祁影霞
邢海洋
余静薇
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University of Shanghai for Science and Technology
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University of Shanghai for Science and Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0006—Controlling or regulating processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0006—Controlling or regulating processes
    • B01J19/0013—Controlling the temperature of the process
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0053—Details of the reactor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0053—Details of the reactor
    • B01J19/0066—Stirrers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
    • B01J3/02—Feed or outlet devices therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
    • B01J3/04—Pressure vessels, e.g. autoclaves
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/50—Carbon dioxide
    • 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
    • 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
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/54—Specific separation steps for separating fractions, components or impurities during preparation or upgrading of a fuel

Abstract

The invention discloses a kind of methods for improving carbon dioxide replacement methane hydrate replacement rate, which is characterized in that by Ar and CO2Mixed gas be passed through CH4Displacement reaction is carried out in the reaction kettle of hydrate.The present invention obtains good effect as small molecule promotor using Ar in an experiment, is a kind of raising CO2Replace CH4The efficient scheme of hydrate displacement efficiency.

Description

A method of improving carbon dioxide replacement methane hydrate replacement rate
Technical field
The present invention relates to a kind of raising CO2Replace CH4The method of hydrate replacement rate, and in particular to a kind of to use small molecule Gas Ar improves CO as promotor2Replace CH4The method of the displacement efficiency of hydrate.
Background technique
Clean gas hydrates can be directly ignited like ice and snow, be commonly called as " combustible ice ", be by hydrocarbon molecules and Hydrone formed under certain low temperature, condition of high voltage like ice-like crystalline compounds；Wherein ingredient is based on methane molecule, therefore Also referred to as methane hydrate.Gas hydrates are distributed in all parts of the world, and storage scale is big, and energy density is high, are a kind of Clear energy sources are good for the environment the sustainable development with national economy.Expert thinks all over the world, and gas hydrates will become The most potential alternative energy source of this century tradition conventional energy resource.
Compared to traditional mineral reserve energy, the technical difficulty of exploitation of gas hydrate seems bigger.The shape of gas hydrates At more complicated with mode of occurence, there is phase transformation reaction etc. in decomposable process, recovery process can also be filled with it is many it is uncertain because Element, at present still without effective recovery method technology, still also in theoretical research and laboratory experiment stage.Exploitation of gas hydrates Thinking substantially first by the gas hydrates contained in deposit deviation phase balance condition decompose, then plus To utilize.Respectively there are its advantage and disadvantage in traditional several recovery methods:
(1) voltage drop method: biggest advantage be without continuous agitation, without heat consumption loss, operating process is simple, equipment At low cost and preferable economic benefit.It is maximum the disadvantage is that opening but since voltage drop method is a kind of reduction passive type exploitation It adopts that natural gas is very slow, and has certain limitation.
(2) heat shock method: advantage is that heat transfer is fast, and decomposition of hydrate is fast；It can control heat resolve position, make hydrate Layer can be thermally decomposed directly；Effect on environment is small, can develop a variety of hydrate reservoirs.And cause a large amount of heat loss, heat It is the main shortcoming of heat shock method that utilization rate is very low.
(3) chemical-agent technique: chemical-agent technique has the advantages that simple to operate and initial energy less investment；But it is lacked Point is chemical-agent technique compared with temperature activation method, and inhibiting effect is slow, and cost of winning is high, also has certain pollution to environment.
In this century, other than world community is in addition to the energy shortage to be faced the problem of, it is necessary to the problem of coping with climate change. Under existing scientific and technological level and productive consumption mode, carbon emission is the inevitable outcome of socio-economic development process.The industrial revolution with Come, with CO2It increases sharply in an atmosphere for the greenhouse gases of main representative, exacerbates the process of climate change, CO2The place of greenhouse gases Reason becomes a big important task of countries in the world.
1986, Ebinuma and Ohgaki etc., which are put forward for the first time, used CO2Replace the imagination of methane in hydrate, this method The problem of not only solving natural gas gas-field exploitation, while can be by CO2Gas non-recoverable storage in the form of solid hydrate exists Deep seafloor becomes the new approaches for solving the key subjects such as global warming, greenhouse effects.CO2Displacement method, which refers to, is being suitable for CO is injected to gas hydrates layer under Temperature-pressure Conditions2Gas contacts and is reached with gas hydrates solid vapor equilibrium, makes water The gas component (main is methane) closed in object releases, and CO2Into hydrate phase, to produce in hydrate CH4Gas.This method mainly utilizes natural gas and CO2Generate the difference of hydrate equilibrium condition, CO2Compared with CH4Gas is easier Hydrate is formed, stability is more preferable.CO2The advantages of displacement method is that hydrate solids are hardly decomposed in whole process, to stratum It disturbs small, will not influence the mechanical stability of storage layer, the equal geological hazards that will not cause that subsea strata collapses；And it is adopting Out by CO while natural gas2Greenhouse gases are stored in stratum in the form of hydrates, reduce the CO in air2Content can slow down Greenhouse effects, environmentally protective, no pollution to the environment.
CH4Hydrate and CO2Hydrate is all structure I type hydrate, and all there are six middle cave, two vesicles.CO2And CH4Phase More larger than its molecular volume, size is just between middle cave and vesicle, and CH4Molecule is less than vesicle.So from reason From, CO2Molecule can only occupy six middle caves, and CH4Molecule can take up eight caves of I type.McGrail is by Raman Small bug hole and when middle bug hole, confirm this theory in spectral technique analysis hydrate, he has found CO2Molecule cannot be introduced into small crystalline substance Cave.It follows that in CO2Replace CH4When hydrate, hydrate is in order to maintain itself stability, part CH4Molecule accounts for again According to small bug hole, cause CH4The small bug hole decomposition rate of hydrate is far below middle bug hole decomposition rate.Even if CO2All occupy middle crystalline substance Still there is 1/4 CH in cave4Remain in hydrate crystal.Therefore laboratory its efficiency of the displacement to be done does not exceed 75%；Hydration The crystal structure of object objectively determines that 75% is exactly theoretical maximum displacement efficiency.Furthermore that there is also reaction speeds is slow for reaction process The disadvantages of and limit the application of this method.
Summary of the invention
The technical problems to be solved by the present invention are: CO2With CH4The displacement of hydrate is reacted, theoretical maximum displacement efficiency office The technical issues of being limited to 75%.
To solve the above-mentioned problems, the present invention provides a kind of raising CO2Replace CH4The method of hydrate replacement rate, it is special Sign is, by Ar and CO2Mixed gas be passed through CH4Displacement reaction is carried out in the reaction kettle of hydrate.
Gas hydrate is liquid by one or several kinds of gases or effumability and water in certain temperature and pressure item The cage modle crystalline compounds of the non-stoichiometry type formed under part.The gas hydrate crystal structure having now been found that has 3 kinds, i.e., I type, II type and H-type structure.Guest molecule (such as methane, propane and carbon dioxide etc.) is filled into the crystalline substance of hydrone formation Cave.It is interacted between guest molecule and main body hydrone with Van der Waals for.In Study of Clathrate Hydrates, the object that is sized for Molecule can be filled to be connected to form in some polyhedron size cage holes by main body hydrone by hydrogen bond, and it is steady to make it have thermodynamics It is qualitative.Cage structure aperture sizes and gas molecular diameter match could stable formation hydrate.Foreign molecules size is Determine whether it is capable of forming gas hydrate, forms which kind of formation gases water platform object and gas hydrate component and stability Most important factor.It is easiest to form gas hydrate when foreign gas molecular dimension and hydrate bug hole size match, And the stability of gas hydrate is also relatively strong.
Ar molecular diameter is between CO2With CH4Between, it can be filled into the small bug hole of methane hydrate, to displace small bug hole In CH4, break 75% theoretical maximum displacement efficiency with this and improve CO2Replace the CH in hydrate4Displacement efficiency.This Outside, it is contemplated that Ar gas hydrate synthesis condition is easily reached, safety is good etc., and the present invention proposes Ar as micro-molecular gas Additive promotes CO2Replace the CH in hydrate4Displacement efficiency.
Preferably, the Ar gas and CO2The mass ratio of the substance of gas is 1:3,1:6 or 1:9.It is provided by the invention Method is through the CH in Ar displacement foveola4Come improve displacement reaction displacement efficiency, the additional amount of Ar is to displacement efficiency Have a direct impact.CH4Hydrate belongs to I type hydrate, and there are six middle bug hole, two small bug holes, CO2In displacement in bug hole CH4, Ar replaces the CH in small bug hole4, therefore Ar and CO2The mass ratio of substance should be lower than 1:3, and with Ar additional amount Increase, displacement efficiency is significantly increased.
Preferably, the temperature in the reaction kettle is -5~10 DEG C, and pressure is 1~6MPa.In the past studies have shown that certain In range, displacement efficiency can increase with the raising of temperature and pressure, i.e., in one timing of pressure, displacement efficiency can be with displacement The raising of temperature and step up；One timing of temperature, displacement efficiency can also be increased with increasing for pressure.Choose suitable temperature Degree, pressure condition are most important for the carry out of displacement reaction.(1)CH4Hydrate and CO2Hydrate is the same, and synthesis pressure is all It increases as the temperature rises.(2)CH4The thermal stability of hydrate is not so good as CO2Hydrate.To a certain extent it could be said that In the range of pressure allows, temperature is higher, then replacement rate is bigger.(3) two compare, at the same temperature CO2Hydrate at Pressure is less than CH4The synthesis pressure of hydrate.So as long as pressure is controlled in CO in an experiment2Lanthanum chloride hydrate pressure it On, while in CH4Under lanthanum chloride hydrate pressure, then CH4Hydrate will decompose, and form CO at the same time2Hydrate.This Sample can be completed to use CO2Remove displacement CH4The process of hydrate.
The present invention is in CO2Replace the CH in hydrate4Micro-molecular gas additive A r is added in the process, it is anti-to improve displacement The displacement efficiency answered.Replacement rate can reach 66%.
Detailed description of the invention
Fig. 1 is the schematic diagram for the consersion unit that embodiment uses；
Fig. 2 is pure CO2With Ar/CO2CH in gaseous mixture replacement process4Replacement amount with the time variation comparison diagram；
Fig. 3 is pure CO2With Ar/CO2CO in gaseous mixture replacement process2Residual volume with the variation of time datagram；
Fig. 4 is Ar/CO2In gaseous mixture replacement process Ar residual volume with the variation of time datagram；
Fig. 5 is pure CO2With Ar/CO2CH in gaseous mixture replacement process4Replacement rate with the variation of time datagram.
Specific embodiment
In order to make the present invention more obvious and understandable, hereby with preferred embodiment, and attached drawing is cooperated to be described in detail below.
Embodiment
A kind of raising CO2Replace CH4The method of hydrate replacement rate:
By Ar and CO2Mass ratio with substance is respectively that the mixed gas of the ratio mixing of 1:3,1:6,1:9 is passed through CH4 Displacement reaction is carried out in the reaction kettle of hydrate；Temperature in reaction kettle is 5 DEG C, and pressure is controlled in 2.5~3.5MPa.
The present embodiment use equipment as shown in Figure 1, its successively include displacement reaction generating system, data collection system, Temperature, pressure control system, gas Flowrate Control System and pumped vacuum systems specifically include the high pressure being placed in thermostatic water bath 22 Reaction kettle 20, the interior blade 19 for being equipped with stirring of autoclave 20, the magnetic agitation at 20 top of blade 19 and autoclave The output end of motor 18 connects；20 bottom of autoclave is equipped with discharge outlet 21.The top of autoclave 20 passes through pipe respectively Road and exhaust outlet 31, sampler bag 27, Agilent data collecting instrument 30 and three raw material gas cylinders (namely for methane gas cylinders 1, carbon dioxide gas Bottle 2 with argon gas gas cylinder 3) be connected to.The pipeline in 1 exit of methane gas cylinder is equipped with pressure reducing valve 1 and regulating valve 1, carbon dioxide The pipeline in 2 exit of gas cylinder is equipped with pressure reducing valve 25 and regulating valve 28, and the pipeline in 3 exit of argon gas gas cylinder is equipped with pressure reducing valve 36 and regulating valve 39, this three pipelines are connect after merging with the gas flowmeter 12 and regulating valve 5 13 being connected in parallel, then It is connect respectively with shut-off valve 3 17, shut-off valve 2 14 by pipeline again, the top inside shut-off valve 3 17 and autoclave 20 Connection, shut-off valve 2 14 are connected to vacuum pump 16, and the pipeline between shut-off valve 2 14 and vacuum pump 16 is equipped with pressure gauge 1； The arrival end of gas flowmeter 12 is connected with shut-off valve 1, and outlet end is connected with regulating valve 4 11.Autoclave 20 and row The pipeline that port 31 connects is equipped with shut-off valve 4 23；Autoclave 20 passes sequentially through regulating valve 6 24, pressure gauge 2 25, cuts Only valve 5 26 is connect with sampler bag 27.Top in autoclave 20 is also acquired by two-way pipeline and Agilent data respectively Instrument 30 connects, wherein pipeline is equipped with pressure sensor 28 all the way, passes through two temperature sensors in parallel on another way pipeline 29 connect with Agilent data collecting instrument 30；Agilent data collecting instrument 30 is connected by circuit and gas flowmeter 12, the end PC 32 It connects.
Operating method are as follows: open dioxide bottle 2 and argon gas gas cylinder 3, pressure reducing valve and adjusting on both adjustment pipeline Valve, by the CO of the Ar of 0.875MPa and 2.625MPa2, 0.7MPa Ar and 2.8MPa CO2, 0.35MPa Ar and 2.625MPa CO2It is filled with after mixing containing CH4In the autoclave of hydrate, displacement reaction is carried out under the conditions of selected temperature, pressure； In CH4After the synthesis of hydrate, magnetic stirring apparatus is closed, the temperature of rapid regulating thermostatic slot is kept for one section to -6 DEG C The stabilization of time is constant to system temperature；It then turns on shut-off valve 4 23 and at the uniform velocity releases CH remaining in reaction kettle4Gas is to normal 15S is pressed and keeps, the rear shut-off valve 4 23 for closing reaction system rapidly；Then turn on regulating valve 1, regulating valve 28, regulating valve 39, it is slowly added to gas to required pressure into reaction kettle and (fills the CO of 3.5MPa in first group of experiment2, in the second set of experiments Fill the CO of the Ar and 2.625MPa of 0.875MPa2, the CO of the Ar and 2.8MPa of 0.7MPa are filled in the experiment of third group2, at the 4th group The CO of the Ar and 2.625MPa of 0.35MPa are filled in experiment2), all valves of reaction system are closed, the temperature of thermostatic water bath is fast Speed is adjusted to 5 DEG C, opens valve 5 26 at regular intervals during displacement reaction and carries out a gas sampling.After reaction, will Hydrate in reaction kettle is placed under room temperature and is decomposed, and when the pressure in reaction kettle is stablized, carries out last time gas and adopts Sample simultaneously analyzes gas phase composition.Experimental data is as shown in Figure 2-5.The present invention is especially suitable for improve CO2Displacement method develops natural gas Gas displacement efficiency.

Claims (3)

1. a kind of method for improving carbon dioxide replacement methane hydrate replacement rate, which is characterized in that by Ar and CO2Gaseous mixture Body is passed through CH4Displacement reaction is carried out in the reaction kettle of hydrate.
2. improving the method for carbon dioxide replacement methane hydrate replacement rate as described in claim 1, which is characterized in that described Ar gas and CO2The mass ratio of the substance of gas is 1:(3~9).
3. improving the method for carbon dioxide replacement methane hydrate replacement rate as described in claim 1, which is characterized in that described Temperature in reaction kettle is -5~10 DEG C, and pressure is 1~6MPa.
CN201910298855.XA 2019-04-15 2019-04-15 A method of improving carbon dioxide replacement methane hydrate replacement rate Pending CN110013797A (en)

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Publication number Priority date Publication date Assignee Title
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CN103221632A (en) * 2010-09-21 2013-07-24 帕尔默实验室有限责任公司 Method of using carbon dioxide in recovery of formation deposits
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Application publication date: 20190716