CN112063424A - Preparation method of natural gas hydrate - Google Patents
Preparation method of natural gas hydrate Download PDFInfo
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- CN112063424A CN112063424A CN202010958500.1A CN202010958500A CN112063424A CN 112063424 A CN112063424 A CN 112063424A CN 202010958500 A CN202010958500 A CN 202010958500A CN 112063424 A CN112063424 A CN 112063424A
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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
- C10L3/108—Production of gas hydrates
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- 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
- C10L2290/24—Mixing, stirring of fuel components
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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
- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
- C10L2290/30—Pressing, compressing or compacting
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Abstract
The invention relates to a preparation method of natural gas hydrate, in particular to a method for preparing natural gas hydrate by using a liquid phase material formed by mixing alkyl glycoside, lower alcohol and water as a hydrating agent and adopting an efficient gas-liquid dispersion mixing technology. The method fully utilizes the characteristics of a reaction system, a reaction process and a product, has simple and easy technical process, high reaction rate, high conversion per pass and low operation cost, is easy to realize large-scale continuous operation, and is a clean and efficient production method which meets the development requirements of green chemical industry. The method of the invention not only can provide technical support for the storage and transportation of natural gas, but also can provide technical support for the formation, exploitation, storage and transportation and the like of natural gas hydrate minerals, and has remarkable economic and social benefits.
Description
Technical Field
A method for preparing natural gas hydrate, especially using liquid phase material formed by mixing alkyl glycoside, lower alcohol and water as hydrating agent, adopting high-efficiency gas-liquid dispersion mixing technique, preparing hydrating agent, compressing natural gas, gas-liquid dispersion mixing, cooling gas-liquid mixture, belonging to natural gas storage and transportation field and natural gas hydrate preparation technical field.
Background
1. Natural gas and storage and transportation thereof
(1) Natural gas
Natural gas is a fossil fuel, commonly referred to as oil field gas and gas field gas. The natural gas contains alkanes as main component, most of which are methane, and small amount of ethane, propane, butane, etc. Methane is the simplest hydrocarbon, and is a colorless, odorless gas at atmospheric pressure and has a density of 0.717kg/m in the standard state3The melting point and the boiling point are-182.5 ℃ and-161.5 ℃ respectively, and the critical temperature and the critical pressure are-82.6 ℃ and 4.59MPa respectively. Methane is very insoluble in water at normal temperature and pressure, and the solubility in water at 17 ℃ is only 3.5mg/100 mL.
Because natural gas mainly contains methane, the physical property of the natural gas is similar to that of methane, and the natural gas is lighter than air, colorless and tasteless. Because the density of the air-permeable membrane is less than that of air, once the air-permeable membrane leaks, the air-permeable membrane can diffuse upwards and is not easy to accumulate to form explosive gas; in addition, natural gas does not contain carbon monoxide, and therefore natural gas is one of safer fuel gases. Natural gas as a fuel has the advantages of high unit calorific value, low exhaust pollution, low price and the like, and has become the development direction of clean fuels. Besides being used as fuel, natural gas is also an important raw material for producing carbon black, liquefied petroleum gas, chemicals and the like.
(2) Storage and transportation of natural gas
Natural gas, whose main component is methane, changes from a gaseous state to a liquid state when cooled to about-162 c under atmospheric pressure, is called liquefied natural gas. Because the liquefaction temperature of the liquefied natural gas at normal pressure is very low, the normal-pressure liquefaction storage and transportation of the natural gas are difficult to realize. The natural gas can be conveyed by adopting pipeline conveying and compressed steel cylinder conveying, the pipeline conveying needs to be provided with a pipeline, and the construction and maintenance cost of the conveying pipeline is higher; the transportation by the compression steel cylinder has low efficiency and is difficult to use on a large scale.
(3) Natural gas hydrate and storage and transportation thereof
Under certain conditions of temperature, pressure and gas-water ratio, natural gas can be mixed with water to form ice-like, non-stoichiometric, cage-like crystalline compounds called gas hydrates, i.e., combustible ice. Because the natural gas is mainly methane, the natural gas hydrate can use mCH4·nH2And O, wherein m is the number of gas molecules in the natural gas hydrate, and n is the hydration index (namely the number of water molecules). Natural gas hydrates with a methane content of more than 99% may also be referred to as methane natural gas hydrates.
The natural gas is stored and transported in the form of natural gas hydrate, so that the transportation efficiency is high, the safety is good, the storage and transportation mode is flexible and convenient, the pipeline construction and maintenance cost can be avoided, a novel storage and transportation way is provided for the development of small or remote gas fields without pipeline facilities or without being worth laying pipelines, and the natural gas storage and transportation device can play a role in the development of offshore gas fields or ocean imported natural gas storage and transportation. Therefore, in recent years, the preparation of natural gas hydrates has attracted attention, and has become a new field in natural gas storage and transportation research.
2. The main problems existing in the prior natural gas hydrate preparation
The process of preparing the natural gas hydrate is a gas-liquid heterogeneous reaction process, and generally can be carried out under the conditions of below 10 ℃ and above 3MPa, and the reaction process of the natural gas hydrate requires certain gas/liquid specific surface area and heat transfer specific surface area, so that large-scale industrial implementation is difficult. The preparation of the natural gas hydrate mainly has the following problems:
(1) gas-liquid dispersion mixing problems. Because hydrocarbon gas in the natural gas is insoluble in water, the natural gas reacts with water to generate natural gas hydrate, which is a gas-liquid heterogeneous reaction process. If the natural gas and the water are not sufficiently contacted, the reaction is difficult to proceed, and a sufficient gas/liquid specific surface area is required to provide a reaction interface in order to allow the process to have a certain reaction rate.
(2) The heat of formation of natural gas hydrates is a problem. The process for preparing natural gas hydrates is exothermic and the heat generated by the reaction must be removed in time to maintain the low temperature conditions required for the reaction. The small-scale hydration reactor has small volume, large specific surface area and easy reaction heat export. However, since the removal of the heat of reaction becomes very difficult as the volume of the reactor increases, the heat transfer specific surface area of the reactor must be sufficient on a commercial scale.
(3) There is a problem of clogging of the aqueous feed system. The operation temperature for preparing the natural gas hydrate is close to the freezing point of water, so that the water-phase material is easy to be transformed into a solid state, and the pipeline, the pump and the like are blocked, so that the natural gas hydrate preparation process cannot be normally carried out.
(4) There is a problem of clogging of the solid material system. Because the prepared natural gas hydrate is solid, the problems of pipeline blockage, difficult normal work of a circulating pump and the like necessarily exist in the circulating reaction process of the solid material system.
(5) There is a conflict between increasing the gas-liquid ratio and increasing the single pass conversion. In order to reduce the material circulation, the conversion rate needs to be increased as much as possible, and the contradiction between the improvement of the gas-liquid ratio and the improvement of the single-pass conversion rate needs to be solved.
In order to solve the problems of the preparation of the natural gas hydrate, a material system and a gas-liquid dispersion mixing technology must be started. Therefore, the research and development of the hydrating agent with excellent performance and the preparation of the natural gas hydrate by applying the efficient gas-liquid dispersion mixing technology have important significance.
Disclosure of Invention
The invention discloses a preparation method of natural gas hydrate, in particular to a method for preparing the natural gas hydrate by taking a liquid phase material formed by mixing alkyl glycoside, lower alcohol and water as a hydrating agent, adopting an efficient gas-liquid dispersion mixing technology, and carrying out hydrating agent preparation, natural gas compression, gas-liquid dispersion mixing and gas-liquid mixture cooling. The method can improve the gas-liquid ratio of the natural gas hydrate, realize the micro mixing of gas and water, improve the gas-liquid contact specific surface area, and form micro bubbles and liquid drops with certain stability, thereby meeting the requirements of the preparation process of the natural gas hydrate.
The technical scheme for realizing the aim is as follows: a method for preparing natural gas hydrate, especially use liquid phase material that alkyl glycoside, lower alcohol mix with water and form as the hydrate, adopt the high-efficient gas-liquid dispersion mixing technique to prepare natural gas hydrate, characterized by that the said method step is as follows:
(1) preparing a hydrating agent: mixing alkyl glycoside, lower alcohol and water in a mixing device to prepare a hydrating agent, wherein the mass percent concentration of the alkyl glycoside is 0.1-1.0%, the mass percent concentration of the lower alcohol is 1.0-10.0%, and the prepared hydrating agent enters the next step;
(2) cooling the hydration agent: cooling the hydration agent prepared in the last step in heat exchange equipment, and allowing the cooled liquid-phase material to enter a gas-liquid dispersion mixing step in the fifth step;
(3) compressing natural gas: compressing and boosting natural gas in gas compression equipment, and then entering the next step;
(4) cooling natural gas: cooling the compressed and boosted natural gas in the previous step in heat exchange equipment, and allowing the cooled and boosted natural gas to enter the next step;
(5) gas-liquid dispersion mixing: in a high-efficiency gas-liquid dispersion mixing device, gas-liquid dispersion mixing is carried out on the gas-phase material obtained in the last step and the liquid-phase material obtained in the second step, and the dispersed and mixed material enters the next step;
(6) cooling the gas-liquid mixture: and cooling the gas-liquid dispersion mixture prepared in the last step in heat exchange equipment to prepare the natural gas hydrate.
The alkyl glycoside is any one or any combination of octyl glycoside, decyl glycoside, dodecyl glycoside, tetradecyl glycoside, hexadecyl glycoside and octadecyl glycoside, and the glucose polymerization degree of the alkyl glycoside is 1.6-2.0.
Further, the lower alcohol is any one or any combination of methanol, ethanol, ethylene glycol, propanol, propylene glycol and glycerol.
Further, the heat exchanger used for cooling the hydration agent in the second step can be any one of a jacketed heat exchanger, a double-pipe heat exchanger and a shell-and-tube heat exchanger, and the material is cooled to-10 ℃ to 10 ℃.
Further, in the third step of natural gas compression, the gas phase material is compressed to the absolute pressure of 3.0MPa to 6.0 MPa.
Further, the heat exchanger adopted by the natural gas cooling in the fourth step can be any one of a double-pipe heat exchanger, a shell-and-tube heat exchanger, a plate-shell heat exchanger and a plate-fin heat exchanger, and the material is cooled to-10 ℃ to 10 ℃.
Further, the gas-liquid dispersion mixing device in the fifth step of gas-liquid dispersion mixing is any one of a static mixer, a jet mixer and a venturi mixer, and the molar ratio of the natural gas to the water is 1.0: 1.0-1.0: 10.0.
Further, the heat exchanger used for cooling the gas-liquid mixture in the sixth step may be any one of a double-pipe heat exchanger, a shell-and-tube heat exchanger, a plate-shell heat exchanger and a plate-fin heat exchanger, and the material is cooled to 0 ℃ to 10 ℃.
The invention adopts the technical principle that:
(1) fully utilizes the characteristics of the alkyl glycoside of the green surfactant
The alkyl glycoside surfactant is prepared from natural renewable resources, and mainly comprises octyl glycoside, decyl glycoside, dodecyl glycoside, tetradecyl glycoside, hexadecyl glycoside, octadecyl glycoside and the like. The alkyl glycoside is not only an excellent surfactant, but also has good biodegradability, can meet the requirement of preparing a hydrating agent, and simultaneously does not bring influence on ecological environment.
(2) Makes full use of the characteristic of the lower alcohol of lowering the freezing point of water
The lower alcohol comprises methanol, ethanol, ethylene glycol, propanol, propylene glycol, glycerol and the like, and any one or any combination of the lower alcohols is added during the preparation of the hydrate, so that the freezing point of the aqueous phase system can be reduced, the risk caused by the solidification of the aqueous phase system under the low temperature condition can be effectively prevented, and the operating condition range of the preparation process of the natural gas hydrate is widened.
(3) Fully utilizes the characteristic that the lower alcohol has the effect of improving the solubility of natural gas in water
Because the alcohol and the water both have hydroxyl groups and can form hydrogen bonds with each other, the lower alcohol and the water can be mutually soluble in any proportion. The lower alcohol in the hydrating agent not only can play a role in reducing the freezing point of an aqueous phase system, but also can increase the solubility of natural gas in the aqueous phase system, thereby improving the efficiency of a gas-liquid dispersion mixing process in a thermodynamic sense.
(4) Fully utilizes the reaction characteristic of natural gas and water to form natural gas hydrate
The process of forming natural gas hydrate by natural gas and water is exothermic, reversible, gas-liquid multiphase reaction. Therefore, the reaction is favorably carried out towards the direction of forming the natural gas hydrate by increasing the specific surface area of gas-liquid contact, removing the reaction heat in time and increasing the reaction pressure. There are three basic conditions for natural gas hydrate formation from natural gas and water, namely gas-liquid dispersion mixing condition, temperature and pressure.
Firstly, the specific surface area of gas-liquid multiphase contact is increased. By using a novel hydration agent and adopting a dispersion mixing technology with high gas-liquid dispersion mixing efficiency, the gas-liquid multiphase contact specific surface area is effectively improved, and the reaction rate and the single-pass high conversion rate are improved.
Secondly low temperature. Natural gas hydrates are formed at 0-10 ℃ and decompose at temperatures above 20 ℃. Since the process of forming natural gas hydrate by natural gas and water is exothermic, the temperature of the system is maintained by effectively cooling and reducing the temperature to derive the reaction heat.
Thirdly high voltage. At 0 ℃, natural gas hydrates can form at about 3MPa, and the higher the pressure, the more stable the hydrates are. Therefore, the invention ensures the pressure required by the system through the natural gas compression process.
(5) Adopts a high-efficiency mixing technology
Static mixers, jet mixers, venturi mixers and the like can effectively realize the mixing of heterogeneous systems. The gas-liquid ratio of the natural gas hydrate can be improved by adopting the high-efficiency dispersion mixing technology, the micro mixing of gas and water is realized, the gas-liquid contact specific surface area is improved, micro bubbles and liquid drops with certain stability are formed, and the speed and the efficiency of gas-liquid dispersion mixing are remarkably improved from the aspect of dynamics.
(6) Makes full use of the compressible characteristic of natural gas
The critical temperature and the critical pressure of the natural gas are-82.6 ℃ and 4.59MPa respectively, and the natural gas is not liquefied at the formation temperature (0-10 ℃) of the natural gas hydrate, is in a gas state and has compressibility. The basic parameters of natural gas and water under natural gas hydrate formation conditions are as follows:
the composition of natural gas. The volume of 1.0kmol natural gas is 22.4m under normal temperature and pressure3(ii) a But the volume of 1.0kmol natural gas is about 0.76m under the conditions of cooling and compressing to 275K and 3.0MPa3。
② the molar ratio of natural gas to water. 1.0m at normal temperature and pressure3164.0m natural gas3Natural gas and 0.8m3Water of (2)Composition of, wherein 0.8m3The water content was 44.44kmol, 164.0m3The natural gas was 7.32 kmol. Thus, in natural gas hydrates, the molar ratio of natural gas to water is approximately 1: 6.
③ the volume ratio of natural gas to water. Under the gas-liquid dispersion mixing operation condition (275K, 3.0MPa), the volume of water is 0.80m3，164.0 m3The volume of natural gas under 275K and 3.0MPa is about 5.6m3Thus, the volume ratio of natural gas to water is about 7: 1.
The advantages of the invention are embodied in that:
(1) the high-efficiency dispersion and mixing of gas-liquid phase materials are realized. According to the invention, the alkyl glycoside surfactant and the lower alcohol are added into the water, and the high-efficiency dispersion mixing technology is adopted, so that the gas-liquid ratio of the natural gas hydrate is improved, the dispersion of natural gas and water phase materials is effectively promoted, the gas-liquid contact specific surface area is improved, microbubbles and liquid drops with certain stability are formed, and the speed and efficiency of the gas-liquid dispersion mixing process are improved from the aspects of thermodynamics and kinetics.
(2) The contradiction between the improvement of the gas-liquid ratio and the improvement of the single-pass conversion rate is fundamentally solved. The high-efficiency gas-liquid dispersion mixing equipment such as a static mixer, an injection mixer, a Venturi mixer and the like is adopted, and the contradiction between the improvement of the gas-liquid ratio and the improvement of the single-pass conversion rate is solved from the aspect of dynamics.
(3) The adoption of the pre-heat transfer and natural gas pre-compression process creates favorable conditions for leading out reaction heat and gas-liquid dispersion mixing. Natural gas hydrate formation is an exothermic reaction, and the heat generated by the reaction must be removed in time to maintain the low temperature required for the reaction. The pre-cooling of the liquid phase material and the gas phase material and the pre-compression process of the natural gas are adopted, so that favorable conditions are created for heat conduction and gas-liquid dispersion mixing in the reaction process, and the technical problems in the design and continuous operation of industrial scale reactors are fundamentally solved.
(4) Easy to realize continuous operation. The adopted cooling and gas-liquid dispersion mixing technology can be continuously operated, and compared with the intermittent operation, the continuous operation has the outstanding advantages that the product quality is stable and easy to control, thereby creating conditions for preparing the natural gas hydrate with uniform composition, structure and the like.
(5) The problem of the jam of material system has been solved. The lower alcohol is added into the water phase material, so that the freezing point of the material is effectively reduced, the circulation of the natural gas hydrate solid material in a reaction system is avoided, and the problem of material system blockage in the preparation process of the natural gas hydrate is fundamentally solved.
(6) The selected additive is an environment-friendly additive, and accords with the green chemical principle and the clean production concept. Because the traditional surfactant is difficult to biodegrade, the traditional surfactant can bring influence to the ecological environment. The alkyl glycoside is a green surfactant and has excellent biodegradability. The lower alcohol can be completely burnt without residue. The used additives are all environment-friendly additives and do not bring harm to the ecological environment.
The method takes a liquid phase material formed by mixing alkyl glycoside, lower alcohol and water as a hydrating agent, and adopts an efficient gas-liquid dispersion mixing technology to prepare the natural gas hydrate. The method fully utilizes the characteristics of a reaction system, a reaction process and a product, has simple and easy technical process, high reaction rate, high conversion per pass and low operation cost, is easy to realize large-scale continuous operation, and is a clean and efficient production method which meets the development requirements of green chemical industry.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
The main process equipment is gas-liquid dispersion mixing equipment, gas compression equipment, heat exchange equipment and the like.
Example one
A process for preparing natural gas hydrate includes such steps as preparing hydrating agent from the liquid phase of alkyl glucoside, lower alcohol and water, efficient gas-liquid dispersing and mixing, compressing natural gas, gas-liquid dispersing and mixing, and cooling. The method comprises the following specific steps:
(1) preparing a hydrating agent: mixing octyl glucoside with the glucose polymerization degree of 1.6, methanol and water, wherein the mass percent concentration of the octyl glucoside is 0.1%, the mass percent concentration of the methanol is 1.0%, and taking the prepared liquid phase material as a hydrating agent to enter the next step;
(2) cooling the hydration agent: in a jacketed heat exchanger, cooling the hydration agent prepared in the previous step to 10 ℃, and allowing the cooled liquid-phase material to enter a fifth step of gas-liquid dispersion mixing;
(3) compressing natural gas: compressing and boosting natural gas in a gas compression device until the absolute pressure is 6.0MPa, and enabling the gas-phase material to enter the next step;
(4) gas-phase material heat transfer: cooling the natural gas in the previous step to-5 ℃ in a shell-and-tube heat exchanger, and allowing the cooled gas-phase material to enter the next step;
(5) gas-liquid dispersion mixing: in a static mixer, gas-liquid dispersion mixing is carried out on the gas-phase material obtained in the last step and the liquid-phase material obtained in the second step, the molar ratio of natural gas to water-phase material is 1.0:1.0, and the material after gas-liquid dispersion mixing enters the next step;
(6) cooling the gas-liquid mixture: the gas-liquid dispersion mixture was cooled to 8 ℃ in a plate fin heat exchanger to form a stable natural gas hydrate.
Example two
A process for preparing natural gas hydrate includes such steps as preparing hydrating agent from the liquid phase of alkyl glucoside, lower alcohol and water, efficient gas-liquid dispersing and mixing, compressing natural gas, gas-liquid dispersing and mixing, and cooling. The method comprises the following specific steps:
(1) preparing a hydrating agent: mixing octadecyl glucoside with the glucose polymerization degree of 2.0, ethanol and water, wherein the mass percent concentration of the octadecyl glucoside is 1.0%, the mass percent concentration of the ethanol is 10.0%, and the prepared liquid phase material is used as a hydrating agent to enter the next step;
(2) cooling the hydration agent: cooling the hydration agent prepared in the last step to-10 ℃ in a shell-and-tube heat exchanger, and allowing the cooled liquid-phase material to enter a gas-liquid dispersion mixing step in the fifth step;
(3) compressing natural gas: compressing natural gas in a gas compression device until the absolute pressure is 3.0MPa, and enabling the gas-phase material to enter the next step;
(4) cooling natural gas: cooling the natural gas in the previous step to-10 ℃ in a lamella heat exchanger, and allowing the cooled gas-phase material to enter the next step;
(5) gas-liquid dispersion mixing: in a jet mixer, gas-liquid dispersion mixing is carried out on the gas-phase material obtained in the last step and the liquid-phase material obtained in the second step, the molar ratio of natural gas to water-phase material is 1.0:10.0, and the gas-liquid dispersion mixed material enters the next step;
(6) cooling the gas-liquid dispersion mixture: in the double pipe heat exchanger, the gas-liquid dispersion mixture was cooled to 2 ℃ to form a stable natural gas hydrate.
EXAMPLE III
A process for preparing natural gas hydrate includes such steps as preparing hydrating agent from the liquid phase of alkyl glucoside, lower alcohol and water, efficient gas-liquid dispersing and mixing, compressing natural gas, gas-liquid dispersing and mixing, and cooling. The method comprises the following specific steps:
(1) preparing a hydrating agent: mixing decyl glucoside with the glucose polymerization degree of 1.8, ethylene glycol and water, wherein the mass percentage concentration of the decyl glucoside is 0.4%, the mass percentage concentration of the ethylene glycol is 2.0%, and taking the prepared liquid phase material as a hydrating agent to enter the next step;
(2) cooling the hydration agent: cooling the hydration agent prepared in the last step to-4 ℃ in a shell-and-tube heat exchanger, and allowing the cooled liquid-phase material to enter a gas-liquid dispersion mixing step in the fifth step;
(3) compressing natural gas: compressing natural gas in a gas compression device until the absolute pressure is 4.0MPa, and enabling the gas-phase material to enter the next step;
(4) cooling natural gas: cooling the compressed natural gas in the previous step to 0 ℃ in a double-pipe heat exchanger, and allowing the cooled gas-phase material to enter the next step;
(5) gas-liquid dispersion mixing: in a Venturi mixer, gas-liquid dispersion mixing is carried out on the gas-phase material obtained in the last step and the liquid-phase material obtained in the second step, the molar ratio of natural gas to the water-phase material is 1.0:5.0, and the gas-liquid dispersion mixed material enters the next step;
(6) cooling the gas-liquid mixture: in the lamella heat exchanger, the gas-liquid dispersion mixture is cooled to 6 ℃ to form stable natural gas hydrate.
Example four
A process for preparing natural gas hydrate includes such steps as preparing hydrating agent from the liquid phase of alkyl glucoside, lower alcohol and water, efficient gas-liquid dispersing and mixing, compressing natural gas, gas-liquid dispersing and mixing, and cooling. The method comprises the following specific steps:
(1) preparing a hydrating agent: mixing dodecyl glucoside with the glucose polymerization degree of 1.8, propanol and water, wherein the mass percent concentration of the dodecyl glucoside is 0.6%, the mass percent concentration of the propanol is 6.0%, and taking the prepared liquid-phase material as a hydrating agent to enter the next step;
(2) cooling the hydration agent: cooling the hydration agent prepared in the last step to 6 ℃ in a shell-and-tube heat exchanger, and allowing the cooled liquid-phase material to enter a gas-liquid dispersion mixing step in the fifth step;
(3) compressing natural gas: compressing natural gas in a gas compression device until the absolute pressure is 5.0MPa, and enabling the gas-phase material to enter the next step;
(4) cooling natural gas: cooling the compressed natural gas in the previous step to-10 ℃ in a plate-fin heat exchanger, and allowing the cooled gas-phase material to enter the next step;
(5) gas-liquid dispersion mixing: in a static mixer, gas-liquid dispersion mixing is carried out on the gas-phase material obtained in the last step and the liquid-phase material obtained in the second step, the molar ratio of natural gas to water-phase material is 1.0:6.0, and the gas-liquid dispersion mixed material enters the next step;
(6) cooling the gas-liquid dispersion mixture: in the double pipe heat exchanger, the gas-liquid dispersion mixture was cooled to 4 ℃ to form a stable natural gas hydrate.
Besides the above examples, the present invention has many embodiments, and all the technical solutions using equivalent or equivalent substitution are within the protection scope of the present invention.
Claims (8)
1. A method for preparing natural gas hydrate, especially use liquid phase material that alkyl glycoside, lower alcohol mix with water and form as the hydrating agent, adopt the gas-liquid dispersion mixing technique, prepare, natural gas compression, gas-liquid dispersion mix, gas-liquid mixture cooling preparation natural gas hydrate method, characterized by that the said method step is as follows:
(1) preparing a hydrating agent: mixing alkyl glycoside, lower alcohol and water in a mixing device to prepare a hydrating agent, wherein the mass percent concentration of the alkyl glycoside is 0.1-1.0%, the mass percent concentration of the lower alcohol is 1.0-10.0%, and the prepared hydrating agent enters the next step;
(2) cooling the hydration agent: cooling the hydration agent prepared in the last step in heat exchange equipment, and allowing the cooled liquid-phase material to enter a gas-liquid dispersion mixing step in the fifth step;
(3) compressing natural gas: compressing and boosting natural gas in gas compression equipment, and then entering the next step;
(4) cooling natural gas: cooling the compressed and boosted natural gas in the previous step in heat exchange equipment, and allowing the cooled and boosted natural gas to enter the next step;
(5) gas-liquid dispersion mixing: in a high-efficiency gas-liquid dispersion mixing device, gas-liquid dispersion mixing is carried out on the gas-phase material obtained in the last step and the liquid-phase material obtained in the second step, and the gas-liquid mixture obtained by dispersion mixing enters the next step;
(6) cooling the gas-liquid mixture: and cooling the gas-liquid dispersion mixture prepared in the last step in heat exchange equipment to prepare the natural gas hydrate.
2. A method for producing a natural gas hydrate according to claim 1, characterized in that: the alkyl glycoside is any one or any combination of octyl glycoside, decyl glycoside, dodecyl glycoside, tetradecyl glycoside, hexadecyl glycoside and octadecyl glycoside, and the glucose polymerization degree of the alkyl glycoside is 1.6-2.0.
3. A method for producing a natural gas hydrate according to claim 1, characterized in that: the lower alcohol is any one or any combination of methanol, ethanol, ethylene glycol, propanol, propylene glycol and glycerol.
4. A method for producing a natural gas hydrate according to claim 1, characterized in that: the heat exchanger adopted by the second step of cooling the hydration agent can be any one of a jacketed heat exchanger, a double-pipe heat exchanger and a shell-and-tube heat exchanger, and the material is cooled to-10 ℃ to 10 ℃.
5. A method for producing a natural gas hydrate according to claim 1, characterized in that: in the third step of natural gas compression, the gas phase material is compressed to the absolute pressure of 3.0MPa to 6.0 MPa.
6. A method for producing a natural gas hydrate according to claim 1, characterized in that: the heat exchanger adopted by the natural gas cooling in the fourth step can be any one of a double-pipe heat exchanger, a shell-and-tube heat exchanger, a plate-shell heat exchanger and a plate-fin heat exchanger, and the material is cooled to-10 ℃ to 10 ℃.
7. A method for producing a natural gas hydrate according to claim 1, characterized in that: and the gas-liquid dispersion mixing equipment in the fifth step of gas-liquid dispersion mixing is any one of a static mixer, a jet mixer and a Venturi mixer, and the molar ratio of the natural gas to the water is 1.0: 1.0-1.0: 10.0.
8. A method for producing a natural gas hydrate according to claim 1, characterized in that: the heat exchanger used for cooling the gas-liquid mixture in the sixth step can be any one of a double-pipe heat exchanger, a shell-and-tube heat exchanger, a plate-shell heat exchanger and a plate-fin heat exchanger, and the material is cooled to 0-10 ℃.
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