CN1169929C - Method and equipment for preparing natural gas hydrate - Google Patents
Method and equipment for preparing natural gas hydrate Download PDFInfo
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- CN1169929C CN1169929C CNB011301481A CN01130148A CN1169929C CN 1169929 C CN1169929 C CN 1169929C CN B011301481 A CNB011301481 A CN B011301481A CN 01130148 A CN01130148 A CN 01130148A CN 1169929 C CN1169929 C CN 1169929C
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Abstract
The present invention relates to a method for preparing a natural gas hydrate. A chemical promoter and water are prepared into a water solution, and the concentration is from 100 ppm to 1000 ppm; the solution is cooled until the temperature of 1 to 10 DEG C is obtained; under the action of absolute pressure of 3.0 to 8.0 MPa and ultrasonic waves whose power is from 8000 to 12000Hz, natural gas is introduced into the solution, and the molar ratio of the gas to the solution is from 1:30 to 1:80; the natural gas reacts with the water, and natural gas hydrate slurry is obtained; redundant water is separated. The continuous preparation of the natural gas hydrate is carried out in a horizontal type cylindrical reaction kettle (100) which is a device for preparing a natural gas hydrate, and an auxiliary system thereof. The reaction kettle (100) forms a horizontal type cylindrical shape, and the ratio of the diameter to the length of the kettle is 1:2 to 8. The reaction kettle is divided into a chamber A and a chamber B which are not communicated by a piston C. The piston C can freely move along four guide rods arranged in a reactor in the axial direction. An energy converter of an ultrasonic wave device is fixed to the piston C. The method for preparing a natural gas hydrate has the advantages of simple preparation method and device, applicability, low cost and high preparation efficiency.
Description
Technical field
The present invention relates to a kind of preparation method of gas hydrate, further relate to the device for preparing this gas hydrate.
Background technology
The accumulating mode that is applied to gas industry at present has: utilize low temperature technique with natural gas liquefaction (LNG), store, transport with the form of liquid; Adopt the high pressure method transport natural gas by pipeline; Utilize the adsorption natural gas-storing of porous medium; Conversion of natural gas liquid fuel technology (GTL) etc.At present, most Sweet natural gases (account for Sweet natural gas total amount 75%) adopt pipe-line transportation, but its initial investment is big, and trans-oceanic transportation is difficult for realizing.And LNG is owing to will adopt low-temperature liquefaction, running cost height.Gas hydrate (NGH) storaging and transport technology can store the Sweet natural gas of 150-200 standard cubic meter/cubic meter safely; Utilize the characteristics natural gas-storing of gas hydrate object height reserves, can reduce operating charges; The storage of gas hydrate (NGH) simultaneously is low than compressed natural gas, natural gas liquids pressure, has increased the security and the reliability of system, has certain advantage aspect economy.But also there is not sophisticated hydrate production process at present, can be continuously, efficient, economy, environmental protection ground produces hydrate in enormous quantities.
Summary of the invention
Purpose of the present invention and task provide a kind of preparation method of gas hydrate, further purpose of the present invention provides the device of this preparation gas hydrate, method and apparatus of the present invention should be simply, be suitable for, cost is low, produces the productivity height of gas hydrate.
A kind of preparation method of gas hydrate of the present invention is characterized in that chemical promoter and water are mixed with the aqueous solution, and chemical promoter concentration is between 100ppm～1000ppm; Solution is cooled to 1-10 ℃,, feeds Sweet natural gas in 3.0～8.0MPa absolute pressure with under the effect of 8000～12000Hz power ultrasonic, the gas-liquid mol ratio is between 1: 30 to 1: 80, Sweet natural gas and water effect form gas hydrate slurry, and redundant moisture from.
A kind of preparation method of gas hydrate of the present invention is characterized in that successive production is the device of making gas hydrate a kind of---carries out in horizontal round shape reactor 100 and the subsystem thereof, the steps include:
(a) charging: start mixing tank 200 and refrigerant cycles 1.3,2.3,3.3 thereof, fresh current W and chemical promoter Ad are mixed with solution in mixing tank 200, strength of solution is between 100ppm～1000ppm, solution is cooled to 1-10 ℃ of temperature, liquid level in the mixing tank maintain container height 1/2 to 2/3 between, with impeller pump 5 solution is forced into 3.0～8.0MPa, high-pressure solution is regulated through valve V1 or V2, enters the A chamber or the B chamber of reactor 100;
Sweet natural gas Ng is compressed to a little more than solution stream pressure, is cooled to 1-10 ℃ of temperature, regulates through valve V3 or V4, enters reactor A chamber or B chamber; Be installed in the valve synchronous working on gas, liquid logistics pipeline, promptly the two valves while is switched on or switched off with the A chamber or the B chamber of reactor, with stable gas/liquid ratio charging; The gas-liquid mol ratio is between 1: 30 to 1: 80, and ie in solution is significantly excessive; Control above-mentioned vapour-liquid ratio by the lifting rate of regulating impeller pump 5, what generate in the reactor is the hydrate slurry of fluidised form, is easy to discharge from reactor;
(b) reaction: keep reactor 1 to 10 ℃, 3.0～8.0MPa absolute pressure, under the effect of 8000～12000Hz power ultrasonic, Sweet natural gas and water effect, form gas hydrate slurry, gas is consumed, feed stream promotes piston C to-and-fro movement vertically in reactor, keeps normal hydration reaction, and hydrate slurry is constantly pushed separator D or E;
The service temperature that reactor suits is than low several degrees centigrade of equilibrium temperature, to increase the generating rate that generates gas hydrate.In most of the cases, about 1 to 10 ℃ of condensate depression, preferred value is 2 to 6 ℃.For example can make about 1～4 ℃ hydrate slurry in 4.0MPa (absolute pressure).The power ultrasonic of 8000～12000Hz can effectively quicken hydration reaction, and can prevent that hydrate particle from sticking on the wall.Feed stream promotes piston to-and-fro movement vertically in reactor.For example the A chamber of reactor is gone in logistics from the left side, and then piston moves right.After hydrate slurry was full of reactor A chamber, feed stream entered reactor from B chamber one side, promoted piston C and moved to the left.Material reacts in the B chamber, generates hydrate slurry.Simultaneously that A is indoor hydrate slurry pushes separator.
(c) separate: under reaction pressure, separator D or E separate and return mixing tank 200 to the excessive aqueous solution and recycle from hydrate slurry H, lay down pressure then, obtain solid-state gas hydrate product.
Lock out operation is finished under reaction pressure, and under this condition, hydrate is in supercooled state, can not decompose.Treat that excessive moisture content is filtered off, filter cake is full of filter frame, can lay down pressure, takes out the solid water compound." the self-insurance effect " of hydrate protects it can not decompose immediately later at removal pressure.
In the preparation method of gas hydrate recited above, the chemical promoter of hydration reaction is selected from the mixture of a kind of or their arbitrary proportions in Losantin, sodium lauryl sulphate, 1,3 dimethyl cyclohexane, Polyvinylpyrolidone (PVP), tetrahydrofuran (THF), the acetone.
In the preparation method of gas hydrate recited above, preferred reaction conditions is: chemical promoter is preferably Losantin, and temperature is preferably 2～6 ℃, and absolute pressure is preferably 4～6Mpa, the gas-liquid mol ratio is preferably 1: 40 to 1: 60.
A kind of continuous production device for preparation method of gas hydrate recited above, comprise reactor 100 and refrigerant cycles 1.2,2.2,3.2 thereof, mixing tank 200 and refrigerant cycles 1.3,2.3,3.3 thereof, two cover separator D and E, ultrasonic generator S, optical fiber 3.1,3.2 and 4.1,4.2, impeller pump 5, compressor 1.1, water cooler 2.1, valve V1, V2, V3, V4, V5 and V6, and the connecting tube 6-12 between them; It is characterized in that reactor 100 is horizontal round shape, the blade diameter length ratio of still 1: 2～8; Piston C is divided into mutual disconnected A chamber and B chamber to reactor, can be along four tail rod free movements vertically that are installed in the reactor; The transverter of ultrasonic unit is fixed on the piston C; The reactor two ends respectively are provided with an aqueous solution opening for feed Aq, are connected with valve V1, V2 by pipeline 8,7; Respectively be provided with a natural gas feed mouth Ng, be connected with valve V3, V4 by pipeline 12,11; Respectively be provided with a hydrate slurry discharge port H, be connected with valve V5, pipeline 9, separator D and valve V6, pipeline 10, separator E; Above-mentioned valve is magnetic valve, its unlatching, closes by self-service instrument and controls; The left and right two ends equipment optical fiber 3.1,3.2,4.1,4.2 of reactor is used for the induction piston position.
Each opening can be arranged on the left and right end cap of reactor, also can be arranged on the cylindrical shell, if be arranged on the cylindrical shell, aperture position will be tried one's best near end cap.When being reflected at the A chamber and carrying out, feed stream promotes piston from right motion; When the optical fiber in the reactor 4.1,4.2 was sensed piston C and reached the right side range, system closing V1, V3, V6 opened V2, V4, V5, and material enters reactor B chamber, promoted piston to left movement; Same Controlling System is by the open and close related valve when optical fiber 3.1,3.2 is sensed piston C and reached the left side range, and feed stream enters the A chamber, and promotion piston C moves right.Like this, piston C to-and-fro movement in reactor, sucting reaction material, and drainage water compound slurry.
During selecting for use, gas compressor presses reciprocation compressor.The discharge opeing ability of volume pump and the free air delivery of pressure head and compressor are selected according to technological design output.
The plate-and-frame filter press that separator recommendation use is operated automatically or other can quantity-produced equipment.Separator is not equipped with refrigerant cycles, but will be incubated with lagging material.
In the explained hereafter, the aqueous solution is excessive, and gas phase all is converted into hydrate, return opening for feed after excess solution leaches and recycle, so production process does not have the by product of contaminate environment.By the circulation of process water, can also reclaim cold, reduce the energy expenditure of production process.Utilize this explained hereafter solid hydrate, can be used for the accumulating of Sweet natural gas.Other gas also can be used as and generate solid hydrate particulate phase feed.The gas that is suitable for this technology comprises commerical prod, pollution substance and other gas that produces in nature or commercial run.
Processing unit can be built on land or the offshore platform, the process gas hydrate.Can select on land to make gas hydrate near the place in hydrocarbon source.Gas phase can be the mixture of Sweet natural gas or Sweet natural gas and other gas, also can be air-polluting gas, and shipped off-site is so that further handle.
The metaborate monohydrate composition granule can be stored in the storage cellar.Pre-cooled storage room before hydrate is gone in storage freezes airborne water vapor, forms on the surface to isolate ice sheet.Isolate ice sheet and can stop gas evolution.Hydrate can be kept near normal pressure in the isolation storage room.
Metaborate monohydrate also can be stored in the seabed band pressure vessel of offshore platform.Rely on the static pressure of water column to keep-up pressure, and tensimeter and valve are housed, water column is separated container and seawater.Solid hydrate also can be stored in the atmosphere, or is stored in cold water or the hydrocarbon liquids.
The hydrate of land production can be transported to consumption gas place by automobile, train, after the step-down or the decomposition of heating, and the directly-heated utilization.The storage of producing on the offshore platform hydrate of gas through ship, oil tanker, barge or be stated from floating container and transport bank by towboat.)
Advantage of the present invention and positively effect have:
1. on the technology, in reaction system, add chemical promoter, and effectively promote chemical reaction rate, the productivity of unit volume reaction compartment hydrate is improved greatly by ultrasonic wave field.
2. production process mainly comprises two independently unit operations: in reactor, produce hydrate slurry, in separator with hydrate particle and excessive liquid separation.What therefore generate in the reactor is the hydrate slurry of fluidised form, and the product of pulpous state is easy to discharge from reactor.
3. with piston reactor is divided into two mutual disconnected part A chambers and B chamber, the motion of piston makes the volume of A chamber and B chamber alternately increase, reduce, when producing being reflected at the A chamber and carrying out of hydrate, piston moves right, suck the gas, liquid reactant step by step, gas phase reacts with water immediately once charging into reactor, generate hydrate, the mass transfer of the reaction process that the feeding manner of this phase is strengthened effectively; Simultaneously, piston moves right, and the hydrate slurry that the B chamber has been generated pushes separator and carries out lock out operation, and the residence time of hydrate slurry in reactor is short, can prevent to reduce because of the hydrate crystal hypertrophy flowability of hydrate slurry.
4. ultrasonic wave field is followed piston C to-and-fro movement in reactor, has enlarged the useful range of sound field effect, and the efficient hardening sound field improves speed of reaction to the promoter action of reaction.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.Fig. 2 is the reactor structural representation.
Embodiment (embodiment)
Further specify the present invention below in conjunction with embodiment, but the present invention is not construed as limiting.
Be equipped with equipment configuration by Fig. 1 and 2, wherein reactor 100 length 0.4m, diameter 0.2m; Reactor inwall and piston C are slick stainless steel surface.Mixing tank 200 volume 0.5m
3Ultrasonic generator S power 1Kw, frequency 1MHz; Refrigerant cycles 1.3,2.3,3.3 peak power output 1Kw; Refrigerant cycles 1..2,2.2,3.2 peak power output 0.5Kw; Separator D and E are rotary vacuum drum filter, and throughput respectively is 0.5m
3/ h; The discharge opeing ability of impeller pump 5 is 1m
3/ h, pressure head are 400m; Compressor 1.1 free air deliveries are 300m
3/ h; The power of water cooler 2.1 is 0.1Kw; All the other accessories are by general design assembling.
Operate by processing step recited above, condition is 200N m for the Sweet natural gas flow rate
3/ h, the flow rate of fresh water raw material is about 0.1～0.2m
3/ h.Chemical promoter concentration is 200ppm in the aqueous solution, 2～6 ℃ of temperature of reaction, about 1: 50 of absolute pressure 4～6Mpa, gas-liquid mol ratio, ultrasonic power 8000～12000Hz power, as a result, the output of hydrate is about 120～220Kg/h, and concrete output is relevant with the filling ratio of the hydrate of generation.
Claims (8)
1. one kind prepares method of gas hydrate, it is characterized in that chemical promoter and water are mixed with the aqueous solution, chemical promoter concentration is between 100ppm～1000ppm, chemical promoter is selected from the mixture of a kind of or their arbitrary proportions in Losantin, sodium lauryl sulphate, 1,3 dimethyl cyclohexane, Polyvinylpyrolidone (PVP), tetrahydrofuran (THF), the acetone; Solution is cooled to 1-10 ℃,, feeds Sweet natural gas in 3.0～8.0MPa absolute pressure with under the effect of 8000～12000Hz power ultrasonic, the gas-liquid mol ratio is between 1: 30 to 1: 80, Sweet natural gas and water effect form gas hydrate slurry, and redundant moisture from.
2. according to a kind of preparation method of gas hydrate described in the claim 1, it is characterized in that successive production is the device for preparing gas hydrate a kind of---carry out in horizontal round shape reactor (100) and the subsystem thereof, its steps in sequence is:
(a) charging: start mixing tank (200) and refrigerant cycles (1.3 thereof, 2.3,3.3), fresh current (W) and chemical promoter (Ad) are mixed with solution in mixing tank (200), strength of solution is between 100ppm～1000ppm, solution is cooled to 1-10 ℃ of temperature, liquid level in the mixing tank maintain container height 1/2 to 2/3 between, with impeller pump (5) solution is forced into 3.0～8.0MPa, high-pressure solution is regulated through valve (V1 or V2), enters the A chamber or the B chamber of reactor (100);
Sweet natural gas (Ng) is compressed to a little more than solution stream pressure, is cooled to 1-10 ℃ of temperature, regulates through valve (V3 or V4), enters reactor A chamber or B chamber; Be installed in the valve synchronous working on gas, liquid logistics pipeline, promptly the two valves while is switched on or switched off with the A chamber or the B chamber of reactor, with stable gas/liquid ratio charging; The gas-liquid mol ratio is between 1: 30 to 1: 80, and ie in solution is significantly excessive; Control above-mentioned vapour-liquid ratio by the lifting rate of regulating impeller pump (5), what generate in the reactor is the hydrate slurry of fluidised form, is easy to discharge from reactor;
(b) reaction: keep reactor 1 to 10 ℃, 3.0～8.0MPa absolute pressure, under the effect of 8000～12000Hz power ultrasonic, Sweet natural gas and water effect, form gas hydrate slurry, gas is consumed, feed stream promotes piston C to-and-fro movement vertically in reactor, keeps normal hydration reaction, and hydrate slurry is constantly pushed separator (D) or (E);
(c) separate: under reaction pressure, separator (D) or (E) the excessive aqueous solution is separated and return mixing tank (200) from hydrate slurry (H) and recycle is laid down pressure then, obtains solid-state gas hydrate product.
3. according to a kind of preparation method of gas hydrate described in claim 1 or 2, it is characterized in that chemical promoter is a Losantin.
4. according to a kind of preparation method of gas hydrate described in claim 1 or 2, the concentration that it is characterized in that chemical promoter Losantin in the aqueous solution is 200-700ppm.
5. according to a kind of preparation method of gas hydrate described in claim 1 or 2, it is characterized in that temperature of reaction is 2～6 ℃.
6. according to a kind of preparation method of gas hydrate described in claim 1 or 2, absolute pressure is 4～6Mpa when it is characterized in that reacting.
7. according to a kind of preparation method of gas hydrate described in claim 1 or 2, it is characterized in that the gas-liquid mol ratio is 1: 40 to 1: 60 in the reactor.
8. one kind according to a kind of continuous production device for preparation method of gas hydrate described in the claim 2, comprise reactor (100) and refrigerant cycles (1.2 thereof, 2.2,3.2), mixing tank (200) and refrigerant cycles (1.3 thereof, 2.3,3.3), two cover separators (D) and (E), ultrasonic generator (S), optical fiber (3.1,3.2) and (4.1,4.2), impeller pump (5), compressor (1.1), water cooler (2.1), valve (V1), (V2), (V3), (V4), (V5) and (V6), and the connecting tube between them (6)～(12); It is characterized in that reactor (100) is horizontal round shape, the blade diameter length ratio of still 1: 2～8; Piston C is divided into mutual disconnected A chamber and B chamber to reactor, can be along four tail rod free movements vertically that are installed in the reactor; The transverter of ultrasonic unit is fixed on the piston C; The reactor two ends respectively are provided with an aqueous solution opening for feed (Aq), are connected with valve (V1), (V2) by pipeline (8), (7); Respectively be provided with a natural gas feed mouth (Ng),, (V4) connect by pipeline (12), (11) and valve (V3); Respectively be provided with a hydrate slurry discharge port (H), be connected with valve (V5), pipeline (9), separator (D) and valve (V6), pipeline (10), separator (E); Above-mentioned valve is magnetic valve, its unlatching, closes by self-service instrument and controls; The left and right two ends equipment optical fiber (3.1,3.2) of reactor, (4.1,4.2) are used for the induction piston position.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011301481A CN1169929C (en) | 2001-12-29 | 2001-12-29 | Method and equipment for preparing natural gas hydrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011301481A CN1169929C (en) | 2001-12-29 | 2001-12-29 | Method and equipment for preparing natural gas hydrate |
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| CN1429896A CN1429896A (en) | 2003-07-16 |
| CN1169929C true CN1169929C (en) | 2004-10-06 |
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| CNB011301481A Expired - Fee Related CN1169929C (en) | 2001-12-29 | 2001-12-29 | Method and equipment for preparing natural gas hydrate |
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| CN100346104C (en) * | 2004-04-21 | 2007-10-31 | 中国科学院过程工程研究所 | Integration barge for natural gas synthesized hydrate storage and long distance transportation |
| CN100430124C (en) * | 2005-11-25 | 2008-11-05 | 中国石油大学(北京) | Hydrate production process for gas storage and transportation |
| RU2425860C2 (en) | 2006-03-15 | 2011-08-10 | Эксонмобил Апстрим Рисерч Компани | Method to produce hydrate suspension that does not create plug |
| US8430169B2 (en) | 2007-09-25 | 2013-04-30 | Exxonmobil Upstream Research Company | Method for managing hydrates in subsea production line |
| CN101225338B (en) * | 2007-12-19 | 2011-03-23 | 中国科学院广州能源研究所 | Method and device for quickly preparing natural gas hydrate by employing static hypergravity |
| CN101376854B (en) * | 2008-09-09 | 2013-06-05 | 中国石油大学(北京) | Method and apparatus for simulating gas hydrate accumulation process under three-dimensional condition |
| CN101672425B (en) * | 2008-09-12 | 2012-12-26 | 江苏工业学院 | Method for preparing composite hydrate accelerant |
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| CN101818088B (en) * | 2009-12-15 | 2013-05-22 | 江苏工业学院 | Efficient continuous preparation method and device for natural gas hydrate |
| CN103571557B (en) * | 2013-11-12 | 2014-12-24 | 北京化工大学 | Method for preparing natural gas hydrate |
| CN104374800A (en) * | 2014-11-18 | 2015-02-25 | 中国科学院广州能源研究所 | In-situ heat conductivity coefficient testing device and method for gas hydrate |
| CN106552501B (en) * | 2016-10-27 | 2018-11-27 | 山东科技大学 | A kind of device and method using physical field coordination technique separation mixed gas |
| CN107987908A (en) * | 2017-11-23 | 2018-05-04 | 中国石油大学(华东) | Natural gas for combustible ice pilot production process is quickly formed and stored on-site system |
| CN108728194A (en) * | 2018-06-04 | 2018-11-02 | 河南理工大学 | A kind of teas leaching liquor and preparation method and purposes for strengthening coal bed gas purification |
| CN109097120B (en) * | 2018-08-27 | 2020-09-22 | 华南理工大学 | Static strengthening rapid continuous generation device and method for natural gas hydrate |
| CN109900726A (en) * | 2019-04-02 | 2019-06-18 | 中国科学院地质与地球物理研究所 | A kind of large scale gas hydrates reservoir fracturing physical analogy and seam net observation method |
| CN110952958B (en) * | 2019-12-19 | 2020-11-27 | 中国科学院广州能源研究所 | Natural gas hydrate horizontal well balanced liquid drainage testing device and method |
| CN112244184B (en) * | 2020-09-30 | 2022-08-12 | 广东省农业科学院蚕业与农产品加工研究所 | Device and method for concentrating liquid food by hydrate under assistance of frequency conversion ultrasound |
| CN114716294B (en) * | 2022-04-08 | 2024-04-30 | 南方海洋科学与工程广东省实验室(广州) | Method for preparing olefin and co-producing high-purity hydrogen by using natural gas hydrate chemical chain |
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