CN101514300B - Method for preparing gas hydrate accelerant - Google Patents
Method for preparing gas hydrate accelerant Download PDFInfo
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- CN101514300B CN101514300B CN2009100302462A CN200910030246A CN101514300B CN 101514300 B CN101514300 B CN 101514300B CN 2009100302462 A CN2009100302462 A CN 2009100302462A CN 200910030246 A CN200910030246 A CN 200910030246A CN 101514300 B CN101514300 B CN 101514300B
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Abstract
The invention provides a method for preparing gas hydrate accelerant, which takes a high pressure gas cylinder as gas source; the high pressure gas cylinder is regulated to have proper pressure by a pressure regulating valve, and the consumed natural gas is calculated by a mass flowmeter; the temperature and the pressure in a reactor are monitored by a pressure and temperature transmitter; thermostatic waterbath is used for controlling the temperature of the liquid in a trough, thus regulating the temperature in the reactor; a data acquisition system and a computer are used for collecting data, and an opto-electrical lens is used for monitoring the forming situation of hydrate in the reactor. The composite accelerant is low in cost and little in dosage, ensures the generating condition of the hydrate to be reduced, the time to be shortened and the gas storage quantity to be increased, and effectively improves the economic benefit of the production of the hydrate.
Description
Technical field
The present invention relates to gas hydrate production and utilize technical field, refer in particular to a kind of preparation method who quickens the efficient compound promotor of gas hydrate formation.
Background technology
At present; The new technology development of using based on gas hydrate not only develops rapidly in the energy, environmental protection field; And also obtained major progress in some other field, for example the solid-state conveying of Sweet natural gas and storage, gas hydrate are as vehicle fuel, based on the new separation technology that generates hydrate (the concentrating of desalination technology, aqueous organopolysiloxane, separation of gaseous mixture and nearly critical and supercritical extraction etc.) and based on the biotechnology of hydrate and field of new etc.But hydrate is closely bound up with inhibition and promoter action that gas hydrate generates in the application in these fields; The obstruction of factor such as receive that its gas storage density is low, formation speed is slow and induction time is long, the maximum technology barrier that especially current Application of Hydrate technology faces is exactly generating rate and the efficient that how to improve hydrate.For example methane pressure in static pure aquatic system be 5.76MPa,, when temperature was 4.3 ℃, the induction time that forms hydrate was more than 28 hours, the speed of growth of hydrate crystal directly influences the technological popularization of hydrate utilization slowly.For addressing these problems; Adopted several different methods to promote the formation (Lin Yula etc. of hydrate; The chemical industry progress; 2005,24 (11): 1229-1233):, brought some other unfavorable factors again but stir: energy expenditure increase, the reduction of hydrate gas storage density etc. through stirring the speed of growth that can improve hydrate; Adopt ultrasonic atomization, increase the air-water contact area, can improve the hydrate formation speed, but the ultrasonic atomizer that system adds not only makes investment cost increase, and working cost also increases; Spray and bubble method can both increase phase contact area, thereby improve the hydrate formation speed; In hydrate formation system, add some additives and can promote hydrate to generate, improve the hydrate speed of growth, studying more both at home and abroad is in water, to add AS, like sodium lauryl sulphate (SDS), THF etc.Can make hydrate form induction time and shorten to 1～1.5 hour, pressure reduces by 1～2MPa than pure aquatic system.Yet, although this type tensio-active agent can make the hydrate formation speed accelerate, but can not be satisfactory, and hydrate gas storage density is not high.Therefore, studying new compound gas hydrate accelerant, is the only way that advances the hydrate industrialization.
Summary of the invention
The objective of the invention is the deficiency to prior art, a kind of energy expenditure increase, hydrate gas storage density height are provided, capital cost is little, the efficient composite hydrate promotor preparation method of economical operation.For achieving the above object, the present invention adopts following technical scheme:
It is mixed as tensio-active agent as additive and sodium lauryl sulphate (SDS) by sodium-chlor (NaCl).The quality percentage composition that sodium-chlor (NaCl) accounts for solvent is 0.2～6.5%; The concentration of tensio-active agent sodium lauryl sulphate (SDS) is 0.3 * 10
-3～0.8 * 10
-3Mol/L.
The preparation facilities that the present invention adopts comprises gas cylinder, relief valve, mass flowmeter, valve, vacuum pump, pressure, temperature transmitter, water bath with thermostatic control, tank, reactor drum, DAS, computingmachine etc.As source of the gas, be transferred to suitable pressure by gas cylinder, with mass flowmeter stoichiometric consumption Sweet natural gas through relief valve.By the temperature and pressure in pressure, the temperature transmitter monitoring reaction device.Control fluid temperature in the tank by water bath with thermostatic control, thus temperature in the conditioned reaction device.Also form situation by DAS and computer data acquisition through hydrate in the photocell lens monitoring reaction device.This system works pressure is 0～30MPa, and TR is 1 ℃～30 ℃.
Preparation process is following:
1) with vacuum pump reaction kettle, piping system are vacuumized about 40～50min of pumpdown time.
2) with the compound accelerant aqueous solution of the different concns for preparing, inject reaction kettle, stir 3～5min, and be pre-chilled to 1 ℃～10 ℃ temperature earlier.
3) open valve, charge into reaction kettle to High-Voltage Experimentation gas, reacting system pressure is maintained the required pressure 1～30MPa of experiment through relief valve.
4) set 1 ℃～15 ℃ of experimental temperatures, start the temperature controlling system of experimental installation.Utilize water-bath that reaction kettle is cooled off, the temperature in reaction kettle reaches design temperature.
5) carry out hydrate and generate experiment.
In experimentation, zero(ppm) water is with stainless steel electrical distiller self-control, is that the BS200S type analysis balance of 0.1g takes by weighing through precision; Tensio-active agent uses precision to take by weighing as the TG328A type photoelectric analytical balance of 0.1mg.Can gather experimental data and image in real time through computingmachine.
Beneficial effect of the present invention:
(1) it is effective that hydrate generates promoter action
Pure kinetics promotor can only be reduced the hydrate formation condition, can not reduce the hydrate rise time.Pure tensio-active agent can only reduce the hydrate rise time, can not obviously reduce the hydrate formation condition, can not improve hydrate gas storage density.And composite hydrate accelerant can reduce the hydrate formation condition and can reduce the hydrate rise time, improve hydrate gas storage density.
(2) be widely used
Can be used widely in fields such as gas hydrate storaging and transport technology, gas hydrate stripping technique and sea water desaltinations.
(3) cost is low, and is economical good
Compound accelerant cost of the present invention is low, and consumption is few, and the condition that hydrate is generated reduces, and the time shortens, and gas-storing capacity increases, and has improved hydrate production economic benefit effectively.
Description of drawings
Fig. 1 is that hydrate generates the experimental installation schema
1, gas cylinder; 2, relief valve; 3, mass flowmeter; 4, vacuum breaker; 5, gate valve; 6, vacuum pump; 7, pressure, temperature transmitter; 8, water bath with thermostatic control; 9, tank; 10, reaction kettle; 11, DAS; 12, computingmachine; 13, photocell lens.
Embodiment
Make further specific descriptions in the face of the present invention down, but embodiment of the present invention is not limited in this.
The experimental installation that the present invention adopts is as shown in Figure 1, by gas cylinder 1; Relief valve 2; Mass flowmeter 3; Vacuum breaker 4; Gate valve 5; Vacuum pump 6; Pressure, temperature transmitter 7; Water bath with thermostatic control 8; Tank 9; Reaction kettle 10; DAS 11; Computingmachine 12 compositions such as grade.As source of the gas, be transferred to suitable pressure with gas cylinder 1, with mass flowmeter 3 stoichiometric consumption Sweet natural gases through relief valve 2.By the temperature and pressure in pressure, the temperature transmitter 7 monitoring reaction stills 10.Control fluid temperature in the tank 9 by water bath with thermostatic control 8, thus temperature in the conditioned reaction device.Form situation by DAS 11 with computingmachine 12 image data and through hydrate in the photocell lens 13 monitoring reaction devices.Vacuum pump 6 is used for aspirating liquid in the reactor drum.This system works pressure is 0～30MPa, and TR is-10 ℃～50 ℃.
Concrete preparation process:
1) with vacuum pump 6 reaction kettle 10, piping system are vacuumized, the pumpdown time is 40～50min.
2) for getting rid of the air in reaction kettle 10 and the piping system as far as possible, with experimental gas they are replaced twice, and then vacuumize.
3) the compound accelerant aqueous solution with the different concns for preparing injects reaction kettle 10, stirs 3～5min, and is pre-chilled to certain temperature earlier.
4) open vacuum breaker 4, charge into reaction kettle 10 to High-Voltage Experimentation gas, reacting system pressure is maintained the required pressure of experiment through relief valve 2.
6) set experimental temperature, start the temperature controlling system of experimental installation.Utilize 8 pairs of reaction kettles 10 of water bath with thermostatic control to cool off, the temperature in reaction kettle 10 reaches design temperature.
7) carry out hydrate and form experiment.
Embodiment:
The compound promotor of selecting for use consists of: add aqueous quality percentage composition be 0.3～6.5% sodium-chlor (Nacl), tensio-active agent is sodium lauryl sulphate (SDS), concentration is 0.3 * 10
-3～0.8 * 10
-3Mol/L sees table 1.Experimental procedure is the same.Hydrate generate equilibrium conditions be temperature at 1.9～5.5 ℃, pressure is 0.79～2.7Mpa.
Table 1 compound accelerant prepares concentration
Draw through experiment under these conditions, the induction time that hydrate forms is at 3～17min; Gas storage density is at 163m
3/ m
3More than.
Claims (1)
1. the preparation method of a gas hydrate accelerant; It is characterized in that; Mixed as tensio-active agent as additive and sodium lauryl sulphate by sodium-chlor, the quality percentage composition that sodium-chlor accounts for solvent is 0.2～6.5%, and the concentration of tensio-active agent sodium lauryl sulphate is 0.3 * 10
-3～0.8 * 10
-3Mol/L; Its preparation process is:
1) with vacuum pump (6) reaction kettle (10), piping system are vacuumized, the pumpdown time is 40～50min;
2) with experimental gas to the air displacement twice in reaction kettle (10) and the piping system, and then vacuumize;
3) the compound accelerant aqueous solution with the different concns for preparing injects reaction kettle (10), stirs 3～5min, and is pre-chilled to 1 ℃～10 ℃ temperature earlier;
4) open vacuum breaker (4), charge into reaction kettle (10) to High-Voltage Experimentation gas, reacting system pressure is maintained 1MPa～30MPa through relief valve (2);
6) set experimental temperature, start the temperature controlling system of experimental installation, utilize water bath with thermostatic control (8) that reaction kettle (10) is cooled off, the temperature in reaction kettle (10) reaches design temperature;
7) carry out hydrate and form experiment.
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| CN2009100302462A CN101514300B (en) | 2009-03-23 | 2009-03-23 | Method for preparing gas hydrate accelerant |
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| CN2009100302462A CN101514300B (en) | 2009-03-23 | 2009-03-23 | Method for preparing gas hydrate accelerant |
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| CN101514300B true CN101514300B (en) | 2012-05-23 |
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Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101880561B (en) * | 2010-06-30 | 2013-11-20 | 中国科学院力学研究所 | Natural gas hydrate synthesizing device capable of realizing kinds of preparation methods |
| CN104667844B (en) * | 2015-02-12 | 2016-04-13 | 常州大学 | A kind of gas hydrate accelerant and preparation method thereof |
| CN104692383B (en) * | 2015-02-12 | 2017-10-20 | 常州大学 | A kind of degradable hydrate accelerant and its preparation method and application |
| CN104857891B (en) * | 2015-05-20 | 2016-06-08 | 常州大学 | A kind of hydrate accelerant and preparation method thereof |
| CN104974713B (en) * | 2015-05-26 | 2018-04-13 | 华南理工大学 | Hydrate accelerant and its application in high gas storage density gases hydrate is prepared |
| CN104893660B (en) * | 2015-06-01 | 2017-04-05 | 常州大学 | A kind of compound gas hydrate accelerant and its using method |
| CN106381125B (en) * | 2016-08-26 | 2021-03-30 | 华南理工大学 | Chinese herbal medicine extract and application thereof in preparation of gas hydrate with high gas storage density |
| CN106634827B (en) * | 2016-09-09 | 2019-03-22 | 常州大学 | A kind of compound gas hydrate accelerant and preparation method thereof |
| CN106622028A (en) * | 2017-01-12 | 2017-05-10 | 辽宁石油化工大学 | Preparation method of gas hydrate |
| CN109021918B (en) * | 2018-07-02 | 2020-11-24 | 河南理工大学 | Preparation method of low-carbon mixed gas hydrate explosion suppressant |
| CN111706779B (en) * | 2020-05-12 | 2022-01-04 | 湘南学院 | Method suitable for storage and transportation of hydrate above zero DEG C |
| CN113817519B (en) * | 2020-06-18 | 2022-11-08 | 中国石油化工股份有限公司 | Composition for promoting high-efficiency solid hydrate, preparation method thereof and method for enhancing hydrate generation |
| CN117229828A (en) * | 2023-10-13 | 2023-12-15 | 中国科学院广州能源研究所 | Method for regulating and controlling formation crystal form of natural gas hydrate |
Citations (3)
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|---|---|---|---|---|
| CN1181806A (en) * | 1996-01-18 | 1998-05-13 | Bg公开有限公司 | Method of producing gas hydrate |
| CN1429896A (en) * | 2001-12-29 | 2003-07-16 | 中国科学院广州能源研究所 | Method and equipment for preparing natural gas hydrate |
| CN1440832A (en) * | 2003-04-01 | 2003-09-10 | 中国地质大学（武汉） | Comprehensive test equipment for natural gas hydrate |
-
2009
- 2009-03-23 CN CN2009100302462A patent/CN101514300B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1181806A (en) * | 1996-01-18 | 1998-05-13 | Bg公开有限公司 | Method of producing gas hydrate |
| CN1429896A (en) * | 2001-12-29 | 2003-07-16 | 中国科学院广州能源研究所 | Method and equipment for preparing natural gas hydrate |
| CN1440832A (en) * | 2003-04-01 | 2003-09-10 | 中国地质大学（武汉） | Comprehensive test equipment for natural gas hydrate |
Non-Patent Citations (1)
| Title |
|---|
| 陈敏等.海洋天然气水合物氢氧同位素分馏初探.《地球化学》.2005,第34卷(第6期),第305-611页. * |
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Address after: Gehu Lake Road Wujin District 213164 Jiangsu city of Changzhou province No. 1 Patentee after: Jiangsu Polytechnic University Address before: 213016 Baiyun Road, Jiangsu, Changzhou Patentee before: Jiangsu Polytechnic University |
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