CN104692383B - A kind of degradable hydrate accelerant and its preparation method and application - Google Patents
A kind of degradable hydrate accelerant and its preparation method and application Download PDFInfo
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- CN104692383B CN104692383B CN201510073711.6A CN201510073711A CN104692383B CN 104692383 B CN104692383 B CN 104692383B CN 201510073711 A CN201510073711 A CN 201510073711A CN 104692383 B CN104692383 B CN 104692383B
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- degradable
- hydrate
- glycerophosphatide
- alginic acid
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Abstract
The present invention relates to gas hydrate production with utilizing technical field, and in particular to a kind of degradable hydrate accelerant and its preparation method and application.The degradable gas hydrate accelerant, is made up of glycerophosphatide, alginic acid, deionized water；The mass concentration of glycerophosphatide and alginic acid is respectively 12 ~ 18%, 20 ~ 27%, and remaining is deionized water.The product of the present invention is degradable, environment friendly and pollution-free, really realizes industry aluminium extrusions；Cost is low, economical good, using safety, is widely used；Hydrate generation facilitation effect is good, in the range of 1 DEG C~15 DEG C, it is possible to decrease hydrate generates pressure 40 ~ 60%, shortens the generation time 70 ~ 85%.
Description
Technical field
The present invention relates to gas hydrate production with utilizing technical field, carbon dioxide water can be strengthened by refering in particular to one kind
The preparation method of the degradable efficient accelerator of compound formation.It can also be used for the life of other gas hydrates such as natural gas, oxygen
Into promotion.
Background technology
Gas hydrate is that guest molecule acts on to be formed a kind of non-similar to ice under certain temperature and pressure with water
The cage type crystalline compounds of stoichiometry.At present, gas hydrate structure mainly has 3 kinds of I types, II type and H types.
In recent years, the field that gas hydrate technology is related to is more and more wider, mainly separated including natural gas accumulating, gas,
Desalinization, sewage disposal, solution concentration, air conditioner cold accumulation etc..With in the development and nature of Application of Hydrate technical research
A large amount of natural gas hydrate resources are found, and the research field of gas hydrate extends to the energy, chemical industry, environmental protection and geology etc.
Subject.However, Hydrate Formation Conditions are harsh, induction time length, synthesis speed are slow, the low shortcoming of void fraction is greatly limited
The popularization of technology.Such as methane in static pure aquatic system pressure be 5.76MPa, temperature be 4.3 DEG C when, formed hydrate
Induction time more than 28 hours, the speed of growth of hydrate crystal is slow, directly affects the popularization that hydrate utilizes technology.For
These problems are solved, domestic and foreign scholars have carried out numerous studies to this, propose various methods to promote hydrate to quickly generate（King
Extra large show etc., modern chemical industry, 2013,33（10）：28-31）, such as rational reactor types (using stirring reactor), change
Become operating condition (hydrate generation research is carried out under ultrasonic wave, hypergravity, microwave environment), reinforcing mass transfer/heat transfer condition (spray
Mist method, Bubbling method, spiral pipeline flowing method) etc..Above-mentioned physical method can improve hydrate growth speed really, promote hydration
Thing is generated, but its problem of exist jointly can consumption of energy increase, investment operating cost also increase.
At present, chemical method is considered as that hydrate generates optimal schedule of reinforcement.A variety of different rush are worked out
Enter agent, can accelerate hydrate formation speed by adding some additives in gas hydrate synthesis system.But, generally come
Say that the problem of these existing accelerator are maximum is exactly non-degradable, if being directly discharged to circulating water body or entering soil,
Different degrees of infringement is easily caused to environment, hinders hydrate is industrialized to realize.And recycling rate of waterused is low, to hydrate
The promotion efficiency of generation is still not high enough, and cost is big, less economical.Therefore, it is gas to find new and effective degradable accelerator
Gas hydrate technology is able to the key being applied successfully in above field.
The content of the invention
The purpose of the present invention is the deficiency for existing gas hydrate generation reinforcement technique and offer is a kind of efficiently, save
Energy, the hydrate accelerant of environment-friendly degradable, improve generating rate and gas storage density, and cost is low, green environmental protection degradable.For up to
To above-mentioned purpose, the present invention is adopted the following technical scheme that：
A kind of efficient accelerator of degradable gas hydrate, it is made up of glycerophosphatide, alginic acid, deionized water.Institute
State glycerophosphatide structure such as Formulas I, alginic acid structure such as formula II.The mass concentration of glycerophosphatide and alginic acid is respectively 12 ~ 18%,
20 ~ 27%, remaining is deionized water.Glycerophosphatide and alginic acid are degradable biological surface-active in selected accelerator
Agent, pollution-free, nonhazardous, high-efficiency environment friendly.
Formulas I
Formula II
The preparation facilities that the present invention is used includes gas cylinder, pressure regulator valve, mass flowmenter, control valve, vavuum pump, pressure
Power, temperature transmitter, water bath with thermostatic control, tank, reactor, data collecting system, computer etc..By gas cylinder as source of the gas,
Appropriate pressure is transferred to through pressure regulator valve, with mass flowmenter stoichiometric consumption natural gas.In pressure, temperature transmitter monitoring reactor
Temperature and pressure.Fluid temperature in tank is controlled by water bath with thermostatic control, so as to adjust reactor temperature.By data acquisition system
System and computer data acquisition simultaneously monitor gas hydrate synthesis situation in reactor by photocell lenses.Degradable gas of the present invention
Gas hydrate accelerator is using in extensive range, without strict use condition requirement, typically system working pressure be 0~
30MPa, temperature is usable in the range of 0 DEG C~30 DEG C.
The preparation method of the degradable gas hydrate accelerant, comprises the following steps：
1）Obtained aqueous solution：Glycerophosphatide and alginic acid are weighed respectively is made into glycerophosphatide concentration by mass with distilled water
For 12 ~ 15% and solution that marine alga acid concentration is 20 ~ 25%；
2）Temperature is set in the range of 40 DEG C~45 DEG C by the above-mentioned aqueous solution prepared in stirred tank, stirring 70 ~
90 minutes, just obtain degradable hydrate accelerant.
When in use, the above-mentioned hydrate formation promoter prepared is added for the degradable gas hydrate accelerant
Enter in running water, used after the accelerator aqueous solution for being made into 300 ~ 800ppm.
Specifically：1）Accelerator aqueous solution water filling compound is generated in reactor, control valve is opened, High-Voltage Experimentation gas
Body is filled with reactor, and hydrate reaction of formation system pressure is maintained to 0~30MPa of pressure needed for experiment by pressure regulator valve.
2）1 DEG C~15 DEG C of experimental temperature is set, starts the temperature control system of experimental provision.Using water bath with thermostatic control to reaction
Kettle is cooled down, until the temperature in reactor reaches design temperature.
3）Carry out gas hydrate generation experiment.
In experimentation, distilled water is made by oneself with stainless steel electrical distiller, passes through the BS200S types that precision is 0.1g
Assay balance is weighed；The photoelectric analytical balance that various medicines are 0.05mg with precision is weighed.It can be gathered in real time by computer
Hydrate generates experimental data and image.
Beneficial effects of the present invention：
（1）It is degradable, it is environment friendly and pollution-free, really realize industry aluminium extrusions
Accelerator nonhazardous of the present invention.It is pollution-free, it can directly discharge, can not cause to appoint quickly by biological decomposition
What environmental disruption.And raw material sources are abundant, easily extract, be truly realized the theory of " green industry ".For hydrate storage and transportation technology
Realization of industrialization provides powerful basic guarantee.
（2）Cost is low, economical good, using safety, is widely used
Accelerator dosage of the present invention is few, and raw material can be extracted from nature biotechnology, plant, reduce cost.It can promote
Enter gas hydrate to efficiently produce, reduce equalization point, can be applied to gas hydrate storaging and transport technology, gas hydrate isolation technics
With the field such as desalinization.
（3）Hydrate generation facilitation effect is good
In the range of 1 DEG C~15 DEG C, it is possible to decrease hydrate generates pressure 40 ~ 60%, shorten the generation time 70 ~ 85%.
Brief description of the drawings
Fig. 1 hydrates generate experimental provision flow chart
1 gas cylinder；2 pressure regulator valves；3 mass flowmenters；4 check valves；5 gate valves；6 vavuum pumps；7 pressure, temperature transmitter；
8 waters bath with thermostatic control；9 tanks；10 reactors；11 data collecting systems；12 computers;13 photocell lenses.
Embodiment
The present invention is further described in detail below, but embodiments of the present invention are not limited to that.
The experimental provision that the present invention is used is as shown in figure 1, by gas cylinder 1；Pressure regulator valve 2；Mass flowmenter 3；Check valve
4；Gate valve 5；Vavuum pump 6；Pressure, temperature transmitter 7；Water bath with thermostatic control 8；Tank 9；Reactor 10；Data collecting system 11；Calculate
The grade of machine 12 is constituted.Using gas cylinder 1 as source of the gas, appropriate pressure is transferred to through pressure regulator valve 2, with the stoichiometric consumption day of mass flowmenter 3
Right gas.The temperature and pressure in reactor 10 is monitored by pressure, temperature transmitter 7.Liquid in tank 9 is controlled by water bath with thermostatic control 8
Temperature, so as to adjust reactor temperature.By data collecting system 11 and the gathered data of computer 12 and pass through photocell lenses
Gas hydrate synthesis situation in 13 monitoring reactors.Vavuum pump 6 is used for aspirating liquid in reactor.The system working pressure be 0~
30MPa, temperature range is -10 DEG C~50 DEG C.
Specific preparation process：
1）Thoroughly to exclude the air in reactor and pipe-line system, they are replaced twice with experimental gas, Ran Houzai
Vacuumize.
2）Reactor, pipe-line system are vacuumized with vavuum pump, the min of pumpdown time about 40~50.
3）Weighed respectively using balance certain mass glycerophosphatide and alginic acid be made into mass concentration for 12 ~ 18% and 20 ~
27% solution, adds distilled water, and temperature is set in the range of 40 DEG C~45 DEG C in stirred tank and stirred 70 ~ 90 minutes, is just obtained
To compound hydrate accelerant.
3）The hydrate formation promoter prepared is added in running water, the 300 ~ 800ppm accelerator aqueous solution is made into
Inject in hydrate reaction kettle.
4）Open check valve（4）, High-Voltage Experimentation gas is filled with reactor, passes through pressure regulator valve（2）By reacting system pressure
Maintain the pressure needed for experiment.
6）Experimental temperature is set, starts the temperature control system of experimental provision.Utilize water bath with thermostatic control（8）To reactor（10）
Cooled down, until the temperature in reactor reaches design temperature.
7）Carry out gas hydrate formation experiment.
Embodiment 1：
The proportion of surfactant of selection is the alginic acid of 12% glycerophosphatide+20%, and experimental gas is CO2, promote in the aqueous solution
Enter agent concentration for 300 ~ 800 ppm, temperature is 7.5 DEG C.Tested in aforementioned manners, experimental data is as shown in table 1.
The experimental result of table 1
| Test sequence number | Promoter concentration（ppm） | Induction time（min） | Vapor pressure（MPa） |
| 1 | 300 | 13.3 | 2.12 |
| 2 | 400 | 12 | 2.04 |
| 3 | 500 | 9.6 | 2.05 |
| 4 | 600 | 8.0 | 1.97 |
| 5 | 700 | 6.8 | 1.86 |
| 6 | 800 | 6.7 | 1.75 |
Embodiment 2：
The proportion of surfactant of selection is the alginic acid of 18% glycerophosphatide+27%, and experimental gas is CO2, promote in the aqueous solution
Enter agent concentration for 300 ~ 800 ppm, temperature is 6.3 DEG C.Tested in aforementioned manners, experimental data is as shown in table 2.
The experimental result of table 2
| Test sequence number | Promoter concentration（ppm） | Induction time（min） | Vapor pressure（MPa） |
| 1 | 300 | 12.8 | 2.00 |
| 2 | 400 | 11.6 | 1.89 |
| 3 | 500 | 7.9 | 1.80 |
| 4 | 600 | 6.4 | 1.73 |
| 5 | 700 | 4.9 | 1.72 |
| 6 | 800 | 4.5 | 1.72 |
Claims (3)
1. a kind of degradable gas hydrate accelerant, it is characterised in that it is by glycerophosphatide, alginic acid, deionized water group
Into；The mass concentration of glycerophosphatide and alginic acid is respectively 12~18%, 20~27%, and remaining is deionized water；And under
Row method is made：
1) obtained aqueous solution：Glycerophosphatide and alginic acid are weighed respectively be made into glycerophosphatide concentration by mass with deionized water be
12~18% and marine alga acid concentration be 20~27% solution；
2) temperature is set in the range of 40 DEG C~45 DEG C by the above-mentioned aqueous solution prepared in stirred tank, stirs 70~90 points
Clock, just obtains degradable hydrate accelerant.
2. the preparation method of degradable gas hydrate accelerant described in a kind of claim 1, it is characterised in that including following
Step：
1) obtained aqueous solution：Glycerophosphatide and alginic acid are weighed respectively be made into glycerophosphatide concentration by mass with deionized water be
12~18% and marine alga acid concentration be 20~27% solution；
2) temperature is set in the range of 40 DEG C~45 DEG C by the above-mentioned aqueous solution prepared in stirred tank, stirs 70~90 points
Clock, just obtains degradable hydrate accelerant.
3. the application method of degradable gas hydrate accelerant described in claim 1, it is characterised in that degradable gas
Hydrate accelerant is added in running water, is used after the accelerator aqueous solution for being made into 300~800ppm.
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| 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 |
| CN106479434B (en) * | 2016-09-09 | 2018-08-14 | 常州大学 | A kind of gas hydrate accelerant and preparation method thereof |
| CN110577851A (en) * | 2019-09-12 | 2019-12-17 | 华南理工大学 | device and method for quickly and continuously hydrating and separating coal bed gas |
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| CN101514300B (en) * | 2009-03-23 | 2012-05-23 | 江苏工业学院 | Method for preparing gas hydrate accelerant |
| CN101513600B (en) * | 2009-03-23 | 2012-01-18 | 江苏工业学院 | Method for producing gas hydrate and device thereof |
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Effective date of registration: 20220707 Address after: 362268 Daxue Road, Neikeng Town, Jinjiang City, Quanzhou City, Fujian Province Patentee after: Quanzhou Vocational and Technical University Address before: 213164 No. 1, middle Lake Road, Wujin District, Changzhou, Jiangsu Patentee before: CHANGZHOU University |