CN106397124B - A kind of desalination method of saliferous ethylene glycol solution - Google Patents
A kind of desalination method of saliferous ethylene glycol solution Download PDFInfo
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- CN106397124B CN106397124B CN201610819016.4A CN201610819016A CN106397124B CN 106397124 B CN106397124 B CN 106397124B CN 201610819016 A CN201610819016 A CN 201610819016A CN 106397124 B CN106397124 B CN 106397124B
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- ethylene glycol
- desalination
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title claims abstract description 178
- 238000010612 desalination reaction Methods 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000000243 solution Substances 0.000 claims abstract description 74
- 239000003960 organic solvent Substances 0.000 claims abstract description 36
- 239000011259 mixed solution Substances 0.000 claims abstract description 27
- 150000003839 salts Chemical class 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 5
- 239000003513 alkali Substances 0.000 claims abstract description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 34
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 238000006298 dechlorination reaction Methods 0.000 claims 1
- 238000005115 demineralization Methods 0.000 claims 1
- 230000002328 demineralizing effect Effects 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 238000011033 desalting Methods 0.000 abstract 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 20
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 14
- 239000011780 sodium chloride Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 229910001961 silver nitrate Inorganic materials 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- 238000004448 titration Methods 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 230000001172 regenerating effect Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 239000003495 polar organic solvent Substances 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 206010033799 Paralysis Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- NMJORVOYSJLJGU-UHFFFAOYSA-N methane clathrate Chemical compound C.C.C.C.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O NMJORVOYSJLJGU-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
本发明公开一种含盐乙二醇溶液的除盐方法，其特征在于，所述方法为：在乙二醇溶液中加入有机溶剂得到第一混合溶液，加入酸或碱调节第一混合溶液酸碱度得到第二混合溶液，将所述第二混合溶液静置4～12小时。该除盐方法简单易操作，除盐原料来源范围广，成本低，并易回收循环利用，能大大降低能耗成本，节能环保。The invention discloses a desalination method for a salt-containing ethylene glycol solution, which is characterized in that the method is as follows: adding an organic solvent to the ethylene glycol solution to obtain a first mixed solution, and adding acid or alkali to adjust the pH of the first mixed solution A second mixed solution is obtained, and the second mixed solution is allowed to stand for 4 to 12 hours. The desalting method is simple and easy to operate, has a wide range of raw material sources for desalting, low cost, easy recovery and recycling, can greatly reduce energy consumption cost, save energy and protect the environment.
Description
Technical field
The present invention relates to natural gas fields, and in particular to a kind of desalination method of saliferous ethylene glycol solution.
Background technique
During ocean deepwater gas field development, the formation of hydrate will lead to pipeline and equipment blocking is entire to cause
System operation paralysis, therefore, needs to reduce during gas field development the possibility of gas hydrate synthesis using hydrate inhibitor
Property.
Ethylene glycol is a kind of most common hydrate inhibitor, not volatile, can be mixed with arbitrary proportion with water, and mix
It is easily separated from water after conjunction, can realize cycling and reutilization by simple regenerating unit in operation at the scene, greatly subtract
Systematic running cost use is lacked.But it in the ethylene glycol recovery system that offshore natural gas comes into operation at present, encounters as blocked, tying
Refuse, rotten candle, foaming and glycol recycling concentration unqualified etc. the problems such as.
Novel ethylene glycol desalination regeneration process common at present is divided into two kinds: complete desalination process and partially desalted method.Completely
Desalination process is that all saliferous ethylene glycol rich solutions are transported to regenerating unit, carries out desalination, dehydration, is finally obtained salt-free clean
Net lean glycol；Partially desalted method is that saliferous ethylene glycol is divided into two strands, one enters ethylene glycol regenerating device, carries out desalination
Then dehydration is converged with another stock, obtain ethylene glycol lean solution.Saliferous glycol flow into ethylene glycol regenerating device measures
Certainly in technique requirement and the permission salt content of ethylene glycol lean solution.Both methods is all physics desalination process, used device
It is heavier, it takes up a large area, and energy consumption is very high.
Summary of the invention
In view of this, the application provides a kind of desalination method of saliferous ethylene glycol solution, this method is former using chemical decladding
Reason carries out desalination to ethylene glycol using organic solvent, avoids that space can be saved using the desalter taken up a large area, reduces
Energy consumption, method are simple to operation.
In order to solve the above technical problems, technical solution provided by the invention is a kind of desalination side of saliferous ethylene glycol solution
Method, the method is specially that organic solvent is added in ethylene glycol solution to obtain the first mixed solution, molten in first mixing
Acid is added in liquid or alkali adjusts the first mixing pH value and obtains the second mixed solution, the second mixed solution is stood 4~12 hours.
Since solubility is low in low polar solvent for sodium chloride, the second of saliferous is added in low polar organic solvent by the present invention
In glycol solution, the reduction of sodium chloride solubility can be gradually precipitated, and filtering can obtain salt-free ethylene glycol solution.
Preferably, the organic solvent is one or more of acetone, ethyl alcohol, isopropanol.
Acetone, ethyl alcohol, isopropanol are low polar organic solvent.
It is furthermore preferred that the organic solvent is acetone.
Preferably, the volume ratio of the organic solvent and the ethylene glycol solution is (2~6): 1.
It is furthermore preferred that the volume ratio of the organic solvent and the ethylene glycol solution is 5:1.
Preferably, the organic solvent is added at one time in the ethylene glycol solution.
Preferably, the first mixed solution pH value of the adjusting is that acid or alkali adjusting are added in first mixed solution
First mixed solution is to its pH=(5~9).
Preferably, second mixed solution stands 4~12 hours at a temperature of 30 DEG C~50 DEG C.
It is furthermore preferred that second mixed solution stands 8 hours at 50 °C.
Temperature is higher, and organic solvent and the reactant salt in ethylene glycol rich solution are more abundant, and desalination rate is higher.
The application compared with prior art, has the advantages that
(1) present invention carries out desalination to ethylene glycol solution using the principles of chemistry, avoids using large-scale plant, not only saves empty
Between and reduce energy consumption.(2) raw material sources range of the present invention is wide, at low cost, and easily recycles.(3) since this is organic
The desalination mechanism of solvent is to change the solubility of salt using solution polarity is changed, so desalination effect is not by salt content in rich solution
Influence, use scope is wide.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the invention is clearly and completely described,
Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based in the present invention
Embodiment, every other embodiment obtained by those of ordinary skill in the art without making creative efforts, all
Belong to the scope of protection of the invention.
The present invention provides a kind of desalination method for saliferous ethylene glycol solution, the method are as follows: in ethylene glycol solution
Organic solvent is added, adjusts ethylene glycol solution pH value, stands 4~12 hours, the organic solvent is acetone, ethyl alcohol, isopropyl
One or more of alcohol.In some embodiments of the invention, organic solvent is preferably acetone.
Desalination mechanism provided by the invention is that the principle that solubility is low in low polar solvent using sodium chloride carries out desalination
's.
Wherein organic solvent and ethylene glycol solution volume ratio are preferably (2~6): 1, in some specific embodiments of the present invention
In, the volume ratio of organic solvent and ethylene glycol is 2:1；In some embodiments of the invention, organic solvent and ethylene glycol
Volume ratio be 5:1；
In the present invention, the organic solvent needs, which are added at one time in ethylene glycol solution, obtains the first mixed solution,
And the acid-base property of the first mixed solution need to be adjusted.In some embodiments of the invention, the pH of the first mixed solution is adjusted
To 5；In some embodiments of the invention, the pH of the first mixed solution is adjusted to 7；In some embodiments of the invention,
The pH of first mixed solution is adjusted to 9；If from specific embodiment as can be seen that the acid-base property of solution in a certain range,
Desalination rate is influenced little.Also need to adjust the temperature of ethylene glycol, preferably 30~50 DEG C.In some embodiments of the present invention
In, the temperature of the second mixed solution is adjusted to 30 DEG C；In some embodiments of the invention, by the temperature of the second mixed solution
It is adjusted to 40 DEG C；In some embodiments of the invention, the temperature of the second mixed solution is adjusted to 50 DEG C；From specific embodiment
Data can be seen that when the second mixed solution temperature is adjusted to 50 DEG C, desalination rate is higher.In addition, due to the organic solvent
Desalination mechanism be to change the solubility of salt using solution polarity is changed, so desalination effect is not by the shadow of salt content in rich solution
It rings, use scope is wide.
Embodiment 1
The choice experiment of organic solvent:
25mL aqueous 15% is configured, sodium chloride concentration is the ethylene glycol solution of 80000mg/L.Respectively into ethylene glycol solution
The different organic solvent of 50mL is added, adjusts the first mixed solution pH=7, stands 12 hours in 50 DEG C, filters, take filtrate nitre
Sour argentometry determines Cl in lean solution-Content calculates salt content and desalination rate in theoretical lean solution.
The corresponding desalination rate of 1 different organic solvents of table
It can be seen from data in table 1 when selecting acetone is the organic solvent of desalination, desalination rate highest, therefore this hair
Bright selection acetone is best organic solvent.
Embodiment 2
The experiment of desalination temperature test:
25mL aqueous 15% is configured, sodium chloride concentration is the ethylene glycol solution of 80000mg/L.It is added into ethylene glycol solution
Solution is stood 12 hours in 30 DEG C, 40 DEG C, 50 DEG C respectively, filters, take filtrate silver nitrate titration method by 50mL acetone, pH=7
Determine Cl in lean solution-Content calculates salt content and desalination rate in theoretical lean solution.
The corresponding desalination rate of 2 different temperatures of table
Desalination rate is most it can be seen from the data in table 2 when solution temperature is controlled at 50 DEG C, when organic solvent is added
It is high.
Embodiment 3
Desalination pH test experiments
25mL aqueous 15% is configured, sodium chloride concentration is the ethylene glycol solution of 80000mg/L.It is added into ethylene glycol solution
50mL acetone is added the pH value of acid or alkali adjusting solution to pH=5, pH=7, pH=9 into solution respectively, stands in 50 DEG C
It 12 hours, filters, filtrate is taken to determine Cl in lean solution with silver nitrate titration method-Content calculates salt content in theoretical lean solution and removes
Salt rate.
The corresponding desalination rate of 3 different pH values of table
As can be seen from Table 3, when the pH of solution is controlled in 5~9 ranges, the variation of ethylene glycol desalination rate less, illustrates molten
Liquid desalination effect is not influenced by pH.
Embodiment 4
Organic solvent additional proportion test experiments:
25mL aqueous 15% is configured, sodium chloride concentration is the ethylene glycol solution of 80000mg/L.Respectively into ethylene glycol solution
50mL, 75mL, 100mL, 125mL, 150mL acetone is added, adjusts pH value of solution=7, solution is stood 12 hours in 50 DEG C, is taken out
Filter, takes filtrate to determine Cl in lean solution with silver nitrate titration method-Content calculates salt content and desalination rate in theoretical lean solution.
The corresponding desalination rate of 4 different organic solvents additional amount of table
It can be seen from data in table 4 when organic solvent and ethylene glycol solution volume ratio are 5:1, desalination rate reaches most
It is high.
Example 5
Testing response time experiment
25mL aqueous 15% is configured, sodium chloride concentration is the ethylene glycol solution of 80000mg/L.It is added into ethylene glycol solution
125mL acetone, pH=7 respectively stand solution in 50 DEG C, and every 1 hour absorption clear liquid 0.5mL is determined with silver nitrate titration method
Cl in lean solution-Content determines whether reaction terminates to consume silver nitrate volume.
Influence of 5 time of table to desalination effect
It can be seen from 5 data of table when reacted between when reach 8 hours, Cl in solution-Concentration no longer changes, and says
Bright reaction terminated at 8 hours, i.e., it is 8 hours that desalination needs the time completely.
Embodiment 6
Organic solvent adding manner test experiments:
25mL aqueous 15% is configured, sodium chloride concentration is the ethylene glycol solution of 80000mg/L.Respectively into ethylene glycol solution
125mL acetone is added, a copy of it acetone is once to be added in ethylene glycol solution, and in addition a acetone, which divides 5 times, is added to second
In glycol solution, adjust pH value of solution=7, by solution in 50 DEG C of standings total times be 8 hours, suction filtration, take filtrate to be dripped with silver nitrate
The method of determining determines Cl in lean solution-Content calculates salt content and desalination rate in theoretical lean solution.
The corresponding desalination rate of 6 different organic solvents adding manner of table
Desalination rate is higher when organic solvent is added at one time it can be seen from experimental data in table 6.
Embodiment 7
Organic solvent tests the desalination aptitude tests of the ethylene glycol of different salinity:
25mL aqueous 15%, the second two of sodium chloride concentration 40000mg/L, 60000mg/L, 80000mg/L is respectively configured
Alcoholic solution.It is separately added into 125mL acetone into ethylene glycol solution, adjusts pH value of solution=7, solution is stood 8 hours in 50 DEG C, is taken out
Filter, takes filtrate to determine Cl in lean solution with silver nitrate titration method-Content calculates salt content and desalination rate in theoretical lean solution.
The corresponding desalination rate of ethylene glycol of the different salinity of table 7
As can be seen from Table 7, ethylene glycol solution salt content is higher, and the desalination rate of organic solvent is higher, this is because this has
The desalination mechanism of solvent is to change the solubility of salt using solution polarity is changed, so desalination effect is not contained by salt in rich solution
The influence of amount, use scope are wide.
The above is only the preferred embodiment of the present invention, it is noted that above-mentioned preferred embodiment is not construed as pair
Limitation of the invention, protection scope of the present invention should be defined by the scope defined by the claims..For the art
For those of ordinary skill, without departing from the spirit and scope of the present invention, several improvements and modifications can also be made, these change
It also should be regarded as protection scope of the present invention into retouching.
Claims (5)
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85109000A (en) * | 1984-12-10 | 1986-07-09 | 国际壳牌研究有限公司 | From brine waste, reclaim glycerine |
| CN103930393A (en) * | 2011-11-14 | 2014-07-16 | 卡梅伦国际有限公司 | Process scheme to improve divalent metal salts removal from mono ethylene glycol (MEG) |
-
2016
- 2016-09-13 CN CN201610819016.4A patent/CN106397124B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85109000A (en) * | 1984-12-10 | 1986-07-09 | 国际壳牌研究有限公司 | From brine waste, reclaim glycerine |
| CN103930393A (en) * | 2011-11-14 | 2014-07-16 | 卡梅伦国际有限公司 | Process scheme to improve divalent metal salts removal from mono ethylene glycol (MEG) |
Non-Patent Citations (2)
| Title |
|---|
| 深水气田新型乙二醇再生工艺方法;任顺顺等;《油气储运》;20150228;第34卷(第2期);第208-210页 |
| 溶剂析出法分离水溶液中的K2SO4和NaCl;王建成等;《山东化工》;19971231(第2期);第2-4页 |
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Effective date of registration: 20210127 Address after: Intercontinental building, 16 ande Road, Dongcheng District, Beijing, 100007 Patentee after: PetroChina Company Limited Address before: 610500, Xindu Avenue, Xindu District, Sichuan, Chengdu, 8 Patentee before: SOUTHWEST PETROLEUM University |