CN107185275B - A kind of oil water mixture separation method based on hydrate principle - Google Patents
A kind of oil water mixture separation method based on hydrate principle Download PDFInfo
- Publication number
- CN107185275B CN107185275B CN201710549306.6A CN201710549306A CN107185275B CN 107185275 B CN107185275 B CN 107185275B CN 201710549306 A CN201710549306 A CN 201710549306A CN 107185275 B CN107185275 B CN 107185275B
- Authority
- CN
- China
- Prior art keywords
- hydrate
- oil
- water
- hydrating agents
- pressure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000000926 separation method Methods 0.000 title claims abstract description 31
- 235000019476 oil-water mixture Nutrition 0.000 title claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 35
- 230000000887 hydrating effect Effects 0.000 claims abstract description 32
- 235000019198 oils Nutrition 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 238000003828 vacuum filtration Methods 0.000 claims abstract description 7
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 5
- 239000000047 product Substances 0.000 claims description 18
- 238000005057 refrigeration Methods 0.000 claims description 9
- GNDMWRNTJIARLO-UHFFFAOYSA-N ClC(C)Cl.[F] Chemical class ClC(C)Cl.[F] GNDMWRNTJIARLO-UHFFFAOYSA-N 0.000 claims description 7
- 239000012467 final product Substances 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 230000036571 hydration Effects 0.000 claims description 4
- 238000006703 hydration reaction Methods 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 230000008014 freezing Effects 0.000 claims description 3
- 238000007710 freezing Methods 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims description 3
- 230000000994 depressogenic effect Effects 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 9
- 235000013305 food Nutrition 0.000 abstract description 3
- 239000010865 sewage Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000003208 petroleum Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 description 9
- 239000000839 emulsion Substances 0.000 description 3
- 239000003129 oil well Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/04—Breaking emulsions
- B01D17/047—Breaking emulsions with separation aids
Landscapes
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Fats And Perfumes (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of oil water mixture separation method based on hydrate principle, including hydrate generates, hydrate is broken, vacuum filtration, centrifuge separation, decomposition of hydrate, collection of products and hydrating agents recycle six steps.The present invention only excludes the principle except its structure in conjunction with pure water and other substances that cannot generate hydrate using hydrate formation, realizes the purpose using hydrate generating principle oil-water separation mixture.The present invention adds hydrating agents using chemical reaction metering ratio of hydrating agents and water, it is ensured that oil, water, hydrating agents three-phases are kept completely separate, and hydrating agents can be recycled, and save Master Cost.This method can be promoted and applied in industrial circles such as petroleum works, sewage treatment, food engineerings.Separative efficiency of the present invention is high, and operating process is simple, economic value with higher.
Description
Technical field
The invention belongs to separation sciences and technical field, are related to a kind of oil water mixture separation side based on hydrate principle
Method.
Background technique
Under normal circumstances, oil and water objectionable intermingling, but with the fast development of Chemical Engineering Technology, the surface of broad categories
Activating agent is widely applied, and these active chemical reagent, so that this immiscible grease is mutually in specified conditions
Under easily form stable emulsion.In addition, produced liquid in oil well is often different types of the hydrocarbon component, water in oil exploitation
And the mixed liquor of other impurities composition, and normal production and raising oil recovery factor in order to guarantee oil well, often use
The technologies such as In Surfactant Solution Flood, caustic flooding, polymer displacement of reservoir oil, foam flooding, this forms produced liquid in oil well containing higher
The stable suspersion emulsion of moisture.For only needing the industrial circle of oily phase or water phase, stable emulsion can be brought greatly
Negative effect, it is therefore necessary to realize the separation of oil water mixture.
Therefore, oil water mixture isolation technics is obtained in multiple fields such as petrochemical industry, sewage treatment, food engineerings
It is widely applied.But due to the organism kinds in oil mixing with water state, grease content, oil water mixture, water-oil separating pair
As the difference of equal many factors, so that oil water mixture separating difficulty is increasing, single oily water separation technique is had been unable to meet
The demand of development of modern industry and environmental protection.
Summary of the invention
For the deficiency of prior art, the present invention provides a kind of oil water mixture separation sides based on hydrate principle
Method passes through its object is to only be combined the water in oil water mixture to form solid hydrate using with the immiscible hydrating agents of water
It is separated by solid-liquid separation isolated hydrate and oily phase, decomposition of hydrate and obtains water phase and hydrating agents, realize oil water mixture separation.
Technical solution of the present invention:
A kind of oil water mixture separation method based on hydrate principle, comprises the following steps that
(1) hydrate generates: 1. measuring the moisture content of oil water mixture, water content is calculated, by oil water mixture and water
Mixture is passed through in reaction kettle, and records the temperature and pressure in reaction kettle, and wherein the water in oil water mixture and hydrating agents rub
You are than being hydrate chemical reaction metering ratio；2. reactor temperature and pressure is arranged according to the hydrate phasor of hydrating agents used
Power, reacting kettle inner pressure setting range are that atmosphere is depressed into the limiting pressure that reaction kettle can bear, and reaction kettle is placed in refrigeration cycle
In water-bath, setting refrigeration cycle bath temperature be in the corresponding hydrate phase balance temperature of reacting kettle inner pressure or less, freezing point with
On；3. continuing 1h or more when reactor temperature rises after being then reduced to water-bath setting temperature again, obtaining with hydrate
It is the hydrated product of ingredient with oil；
(2) hydrate is broken: hydrated product being transferred to ice crusher from reaction kettle, blocky hydrate therein is crushed
At hydrate partial size in 1mm hydrate slurry below；
(3) it is filtered by vacuum: hydrate slurry is subjected to vacuum filtration 3min or more, obtain oil and primary separation product, wherein
Primary separation product is made of hydrate and oil；
(4) it being centrifugated: primary separation product is centrifuged, setting centrifugal rotational speed is not less than 2000r/min, from
Heart time 5min or more, obtains hydrate and oil after being centrifuged；
(5) decomposition of hydrate: the hydrate that step (4) obtains is decomposed at normal temperatures and pressures, obtain by pure water and
The decomposed solution of hydrating agents composition；
(6) collection of products and hydrating agents recycle: the oil that step (3) vacuum filtration is obtained and step (4) centrifugation point
It is collected together from obtained oil, obtains the oil of one of final product；Step (5) decomposed solution is stood until water and hydrating agents are complete
Full layering obtains hydrating agents and water by layered filtration using the immiscible property of hydrating agents and water, and hydrating agents continue in step
(1) it is recycled in, water is collected as one of final product.
Further, the hydrating agents are one of a fluorine dichloroethanes (R141b), pentamethylene or hexamethylene.Hydration
Agent need to select immiscible, nonflammable, nontoxic with water, can form hydrate liquid chemical reagent under normal pressure.
Further, the pressure of step (2) (3) (4) operating environment is kept and setting pressure in reaction kettle in step (1)
Power is consistent, and temperature keeps consistent with the set temperature of refrigeration cycle water-bath.
Further, the step (1) if in reacting kettle inner pressure need to be set greater than atmospheric pressure, using compressed air plus
Pressure.
Beneficial effects of the present invention are that other only cannot be generated hydration in conjunction with pure water using hydrate formation
The substance of object excludes the principle except its structure, realizes the purpose using hydrate generating principle oil-water separation mixture.
The present invention using hydrating agents and water chemical reaction metering ratio add hydrating agents, it is ensured that oil, water, hydrating agents three-phase it is complete
Separation, and hydrating agents are Ke Xunhuanliyong, save Master Cost.This method can promote and apply at petroleum works, sewage
The industrial circles such as reason, food engineering.Separative efficiency of the present invention is high, and operating process is simple, economic value with higher.
Detailed description of the invention
Fig. 1 is a kind of oil water mixture separation method flow chart based on hydrate principle；
Fig. 2 is a fluorine dichloroethanes hydrate phasor.
In figure: behalf solid, l represent liquid, and v represents gas, and Q (p=0.042MPa, T=281.5K) is one fluorine of liquid
The quadruple point of dichloroethanes, one fluorine dichloroethanes of gas, liquid water and hydrate, ps(T) line represent at each temperature, water and
The sum of the saturated vapour pressure of one fluorine dichloroethanes, Ttri(p) line represents liquid water, hydrate and liquid under each given temperature
The three-phase equilibrium temperature of one fluorine dichloroethanes.
Specific embodiment
Below in conjunction with attached drawing and technical solution, a specific embodiment of the invention is further illustrated.
By taking fluorine dichloroethanes (R141b) hydrate as an example, a kind of oil water mixture separation side based on hydrate principle
Method, steps are as follows:
(1) hydrate generates: using the moisture content of near-infrared absorption spectrum method measurement oil water mixture, calculating aqueous
Oil water mixture and R141b are passed through reaction kettle according to the amount that the molar ratio of water and hydrating agents in oil water mixture is 17 by amount
In, there are three thermocouple and a temperature sensors for reaction kettle connection, and connect and record reactor temperature and pressure on computers
According to the hydrate phasor of hydrating agents used reactor temperature and pressure is arranged, it is big that range, which is arranged, in reacting kettle inner pressure in power
The limiting pressure that air pressure to reaction kettle can bear, if reacting kettle inner pressure need to be arranged greater than atmospheric pressure, using compressed air
Pressurization, reaction kettle are placed in refrigeration cycle water-bath, and setting refrigeration cycle bath temperature is in the corresponding hydration of reacting kettle inner pressure
Below phase balance temperature, it is above freezing, the dash area in specific temperature, pressure setting range such as Fig. 2 can generally be set
Set normal pressure and 277.15K, when reactor temperature rises, be then reduced to water-bath setting temperature 1h or more again, obtain with
Hydrate and oil are the hydrated product of ingredient；
(2) hydrate is broken: hydrated product being transferred to ice crusher from reaction kettle, blocky hydrate therein is crushed
At hydrate partial size in 1mm hydrate slurry below；；
(3) it is filtered by vacuum: hydrate slurry is subjected to vacuum filtration 3min or more, obtain oil and primary separation product, wherein
Primary separation product is made of hydrate and oil；
(4) it being centrifugated: primary separation product is centrifuged, setting centrifugal rotational speed is not less than 2000r/min, from
Heart time 5min or more, obtains hydrate and oil after being centrifuged；
(5) decomposition of hydrate: the hydrate that step (5) obtains is decomposed at normal temperatures and pressures, obtain by pure water and
The decomposed solution of R141b composition；
(6) collection of products and hydrating agents recycle: the oil that step (3) vacuum filtration is obtained and step (4) centrifugation point
It is collected together from obtained oil, obtains one of final product oil, step (5) decomposed solution is static until water and R141b are complete
Layering, obtains R141b and water by layered filtration using the immiscible property of R141b and water, R141b can continue in step
(1) it is recycled in, water is collected as one of final product.
Wherein, the pressure of the operating environment of step (2) (3) (4) should keep and set pressure one in step (1) reaction kettle
It causes, temperature keeps consistent with the set temperature of refrigeration cycle water-bath.
Claims (5)
1. a kind of oil water mixture separation method based on hydrate principle, which comprises the steps of:
(1) hydrate generates: 1. measuring the moisture content of oil water mixture, water content is calculated, by oil water mixture and hydrating agents
It is passed through in reaction kettle, and records the temperature and pressure in reaction kettle, wherein the molar ratio of the water in oil water mixture and hydrating agents
Metering ratio is chemically reacted for hydrate；2. reactor temperature and pressure is arranged, instead according to the hydrate phasor of hydrating agents used
Answering pressure setting range in kettle is that atmosphere is depressed into the limiting pressure that reaction kettle can bear, and reaction kettle is placed in refrigeration cycle water-bath
In, setting refrigeration cycle bath temperature is in the corresponding hydrate phase balance temperature of reacting kettle inner pressure or less, above freezing；③
When reactor temperature rises, continues 1h or more after being then reduced to water-bath setting temperature again, obtain with hydrate and oil
For the hydrated product of ingredient；
(2) hydrate is broken: hydrated product being transferred to ice crusher from reaction kettle, blocky hydrate therein is broken into water
Object partial size is closed in 1mm hydrate slurry below；
(3) it is filtered by vacuum: hydrate slurry is subjected to vacuum filtration 3min or more, obtain oil and primary separation product, wherein primary
Separation product is made of hydrate and oil；
(4) it is centrifugated: primary separation product is centrifuged, setting centrifugal rotational speed is not less than 2000r/min, when centrifugation
Between 5min or more, obtain hydrate and oil after being centrifuged；
(5) decomposition of hydrate: the hydrate that step (4) obtains is decomposed at normal temperatures and pressures, is obtained by pure water and hydration
The decomposed solution of agent composition；
(6) collection of products and hydrating agents recycle: the oil that step (3) vacuum filtration obtains is centrifugated with step (4)
To oil be collected together, obtain the oil of one of final product；Step (5) decomposed solution is stood until water and hydrating agents divide completely
Layer obtains hydrating agents and water by layered filtration using the immiscible property of hydrating agents and water, and hydrating agents continue in step (1)
It recycles, water is collected as one of final product.
2. a kind of oil water mixture separation method based on hydrate principle according to claim 1, which is characterized in that institute
Stating hydrating agents is one of a fluorine dichloroethanes, pentamethylene or hexamethylene.
3. a kind of oil water mixture separation method based on hydrate principle according to claim 1 or 2, feature exist
Pressure in, step (2) (3) (4) operating environment keep and reaction kettle in step (1) in setting pressure it is consistent, temperature keep with
The set temperature of refrigeration cycle water-bath is consistent.
4. a kind of oil water mixture separation method based on hydrate principle according to claim 1 or 2, feature exist
In, step (1) if in reacting kettle inner pressure need to be set greater than atmospheric pressure, utilize pressurized with compressed air.
5. a kind of oil water mixture separation method based on hydrate principle according to claim 3, which is characterized in that step
Suddenly (1) if in reacting kettle inner pressure need to be set greater than atmospheric pressure, utilize pressurized with compressed air.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710549306.6A CN107185275B (en) | 2017-07-07 | 2017-07-07 | A kind of oil water mixture separation method based on hydrate principle |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710549306.6A CN107185275B (en) | 2017-07-07 | 2017-07-07 | A kind of oil water mixture separation method based on hydrate principle |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107185275A CN107185275A (en) | 2017-09-22 |
| CN107185275B true CN107185275B (en) | 2019-04-05 |
Family
ID=59883433
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710549306.6A Active CN107185275B (en) | 2017-07-07 | 2017-07-07 | A kind of oil water mixture separation method based on hydrate principle |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107185275B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112390318A (en) * | 2020-11-18 | 2021-02-23 | 河南理工大学 | Method for removing oil by freezing and thawing carbon dioxide hydrate |
| CN113941173A (en) * | 2021-09-30 | 2022-01-18 | 大连理工大学 | Liquid phase organic mixture separation method by utilizing phase change of hydrate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105771321A (en) * | 2016-03-21 | 2016-07-20 | 重庆工商大学 | Inorganic crystal separation water-in-oil emulsion method |
-
2017
- 2017-07-07 CN CN201710549306.6A patent/CN107185275B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105771321A (en) * | 2016-03-21 | 2016-07-20 | 重庆工商大学 | Inorganic crystal separation water-in-oil emulsion method |
Non-Patent Citations (1)
| Title |
|---|
| "水合物法分离混合物技术研究进展";杨西萍;《化工学报》;20170331;第68卷(第3期);第831-840页 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107185275A (en) | 2017-09-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| O'keefe et al. | Preliminary results from bench-scale testing of a sulfur-iodine thermochemical water-splitting cycle | |
| CN107185275B (en) | A kind of oil water mixture separation method based on hydrate principle | |
| Hogenboom et al. | Magnesium sulfate-water to 400 MPa using a novel piezometer: Densities, phase equilibria, and planetological implications | |
| Kubota et al. | Thermodynamic properties of R13 (CCIF3), R23 (CHF3), R152a (C2H4F2), and propane hydrates for desalination of sea water | |
| Sako et al. | Phase equilibrium study of extraction and concentration of furfural produced in reactor using supercritical carbon dioxide | |
| Gumerov et al. | Supercritical fluid propane-butane extraction treatment of oil sludge | |
| US2090537A (en) | Lecithin product and process | |
| Hanson et al. | Relation of Binary Heats of Mixing and Distribution of Ketone between Phases in some Ketone-Water-Solvent Ternaries. | |
| Partoon et al. | Gas hydrate models | |
| Ho-Van et al. | Implementing cyclopentane hydrates phase equilibrium data and simulations in brine solutions | |
| CN105597372B (en) | A kind of oil-water separating net membrane material of double-decker γ AlOOH coatings and preparation method thereof | |
| Tsivadze et al. | Adsorption of methane on an MOF-199 organometallic framework structure at high pressures in the range of supercritical temperatures | |
| CN105347633A (en) | Method for recovering oil from oil-containing substances and device thereof | |
| Kodama et al. | Volumetric behavior of carbon dioxide+ 2-methyl-1-propanol and carbon dioxide+ 2-methyl-2-propanol mixtures at 313.15 K | |
| Mohl et al. | Multiple steady states in a reactive distillation column for the production of the fuel ether TAME I. Theoretical analysis | |
| Hixson et al. | Mass transfer in liquid-liquid agitation systems | |
| Schoch et al. | Solubility of methane in n-hexane | |
| Maeda et al. | Concentration of sodium chloride in aqueous solution by chlorodifluoromethane gas hydrate | |
| CN103555428A (en) | Method for extracting wool fat in wool-scouring wastewater sludge by extractive distillation | |
| Abdulkadirova et al. | Prediction of phase equilibria in hydrocarbon+ near-critical solvent systems | |
| CN105819462B (en) | Method of preparing fluoroboric acid from fluorine containing wastewater | |
| Moore et al. | Extraction of Inorganic Salts by 2-Octanol. I. Cobalt (II) and Nickel (II) Perchlorates | |
| US2397191A (en) | Spreading agent | |
| Abdi et al. | Mole fraction measurement of methane and ethane in aqueous solutions of NaCl and MgCl2 during hydrate growth | |
| Pearce et al. | Furfural-Water System-Experimental and Theoretical Vapor-Liquid Relationships |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |