CN105440278B - A kind of demulsifier compound system and the preparation method and application thereof - Google Patents
A kind of demulsifier compound system and the preparation method and application thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33348—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group
- C08G65/33355—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group cyclic
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2612—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aromatic or arylaliphatic hydroxyl groups
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
- C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with monohydric phenols having only one hydrocarbon substituent ortho on para to the OH group, e.g. p-tert.-butyl phenol
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G33/00—Dewatering or demulsification of hydrocarbon oils
- C10G33/04—Dewatering or demulsification of hydrocarbon oils with chemical means
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1033—Oil well production fluids
Abstract
The present invention provides a kind of demulsifier compound systems and the preparation method and application thereof.The composition of the demulsifier compound system includes p-tert-butylphenol aldehyde polyether demulsification agent, modified p-tert-butylphenol aldehyde polyether demulsification agent and acetic acid.The preparation method of the p-tert-butylphenol aldehyde polyether demulsification agent includes：1) para-tert-butyl phenolic resin and catalyst are added in the reaction vessel；2) ethylene oxide is added；3) when pressure and temperature is fallen after rise, pressure is down to negative value, is heated up, propylene oxide is added and is reacted；4) after temperature and pressure is fallen after rise, p-tert-butylphenol aldehyde polyether demulsification agent is obtained.The preparation method of the modified p-tert-butylphenol aldehyde polyether demulsification agent includes：A, acrylic acid is added after mixing p-tert-butylphenol aldehyde polyether demulsification agent obtained with propylene glycol polyether demulsification agent；B, toluene di-isocyanate(TDI) is added, obtains modified p-tert-butylphenol aldehyde polyether demulsification agent.Demulsifier compound system synthesis technology provided by the invention is simple, and dehydrating effect is good.
Description
Technical field
The present invention relates to a kind of demulsifier compound system and the preparation method and application thereof, especially a kind of p-tert-butylphenol aldehyde
Polyether demulsification agent, by its modified p-tert-butylphenol aldehyde polyether demulsification agent obtained and demulsifier compound system.
Background technology
In recent years, major part oil field in China's all enters development late stage, the deep profile correction oil recovery skill based on polymer flooding
Art has become one of major measure of agent for improving oilfield recovery.Compared with filled drive, the physico-chemical property of poly- flooding produced liquid is noted more
Complexity causes water-oil separating difficulty to increase due to the increase of polymer, it is therefore desirable to develop new breaker system, meet oil
The needs of field production.
Foreign countries see 1914 earliest about the data of demulsifier, the last century 20's to the thirties, to solve water packet
The anionic demulsifier of the demulsification problem of oil type crude oil emulsion, first generation low molecular weight comes out, such as fatty acid salt, aphthenic acids
Salt, petroleum sulfonate, Turkey red oil etc., its advantage is that it is cheap, the disadvantage is that easily being influenced by electrolyte, similarly imitating
The dosage of such demulsifier is larger etc. under fruit；The forties to the fifties, ethylene oxide realize industrialized production so that epoxy second
Alkane propylene oxide block copolymer starts to occur；Begin to use non-ionic demulsifier, such as alkyl 20th century 50 to the sixties
Phenol, the polyoxyethylene ether that fatty alcohol is initiator, used later based on polyoxyethylene polyoxypropylene block copolymer
Demulsifier, since the demulsifier effect of this type is good, so being still the crude oil demulsifier being most widely used at present；Into
After the eighties, polyamine class, amphoteric ion type, polymer demulsifier start to occur, instead of simple ethylene oxide propylene oxide
Block polymer demulsifier, the minimum amount of such demulsifier is in 100mg/L hereinafter, but the shortcomings that this kind of demulsifier is specificity
By force, bad adaptability.
Since the later stage eighties, the research and development of external demulsifier enters a more rapid period, in third
On the basis of high-molecular-weight poly ethers demulsifier, people have carried out the research and development of a large amount of novel demulsifier products, and obtain
Huge advance, has obtained the more excellent demulsifier of demulsification performance.Mainly have：Methyl methacrylate vinegar, Butyl acrylate with
Polyoxyethylene acid esters, the copolymer of polyoxypropylene, highly polar organic amino derivative, cationic phthalein amine compounds and they between
Compound system.
There is be demulsified temperature height, the separation of viscous crude emulsus in use in traditional demulsifier.
Currently, the research about demulsifier is concentrated mainly on the following aspects：First, study various expansions with deepening continuously
The use of chain agent and a variety of chain extenders；Second is that the research and development of oil-soluble or mixed type demulsifier；Third, branched chain type demulsifier is ground
Hair；Fourth, adaptable high molecular weight demulsifier.
Therefore providing a kind of novel demulsifier for oil field mining liquid demulsification becomes this field urgent problem to be solved
One of.
Invention content
In order to solve the above technical problems, the purpose of the present invention is to provide a kind of demulsifier compound system, the demulsifier is multiple
Simple with system synthesis technology, dehydrating effect is good.
In order to achieve the above objectives, the present invention provides a kind of preparation method of p-tert-butylphenol aldehyde polyether demulsification agent, this method
Include the following steps：
Step 1: para-tert-butyl phenolic resin and catalyst are added in the reaction vessel, then heat up；
Step 2: when temperature rises to 100-150 DEG C, preferably 120 DEG C, ethylene oxide is added into reaction vessel, after
Temperature of continuing rising；
Step 3: when the pressure and temperature in reaction vessel starts to fall after rise, the pressure in reaction vessel is down to negative value,
Temperature in reaction vessel is risen into 100-150 DEG C, preferably 135 DEG C；Then propylene oxide is added into reaction vessel to carry out
Reaction；
Step 4: after the temperature and pressure in reaction vessel is fallen after rise, p-tert-butylphenol aldehyde polyether demulsification agent is obtained.
The technique still without synthesis p-tert-butylphenol aldehyde polyethers as demulsifier, technical solution provided by the invention are adopted at present
With the synthetic method of negative pressure high temperature, it ensure that final p-tert-butylphenol aldehyde polyether demulsification agent obtained has higher purity.
In the above-mentioned methods, it is preferable that in step 2, continue heating during control reaction vessel in temperature not
More than 150 DEG C, the pressure in reaction vessel is no more than 0.5MPa；It is highly preferred that the pressure in control reaction vessel is 0.3-
0.5MPa。
In the above-mentioned methods, it is preferable that in step 3, when into reaction vessel, addition propylene oxide is reacted, control
Temperature in reaction vessel processed is no more than 150 DEG C, and pressure is no more than 0.5MPa；It is highly preferred that the pressure in control reaction vessel
For 0.3-0.5MPa.
In the above-mentioned methods, it is preferable that in step 1, the catalyst includes potassium hydroxide.
In the above-mentioned methods, it is preferable that the molar ratio of the para-tert-butyl phenolic resin and ethylene oxide is 1:9；It is described
The molar ratio of ethylene oxide and propylene oxide is 1:(1-2)；The dosage of the catalyst accounts for the 1.0%- of all raw material gross masses
1.4%, more preferably 1.2%.
In the above-mentioned methods, it is preferable that in step 1, the preparation method of the para-tert-butyl phenolic resin includes following
Step：
1mol p-tert-butylphenols, 1.1mol formaldehyde and 1.5-1.6mol dimethylbenzene are added in reaction vessel, will be reacted
Container is warming up to 75 DEG C, and the ammonium hydroxide that 47.37g mass concentrations are 37%, isothermal reaction 1h are added into reaction vessel；Then it rises
Temperature to 100 DEG C reaction 1h；It is warming up to 120 DEG C of reaction 1h, and the water in elimination reaction container again；Finally it is warming up to 140 DEG C of reactions
2h, and the water in elimination reaction container, obtain para-tert-butyl phenolic resin.
The present invention also provides a kind of p-tert-butylphenol aldehyde polyether demulsification agent, broken by above-mentioned p-tert-butylphenol aldehyde polyethers
Made from the preparation method of emulsion.
Invention additionally provides one kind preparing modified p-tert-butylphenol aldehyde by above-mentioned p-tert-butylphenol aldehyde polyether demulsification agent
The method of polyether demulsification agent, this approach includes the following steps：
A, p-tert-butylphenol aldehyde polyether demulsification agent and propylene glycol polyether demulsification agent are added in reaction vessel, by reaction vessel
Interior temperature rises to 60-100 DEG C, preferably 80 DEG C；Then acrylic acid is added dropwise into reaction vessel, reacts 0.5- after being added dropwise
2h, preferably 1h,
B, toluene di-isocyanate(TDI) is added dropwise into above-mentioned reaction vessel, 0.2-2h, preferably 1h is reacted after being added dropwise, is obtained
To modified p-tert-butylphenol aldehyde polyether demulsification agent.
Modification to tertiary butyl polyether demulsification agent be by be added toluene di-isocyanate(TDI) (TDI) with it is active on demulsifier
Hydrogen reaction realizes that modification can greatly increase the molecular weight and branch number of p-tert-butylphenol aldehyde polyethers.Relative molecular mass is got over
Height, modified p-tert-butylphenol aldehyde polyether demulsification agent occupy that the surface area on oil-water interfaces is also bigger, and dewatering speed is faster, with this
Meanwhile the highly branched chain group that modified p-tert-butylphenol aldehyde polyether demulsification agent contains has preferable wetability and permeability, it can be with
So that it is rapidly entered oil-water interfaces, further speeds up dewatering speed.
In the above-mentioned methods, it is preferable that the matter of the p-tert-butylphenol aldehyde polyether demulsification agent and propylene glycol polyether demulsification agent
Amount is than being (0.2-0.5):1, more preferably 1:3.
In the above-mentioned methods, it is preferable that the quality of the acrylic acid accounts for p-tert-butylphenol aldehyde polyether demulsification agent and propylene glycol
The 8%-12% of both polyether demulsification agents gross mass, more preferably 10%.
In the above-mentioned methods, it is preferable that the dosage of the toluene di-isocyanate(TDI) is the 2.0%- of acrylic acid dosage
3.0%, more preferably 2.5%.
Propylene glycol demulsifier is prepared according to the preparation method of p-tert-butylphenol aldehyde polyether demulsification agent in the present invention, is prepared
The molar ratio of propylene glycol initiator and ethylene oxide is 1 in the process:9；The molar ratio of ethylene oxide and propylene oxide is 1:(1-
2)；The dosage of catalyst (potassium hydroxide) is account for all raw material gross masses 0.5%.
The present invention still further provides a kind of modified p-tert-butylphenol aldehyde polyether demulsification agent, is utilized to tertiary fourth by above-mentioned
Base phenolic aldehyde polyether demulsification agent is prepared made from the above-mentioned method of method of modified p-tert-butylphenol aldehyde polyether demulsification agent.
The present invention also provides a kind of demulsifier compound systems, wherein：The composition of the demulsifier compound system includes upper
State p-tert-butylphenol aldehyde polyether demulsification agent obtained, modified p-tert-butylphenol aldehyde polyether demulsification agent and acetic acid obtained above.
Compared with existing demulsification system, which can quickly enter oil-water interfaces, and divide in compound system
Son amount is higher can to occupy larger area on oil-water interfaces, to considerably increase phase separation.
In above-mentioned demulsifier compound system, it is preferable that with the stereometer of demulsifier compound system, the p-tert-butylphenol
A concentration of 80-110mg/L of aldehyde polyether demulsification agent, a concentration of 80- of the modified p-tert-butylphenol aldehyde polyether demulsification agent
110mg/L, a concentration of 45-55mg/L of the acetic acid.
The present invention also provides demulsifier compound system can oil field mining liquid demulsification in apply.
Beneficial effects of the present invention：
1) technical solution synthesis technology provided by the invention is simple, easily operated；
2) when demulsifier compound system provided by the invention is applied in Agent of Polymer Drive Produced Fulid, there is excellent take off
Water effect can effectively solve the problem that the technical problem of extraction fluid dewatering difficulty；
3) demulsifier provided by the invention meets system when dosage is in 200mg/L or so, it will be able to reach good
Demulsification；When reaching 60min between when treated, dehydration rate can reach 95% or more.
Specific implementation mode
In order to which technical characteristic, purpose and the advantageous effect to the present invention are more clearly understood, now to the skill of the present invention
Art scheme carry out it is described further below, but should not be understood as to the present invention can practical range restriction.
Embodiment 1
Present embodiments provide a kind of preparation method of p-tert-butylphenol aldehyde polyether demulsification agent comprising following steps：
1) para-tert-butyl phenolic resin is prepared
1mol p-tert-butylphenols, 1.1mol formaldehyde and 1.5-1.6mol dimethylbenzene are added in round-bottomed flask, starts and stirs
Mix device to stir evenly, and be warming up to 75 DEG C, be slowly added dropwise 47.37g mass concentration be 37% ammonium hydroxide, isothermal reaction 1h, so
After be warming up to 100 DEG C reaction 1h, be continuously heating to 120 DEG C reaction 1h (dehydration), be warming up to 140 DEG C react 2h (dehydration), obtain
Para-tert-butyl phenolic resin；
2) p-tert-butylphenol aldehyde polyether demulsification agent is prepared
Using para-tert-butyl phenolic resin as initiator, totally dry reaction kettle is added in itself and catalyst (potassium hydroxide)
In, closed good reaction kettle is first replaced with nitrogen before heating, is then vacuumized, repeatedly twice, started blender and heat up；
When temperature rises to 120 DEG C, inlet valve is opened, ethylene oxide is added and continues to increase temperature, it is ensured that temperature is no more than
135 DEG C control with pressure in 0.4MP or less；
It is fallen after rise after pressure, after temperature decline, material reaction finishes, and the pressure in reaction kettle is made to be down to negative pressure after 30min, will
Temperature of reaction kettle rises to 135 DEG C, and propylene oxide is added, and controls temperature and be no more than 0.4MP with pressure no more than 145 DEG C；
It is fallen after rise after pressure, after temperature decline, material reaction finishes, and pressure is made to be down to negative pressure after 30min, and finally cooling down
Material, obtains p-tert-butylphenol aldehyde polyether demulsification agent；Wherein,
The molar ratio of para-tert-butyl phenolic resin and ethylene oxide is 1:9, the molar ratio of ethylene oxide and propylene oxide is
1:(1-2), the dosage of catalyst potassium hydroxide are the 1.2% of total quality of material.
The p-tert-butylphenol aldehyde polyethers of 1 different model of table is demulsified
| Model | Block number | EO：PO (molar ratio) |
| H13 | 2 | 1:1 |
| H23 | 2 | 1:1.1 |
| H33 | 2 | 1:1.4 |
| H43 | 2 | 1:1.8 |
| H53 | 2 | 1:2 |
According to the method described above, according to the difference for connecing ethylene oxide (EO) and propylene oxide (PO) dosage, it is prepared for series (H
Series) p-tert-butylphenol aldehyde polyether demulsification agent, as shown in table 1.
Embodiment 2
Present embodiments provide a kind of preparation method of modified p-tert-butylphenol aldehyde polyether demulsification agent comprising following step
Suddenly：
1) it is 1 in mass ratio by the p-tert-butylphenol aldehyde polyether demulsification agent provided by embodiment 1 and propylene glycol demulsifier:3
Ratio compounding after, be slowly added dropwise acrylic acid at 80 DEG C, dosage is that p-tert-butylphenol aldehyde polyether demulsification agent and propylene glycol are broken
The 10% of emulsion gross mass reacts 1h after being added dropwise；
2) crosslinking agent is done using toluene di-isocyanate(TDI) (TDI), dosage is the 2.5% of acrylic acid dosage, and knot is slowly added dropwise
Shu Houzai reacts 1h, obtains modified p-tert-butylphenol aldehyde polyether demulsification agent；Wherein,
Propylene glycol demulsifier to the preparation method of butyl phenolic aldehyde polyether demulsification agent, is prepared during the preparation method is the same as that of Example 1
When, the molar ratio of propylene glycol initiator and ethylene oxide is 1:9, the molar ratio of ethylene oxide and propylene oxide is 1:(1-2), is urged
The dosage of agent potassium hydroxide is the 0.5% of total quality of material.
The modification p-tert-butylphenol aldehyde polyether demulsification agent of 2 different model of table
| P-tert-butylphenol aldehyde polyether demulsification agent | Modified p-tert-butylphenol aldehyde polyether demulsification agent |
| H13 | P13 |
| H23 | P23 |
| H33 | P33 |
| H43 | P43 |
| H53 | P53 |
According to the method described above, the H series p-tert-butylphenol aldehyde polyether demulsification agents provided by embodiment 1 are prepared corresponding
Series modified p-tert-butylphenol aldehyde polyether demulsification agent (P series), as shown in table 2.
Embodiment 3
The present embodiment provides a kind of demulsifier compound systems.
The group of the demulsifier compound system becomes to tertiary butyl polyether demulsification agent (being provided by embodiment 1), is modified to tertiary fourth
Base polyether demulsification agent (being provided by embodiment 2) and acetic acid, detailed constituent content are as shown in table 3.
The composition and demulsification of 3 different model demulsifier compound system of table
The modification that H series that embodiment 1 provides provides tertiary butyl polyether demulsification agent, embodiment 2 is to tertiary butyl polyethers
According to above-mentioned compound proportion serial demulsifier compound system is prepared, and be applied to Liaohe Oil Field in demulsifier, acetic acid
In the processing of Produced Liquid, a concentration of 200mg/L of the demulsifier compound system in Produced Liquid, treatment temperature is 50 DEG C, separation effect
Fruit is as shown in table 3, and the demulsifier compound system " 100H13+100P53+50 glacial acetic acid " of serial number 1 indicates " 100mg/ in table 3
L H13+100mg/L P53+50mg/L glacial acetic acid ", other and so on.
From table 3 it can be seen that when the dosage of demulsifier compound system is in 200mg/L, it will be able to obtain broken well
Newborn effect；When processing time is 60min, dehydration rate reaches 95% or more.
Claims (19)
1. a kind of method preparing modified p-tert-butylphenol aldehyde polyether demulsification agent by p-tert-butylphenol aldehyde polyether demulsification agent, this method
Include the following steps：
A, p-tert-butylphenol aldehyde polyether demulsification agent and propylene glycol polyether demulsification agent are added in reaction vessel, it will be in reaction vessel
Temperature rises to 60-100 DEG C；Then acrylic acid is added dropwise into reaction vessel, reacts 0.5-2h after being added dropwise；
B, toluene di-isocyanate(TDI) is added dropwise into above-mentioned reaction vessel, reacts 0.2-2h after being added dropwise, obtain modified to tertiary fourth
Base phenolic aldehyde polyether demulsification agent；Wherein,
The preparation of the p-tert-butylphenol aldehyde polyether demulsification agent includes the following steps：
Step 1: para-tert-butyl phenolic resin and catalyst are added in the reaction vessel, then heat up；
Step 2: when temperature rises to 100-150 DEG C, ethylene oxide is added into reaction vessel, continues to heat up；
Step 3: when the pressure and temperature in reaction vessel starts to fall after rise, the pressure in reaction vessel is down to negative value, it will be anti-
The temperature in container is answered to rise to 100-150 DEG C, propylene oxide is then added into reaction vessel is reacted；
Step 4: after the temperature and pressure in reaction vessel is fallen after rise, p-tert-butylphenol aldehyde polyether demulsification agent is obtained.
2. according to the method described in claim 1, wherein：In step a, the temperature in reaction vessel is risen to 80 DEG C.
3. according to the method described in claim 1, wherein：In step a, 1h is reacted after being added dropwise.
4. according to the method described in claim 1, wherein：In stepb, 1h is reacted after being added dropwise.
5. according to the method described in claim 1, wherein：
The mass ratio of the p-tert-butylphenol aldehyde polyether demulsification agent and propylene glycol polyether demulsification agent is (0.2-0.5):1.
6. method according to claim 1 or 5, wherein：The p-tert-butylphenol aldehyde polyether demulsification agent and propylene glycol polyethers
The mass ratio of demulsifier is 1:3.
7. according to the method described in claim 1, wherein：The dosage of the acrylic acid be p-tert-butylphenol aldehyde polyether demulsification agent and
The 8%-12% of propylene glycol polyether demulsification agent gross mass.
8. method according to claim 1 or claim 7, wherein：The dosage of the acrylic acid is demulsified for p-tert-butylphenol aldehyde polyethers
The 10% of agent and propylene glycol polyether demulsification agent gross mass.
9. according to the method described in claim 1, wherein：The dosage of the toluene di-isocyanate(TDI) is acrylic acid dosage
2.0%-3.0%.
10. the method according to claim 1 or 9, wherein：The dosage of the toluene di-isocyanate(TDI) is acrylic acid dosage
2.5%.
11. according to the method described in claim 1, wherein：In step 2, the temperature controlled in reaction vessel is no more than 150
DEG C, the pressure in reaction vessel is no more than 0.5MPa.
12. the method according to claim 1 or 11, wherein：In step 2, it is 0.3- to control the pressure in reaction vessel
0.5MPa。
13. according to the method described in claim 1, wherein：In step 1, the catalyst includes potassium hydroxide.
14. according to the method described in claim 1, wherein：When preparing p-tert-butylphenol aldehyde polyether demulsification agent,
The molar ratio of the para-tert-butyl phenolic resin and ethylene oxide is 1:9；
The molar ratio of the ethylene oxide and propylene oxide is 1:(1-2)；
The quality of the catalyst accounts for the 1.0%-1.4% of all raw material gross masses.
15. the method according to claim 1 or 14, wherein：When preparing p-tert-butylphenol aldehyde polyether demulsification agent, the catalysis
The quality of agent accounts for the 1.2% of all raw material gross masses.
16. according to the method described in claim 1, wherein：In step 1, the preparation method of the para-tert-butyl phenolic resin
Include the following steps：
1mol p-tert-butylphenols, 1.1mol formaldehyde and 1.5-1.6mol dimethylbenzene are added in reaction vessel, by reaction vessel
75 DEG C are warming up to, and the ammonium hydroxide that 47.37g mass concentrations are 37%, isothermal reaction 1h are added into reaction vessel；It then heats to
100 DEG C of reaction 1h；It is warming up to 120 DEG C of reaction 1h, and the water in elimination reaction container again；140 DEG C of reaction 2h are finally warming up to, and
Water in elimination reaction container, obtains para-tert-butyl phenolic resin.
17. a kind of modified p-tert-butylphenol aldehyde polyether demulsification agent is made by claim 1-16 any one of them methods
's.
18. a kind of demulsifier compound system, composition includes p-tert-butylphenol aldehyde polyether demulsification agent, changing described in claim 17
Property p-tert-butylphenol aldehyde polyether demulsification agent and acetic acid；Wherein, described to tertiary butyl with the stereometer of demulsifier compound system
A concentration of 80-110mg/L of phenolic aldehyde polyether demulsification agent, a concentration of 80- of the modified p-tert-butylphenol aldehyde polyether demulsification agent
110mg/L, a concentration of 45-55mg/L of the acetic acid；Wherein,
The preparation of the p-tert-butylphenol aldehyde polyether demulsification agent includes the following steps：
Step 1: para-tert-butyl phenolic resin and catalyst are added in the reaction vessel, then heat up；
Step 2: when temperature rises to 100-150 DEG C, ethylene oxide is added into reaction vessel, continues to heat up；
Step 3: when the pressure and temperature in reaction vessel starts to fall after rise, the pressure in reaction vessel is down to negative value, it will be anti-
The temperature in container is answered to rise to 100-150 DEG C, propylene oxide is then added into reaction vessel is reacted；
Step 4: after the temperature and pressure in reaction vessel is fallen after rise, p-tert-butylphenol aldehyde polyether demulsification agent is obtained.
19. application of the demulsifier compound system in oil field mining liquid demulsification described in claim 18.
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| CN105885029B (en) * | 2016-05-07 | 2018-04-17 | 中国海洋石油总公司 | A kind of polyether demulsification agent and its synthetic method based on alkamine modified phenolic resin |
| CN106243358A (en) * | 2016-07-29 | 2016-12-21 | 北京迪威尔石油天然气技术开发有限公司 | A kind of preparation method of compound MethylethoxylsiliconFluid Fluid demulsifier |
| CN109135806A (en) * | 2018-08-17 | 2019-01-04 | 滨州市丰泰技术开发有限公司 | A kind of manufacturing method of marine oil field high-efficient demulsifier |
| CN109609178B (en) * | 2018-12-19 | 2021-07-16 | 克拉玛依新科澳石油天然气技术股份有限公司 | Demulsifier for treating thick oil and preparation method thereof |
| CN110975338B (en) * | 2019-11-22 | 2022-03-11 | 山东清博生态材料综合利用有限公司 | Composite demulsifier suitable for hazardous waste industry |
| CN111154055A (en) * | 2020-01-20 | 2020-05-15 | 金浦新材料股份有限公司 | Synthetic method of special initiator for polyether crude oil demulsifier |
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