CN101717483A - Preparation method of high-efficiency oil soluble macromolecule emulsion breaker - Google Patents
Preparation method of high-efficiency oil soluble macromolecule emulsion breaker Download PDFInfo
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- CN101717483A CN101717483A CN200910230381A CN200910230381A CN101717483A CN 101717483 A CN101717483 A CN 101717483A CN 200910230381 A CN200910230381 A CN 200910230381A CN 200910230381 A CN200910230381 A CN 200910230381A CN 101717483 A CN101717483 A CN 101717483A
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Abstract
The invention provides a preparation method of a high-efficiency oil soluble macromolecule emulsion breaker, mainly comprising the following steps of: preparing benzene vinylphenol from styrene and phenol reaction; carrying out condensation on the benzene vinylphenol and formaldehyde to obtain thermoplastic and thermosetting resins with a certain molecular weight range; then carrying out ring-opening polymerization on the resins, ethylene oxide and propylene oxide according to a certain sequence; and amplifying the chain of the product after polymerization by using quantitative TDI. The prepared emulsion breaker overcomes the disadvantages of large use level, long action time, poor effect and the like of the traditional soluble emulsion breaker and has the advantages of favorable interfacial activity, flocculation, coalescence and wetting penetration ability, little use level, strong suitability, favorable demulsification efficiency and the like.
Description
Affiliated technical field
The invention provides the preparation method of a class high-efficiency oil soluble macromolecule emulsion breaker, belong to oil field mining liquid chemical processing agent field.
Background technology
In recent years, along with the increase of oilfield exploitation amount and the application of various oil recovery techniques, extraction liquid comprehensive water cut is more and more higher, and the aqueous condition of extraction becomes increasingly complex, and intractability continues to increase, and old liberated area, oil field piece extraction liquid comprehensive water cut has reached more than 95%; The extraction liquid that the on-the-spot at present water-soluble demulsifier that uses has been difficult to adapt under the application of oil recovery new technology is handled.From the mechanism of action, water-soluble demulsifier has increased the process of reallocation than oil soluble medicament after injection, makes hysteresis action time, the process result degrades of chemical agent; And the water-soluble demulsifier part can remain in aqueous phase, causes the loss of useful effect chemical dose; This will inevitably cause the increase of chemical agent consumption, and extraction liquid processing cost increases.The variation of extraction liquid needs the appearance of the oil-soluble demulsifier that action time is fast, continuous capability is strong, result of use is good.But the oil-soluble demulsifier of lower molecular weight existed equally that consumption is big, weak effect, was subject to the shortcoming of ionogen influence in the past.And high molecular weight demulsifier has multiple-branching construction, not only is easy to substitute the emulsifying agent on the interface, can also adsorb a plurality of globules simultaneously, makes the easier collision of the globule, coalescent, and makes extraction liquid breakdown of emulsion, oily water separation.Along with the carrying out of oil-field development, the complexity day by day of the aqueous condition of extraction will require the appearance of more effectively extraction liquid comprehensive treating process with chemical.
Summary of the invention
For solve present scene handle with extraction liquid big with the emulsion splitter consumption, effect is slow, a little less than the universality, shortcoming such as weak effect, the present invention proposes the preparation method of high-efficiency oil soluble macromolecule emulsion breaker.
The present invention makes styryl phenol by vinylbenzene, phenol reactant, styryl phenol and formaldehyde condensation obtain thermoplastic, the thermosetting resin of certain molecular weight scope, then resin is carried out ring-opening polymerization with ratio and oxyethane, propylene oxide in certain sequence, product after the polymerization is carried out the chain extension growth with quantitative TDI make product.
Of the present inventionly to the effect that realize by following technical scheme:
(1) phenol is added in the conversion unit, add 0.5%～3.0% the vitriol oil, drip styrene in the time of 80～120 ℃, control dropping temperature and speed.Make vinylbenzene phenol.
(2) vinylbenzene phenol is dropped in the reactor, add 1.0%～5.0% potassium hydroxide, between 20～60 ℃, drip formaldehyde, dropwise back intensification vacuum hydro-extraction, reach 130～160 ℃ until temperature, not till moisture is arranged.
(3) with (2) products obtained therefrom vacuum 15 minutes, reach minimumly to reactor pressure, add 1.0 ‰～6.0 ‰ potassium hydroxide (can be 50% aqueous solution), stir, steadily be warming up to 110～140 ℃, vacuum hydro-extraction is warming up to 140 ℃ after moisture purifies; Inflated with nitrogen drips oxyethane, propylene oxide with ratio in order to normal pressure, keeps temperature of reaction between 120～160 ℃, dripped the back insulation reaction 1～1.5 hour, vacuum 15 minutes is cooled to 70～98 ℃, add acetate 1.0 ‰～7.5 ‰, stirred 20 minutes, standby.
(4) quantitative (3) synthetic block polymer is added in the reactor, stir and heat up, keep 40～80 ℃ of temperature of reaction, drip chainextender, add-on is 0～6% of a total mass, the control rate of addition, and the mobility variations of attention material, dropwised the back insulation reaction 30 minutes, when increasing rapidly as if the discovery material viscosity, the adding part of can meeting an urgent need low mass molecule alcohol makes the stopping of reaction.
(5) after reaction is finished, be cooled to 80 ℃, take out and add organic solvent, stir, blowing, product is synthetic to finish.
Chemical reaction of the present invention is:
Remarks: n=1～3, respectively adjacent,, contraposition carries out addition.
Remarks: m=0～50, A is the product in (1) formula.
Remarks: n1+n2=a, m1+m2=b, n1=0～160, n2=0～260, m1=0～500, m2=0～120, B is the product in (2) formula.
Remarks: X=0～20, the product in (3) formula.
Add oxyethane earlier, after add propylene oxide order, the ratio of the amount of adding is oxyethane=n1+n2, propylene oxide=m1+m2.
The potassium hydroxide of described adding is that concentration is 50% the aqueous solution.
The main physico-chemical parameter of emulsion splitter according to preparation method's gained of high-efficiency oil soluble macromolecule emulsion breaker disclosed in this invention is:
Outward appearance: faint yellow to the brown uniform liquid, there is not mechanical impurity
Hydroxyl value: 160～25mgKOH
Effective content: 〉=93%
PH value: 6～8
Moisture :≤0.5%
The main physico-chemical parameter of 50% organic solution:
Density (20 ℃): 〉=0.95g/cm3
Absolute dehydration rate: 〉=93%
Kinematic viscosity (25 ℃) :≤500mpas
Flash-point: 〉=18 ℃
Condensation point :≤-15 ℃
It is big that the emulsion splitter that the present invention makes has overcome traditional water-soluble emulsion splitter consumption, action time shortcoming such as slow, weak effect, have good interface activity, coalescent, the wetting penetrating power of flocculation, advantage such as consumption is little, adaptability is strong, demulsification is good, dropped into suitability for industrialized production at present, and be applied in on-the-spot the use.
Description of drawings
Accompanying drawing is a process flow sheet of the present invention
Embodiment
Below in conjunction with accompanying drawing the present invention is described in detail
Embodiment 1:
(1), phenol 200kg is added in the conversion unit, the vitriol oil that adds 5kg is made catalyzer, drips 300kg vinylbenzene, control dropping temperature and speed in the time of 80～120 ℃.Add potassium hydroxide 2.5kg after reaction is finished and neutralize, transfer pH value to 6～7, make vinylbenzene phenol.
(2), vinylbenzene phenol 200kg is dropped in the reactor, add dimethylbenzene 200kg, make catalyzer, Dropwise 5 5kg formaldehyde between 20～50 ℃ at the 1.5kg potassium hydroxide that adds as solvent.
(3), with (2) products obtained therefrom vacuum 15 minutes, reach minimum to vacuum, the 15kg potassium hydroxide that adds is made catalyzer, steadily be warming up to 140 ℃, drip propylene oxide 6040kg, keep temperature of reaction between 135～155 ℃, drip off back insulation reaction 1～1.5 hour, vacuum 15 minutes, blowing is standby.
(4), (3) gained emulsion splitter intermediate 500kg is dropped in the reactor, add potassium hydroxide 50% solution compositing catalyst of 2kg, stir, steadily be warming up to 110～120 ℃, vacuum hydro-extraction is warming up to 140 ℃ after moisture purifies; Inflated with nitrogen drips oxyethane 260kg to normal pressure, keeps temperature of reaction between 135～155 ℃, drips the back insulation reaction 1～1.5 hour, and vacuum 15 minutes is cooled to 95 ℃, adds 3kg acetate, transfers pH value to 6～7, stirs 20 minutes, and is standby.
(5), 1000kg (4) synthetic block polymer is added in the reactor, stir and heat up, keep 60～80 ℃ of temperature of reaction, drip 15kg chainextender TDI, the control rate of addition, and note the mobility variations of material dropwising the back insulation reaction 30 minutes.
(6), after reaction finishes, be cooled to 80 ℃, take out and add dimethylbenzene 1000kg, be made into 50% finished product, blowing, sampling is estimated.
Embodiment 2:
(1), phenol 200kg is added in the conversion unit, the vitriol oil that adds 8kg is made catalyzer, Dropwise 5 00kg vinylbenzene in the time of 80～120 ℃, control dropping temperature and speed.Add potassium hydroxide 3.5kg after reaction is finished and neutralize, transfer pH value to 6～7, make vinylbenzene phenol.
(2), vinylbenzene phenol 200kg is dropped in the reactor, add dimethylbenzene 200kg, make catalyzer, Dropwise 35 kg formaldehyde between 20～50 ℃ at the 1.5kg potassium hydroxide that adds as solvent.
(3), with (2) products obtained therefrom vacuum 15 minutes, reach minimum to vacuum, the 20kg potassium hydroxide that adds is made catalyzer, steadily be warming up to 140 ℃, drip propylene oxide 8190kg, keep temperature of reaction between 135～155 ℃, drip off back insulation reaction 1～1.5 hour, vacuum 15 minutes, blowing is standby.
(4), (3) gained emulsion splitter intermediate 500kg is dropped in the reactor, add potassium hydroxide 50% solution compositing catalyst of 5kg, stir, steadily be warming up to 110～120 ℃, vacuum hydro-extraction is warming up to 140 ℃ after moisture purifies; Inflated with nitrogen drips oxyethane 510kg to normal pressure, keeps temperature of reaction between 135～155 ℃, drips the back insulation reaction 1～1.5 hour, vacuum 15 minutes; Dripping propylene oxide 260kg, keeping temperature of reaction between 135～155 ℃, dripping the back insulation reaction 1～1.5 hour, vacuum 15 minutes is cooled to 95 ℃, adds 27kg acetate, transfers pH value to 6～7, stirs 20 minutes, and is standby.
(5), after reaction finishes, be cooled to 80 ℃, take out and add dimethylbenzene 1270kg, be made into 50% finished product, blowing, sampling is estimated.
Embodiment 3:
(1), phenol 200kg is added in the conversion unit, the vitriol oil that adds 8kg is made catalyzer, drips 600kg vinylbenzene, control dropping temperature and speed in the time of 80～120 ℃.Add potassium hydroxide after reaction is finished and neutralize, transfer pH value to 6～7, make vinylbenzene phenol.
(2), vinylbenzene phenol 200kg is dropped in the reactor, vacuum 15 minutes reaches minimumly to vacuum, add dimethylbenzene 200kg as solvent, stirs, and steadily is warming up to 140 ℃; Inflated with nitrogen drips oxyethane 410kg to normal pressure, keeps temperature of reaction between 135～155 ℃, drips the back insulation reaction 1～1.5 hour, vacuum 15 minutes; Blowing is standby.
(3), (2) gained emulsion splitter intermediate 200kg is dropped in the reactor, add potassium hydroxide 50% solution compositing catalyst of 15kg, stir, steadily be warming up to 140 ℃; Drip propylene oxide 3100kg, keeping temperature of reaction between 135～155 ℃, dripping the back insulation reaction 1～1.5 hour, vacuum 15 minutes; Dripping oxyethane 1500kg, keeping temperature of reaction between 135～155 ℃, dripping the back insulation reaction 1～1.5 hour, vacuum 15 minutes is cooled to 95 ℃, adds 17kg acetate, transfers pH value to 6～7, stirs 20 minutes, and is standby.
(4), after reaction finishes, be cooled to 80 ℃, take out and add dimethylbenzene 4800kg, be made into 50% finished product, blowing, sampling is estimated.
The vinylbenzene phenol emulsion splitter that aforesaid method makes, reached the quality index of expection, get different oil fields block crude oil (east, Shengli Oil Field Gu Dong oil recovery factory tetrad, Lean, existing oil recovery factory, river connection, stake west, the western oil recovery factory of stake joint station, Bin Nan oil recovery factory viscous crude initial station, oil recovery factory, Jianghan Oil-field Qinghe joint station, Liaohe Oil Field hollow one, No. one, northwest branch office of China Petrochemical Industry connection, No. two connection) carry out the breakdown of emulsion screening experiment and learn, this series products consumption is little, applied widely, demulsification is good, has reached the use standard of expection.
Claims (4)
1. the preparation method of high-efficiency oil soluble macromolecule emulsion breaker, mainly be by vinylbenzene, phenol reactant makes styryl phenol, styryl phenol and formaldehyde condensation obtain the thermoplastic of certain molecular weight scope, thermosetting resin, then with resin in certain sequence with ratio and oxyethane, propylene oxide carries out ring-opening polymerization, product after the polymerization is carried out the chain extension growth with quantitative TDI to be made, preparation process is: phenol adds in the conversion unit, the vitriol oil that adds 0.5%～3.0% (is the mass percent of benchmark in phenol), drip styrene in the time of 80～120 ℃, control dropping temperature and speed.Make vinylbenzene phenol, it is characterized in that (1) is with in the vinylbenzene phenol input reactor, the potassium hydroxide that adds 1.0%～5.0% (is the mass percent of benchmark in vinylbenzene phenol), when being 20～60 ℃, temperature drips formaldehyde 30～70kg, speed according to 30kg/h drips, dropwise back intensification vacuum hydro-extraction, reach 130～160 ℃ until temperature, not till moisture is arranged; (2) with (1) products obtained therefrom vacuum 15 minutes, reach-0.095Mpa to reactor pressure, the potassium hydroxide that adds 1.0 ‰～6.0 ‰ (are the mass percent of benchmark in (1) products obtained therefrom), stir, steadily be warming up to 110～140 ℃, vacuum hydro-extraction after purifying to moisture, is warming up to 140 ℃; Inflated with nitrogen is to normal pressure, drip oxyethane, propylene oxide with ratio sequentially, keep temperature of reaction between 120～160 ℃, originally the speed according to 300kg/h drips, after confirming reaction, speed according to 500～1000kg/h drips, and drips off back insulation reaction 1～1.5 hour, vacuum 15 minutes, be cooled to 70～98 ℃, the acetate that adds 1.0 ‰～7.5 ‰ (are the mass percent of benchmark in (1) products obtained therefrom) stirred 20 minutes, and is standby; (3) quantitative (2) synthetic block polymer is added in the reactor, stirring is warming up to 40～80 ℃, drip 0.1～6% (is the mass percent of benchmark in quantitative block polymer) chainextender TDI, speed according to 20kg/h drips, the back insulation reaction that finishes 30 minutes, strict control rate of addition, if drip too fastly, can cause partial cross-linking to spend greatly, material viscosity is increased sharply, even solidify, easy to hang on still wall or stirring rake, be difficult to remove, easily there is particle in product inside simultaneously, molecular weight product is inhomogeneous, and performance difference is big; If this thing happens, can meet an urgent need adds low mass molecule alcohol (optional ethanol, propyl alcohol, the butanols) stopping of reaction; (4) after reaction is finished, be cooled to 80 ℃, take out and add organic solvent (low mass molecule alcohol of the alkane of optional C6～C14 or aromatic hydrocarbons, C1～C8 etc.), stir, blowing, product is synthetic to finish.
2. the preparation method of high-efficiency oil soluble macromolecule emulsion breaker according to claim 1 is characterized in that chemical reaction of the present invention is:
N=1-3, respectively adjacent,, contraposition carries out addition;
M=0-50, A are the product in (1) formula;
N1+n2=a, m1+m2=b, n1=0-160, n2=0-260, m1=0-500, m2=0-120, B are the product in (2) formula,
X=0-20, C are the product in (3) formula.
3. the preparation method of high-efficiency oil soluble macromolecule emulsion breaker according to claim 1 and 2 is characterized in that in the step (2) by adding oxyethane earlier, after add the propylene oxide order, the ratio of the amount of adding is oxyethane=n1+n2, propylene oxide=m1+m2.
4. the preparation method of high-efficiency oil soluble macromolecule emulsion breaker according to claim 1 is characterized in that the potassium hydroxide that adds in the step (2) is that concentration is 50% the aqueous solution.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102977331A (en) * | 2012-11-15 | 2013-03-20 | 山东德仕化工集团有限公司 | Preparation method for efficient oil-soluble macromolecular demulsifier |
| CN106753523A (en) * | 2016-11-18 | 2017-05-31 | 东营明德石油科技有限公司 | A kind of synthetic method of broad-spectrum high efficacy crude oil demulsifier |
| CN109593189A (en) * | 2018-11-27 | 2019-04-09 | 句容宁武高新技术发展有限公司 | A kind of super high molecular weight is rich in more ring structures demulsifier and preparation method thereof |
| CN111171860A (en) * | 2020-01-21 | 2020-05-19 | 中海油天津化工研究设计院有限公司 | Demulsifier for aged crude oil water-in-oil emulsion and preparation method thereof |
| CN111718745A (en) * | 2020-06-30 | 2020-09-29 | 荆州市隆华石油化工有限公司 | Macromolecule crude oil demulsifier |
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2009
- 2009-11-16 CN CN200910230381A patent/CN101717483A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102977331A (en) * | 2012-11-15 | 2013-03-20 | 山东德仕化工集团有限公司 | Preparation method for efficient oil-soluble macromolecular demulsifier |
| CN106753523A (en) * | 2016-11-18 | 2017-05-31 | 东营明德石油科技有限公司 | A kind of synthetic method of broad-spectrum high efficacy crude oil demulsifier |
| CN109593189A (en) * | 2018-11-27 | 2019-04-09 | 句容宁武高新技术发展有限公司 | A kind of super high molecular weight is rich in more ring structures demulsifier and preparation method thereof |
| CN111171860A (en) * | 2020-01-21 | 2020-05-19 | 中海油天津化工研究设计院有限公司 | Demulsifier for aged crude oil water-in-oil emulsion and preparation method thereof |
| CN111171860B (en) * | 2020-01-21 | 2021-08-20 | 中海油天津化工研究设计院有限公司 | Demulsifier for aged crude oil water-in-oil emulsion and preparation method thereof |
| CN111718745A (en) * | 2020-06-30 | 2020-09-29 | 荆州市隆华石油化工有限公司 | Macromolecule crude oil demulsifier |
| CN111718745B (en) * | 2020-06-30 | 2022-05-13 | 荆州市隆华石油化工有限公司 | Macromolecule crude oil demulsifier |
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Application publication date: 20100602 |