CN103113571B - Preparation method of demulsifier polyether intermediate compound - Google Patents
Preparation method of demulsifier polyether intermediate compound Download PDFInfo
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- CN103113571B CN103113571B CN201310063114.6A CN201310063114A CN103113571B CN 103113571 B CN103113571 B CN 103113571B CN 201310063114 A CN201310063114 A CN 201310063114A CN 103113571 B CN103113571 B CN 103113571B
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Abstract
The invention relates to a preparation method of a demulsifier polyether intermediate compound, which comprises the following steps: adding a catalyst into a thermoplastic resin, stirring while heating, heating to 90 DEG C, starting a vacuum pump, and performing vacuum treatment for 30 minutes; controlling the temperature at 115-135 DEG C, respectively adding epoxypropane and epoxyethane continuously, and reacting for 30 minutes under the conditions that the temperature is 115-135 DEG C and the pressure is 0.1-0.3 Mpa after the addition is finished; and cooling to 90 DEG C, starting the vacuum pump, and performing vacuum treatment for 30 minutes to obtain the polyether intermediate compound. The intermediate compound prepared by the method can improve multiple indices such as dehydration rate and dehydration speed of the synthesized demulsifier, oil content and oil-water interface of extracted sewage and the like, and has favorable market prospects.
Description
Technical field
The present invention relates to oily emulsion splitter technical field, be specifically related to a kind of preparation method of demulsifier polyether intermediate compound.
Background technology
In recent years, along with continually developing of oil field, oil field is progressively aging, and in the crude oil of extraction, water content is more and more higher, and the crude oil even had changes towards heaviness.In order to improve tar productivity, Ge You district all adopts different intensified oil reduction technology according to stratum characteristic, as alkali drive, acid fracturing operation, foam flooding, polymer flooding, steam flood, surfactant flooding, surfactant and polymer binary are driven and alkali, surfactant and polymer ternary composite driving etc., the application of these technology, for oilfield stable production, volume increase provide effective measures, achieve huge economic benefit.But due to the enforcement of these measures, a large amount of chemical substance (as: alkali, tensio-active agent, polymkeric substance etc.) is injected oil reservoir, not only make the salinity of stratum water quality significantly raise, and the oil property in Shi Zhu heavy wool district there occurs larger change.The emulsification degree of extraction crude oil is strengthened further, high alkalinity crude oil, crude oil with high acid value, viscous crude, special thick oil, high condensation point crude oil, tertiary oil recovery crude oil, high-salinity water quality crude oil etc. are there is, the crude oil of extraction and water is even made to form oil-in-water-type (O/W) and multiple (O/W/O, W/O/W) milk sap, cause the difference of crude state, and to there is breaking emulsion and dewatering temperature at present high in oil field, dosage is large, deviates from the problems such as sewage is undesirable, causes the huge waste of the energy.And conventional emulsion splitter is difficult to process such Produced Liquid, processing cost is remained high.
To the modification of non-ionic polyoxyethylene polyoxypropylene block copolymers class emulsion splitter, usually can adopt and change head, change tail, add bone, chain extension, connect skill, the method such as crosslinked, composite.Lot of documents is reported, the demulsification of emulsion splitter is determined by the character of initial compounds on the one hand, and the opposing party is by being that proportioning by segmented copolymer determines.Experimental studies have found that, the content of oxyethylene group EO, oxypropylene group PO and the breaking emulsion and dewatering efficiency of block order equal energy remarkably influenced milk sap in emulsion splitter molecule; In emulsion splitter molecule, EO block has wetting ability, increases with EO content, and the HLB value of emulsion splitter improves, and dehydrate and desalt of crude oil rate has an optimum value; The EO content of fixing emulsion splitter, increases PO content, and namely increase emulsion splitter relative molecular mass, dewatering and desalting rate also has an optimum value.This may be relevant with the form that emulsion splitter molecule adsorbs at water-oil interface.This shows, for a certain specific crude oil, a series of emulsion splitter, should have a best EO and PO content than the relative molecular mass scope with the best.
As can be seen here, the basis that initiator is determined is carried out epoxy ethane-epoxy propane segment the exploration of block polymerization condition, and then optimum synthesis condition, obtain the polyethers of more complex construction, filtering out best EO/PO ratio, is an important directions of emulsion splitter research.
Summary of the invention
For the deficiencies in the prior art, the present invention proposes a kind of preparation method of demulsifier polyether intermediate compound, intermediate prepared by the method can improve dehydration rate, the dewatering speed of synthesized emulsion splitter and deviate from the many indexs such as sewage with oil degree and water-oil interface, has good market outlook.
The preparation method of a kind of demulsifier polyether intermediate compound of the present invention is as follows:
Catalyzer is added in thermoplastic resin, heat while stirring, be heated to 90 DEG C, open vacuum pump vacuum-treat 30 minutes, temperature control is at 115-135 DEG C, adding propylene oxide, oxyethane continuously respectively, after charging, is 115-135 DEG C in temperature, pressure is react 30 minutes under the condition of 0.1-0.3Mpa, cool to 90 DEG C, open vacuum pump vacuum-treat 30 minutes, obtain polyether intermediate.
Wherein each component add-on is 1 ︰ 50-400 ︰ 25-200 by the ratio of weight and number of Re Su Shu Zhi ︰ Huan Yang Bing Wan ︰ oxyethane, and catalyst charge is the 0.1-0.5% adding propylene oxide and oxyethane total amount.
Wherein said catalyzer is sodium hydroxide, one or more in potassium hydroxide, boron trifluoride, ether.
The preparation method of thermoplastic resin described is in addition: the ratio mixing by organic phenol and organic amine being 1 ︰ 2-4 in mass ratio, heated for controlling temperature is at 30-40 DEG C, stir 30 minutes, You Ji Fen ︰ formaldehyde is the ratio dropping formaldehyde of 1 ︰ 2-6 in mass ratio, be warmed up to 150-170 DEG C after dropwising, temperature control reacts the product after 3 hours.
Wherein said organic phenol is C
4-9organic phenol.
Wherein said organic amine is one or more in diethylenetriamine, triethylene tetramine, tetraethylene pentamine, five ethene hexamines.
Advantageous Effects of the present invention for: the demulsification due to emulsion splitter is determined by the proportioning of segmented copolymer to a certain extent, therefore the present invention is on the basis of special initiator, selected propylene oxide and oxyethane are segmented copolymer, and the ratio and reaction conditions etc. of segmented copolymer are adjusted and optimized, the demulsifier polyether intermediate compound of synthesis can improve the dehydration rate of synthesized emulsion splitter greatly, dewatering speed and deviate from the many indexs such as sewage with oil degree and water-oil interface, reduce crude oil demulsification dehydration cost, reduce environmental pollution, there is good economic benefit and social benefit.
Embodiment
In order to make technical scheme of the present invention clearly understand, below in conjunction with specific embodiment, the present invention is further illustrated.
The preparation of polyether intermediate
1. main raw material
EO, industrial first grade; PO, industrial first grade; KOH, industrial first grade; Chain link agent, industrial first grade; Conditioning agent, self-control; Solvent, industrial salable product; Organic phenol, industrial first grade; Organic amine, industrial first grade; Formaldehyde, industrial first grade.
2. lab scale key instrument equipment
G type high pressure stainless steel cauldron 2 L, vacuum pump 1406 type, glass water bath with thermostatic control.
3. composition principle
Initiator, under the effect of catalyzer, is polymerized with POEO and generates polyethers, can be represented by the formula:
WF-（OH）x+nPO+mEO→WF［（PO）n（EO）m］x，
AF-(NH
2)y+nPO+mEO→AF［（PO）n（EO）m］y，
WF-(OH) x is with polyhydric WF resin,
AF-(NH
2) y is with the AF resin of polyamines base,
Active hydrogen group number in X, Y initiator,
M:EO chain number,
N:PO chain number,
PO: be propylene oxide,
EO: be oxyethane,
Wherein thermoplastic resin is WF-(OH) x is with polyhydric WF resin, AF(NH
2) y is with the mixture of the AF resin of polyamines base, the polyether intermediate finally obtained is WF and AF polyether mixture.
4. synthetic method
Embodiment 1:
The preparation of initiator thermoplastic resin: by C
4-9organic phenol and diethylenetriamine are the ratio mixing of 1 ︰ 2 in mass ratio, and heated for controlling temperature, at 30-40 DEG C, stirs 30 minutes, C in mass ratio
4-9you Ji Fen ︰ formaldehyde is that the ratio of 1 ︰ 2 drips formaldehyde, and be warmed up to 150-170 DEG C after dropwising, temperature control reacts 3 hours, obtains novel thermoplastic resin.
The preparation of polyether intermediate: add sodium hydroxide in thermoplastic resin, heat while stirring, be heated to 90 DEG C, open vacuum pump vacuum-treat 30 minutes, temperature control is at 115-135 DEG C, adding propylene oxide, oxyethane continuously respectively, after charging, is 115-135 DEG C in temperature, pressure is react 30 minutes under the condition of 0.1-0.3Mpa, cool to 90 DEG C, open vacuum pump vacuum-treat 30 minutes, obtain polyether intermediate.
Wherein each component add-on is 1 ︰ 50 ︰ 25 by the ratio of weight and number of Re Su Shu Zhi ︰ Huan Yang Bing Wan ︰ oxyethane, and catalyzer addition amount of sodium hydroxide is add propylene oxide and oxyethane total amount 0.1%.
Embodiment 2:
The preparation of initiator thermoplastic resin: by C
4-9organic phenol and triethylene tetramine are the ratio mixing of 1 ︰ 3 in mass ratio, and heated for controlling temperature, at 30-40 DEG C, stirs 30 minutes, C in mass ratio
4-9you Ji Fen ︰ formaldehyde is that the ratio of 1 ︰ 6 drips formaldehyde, and be warmed up to 150-170 DEG C after dropwising, temperature control reacts 3 hours, obtains novel thermoplastic resin.
The preparation of polyether intermediate: add potassium hydroxide in thermoplastic resin, heat while stirring, be heated to 90 DEG C, open vacuum pump vacuum-treat 30 minutes, temperature control is at 115-135 DEG C, adding propylene oxide, oxyethane continuously respectively, after charging, is 115-135 DEG C in temperature, pressure is react 30 minutes under the condition of 0.1-0.3Mpa, cool to 90 DEG C, open vacuum pump vacuum-treat 30 minutes, obtain polyether intermediate.
Wherein each component add-on is 1 ︰ 400 ︰ 200 by the ratio of weight and number of Re Su Shu Zhi ︰ Huan Yang Bing Wan ︰ oxyethane, and catalyzer potassium hydroxide add-on is add propylene oxide and oxyethane total amount 5%.
Embodiment 3:
The preparation of initiator thermoplastic resin: by C
4-9organic phenol and tetraethylene pentamine are the ratio mixing of 1 ︰ 4 in mass ratio, and heated for controlling temperature, at 30-40 DEG C, stirs 30 minutes, C in mass ratio
4-9you Ji Fen ︰ formaldehyde is that the ratio of 1 ︰ 3 drips formaldehyde, and be warmed up to 150-170 DEG C after dropwising, temperature control reacts 3 hours, obtains novel thermoplastic resin.
The preparation of polyether intermediate: add boron trifluoride in thermoplastic resin, heat while stirring, be heated to 90 DEG C, open vacuum pump vacuum-treat 30 minutes, temperature control is at 115-135 DEG C, adding propylene oxide, oxyethane continuously respectively, after charging, is 115-135 DEG C in temperature, pressure is react 30 minutes under the condition of 0.1-0.3Mpa, cool to 90 DEG C, open vacuum pump vacuum-treat 30 minutes, obtain polyether intermediate.
Wherein each component add-on is 1 ︰ 100 ︰ 50 by the ratio of weight and number of Re Su Shu Zhi ︰ Huan Yang Bing Wan ︰ oxyethane, and catalyzer boron trifluoride add-on is add propylene oxide and oxyethane total amount 0.2%.
Embodiment 4:
The preparation of initiator thermoplastic resin: by C
4-9organic phenol and five ethene hexamines are the ratio mixing of 1 ︰ 3 in mass ratio, and heated for controlling temperature, at 30-40 DEG C, stirs 30 minutes, C in mass ratio
4-9you Ji Fen ︰ formaldehyde is that the ratio of 1 ︰ 5 drips formaldehyde, and be warmed up to 150-170 DEG C after dropwising, temperature control reacts 3 hours, obtains novel thermoplastic resin.
The preparation of polyether intermediate: add ether in thermoplastic resin, heat while stirring, be heated to 90 DEG C, open vacuum pump vacuum-treat 30 minutes, temperature control is at 115-135 DEG C, adding propylene oxide, oxyethane continuously respectively, after charging, is 115-135 DEG C in temperature, pressure is react 30 minutes under the condition of 0.1-0.3Mpa, cool to 90 DEG C, open vacuum pump vacuum-treat 30 minutes, obtain polyether intermediate.
Wherein each component add-on is 1 ︰ 200 ︰ 100 by the ratio of weight and number of Re Su Shu Zhi ︰ Huan Yang Bing Wan ︰ oxyethane, and catalyzer ether add-on is add propylene oxide and oxyethane total amount 0.3%.
Embodiment 5:
The preparation of initiator thermoplastic resin: by C
4-9organic phenol and five ethene hexamines are the ratio mixing of 1 ︰ 2.5 in mass ratio, and heated for controlling temperature, at 30-40 DEG C, stirs 30 minutes, C in mass ratio
4-9you Ji Fen ︰ formaldehyde is that the ratio of 1 ︰ 4 drips formaldehyde, and be warmed up to 150-170 DEG C after dropwising, temperature control reacts 3 hours, obtains novel thermoplastic resin.
The preparation of polyether intermediate: add ether and sodium hydroxide in thermoplastic resin, heat while stirring, be heated to 90 DEG C, open vacuum pump vacuum-treat 30 minutes, temperature control is at 115-135 DEG C, adding propylene oxide, oxyethane continuously respectively, after charging, is 115-135 DEG C in temperature, pressure is react 30 minutes under the condition of 0.1-0.3Mpa, cool to 90 DEG C, open vacuum pump vacuum-treat 30 minutes, obtain polyether intermediate.
Wherein each component add-on is 1 ︰ 300 ︰ 150 by the ratio of weight and number of Re Su Shu Zhi ︰ Huan Yang Bing Wan ︰ oxyethane, and catalyzer ether and addition amount of sodium hydroxide are add propylene oxide and oxyethane total amount 0.4%.
Embodiment 6:
The preparation of initiator thermoplastic resin: by C
4-9organic phenol and five ethene hexamines are the ratio mixing of 1 ︰ 2.5 in mass ratio, and heated for controlling temperature, at 30-40 DEG C, stirs 30 minutes, C in mass ratio
4-9you Ji Fen ︰ formaldehyde is that the ratio of 1 ︰ 4 drips formaldehyde, and be warmed up to 150-170 DEG C after dropwising, temperature control reacts 3 hours, obtains novel thermoplastic resin.
The preparation of polyether intermediate: add ether in thermoplastic resin, heat while stirring, be heated to 90 DEG C, open vacuum pump vacuum-treat 30 minutes, temperature control is at 115-135 DEG C, adding propylene oxide, oxyethane continuously respectively, after charging, is 115-135 DEG C in temperature, pressure is react 30 minutes under the condition of 0.1-0.3Mpa, cool to 90 DEG C, open vacuum pump vacuum-treat 30 minutes, obtain polyether intermediate.
Wherein each component add-on is 1 ︰ 100 ︰ 100 by the ratio of weight and number of Re Su Shu Zhi ︰ Huan Yang Bing Wan ︰ oxyethane, and catalyzer ether add-on is add propylene oxide and oxyethane total amount 0.1%.
Synthesis emulsion splitter is to the treatment effect of different crude oils
Table 1 for dehydration temperaturre be 40 DEG C, crude oil sample is THE WESTERN SOUTH CHINA SEA Wei 11-4A platform crude oil sample.
The polyethers dehydration test of table 1 PO, EO different ratios
Note: HYP9602, RP3562 are U.S.'s product.
Found out by table 1 data, 8-5 and 10-6 two polyether component dehydration effect efficiency are best, can reach U.S. product HYP9602 and RP3562 level.
Table 2 is WF(AF) dehydrating effect of polyether intermediate emulsion splitter to pure beam one Dormant oils sample (moisture 40%, dehydration temperaturre 40 DEG C) compare.Emulsion splitter dosage 100ppm.
Table 2 WF(AF) test of emulsion splitter ether dewatering
Test-results shows, WF-4 and AF-4 dewatering is good.Therefore, can select WF-4 and AF-4 two kinds of polyethers is intermediate, and preparation can be applicable to the SD-3 type emulsion splitter of low temperature high-salinity water quality crude oil further.
Claims (2)
1. a preparation method for demulsifier polyether intermediate compound, is characterized in that: add catalyzer in thermoplastic resin, heats while stirring, be heated to 90 DEG C, open vacuum pump vacuum-treat 30 minutes, temperature control is at 115-135 DEG C, first add propylene oxide, after add oxyethane, after charging, be 115-135 DEG C in temperature, pressure is react 30 minutes under the condition of 0.1-0.3MPa, cool to 90 DEG C, open vacuum pump vacuum-treat 30 minutes, obtain polyether intermediate;
Wherein each component add-on is 1 ︰ 100-400 ︰ 50-200 or 1 ︰ 50 ︰ 25 by the ratio of weight and number of Re Su Shu Zhi ︰ Huan Yang Bing Wan ︰ oxyethane, and catalyst charge is the 0.1-0.5% adding propylene oxide and oxyethane total amount;
The preparation method of described thermoplastic resin is by C
4organic phenol and organic amine are the ratio mixing of 1 ︰ 2-4 in mass ratio, and heated for controlling temperature, at 30-40 DEG C, stirs 30 minutes, C in mass ratio
4you Ji Fen ︰ formaldehyde is that the ratio of 1 ︰ 2-6 drips formaldehyde, and be warmed up to 150-170 DEG C after dropwising, temperature control reacts 3 hours and get final product;
Described catalyzer is one or more in sodium hydroxide, potassium hydroxide.
2. the preparation method of a kind of demulsifier polyether intermediate compound according to claim 1, is characterized in that: described organic amine is one or more in diethylenetriamine, triethylene tetramine, tetraethylene pentamine, five ethene hexamines.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1537924A (en) * | 2003-10-22 | 2004-10-20 | 山东大学 | Low-temperature quick deemulsifying agent for water-containing wax-containing erude oil and its preparation method |
| CN1810933A (en) * | 2006-03-13 | 2006-08-02 | 辽宁奥克化学集团有限公司 | Thick oil demulsifier and its prepn |
| CN101418230A (en) * | 2007-10-25 | 2009-04-29 | 中国科学院化学研究所 | Crude de-emulsifier and its preparing process |
| CN102746470A (en) * | 2011-04-19 | 2012-10-24 | 克拉玛依奥克化学有限公司 | Preparation method of efficient deemulsifier for naphthenic extra heavy oil and product thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1537924A (en) * | 2003-10-22 | 2004-10-20 | 山东大学 | Low-temperature quick deemulsifying agent for water-containing wax-containing erude oil and its preparation method |
| CN1810933A (en) * | 2006-03-13 | 2006-08-02 | 辽宁奥克化学集团有限公司 | Thick oil demulsifier and its prepn |
| CN101418230A (en) * | 2007-10-25 | 2009-04-29 | 中国科学院化学研究所 | Crude de-emulsifier and its preparing process |
| CN102746470A (en) * | 2011-04-19 | 2012-10-24 | 克拉玛依奥克化学有限公司 | Preparation method of efficient deemulsifier for naphthenic extra heavy oil and product thereof |
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