CN1036524C - Dispersing agent for wax in crude oil and its production - Google Patents
Dispersing agent for wax in crude oil and its production Download PDFInfo
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- CN1036524C CN1036524C CN 93120288 CN93120288A CN1036524C CN 1036524 C CN1036524 C CN 1036524C CN 93120288 CN93120288 CN 93120288 CN 93120288 A CN93120288 A CN 93120288A CN 1036524 C CN1036524 C CN 1036524C
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- dispersing agent
- wax
- crude oil
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Abstract
The present invention relates to a dispersing agent for wax in crude oil, which is formed by polymerizing olefin and olefinic unsaturated salts, olefinic unsaturated amide or carboxylate or olefinic alkyl sulfonate. The dispersing agent for wax in crude oil has a chemical structural formula that the ester content of the dispersing agent is from 18 to 35%, the average molecular weight Mn is from 10000 to 20000, and the intrinsic viscosity (eta) is from 40 to 65 ml/g. The dispersing agent for wax is suitable for crude oil whose wax content is from 2 to 26% and specific gravity d4<20> is from 0.8450 to 0.9070; the dispersing agent has a good effect of reducing coagulation and viscosity. The dispersing agent has the advantages of simple production technique, easy operation, stable product quantity and high conversion rate (ester as a reference).
Description
The invention belongs to a kind of high molecular polymer, dispersing agent for wax and preparation method thereof in particularly a kind of crude oil.
Waxy crude oil, especially high wax content oil condensation point height generally at normal temperatures, even are higher than and have just lost flowability under the normal temperature, have therefore increased difficulty for pipe-line transportation.People are exploring the method that reduces condensation point of crude oil for this reason, to solve the problem that waxy crude oil exists in exploitation and course of conveying.Many methods of improving the waxy crude oil flowability have been proposed for this reason technically, as having described the improvement technology that wax-containing oil pipe is carried in the US3675671 patent document.This technology is to add a spot of oil soluble high molecular polymer again after high condensation point waxy crude oil and the fusion by a certain percentage of low condensation point crude oil, to reduce the condensation point of waxy crude oil.The method that this technology reduces condensation point of crude oil is at specific low condensation point crude oil " ArabianLight " and high condensation point crude oil " Amna ". and will above-mentioned two kinds of crude oil concoct by a certain percentage afterwards that adding ethylene-vinylacetate multipolymer just has the pour point depression effect.And any waxy crude oil be there is no universal significance.In the US3735770 patent documentation, also introduced a kind of pour point depression of crude oil method, its method is with after ethene and vinyl acetate polymer mix with crude oil, be warming up to than wax partial crystallization in the crude oil to go out under the higher temperature, again with rate of temperature fall less than 10/hr, crude oil is cooled to the temperature of wax crystalline substance when all separating out, thereby realize the pour point depression of crude oil effect, improve the flowability of crude oil.In the EPO341499 patent documentation, introduced a kind of preparation method of ethylene-vinylacetate multipolymer.This method is to adopt series connection still of 4-5 autoclave composition, feeds ethene and vinyl acetate, solvent continuously, initiator makes multipolymer under certain temperature and pressure.This method complex process, equipment material require high, the working pressure height, transformation efficiency is low, and the multipolymer of preparation is not the improvement that is used for the waxy crude oil flowability as fluidity improver, glue paste and thermoset(ting)plastic and the pressure-resistant plastic of lubricant, hydraulic efficiency system.
One of purpose of the present invention provides dispersing agent for wax in a kind of crude oil.
Two of purpose of the present invention provides the preparation method of dispersing agent for wax in a kind of crude oil.
Purpose of the present invention can realize by following measure:
Dispersing agent for wax is the terpolymer of alkene, ethylenic unsaturated acid ester, olefinic unsaturated amides or ethylenically unsaturated carboxylic acids salt or thiazolinyl alkyl sulfonate in the crude oil, and its chemical structural formula is:
R in the formula
1, R
2, R
4Be-H or-CH
3Or-(CH
2)
nCH
3 Or
Or
R
5Be the polar functional group of amide-containing or carboxylate group or methylene sulphonate-base, as:
Or
Or-CH
2SO
3Na
The rerum natura of multipolymer is: ester content is 18～35%; Average molecular mass Mn is 10000～20000;
Limiting viscosity (η) is 40～65
The preparation technology of dispersing agent for wax comprises the following steps: successively in the crude oil
1. ethylenic unsaturated acid ester, olefinic unsaturated amides or ethylenically unsaturated carboxylic acids salt or thiazolinyl alkyl sulfonate and organic solvent, water and initiator are mixed and made into mixture in following ratio (weight %);
With ethylenic unsaturated acid ester (being designated hereinafter simply as ester) is radix;
Olefinic unsaturated amides or ethylenically unsaturated carboxylic acids salt or thiazolinyl alkyl sulfonate are 4～20% of esters;
Initiator is 1～5% of an ester;
Organic solvent and water are 500～1500% of esters, and wherein the amount ratio of organic solvent and water is 2～8: 1;
2. said mixture being added vacuum tightness is higher than in the autoclave of 0.0986MPa;
3. add alkene in autoclave, its add-on is 200～500% of an ester;
4. be 50～100 ℃ in temperature, pressure is under the condition of 5～15MPa, polyase 13～8 hour;
5. emit residual gas in the still;
6. post reaction mixture is put into still kettle, water and solvent are steamed, promptly obtain dispersing agent for wax in terpolymer-crude oil.Its transformation efficiency is 99.5～100% (are benchmark with the ester).
Above-mentioned said initiator is radical initiator or peroxide initiator, as Diisopropyl azodicarboxylate or benzoyl peroxide; Said organic solvent is the trimethyl carbinol.
When above-mentioned said dispersing agent for wax uses, use earlier organic solvent, as: after dimethylbenzene, kerosene etc. dissolve, add wax content to and be 2～26%, proportion d
20Be in 0.8450～0.9070 the crude oil, be heated to 70 ℃ and thorough mixing after, can manage defeated.
The present invention compared with prior art has following advantage:
Production technique is simple, and working pressure is low, and operational condition is easy to control, constant product quality, and the transformation efficiency height, effective to dispersion, the pour-viscosity reduction of wax in the crude oil, unload that still cleans very easily, the intermittent time is short.
The invention will be further described below in conjunction with embodiment:
Embodiment 1
1. autoclave is vacuumized, its vacuum tightness is 0.099MPa;
2. the ethyl propenoate of 21.2g and the trimethyl carbinol of 276.5g are mixed, obtain the mixture of 297.7g;
The water of 35g and the acrylamide of 4.2g are mixed the mixture that obtains 39.2g;
3. with above-mentioned two kinds of mixtures and 1.1g Diisopropyl azodicarboxylate initiator, once all add in the autoclave;
4. the ethene that in autoclave, adds 42.7g again;
5. be that 90 ℃, pressure are polyase 13 hour under 14.8MPa～8MPa condition in temperature;
6. emit residual gas in the still;
7. post reaction mixture is put into still kettle, the water and the trimethyl carbinol are steamed, promptly obtain terpolymer---dispersing agent for wax.Its chemical structural formula is:
The rerum natura of multipolymer is as follows after measured:
Ester content is 34.7%, and average molecular mass Mn is 10500, and limiting viscosity (η) is 42, and transformation efficiency is 99.5%.
Embodiment 2
1. autoclave is vacuumized, its vacuum tightness is 0.099MPa;
2. the vinyl acetate of 35.6g and the trimethyl carbinol of 234.7g are mixed, obtain the mixture of 270.3g; The water of 64.1g and the sodium acrylate of 3.9g are mixed, obtain the mixture of 68g;
3. with the Diisopropyl azodicarboxylate initiator of above-mentioned two kinds of mixtures and 1g, once all add in the autoclave;
4. the 1-butylene that in autoclave, adds 106.8g again;
5. be that 55 ℃, pressure are polyreaction 7.5 hours under 8.5MPa～5.5MPa condition in temperature;
6. emit residual gas in the still;
7. post reaction mixture is put into still kettle, the water and the trimethyl carbinol is steamed, promptly obtain terpolymer---dispersing agent for wax in the crude oil.Its chemical structural formula is:
The rerum natura of multipolymer is as follows after measured:
Ester content is 28.6%, and average molecular mass Mn is 15000, and limiting viscosity (η) is 56.1, and transformation efficiency is 99.7%.
Embodiment 3
1. autoclave is vacuumized, its vacuum tightness is 0.099MPa;
2. the 2-methyl methacrylate of 30.1g and the trimethyl carbinol of 105g are mixed, obtain the mixture of 135.1g; The water of 50g and the 2-sodium allylsulfonate of 1.3g are mixed, obtain the mixture of 51.3g;
3. with the benzoyl peroxide initiator of above-mentioned two kinds of mixtures and 0.30g, once all add in the autoclave;
4. the propylene that in autoclave, adds 144.5g again;
5. be that 75 ℃, pressure are polyreaction 6 hours under 11MPa～8.5MPa condition in temperature;
6. emit residual gas in the still;
7. post reaction mixture is put into still kettle, the water and the trimethyl carbinol is steamed, promptly obtain terpolymer---dispersing agent for wax in the crude oil.Its chemical structural formula is:
The rerum natura of multipolymer is as follows after measured:
Ester content is 18.6%, and average molecular mass Mn is 19400, and limiting viscosity (η) is 64.3, and transformation efficiency is 99.9%.
Embodiment 4
1. autoclave is vacuumized, its vacuum tightness is 0.099MPa;
2. the 2--Jia Jibingxisuanyizhi of 28.6g and the trimethyl carbinol of 228.8g are mixed, obtain the mixture of 274.4g;
The water of 45.7g and the 2--crotonamide of 2.3g are mixed, obtain the mixture of 48g;
3. with the Diisopropyl azodicarboxylate initiator of above-mentioned two kinds of mixtures and 1g, once all add in the autoclave;
4. the ethene that in autoclave, adds 113.8g again;
5. be that 65 ℃, pressure are polyreaction 5 hours under 9.5MPa～6.5MPa condition in temperature;
6. emit residual gas in the still;
7. post reaction mixture is put into still kettle, the water and the trimethyl carbinol is steamed, promptly obtain terpolymer---dispersing agent for wax in the crude oil.Its chemical structural formula is:
The rerum natura of multipolymer is as follows after measured:
Ester content is 29.6%, and average molecular mass Mn is 17500, and limiting viscosity (η) is 59, and transformation efficiency is 99.8%.
Embodiment 5
1. autoclave is vacuumized, its vacuum tightness is 0.099MPa;
2. the vinyl acetate of 33.7g and the trimethyl carbinol of 121.3g are mixed, obtain the mixture of 155g; The water of 59.8g and the 2-butylene sodium sulfonate of 3.1g are mixed, obtain the mixture of 62.9g;
3. with the Diisopropyl azodicarboxylate initiator of above-mentioned two kinds of mixtures and 1.35g, once all add in the autoclave;
4. the ethene that in autoclave, adds 104.6g again;
5. be that 62 ℃, pressure are polyreaction 5 hours under 10.3MPa～7.4MPa condition in temperature;
6. emit residual gas in the still;
7. post reaction mixture is put into still kettle, the water and the trimethyl carbinol is steamed, promptly obtain terpolymer---dispersing agent for wax in the crude oil.Its chemical structural formula is:
The rerum natura of multipolymer is as follows after measured:
Ester content is 26.5%, and average molecular mass Mn is 16600, and limiting viscosity (η) is 58.1, and transformation efficiency is 99.8%.
With the multipolymer of above-mentioned example 1～5 gained with organic solvent dissolution (organic solvent is that the dimethylbenzene of equivalent and 3～7 times are to the kerosene of multipolymer).Then, to add in right amount in the lubricating cup that fills crude oil (wax content 2～26%), lubricating cup is placed and can thermoregulated water-bath heat up, constant temperature is 5 minutes when treating oily temperature rise to 70 ℃, subsequently with 0.5 ℃/minute rate of temperature fall, with oily temperature drop to probe temperature and constant temperature.Press petroleum products questionable points assay method (GB510-83) and measure the condensation point of crude oil in the lubricating cup, reduce to 11 ℃ from 31.5 ℃, the pour point depression amplitude is 20.5 ℃.In the time of 25 ℃, sheared 72 hours effect stability continuously.Static 120 hours of 25 ℃ of constant indoor temperature, treatment effect was compared when initial, and the flowability of crude oil is constant substantially.
Through pour point depression, viscosity reducing effect such as the following table of measuring dispersing agent for wax to Qinghai crude oil
| Experiment condition | Probe temperature ℃ | Dispersing agent for wax addition PPM | Condensation point ℃ | Condensation point reduces amplitude ℃ | Surface viscosity (shearing rate 11.5S -1) MPa、s | Apparent viscosity reduced rate % | Yield value Pa |
| The blank sample of crude oil | 20 | / | 31.5 | / | 5158.9 | / | 73.6 |
| Handle slow cooling to 20 ℃ for 70 ℃ | 20 | 150 | 12.0 | 19.5 | 79.2 | 98.5 | 0 |
| 65 ℃ of re-treatment slow cooling to 20 ℃ | 20 | 150 | 11.0 | 20.5 | 96.5 | 98.1 | 0 |
| Constant temperature is static 120 hours under 20 ℃ of states | 20 | 150 | 9.5 | 22.0 | 27.4 | 99.5 | 0 |
As can be seen from the above table, dispersing agent for wax is remarkable to pour point depression, the viscosity reducing effect of Qinghai crude oil.Under test condition, the condensation point of crude oil is reduced to 12 ℃ from 31.5 ℃, the pour point depression amplitude is 19.5 ℃. and repeatability and to leave standstill performance all very desirable.And under test condition, the apparent viscosity of crude oil can be reduced to 79.2MPa, s from 5158.9MPa, s, reduced rate is 98.5%, and repeatability and leaving standstill property also very good.
Claims (2)
1, dispersing agent for wax in a kind of crude oil is characterized in that: dispersing agent for wax is the terpolymer of alkene, vinyl acetate, thiazolinyl alkyl sulfonate, and its chemical structural formula is:
R in the formula
1Be-H or-CH
3Or-C
2H
5R
2Be-H; R
3Be
R
4Be-H or-CH
3R
5Be-CH
2SO
3Na;
The rerum natura of multipolymer is: wherein ester content is 18～35%, and the thiazolinyl alkyl sulfonate is 4～20% of an ester, and average molecular mass Mn is 10000～20000, and limiting viscosity (η) is 40～65ml/g.
2, the preparation method of dispersing agent for wax in a kind of crude oil, it is characterized in that: the technology of preparation follows these steps to carry out:
1. vinyl acetate, thiazolinyl alkyl sulfonate and the trimethyl carbinol, water and Diisopropyl azodicarboxylate or benzoyl peroxide are mixed and made into mixture by following weight ratio:
With vinyl acetate (hereinafter to be referred as ester) is radix;
The thiazolinyl alkyl sulfonate is 4～20% of an ester;
Diisopropyl azodicarboxylate or benzoyl peroxide are 1～5% of esters;
The trimethyl carbinol and water are 500～1500% of esters, and wherein the amount ratio of the trimethyl carbinol and water is 2～8: 1;
2. said mixture being added vacuum tightness is higher than in the autoclave of 0.0986MPa;
3. add alkene in autoclave, its add-on is 200～500% of an ester;
4. be that 50～100 ℃, pressure are under the condition of 5～15MPa in temperature, polyase 13～8 hour;
5. emit residual gas in the still;
6. post reaction mixture is put into still kettle, water and solvent are steamed, promptly obtain dispersing agent for wax in terpolymer-crude oil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93120288 CN1036524C (en) | 1993-12-04 | 1993-12-04 | Dispersing agent for wax in crude oil and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93120288 CN1036524C (en) | 1993-12-04 | 1993-12-04 | Dispersing agent for wax in crude oil and its production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1094062A CN1094062A (en) | 1994-10-26 |
| CN1036524C true CN1036524C (en) | 1997-11-26 |
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ID=4993232
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 93120288 Expired - Fee Related CN1036524C (en) | 1993-12-04 | 1993-12-04 | Dispersing agent for wax in crude oil and its production |
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| Country | Link |
|---|---|
| CN (1) | CN1036524C (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101712787B (en) * | 2008-10-08 | 2012-01-11 | 中国石油天然气集团公司 | Sulfonic acid-containing organic macromolecule reaction type crude oil flow modifying agent |
| CA2998464C (en) | 2015-09-15 | 2024-01-16 | Kuraray Co., Ltd. | Crude oil dispersion stabilizer containing vinyl-alcohol-based polymer |
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1993
- 1993-12-04 CN CN 93120288 patent/CN1036524C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN1094062A (en) | 1994-10-26 |
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