CN1035676C - Process for diesel flow improving agent - Google Patents
Process for diesel flow improving agent Download PDFInfo
- Publication number
- CN1035676C CN1035676C CN91111489A CN91111489A CN1035676C CN 1035676 C CN1035676 C CN 1035676C CN 91111489 A CN91111489 A CN 91111489A CN 91111489 A CN91111489 A CN 91111489A CN 1035676 C CN1035676 C CN 1035676C
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- vinyl acetate
- reaction
- pressure
- plastic
- reactor
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Classifications
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
- F02B3/00—Engines characterised by air compression and subsequent fuel addition
- F02B3/06—Engines characterised by air compression and subsequent fuel addition with compression ignition
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
- F02B47/00—Methods of operating engines involving adding non-fuel substances or anti-knock agents to combustion air, fuel, or fuel-air mixtures of engines
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
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- Liquid Carbonaceous Fuels (AREA)
Abstract
The present invention relates to a method for preparing ethene-vinyl acetate copolymer type diesel oil flow improver with the average molecular weight of 1000 to 2500 by intermittent polymerization reactions under the temperature of 40 DEG C to 60 DEG C and the pressure of and 5MPa to 10MPa. In the method, ethene and vinyl acetate are used as materials, di cyclohexylperoxy dicarbonate is used as an initiator, and industrial gasoline is used as solvent. Compared with the prior art, the present invention has the advantages of low reaction temperature, energy saving, simple technology, low production cost, etc.
Description
The invention belongs to the preparation method of diesel flow improver, or rather, it is to belong to ethene and vinyl acetate between to for plastic to be raw material, to adopt single still intermittent polyreaction to prepare the method for ethylene-vinyl acetate copolymer type diesel flow improver.
Diesel flow improver, be commonly called as diesel pour inhibitor, as a kind of diesel-dope, industrial important role arranged: it not only can improve flowability of diesel oil greatly, make diesel oil under cryogenic environment, be able to normal use, also to improving refinery's solar oil production handiness, save kerosene, volume increase solar oil, increase economic benefit simultaneously, extremely important meaning is arranged.And low-molecular-weight ethylene-vinyl acetate copolymer then is the most a kind of both at home and abroad at present diesel flow improver.
Disclose among the USP3981850 and a kind ofly be raw material, be solvent with benzene, be initiator with the di-tert-butyl peroxide compound with ethene and vinyl acetate between to for plastic, adopt the method for single still intermittence type polymerization prepared in reaction ethene-vinyl acetate type diesel flow improver, this method is a reaction solvent owing to having adopted higher benzene of price or pure reagent, thereby causes the increase of production cost; Because the temperature of reaction of this method is higher, cause energy consumption of reaction to increase in addition.
The objective of the invention is to overcome the shortcoming of prior art, it is the method for solvent, cryogenic synthesising ethylene-vinyl acetate between to for plastic type diesel flow improver that a kind of non-leaded gasoline that adopts is provided.
Technical characterictic of the present invention is: with vinyl acetate between to for plastic and excessive ethylene gas, place the reactor that industrial solvent gasoline is housed, under the peralcohol action of evocating, in 40～60 ℃, preferably 50～60 ℃ of temperature, 5～10MPa preferably under 7.5～8.5 pressure, adopt the single reaction still to carry out the intermittence type polymerization reaction, can synthesize molecular-weight average and be 1000～2500 ethylene-vinyl acetate copolymer type diesel flow improver, its concrete operations are:
(1) vinyl acetate between to for plastic, initiator and solvent gas and oil are rendered in the reactor respectively or simultaneously by a certain percentage, mix, by pressure control system ethylene gas is charged in the reactor again, be warming up to temperature of reaction and with pressure-controlling under the required pressure of reaction, begin to carry out polyreaction.
(2) after question response carried out 4～8 hours, stopped reaction, cooling, pressure release just can obtain required product after steaming gasoline fraction and unreacted vinyl acetate between to for plastic.
Before above-mentioned polyreaction begins, when having air or other gas in the reactor, need usually be replaced with ethylene gas earlier, promptly in reactor, pack into behind a certain amount of reaction liquid material, open the control valve of ethene gas circuit, in still, fill ethylene gas 1.0MPa, then emptying; Repeat so altogether 3 times, just can wherein air or other gas displacements is clean.
Needing in the process to carry out according to the pressure change in the system in reaction, the pressure of regulation system is controlled at the required pressure range of reaction all the time with it at any time.This mainly is because this polyreaction is that vinyl acetate between to for plastic and excessive ethene carry out under liquid phase, and solubleness and its pressure on liquid level of ethene in liquid material has certain proportionlity.When too high or too low, its solubleness in liquid material will change thereupon, thereby makes the mol ratio of reactant change, and finally will influence product structure and quality product as ethylene pressure.
Cooling after reaction stops is adopted usually and is forced cooling; The type of cooling can be air-cooled or water-cooled, also can be the air-cooled water-cooled again of elder generation.
The material that obtains after the pressure release need be transferred in the distillation tower and distill, and steams gasoline fraction and unreacted vinyl acetate between to for plastic (being that boiling range is 70～120 ℃ the thing that steams) recyclable recycling after oxygenatedchemicals is removed in the water wash column washing.
The industrial rotation book Membrane-distillation tower that normally adopts of above-mentioned distillation tower; Water wash column normally adopts the material filling type water wash column, generally takes to be washed the mode of material and bath water convection current in the application.
The feed ratio of described vinyl acetate between to for plastic, initiator and industrial solvent gasoline is 1: 0.03～0.05: 2.5～3.5 (weights).
Described industrial solvent gasoline is that alkene and methylbenzene kind compound content all are not more than 0.5 heavy %, boiling range is 60～150 ℃, and preferably boiling range is the gasoline fraction of 60～90 ℃ or 80～120 ℃.
Described peralcohol initiator is di-cyclohexylperoxy dicarbonate preferably.
Described ethene and vinyl acetate between to for plastic be the polymerization-grade product preferably.
The present invention is an initiator owing to having adopted di-cyclohexylperoxy dicarbonate, greatly reduces temperature of reaction, thereby has reduced energy consumption; Because adopting non-leaded gasoline to replace pure hydrocarbon is solvent, thereby has also reduced production cost.
Further describe technical characterstic of the present invention below by embodiment and Comparative Examples.
Its raw material source and specification see Table 1 in the example below.
Example 1
Vinyl acetate between to for plastic, gasoline and di-cyclohexylperoxy dicarbonate are evenly placed reactor by the mixed of 1: 3: 0.04 (weight), and the reactant volume feeds intake and drops into by 70% of reactor cubic capacity.Open the ethylene pressure control valve and in system, fill ethylene gas to 1.0MPa, emptying; Repeat the closing presure control valve so altogether three times.Open the ethylene pressure control valve and in still, be inflated to 6.5MPa and in reaction process, remain this pressure, stir, begin to be warming up to 55 ℃ and constant temperature simultaneously.Reaction mass just begins to carry out polyreaction in this still.React stop after 6 hours the heating, cool, reactor is opened in pressure release.Material in the still is placed distillation tower, steam and remove reaction solvent and unreacted vinyl acetate between to for plastic, residuum is described diesel flow improver and does agent A.The molecular-weight average of this polymkeric substance is 1713, and vinyl acetate content is 27.8 heavy % in the product.
Get the above-mentioned dried agent A of 1 gram, after the carbon-9 heavy aromatics dilution with identical weight, join in the diesel oil of 2000 grams, measure the zero pour and the cold filter clogging temperature of oil product respectively according to the method for GB510-77 and SY2413-83, to observe the result of use of diesel flow improver, it the results are shown in Table 2.
Example 2
Vinyl acetate between to for plastic, gasoline and di-cyclohexylperoxy dicarbonate are evenly placed reactor by the mixed of 1: 3: 0.04 (weight), and the reactant volume feeds intake and drops into by 70% of reactor cubic capacity.Open the ethylene pressure control valve and in system, fill ethylene gas to 1.0MPa, emptying; Repeat the closing presure control valve so altogether three times.Open the ethylene pressure control valve and in still, be inflated to 6.5MPa and in reaction process, remain this pressure, stir, begin to be warming up to 40 ℃ and constant temperature simultaneously.Reaction mass just begins to carry out polyreaction in this still.React stop after 6 hours the heating, cool, reactor is opened in pressure release.Material in the still is placed distillation tower, steam and remove reaction solvent and unreacted vinyl acetate between to for plastic, residuum is described diesel flow improver and does agent B.The molecular-weight average of this polymkeric substance is 1500, and vinyl acetate content is 33.4 heavy % in the product.
Get the above-mentioned dried agent B of 1 gram, after the carbon-9 heavy aromatics dilution with identical weight, join in the diesel oil of 2000 grams, measure the zero pour and the cold filter clogging temperature of oil product respectively according to the method for GB510-77 and SY2413-83, to observe the result of use of diesel flow improver, it the results are shown in Table 2.
Example 3
Vinyl acetate between to for plastic, gasoline and peroxy dicarbonate two hexamethylene vinegar are evenly placed reactor by the mixed of 1: 3: 0.03 (weight), and the reactant volume feeds intake and drops into by 70% of reactor cubic capacity.Open the ethylene pressure control valve and in system, fill ethylene gas to 1.0MPa, emptying; Repeat the closing presure control valve so altogether three times.Open the ethylene pressure control valve and in still, be inflated to 4.2MPa and in reaction process, remain this pressure, stir, begin to be warming up to 55 ℃ and constant temperature simultaneously.Reaction mass just begins to carry out polyreaction in this still.React stop after 5 hours the heating, cool, reactor is opened in pressure release.Material in the still is placed distillation tower, steam and remove reaction solvent and unreacted vinyl acetate between to for plastic, residuum is described diesel flow improver and does agent C.The molecular-weight average of this polymkeric substance is 1300, and vinyl acetate content is 38.6 heavy % in the product.
Get the above-mentioned dried agent C of 1 gram, after the carbon-9 heavy aromatics dilution with identical weight, join in the diesel oil of 2000 grams, measure the zero pour and the cold filter clogging temperature of oil product respectively according to the method for GB510-77 and SY2413-83, to observe the result of use of diesel flow improver, it the results are shown in Table 2.
Example 4
Vinyl acetate between to for plastic, gasoline and di-cyclohexylperoxy dicarbonate are evenly placed reactor by the mixed of 1: 3: 0.05 (weight), and the reactant volume feeds intake and drops into by 70% of reactor cubic capacity.Open the ethylene pressure control valve and in system, fill ethylene gas to 1.0MPa, emptying; Repeat the closing presure control valve so altogether three times.Open the ethylene pressure control valve and in still, be inflated to 10MPa and in reaction process, remain this pressure, stir, begin to be warming up to 55 ℃ and constant temperature simultaneously.Reaction mass just begins to carry out polyreaction in this still.React stop after 6 hours the heating, cool, reactor is opened in pressure release.Material in the still is placed distillation tower, steam and remove reaction solvent and unreacted vinyl acetate between to for plastic, residuum is described diesel flow improver and does agent D.The molecular-weight average of this polymkeric substance is 1740, and vinyl acetate content is 30.4 heavy % in the product.
Get the above-mentioned dried agent D of 1 gram, after the carbon-9 heavy aromatics dilution with identical weight, join in the diesel oil of 2000 grams, measure the zero pour and the cold filter clogging temperature of oil product respectively according to the method for GB510-77 and SY2413-83, to observe the result of use of diesel flow improver, it the results are shown in Table 2.
Example 5
Vinyl acetate between to for plastic, gasoline and di-cyclohexylperoxy dicarbonate are evenly placed reactor by the mixed of 1: 3: 0.04 (weight), and the reactant volume feeds intake and drops into by 70% of reactor cubic capacity.Open the ethylene pressure control valve and in system, fill ethylene gas to 1.0MPa, emptying; Repeat the closing presure control valve so altogether three times.Open the ethylene pressure control valve and in still, be inflated to 8.2MPa and in reaction process, remain this pressure, stir, begin to be warming up to 57 ℃ and constant temperature simultaneously.Reaction mass just begins to carry out polyreaction in this still.React stop after 6 hours the heating, cool, reactor is opened in pressure release.Material in the still is placed distillation tower, steam and remove reaction solvent and unreacted vinyl acetate between to for plastic, residuum is described diesel flow improver and does agent E.The molecular-weight average of this polymkeric substance is 1992, and vinyl acetate content is 40.3 heavy % in the product.
Get the above-mentioned dried agent E of 1 gram, after the carbon-9 heavy aromatics dilution with identical weight, join in the diesel oil of 2000 grams, measure the zero pour and the cold filter clogging temperature of oil product respectively according to the method for GB510-77 and SY2413-83, to observe the result of use of diesel flow improver, it the results are shown in Table 2.Annotate: in the test method of example 1～5
Vinyl acetate content adopts saponification-volumetry in the product: take by weighing 0.2 gram testing sample and place container, adding 20 milliliters of xylene solvents and 5 ml concns is the potassium hydroxide-ethanol solution of 0.5N, reflux 2.5 hours, the cooling back gets final product with the sulfuric acid titration of 0.1N; The molecular-weight average of product adopts vapour pressure osmometry (VPO method).
Table 1
| Sequence number | Title | Specification | The place of production | Purposes |
| 1 | Ethene | Purity＞99.0% | Beijing evolution factory | Polymerization single polymerization monomer |
| 2 | Vinyl acetate between to for plastic | Purity＞98.5% | Beijing Organic Chemical Plant | Polymerization single polymerization monomer |
| 3 | Diisopropyl azodicarboxylate | Purity＞98.0% | The Beijing Chemical Plant | Initiator |
| 4 | Di-cyclohexylperoxy dicarbonate | Purity＞98.0% | Tianjin Chemical Plant | Initiator |
| 5 | No. 120 industrial napthas | 80～120℃ | The commercial goods | Solvent |
| 6 | Carbon-9 heavy aromatics | 159～185 ℃ of reformation still bottom oils | Beijing Yanshan Petrochemical Company's refinery | Thinner |
Table 2
[notes]: go up in the table
| Oily number | Improving agent | Do not add improving agent, ℃ | Add improving agent, ℃ | Test method | ||
| Zero pour | Cold filter clogging temperature | Zero pour | Cold filter clogging temperature | |||
| ①，-20 | A | -20 | -11 | -45 | -31 | The described method of GB510-77 is all adopted in the test of zero pour |
| ①，-20 | E | -20 | -11 | -37 | -24 | |
| ②，-20 | C | -21 | -10 | -40 | -26 | |
| The described method of SY2413-83 is all adopted in the test of cold filter clogging temperature | ||||||
| ②，-20 | D | -21 | -10 | -46 | -25 | |
| ②，-20 | B | -21 | -10 | -43 | -28 | |
1. ,-20 represent-No. 20 diesel oil that the Fushun second branch factory of oil is produced.
2. ,-20 represent-No. 20 diesel oil that the grand celebration refinery produces.
Claims (3)
1. one kind is the method for feedstock production diesel flow improver with ethene and vinyl acetate between to for plastic, it is characterized in that vinyl acetate between to for plastic and excessive ethylene gas, place and alkene and methylbenzene kind compound content are housed are not more than 0.5 heavy %, boiling range is in the reactor of 60～150 ℃ of industrial solvent gasoline, under the di-cyclohexylperoxy dicarbonate action of evocating, in 40～60 ℃ of temperature, under 5～10MPa ethylene pressure, adopt the single reaction still to carry out the intermittence type polymerization reaction, can synthesize molecular-weight average and be 1000～2500 ethylene-vinyl acetate copolymer type diesel flow improver, its concrete operations are:
(1) vinyl acetate between to for plastic, initiator and industrial naptha are pressed 1: 0.03～0.05: 2.5～3.5 (weight) mixed, and put it in the reactor, by pressure control system ethylene gas is charged in the reactor again, be warming up to temperature of reaction and with pressure-controlling under the required pressure of reaction, begin to carry out polyreaction;
(2) after question response carried out 4～8 hours, stopped reaction, cooling, pressure release just can obtain required product after steaming gasoline fraction and unreacted vinyl acetate between to for plastic.
2. in accordance with the method for claim 1, it is characterized in that described temperature of reaction is that 50～60 ℃, pressure are 7.5～8.5MPa.
3. in accordance with the method for claim 1, it is characterized in that described industrial solvent gasoline is that alkene and methylbenzene kind compound content are not more than the gasoline fraction that 0.5 heavy %, boiling range are 60～90 ℃ or 80～120 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN91111489A CN1035676C (en) | 1991-12-12 | 1991-12-12 | Process for diesel flow improving agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN91111489A CN1035676C (en) | 1991-12-12 | 1991-12-12 | Process for diesel flow improving agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1073186A CN1073186A (en) | 1993-06-16 |
| CN1035676C true CN1035676C (en) | 1997-08-20 |
Family
ID=4910668
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN91111489A Expired - Fee Related CN1035676C (en) | 1991-12-12 | 1991-12-12 | Process for diesel flow improving agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1035676C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100434498C (en) * | 2006-12-26 | 2008-11-19 | 南京石油化工股份有限公司 | Agent for improving flowability of diesel oil |
| CN103626910B (en) * | 2013-11-29 | 2017-05-10 | 西南化工研究设计院有限公司 | Solid ethylene-vinyl acetate copolymer and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3891850A (en) * | 1970-11-27 | 1975-06-24 | Picker X Ray Mfg Ltd | X-ray table |
| EP0254284A1 (en) * | 1986-07-25 | 1988-01-27 | Hoechst Aktiengesellschaft | Process to improve the flowability of mineral oils and mineral oil distillates |
-
1991
- 1991-12-12 CN CN91111489A patent/CN1035676C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3891850A (en) * | 1970-11-27 | 1975-06-24 | Picker X Ray Mfg Ltd | X-ray table |
| EP0254284A1 (en) * | 1986-07-25 | 1988-01-27 | Hoechst Aktiengesellschaft | Process to improve the flowability of mineral oils and mineral oil distillates |
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| Publication number | Publication date |
|---|---|
| CN1073186A (en) | 1993-06-16 |
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