CN1035437C - Diesel-oil flow improving agent and its preparation method - Google Patents
Diesel-oil flow improving agent and its preparation method Download PDFInfo
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- CN1035437C CN1035437C CN 93120930 CN93120930A CN1035437C CN 1035437 C CN1035437 C CN 1035437C CN 93120930 CN93120930 CN 93120930 CN 93120930 A CN93120930 A CN 93120930A CN 1035437 C CN1035437 C CN 1035437C
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- CN
- China
- Prior art keywords
- flow improver
- maleic anhydride
- diesel
- add
- aliphatic amide
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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
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- Liquid Carbonaceous Fuels (AREA)
Abstract
The present invention relates to a method for preparing a flow improver for diesel oil, which is mainly characterized in that wax cracked alpha-olefin, alkyl acrylate and maleic anhydride are used as raw materials, azodiisobutyronitrile is utilized to initiate copolymerization under normal pressure, at 70-120 DEG C and under the protection of N2, and then a terpolymer type flow improver for diesel oil, which has the molecular weight of 5000 to 9000, is obtained through amination. The present invention has the advantages of simplicity and low cost, and the raw materials are easy to obtain. The flow improver has a favorable effect on reducing the cold filter plugging point.
Description
The invention belongs to the preparation method of diesel flow improver, or rather, is a kind of preparation method who is used to reduce the additive of diesel cloud point, cold filter clogging temperature, condensation point.
Diesel flow improver not only can improve the diesel oil at low-temperature flowing property, and diesel oil can normally be used in low temperature environment, but the while increasing output of diesel oil, save kerosene, improve the handiness that refinery is produced, increase the economic benefit of refinery, therefore, it has an effect of crucial importance industrial.
At present, terpolymer is newer in the world a kind of diesel flow improver, it is raw material with alpha-olefin, alpha, beta-unsaturated esters or acid anhydride and unsaturated monocarboxylic acid or ester that USP4731095 discloses a kind of, is the method that initiator prepares turbidity removal agent with the benzoyl peroxide.The alpha-olefin carbochain that this method adopts is an even number, and carbon chain lengths is C
16～C
30, raw material is difficult to obtain, and the large usage quantity of maleic anhydride (20～70mol%), thereby cost is higher.
The US4511369 patent disclosure a kind of preparation method of tetrapolymer.This method is with alpha-olefin, α, and beta-unsaturated carboxylic acid acid anhydride or ester, esters of unsaturated carboxylic acids and vinylbenzene are raw material, and copolymerization forms under the benzoyl peroxide effect.In this method owing to adopt the alpha-olefin of high carbon number and the acrylate of high carbon number, and α, the large percentage of beta-unsaturated carboxylic acid or ester, so raw material is difficult to obtain, cost is also than higher.
The objective of the invention is to overcome the shortcoming of prior art, provide one adopt waxcrack, be the method for raw material combined diesel oil FLOW IMPROVERS than the acrylate of low carbon number and maleic anhydride and aliphatic amide.
The present invention is realized by following proposal: with waxcrack, alkyl acrylate and maleic anhydride is raw material; under normal pressure, nitrogen protection and certain temperature condition; cause copolymerization by Diisopropyl azodicarboxylate, promptly obtain the terpolymer type diesel flow improver of molecular weight 5000～9000 again through amination.
Method concrete operations step of the present invention is as follows:
(1) be added to waxcrack, maleic anhydride and solvent in the reactor by a certain percentage, fed nitrogen 5～10 minutes, stir then, heat temperature raising to 70～120 ℃, best 75～95 ℃, add a certain amount of alkyl acrylate and initiator, reacted 1～4 hour, best 0.5～1 hour, obtain terpolymer;
(2) a certain amount of aliphatic amide is joined in the reactor, make the terpolymer amidation, 0.2～1 hour amination time;
(3) (2) step reaction soln is distilled, boil off solvent, the aromatic hydrocarbons thinning oil of weight such as adding and multipolymer promptly obtains diesel flow improver.
Above-mentioned steps (1) displacement nitrogen will be kept 5 minutes, at least with abundant displaced air, particularly oxygen, because the existence of oxygen will hinder copolyreaction.
Described waxcrack is that paraffin high temperature vapor-phase thermal cracking under the water vapor dilution obtains, and its boiling range is 245～345 ℃, and carbon number distribution is C
6～C
23, C preferably
14～C
19
The carbon number length of alkyl is C in the described alkyl acrylate
14～C
18
The ratio (mol ratio) of described waxcrack, alkyl acrylate, maleic anhydride raw material is 30～50: 50～60: 5～15.
The carbon chain lengths of described aliphatic amide is C
14～C
18, stearylamine preferably, the mol ratio of it and maleic anhydride is 1: 1.
Described solvent is gasoline or benzene, and its add-on is 30～60 heavy % of the material total amount of polymerization single polymerization monomer.
Described initiator is a Diisopropyl azodicarboxylate, and its add-on is 0.5～4 heavy % of the material total amount of polymerization single polymerization monomer.
The present invention compared with prior art, major advantage has: because the 'alpha '-olefin monomers that the present invention adopts is a waxcrack, this type of raw material is compared with higher carbon number and be easier the obtaining of alpha-olefin of even carbon chain; The boiling range of waxcrack is 245～345 ℃, and is more approaching with fraction of diesel oil (200～360 ℃), and the wax crystalls in the easier and diesel oil is had an effect, and falls the cold filter clogging temperature effect preferably thereby show; According to processing condition of the present invention, the consumption of maleic anhydride raw material decreases compared with the disclosed data of prior art, and the consumption of aliphatic amide also reduces accordingly, has so just reduced the cost of product.
Further specify characteristics of the present invention with example below.
Used main chemical feedstocks situation in the example: maleic anhydride and Diisopropyl azodicarboxylate are that the Beijing Chemical Plant produces, and all are CP levels; Stearylamine is that Wu Jing chemical plant, Shanghai produces the CP level; Waxcrack (245～345 ℃) is Lanzhou oil-refining chemical head factory production; Aromatic hydrocarbons thinning oil boiling range is 159～185 ℃, and Yanshan Petrochemical Co.'s refinery is produced.Used octadecyl acrylate is that (Science Press published in 1981 for E.C. Huo Ning chief editor, " (organic synthesis " the 3rd collection) is synthetic in the laboratory in accordance with known methods.The diesel oil of experiment usefulness is that the component oil blending of Nanjing Refinery forms blending ratio: normal two wires diesel oil 5%, atmosphere 3rd side cut diesel oil 5%, catalytic cracking diesel oil 55%, electrofining diesel oil 30%, second line of distillation diesel oil 5%.
Example 1
This example is a Comparative Examples, and the alkene of employing is octadecylene-1, according to the diesel flow improver of the method for USP4731095 preparation.
Agitator, N are being housed
2In the four-hole bottle of gas ingress pipe, dropping funnel and thermometer, add 2.50 gram (0.01 mole) octadecylenes-1,1.47 gram (0.015 mole) maleic anhydride and 15 milliliters of toluene, feed N
2Gas 5 minutes, beginning heat temperature raising to 90 ℃ starts agitator; In dropping funnel, add 3.20 gram (0.01 mole) octadecyl acrylates, 0.08 gram benzoyl peroxide and 10ml toluene, when the temperature in the reaction flask reaches 90 ℃ of temperature, the toluene mixture of beginning dropwise addition of acrylic acid octadecyl ester and Diisopropyl azodicarboxylate, the control rate of addition added material in 30 minutes, react the stearylamine that added 4.00 grams (0.015 mole) in 2 hours afterwards, under 90 ℃ of temperature, continue to stir 0.5 hour; Reaction soln is poured in the matrass, boiled off toluene wherein, be blended into the aromatic hydrocarbons thinning oil heavy again, promptly obtain diesel flow improver A with multipolymer etc.
Get the above-mentioned diesel flow improver A of 0.04 gram, join in the diesel oil of 40 grams, measure condensation point and the cold filter clogging temperature and the cloud point of oil product respectively according to the method for GB510-77,5Y2413-83 and GB6986-86, to observe the result of use of diesel flow improver, it the results are shown in Table 1.
Example 2
Agitator, N are being housed
2In the four-hole bottle of gas ingress pipe, dropping funnel and thermometer, add 3.80 gram (0.01 mole) wax olefin crackings (245～345 ℃) and 0.14 gram (0.0014 mole) maleic anhydride and 15 milliliters of toluene, feed N
2Gas 5 minutes is heated to 75 ℃ then, starts agitator; Add 5.51 gram (0.017 mole) octadecyl acrylates and 0.15 gram Diisopropyl azodicarboxylate initiator and 10 milliliters of toluene, dripped material in 60 minutes, copolyreaction was kept 2 hours; Add 0.38 gram (0.0014 mole) stearylamine, amidation was poured reaction soln in the matrass into after 0.5 hour, boiled off toluene, and the aromatic hydrocarbons thinning oil of weight such as adding promptly gets diesel flow improver B, records its molecular weight Mw=8200.
Get 0.04 gram diesel flow improver B, join in the 40 gram diesel oil, measure condensation point, cold filter clogging temperature and the cloud point of oil product, the results are shown in Table 1.
Example 3
Agitator, N are being housed
2In the four-hole bottle of gas ingress pipe, dropping funnel and thermometer, add the wax olefin cracking (245～345 ℃) of 1.90 grams (0.005 mole) and the maleic anhydride and the 15ml toluene of 0.25 gram (0.0025 mole), feed N
2Gas 5 minutes is heated to preset temperature (105 ℃) afterwards, begins to stir; In dropping funnel, add 2.92 gram (0.009 mole) octadecyl acrylates and 0.04 gram Diisopropyl azodicarboxylate initiator and 10ml toluene, in 60 minutes, drip material; Keep copolyreaction 2 hours, and added 0.67 gram (0.0025 mole) stearylamine and carry out amidate action, after 0.5 hour reaction solution is poured in the matrass, boil off toluene and be blended into the aromatic hydrocarbons thinning oil that waits weight, promptly get diesel flow improver C.Record molecular weight: Mw=6800.
Get above-mentioned diesel flow improver C, add in the 40 gram diesel oil, survey its condensation point, cold filter clogging temperature and cloud point, it the results are shown in Table 1.
Example 4
Agitator, N are being housed
2In the four-hole bottle of gas ingress pipe, dropping funnel and thermometer, add the wax olefin cracking (245～345 ℃) of 3.8 grams (0.01 mole), the maleic anhydride and the 15ml toluene of 0.25 (0.0025 mole), feed N
2Gas 5 minutes, heating makes that temperature reaches 90 ℃ of temperature in the reaction flask then, starts agitator; In dropping funnel, add 4.10 gram (0.0125) octadecyl acrylates and 0.24 gram Diisopropyl azodicarboxylate initiator, 10ml toluene, when temperature in the reaction flask reaches 90 ℃, begin to drip the mixture of toluene, octadecyl acrylate and initiator, the control rate of addition added material in 30 minutes, reacted afterwards 2 hours; The stearylamine that adds 0.67 gram (0.0025 mole) continues to stir 0.5 hour under 90 ℃ of temperature; At last reaction soln is poured in the matrass, boiled off toluene, the aromatic hydrocarbons thinning oil of weight such as adding and multipolymer promptly gets diesel flow improver D again, records molecular weight Mw=5700.
Get 0.04 gram diesel flow improver D, join in the 40 gram diesel oil, survey its condensation point, cold filter clogging temperature, cloud point, it the results are shown in Table 1.
Table 1
| FLOW IMPROVERS | Before adding agent | After adding agent | ||||
| Cloud point | Cold filter clogging temperature | Condensation point | Cloud point | Cold filter clogging temperature | Condensation point | |
| A | 10 | 6 | 2 | 8 | 5 | 1 |
| B | 10 | 6 | 2 | 8 | 3 | 1 |
| C | 10 | 6 | 2 | 8 | 4 | -1 |
| D | 10 | 6 | 2 | 8 | 3 | 0 |
Claims (5)
1. the preparation method of a diesel flow improver, it is characterized in that adopting carbon number distribution is C
6～C
23Wax destructive distillation alhpa olefin, octadecyl acrylate and maleic anhydride be raw material, under polymeric reaction condition, react, polymkeric substance obtains the terpolymer type diesel flow improver of molecular weight 5000～9000 after with the aliphatic amide acidylate, its preparation process is as follows:
(1) with C
6～C
23Waxcrack, maleic anhydride and solvent be added in the reactor, fed nitrogen 5～10 minutes, stir then, 70～120 ℃ of heat temperature raisings add octadecyl acrylate and Diisopropyl azodicarboxylate initiator again, react 1～4 hour, obtain terpolymer, described alpha-olefin, propylene hydrocarbon octadecyl ester, maleic anhydride mol ratio are 30～50: 50～60: 5～15, and the add-on of initiator is 30～60% of a polymerization single polymerization monomer material total amount
(2) a certain amount of aliphatic amide is added in the reactor, make the terpolymer amidation, 0.2～1 hour amination time,
(3) (2) step reaction soln is distilled, boil off solvent, the aromatic hydrocarbons thinning oil of weight such as adding and multipolymer promptly gets to required FLOW IMPROVERS.
2. in accordance with the method for claim 1, the carbon number that it is characterized in that waxcrack is C
14～C
19
3. in accordance with the method for claim 1, the carbon chain lengths that it is characterized in that aliphatic amide is C
14～C
18
4. according to claim 1 or 3 described methods, it is characterized in that aliphatic amide is a stearylamine.
5. in accordance with the method for claim 1, it is characterized in that used solvent is gasoline or benzene, its add-on is 30～60 heavy % of the material total amount of polymerization single polymerization monomer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93120930 CN1035437C (en) | 1993-12-21 | 1993-12-21 | Diesel-oil flow improving agent and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93120930 CN1035437C (en) | 1993-12-21 | 1993-12-21 | Diesel-oil flow improving agent and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1104221A CN1104221A (en) | 1995-06-28 |
| CN1035437C true CN1035437C (en) | 1997-07-16 |
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ID=4993475
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 93120930 Expired - Fee Related CN1035437C (en) | 1993-12-21 | 1993-12-21 | Diesel-oil flow improving agent and its preparation method |
Country Status (1)
| Country | Link |
|---|---|
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1110536C (en) * | 1999-07-29 | 2003-06-04 | 北京师范大学化工实验厂 | Diesel oil flowability improver and its preparation |
| CN100389137C (en) * | 2004-12-30 | 2008-05-21 | 中国石油化工股份有限公司 | Method for preparing polymer of butene diacid |
| JP5450411B2 (en) * | 2008-07-10 | 2014-03-26 | 株式会社Ａｄｅｋａ | Low temperature fluidity improver for biodiesel fuel |
-
1993
- 1993-12-21 CN CN 93120930 patent/CN1035437C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1104221A (en) | 1995-06-28 |
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