CN1035776C

CN1035776C - Diesel flow improver

Info

Publication number: CN1035776C
Application number: CN 92114999
Authority: CN
Inventors: 黄燕民; 朱国荣; 许白敏
Original assignee: Sinopec Research Institute of Petroleum Processing
Current assignee: Sinopec Research Institute of Petroleum Processing
Priority date: 1992-12-29
Filing date: 1992-12-29
Publication date: 1997-09-03
Anticipated expiration: 2007-12-29
Also published as: CN1088962A

Abstract

The present invention relates to a diesel oil flow improver which is characterized in that the diesel oil flow improver is composed of polyethylene acetic ester and a terpolymer, wherein the terpolymer is prepared by polymerizing alpha-alkene, alkyl acrylate and unsaturated fatty acid anhydride according to a conventional preparation method; the weight ratio of the polyethylene acetic ester to the terpolymer is 1: 0.1 to 10. The present invention is suitable for improving the flow performance of middle distillate oil, especially diesel oil, and particularly improving low-temperature flow performance.

Description

Diesel flow improver

The present invention relates to a kind of diesel flow improver, relate to a kind of additive that is used to improve the diesel oil at low-temperature flowing property in other words conj.or perhaps.

Diesel flow improver has a crucial effect industrial: it not only can improve the low temperature flowability of diesel oil, make diesel oil in low temperature environment, be able to normal use, also significance is arranged simultaneously, therefore pay attention to industrial having caused widely to improving aspects such as refinery production handiness, saving mixed oil, volume increase solar oil.

In the prior art, there is multiple compound once to be used as diesel flow improver, to improve the performance of diesel oil.

DE856682, USP3640824, GB847777 and USP3454379 adopt a class to have the ethene polymers of side chain, as diesel flow improver.But the ethene polymers that only has side chain with this type of, as the component of unique diesel flow improver, in fact to improving the low-temperature performance aspect of diesel oil, effect is very not obvious.

USP3660057, USP3640691, USP3961916 and FR2061457 be a compounds, as with alpha-olefin, acetic ester and have the ester and the resulting compound of ethylene copolymer of unsaturated link(age), as the additive of the low-temperature performance of improving diesel oil.Use this compounds than using ethene polymers separately, improving aspect the low-temperature performance of diesel oil, though effect makes moderate progress, but still undesirable, especially for the higher diesel oil of wax content, effect is relatively poor.

Use a kind of composition that constitutes by ethene polymers and multipolymer as diesel flow improver among the USP4664676, improved the low-temperature performance of diesel oil largely, but because this agent is to adopt polyethylene and with alpha-olefin, acid anhydrides or α, beta-unsaturated acid ester, unsaturated acid ester are that the compound allotment of terpolymer that raw material is made forms, the compatibleness of whole improving agent is relatively poor, thereby make it to diesel oil, the higher diesel oil of wax content particularly is as the pour point depression of No. 0 diesel oil of China and fall the cold filter clogging temperature effect and be restricted.

The objective of the invention is to overcome the shortcoming of prior art, a kind of diesel flow improver that has good pour point depression and fall the cold filter clogging temperature effect is provided.

Technical characteristic of the present invention is, it be by molecular-weight average be 1500～2000 polyvinyl acetate and by alpha-olefin, acrylic acid alkyl fat and unsaturated fatty acids acid anhydrides be 1: 1～2: 0.08～0.5 mixed according to weight ratio after, be polymerized with conventional preparation method, molecular-weight average is that 5000～9000 terpolymer is formed; Wherein the weight ratio of polyvinyl acetate and described terpolymer is 1: 0.1～10.

Described polyvinyl acetate is the polyethylene vinyl acetate preferably, its molecular-weight average preferably 1800～2000; The weight ratio of polyvinyl acetate and described terpolymer better is 1: 0.25～4.

Diesel flow improver of the present invention, can adopt following method to allocate:

Described terpolymer and polyvinyl acetate by after the required mixed, are placed the blending container, be warming up to 30～80 ℃, can obtain product after stirring.

The preparation of above-mentioned terpolymer, adopt disclosed method among the USP4664676, be about to alpha-olefin, acrylic acid alkyl fat and unsaturated fatty acids acid anhydrides, be after 1: 1～2: 0.08～0.5 the mixed according to weight ratio, place the reaction vessel that solvent is housed, heat up and the adding initiator, carry out copolyreaction; Add amine compound then, carry out amidate action under 90 ℃, can obtain described terpolymer.

The used unsaturated fatty acids acid anhydrides of preparation terpolymer is α, β-unsaturated fatty acids acid anhydrides, preferably maleic anhydride; Used acrylic acid alkyl fat is C4～30 CALCIUM ACRYLATE preferably; Used solvent is the fraction oil of 120～250 ℃ of boiling ranges; Used initiator is benzoyl peroxide or Diisopropyl azodicarboxylate preferably.

One of technical characterictic that the present invention gives prominence to is to substitute polyethylene and the terpolymer assembly used in the prior art with polyvinyl acetate to prepare diesel flow improver.This mainly is because we are by discovering: polyvinyl acetate and terpolymer have compatibleness preferably, diesel oil had good susceptibility, can suppress growing up of wax crystallization in the diesel oil, therefore between polyvinyl acetate and the terpolymer good synergistic is arranged, and produced unforeseeable synergism, thereby improve the flowing property of diesel oil under the low temperature widely.

Another one technical characterictic of the present invention is to have changed terpolymer component content: promptly reduced the consumption of the higher maleic anhydride of price wherein, by the reasonable assembly to other component content, final product performance have been increased simultaneously.

The present invention is applicable to that boiling range is 160～360 ℃ middle distillate oil, particularly a diesel oil, can improve its flowing property, especially improves its low temperature flowability, more particularly, can reduce the cold filter clogging temperature and/or the condensation point of described base oil exactly.

The test of described base oil cold filter clogging temperature and condensation point, the method for employing SY2413-83 and GB510-77.

Using method of the present invention is: a small amount of diesel flow improver of the present invention is joined base oil, and in diesel oil, stirring gets final product.

The present invention is owing to adopted polyvinyl acetate to substitute the polyethylene that uses in the prior art, and terpolymer carried out reasonable assembly, the preparation diesel flow improver makes it compared with prior art have more good cold filter clogging temperature and/or the pour point depression point performance of falling; Simultaneously, its cost is decreased owing to reduced the consumption of the higher maleic anhydride of price wherein.

Further describe technical characterstic of the present invention below by embodiment and Comparative Examples.

Example 1～5

Example 1～5 has been introduced the preparation process of terpolymer.

With octadecylene-1 (Lanzhou Oil Refinery product), maleic anhydride (chemical pure, Beijing Chemical Plant's product), octadecyl acrylate (chemical pure, Beijing Chemical Plant's product) and the solvent oil (technical grade of 120～250 ℃ of fractions, dawn chemical plant, Beijing product) ratio of giving according to table 1 is positioned in the reaction vessel, be warming up to 90 ℃, stir Diisopropyl azodicarboxylate (chemical pure, the Beijing Chemical Plant's product) initiator that adds down with the dilution of a small amount of solvent oil, carry out copolyreaction, stopped reaction after 2 hours; Reaction product and an amount of stearylamine (chemical pure, Wu Jing chemical plant, Shanghai product) are carried out amidate action 2 hours under 90 ℃ temperature, steam and desolventize oil, can obtain molecular-weight average and be 5000～9000 terpolymer A, B, C, D and E.

Example 6

Example 6～11 has been introduced the process for preparation of described improving agent mixture.

Above-mentioned terpolymer A and plastic of poly vinyl acetate (Shanghai general petrochemicals factory product) according to 1: 2 ratio of weight ratio, are mixed at 30 ℃, promptly obtain described improving agent A-1.

Example 7

Above-mentioned terpolymer E and plastic of poly vinyl acetate (Shanghai general petrochemicals factory product) according to 1: 0.5 ratio of weight ratio, are mixed at 80 ℃, promptly obtain described improving agent E-1.

Example 8～11

Respectively with above-mentioned terpolymer B, C, D and plastic of poly vinyl acetate (Shanghai general petrochemicals factory product) according to weight ratio 1: 1, the ratio of 1: 4 and 1: 0.25 mixes at 50 ℃, promptly obtains described improving agent B-1, C-1, D-1.

Comparative Examples

This case introduction process and practical effect that terpolymer and ethene polymers are carried out assembly.

Terpolymer A and polyethylene (molecular-weight average is 1000～1400, dawn chemical plant, Beijing product) are carried out assembly according to 1: 1 ratio of weight ratio, obtain contrasting improving agent DD.

After diesel oil mixed with 40 grams with 0.04 gram improving agent DD, zero pour and cold filter clogging temperature with the method measurement oil product that GB510-77 and SY2413-83 gave the results are shown in Table 2.

Example 12

Example 12 has been introduced and has been added above-mentioned improving agent to reach diesel fuel characteristics in the diesel oil test process.

With above-mentioned improving agent and diesel oil be by weight 1: 1000 mixed evenly after, obtain experimental oil, zero pour and cold filter clogging temperature with the method measurement oil product that GB510-77 and SY2413-83 gave the results are shown in Table 2.

Table 1

The terpolymer numbering	A	B	C	D	E
The terpolymer numbering	A	B	C	D	E	Octadecylene-1, gram	2.50	3.75	5.00	7.51	5.00
The octadecyl acrylate gram	6.40	6.40	6.40	13.00	13.00	Octadecylene-1, gram	2.50	3.75	5.00	7.51	5.00
The octadecyl acrylate gram	6.40	6.40	6.40	13.00	13.00	Maleic anhydride, gram	0.20	0.50	1.00	2.00	2.50
Solvent oil, milliliter	250	250	250	250	250	Maleic anhydride, gram	0.20	0.50	1.00	2.00	2.50
Solvent oil, milliliter	250	250	250	250	250	Initiator, gram	0.06	0.15	0.07	0.05	0.06
Stearylamine, gram	0.55	1.37	2.74	5.48	6.86	Initiator, gram	0.06	0.15	0.07	0.05	0.06
Stearylamine, gram	0.55	1.37	2.74	5.48	6.86	The average mark molecular weight	5190	7230	6490	8280	6740

Table 2

The oil sample numbering	Used improving agent	Add the preceding oil sample performance of improving agent, ℃		Oil sample performance behind the adding improving agent, ℃
				Oil sample performance behind the adding improving agent, ℃		Cold filter clogging temperature	Condensation point	Cold filter clogging temperature	Condensation point
		I[1]	A-1	6	2	Cold filter clogging temperature	Condensation point	Cold filter clogging temperature	Condensation point	-1	-22
I	B-1	I[1]	A-1	6	2	6	2	-1	-19	-1	-22
I	B-1	I	C-1	6	2	6	2	-1	-19	0	-16
I	D-1	I	C-1	6	2	6	2	1	-18	0	-16
I	D-1	I	E-1	6	2	6	2	1	-18	0	-24
I	D-D	I	E-1	6	2	6	2	5	-2	0	-24
I	D-D	II[2]	B-1	8	4	6	2	5	-2	6	-6
II	C-1	II[2]	B-1	8	4	8	4	5	-5	6	-6
II	C-1	II	D-1	8	4	8	4	5	-5	6	-6
II	E-1	II	D-1	8	4	8	4	6	-8	6	-6

Annotate:

[1]-and used diesel oil is the Nanjing Refinery product, its boiling range is 204～364 ℃;

[2]-and used diesel oil is refinery product of Yanshan Petrochemical company, its boiling range is

228～358℃。

Claims

1. diesel flow improver, it is characterized in that it by molecular-weight average be 1500～2000 polyethylene vinyl acetate and by alpha-olefin, acrylic acid alkyl fat and unsaturated fatty acids acid anhydrides according to weight ratio be polymerized with conventional preparation method after 1: 1～2: 0.08～0.5 mixed, molecular-weight average is that 5000～9000 terpolymer is formed; Wherein the weight ratio of polyvinyl acetate and described terpolymer is 1: 0.1～10.

2. according to the described improving agent of claim 1, it is characterized in that described polyethylene vinyl acetate molecular-weight average is 1800～2000, the weight ratio of polyethylene vinyl acetate and described terpolymer is 1: 0.25～4.