DE2037673A1 - Liquid fuel preparations - Google Patents

Description

DR. BERG DIPL.-ING. STAPF

PATENTANWÄLTE 8 MÜNCHEN 2, HILBLESTRASSE 2O

Dr. Berg Dipl.-Ing. Stapf, 8 Manchen 2, Hllblastrafie 20 Our sign

Attorney file 19 673
He / A.

date

July 29, 1970

Esso Research and Engineering Company Linden, W.J. (UNITED STATES.).

"Iruaaige Br ennaboff silver u ulations"

The present invention relates to Clüsaige Kohlenwanaer- ii bot't'-jrünnjjtoff- or Kraf Us boffzuberüibungen and for this purpose iieoLgn-j tu Fiiei3verbeaaerer and in particular the Yorboaaoriuif · au 'E ¹ Laid L bat by Ki'dol-Düa biLLubl: r a 'b.-iboff au (tironn ··: itoL'fan) with a üiedebereLoh of. IOC) Dia 45O ° ü odor

BATH ORIQINAL. ~ ² ~

109084/0993

such fuels mixed with flash distillate fuels. Both types of Distillate hydrogens, which can be present as fuel or fuels, are furthermore simplified as fuels designated.

The applicant has developed certain polymers as pour improvers for petroleum distillate fuels ₉ as described, for example, in British patents 900 202, 913 715, 922 748 and 1 003 3H.

Other polymers have been used in residue fuels and crude oils such as those disclosed in Applicant's British Patent 1,147,904 are described.

It has been found in practice that it is sometimes difficult to improve the fluidity of the fuel preparations with which the invention is concerned. In such difficult cases, the petroleum distillate plies disclosed above are some improvement, but not sufficient. Similar Ergeonisae are obtained when the _two lUiokabandaöl flow improvers mentioned above are used for the specified Üöerwindung Jchwiorigkeiten "

Eu was now found übarruiiuhönd go that the niürlcLioh spanked ; u ■ ^r ; , i-ivAm can, // urine man "the two types

09834 / Θ9Ι3 '' _SÄ0

Used together by mold improvers, the improvement as an unexpected one about the addition effect of the two types results in a going beyond effect.

Accordingly, the present invention provides in one embodiment a polymer mixture which is a first copolymer of ethylene and an olefinically unsaturated non-hydrocarbon monomer containing 3 to 30 carbon atoms per molecule and has a number average molecular weight of 700 to 3,000 and a second Copolymer of ethylene and an olefinically unsaturated one Mcht hydrocarbon monomer ranging from 30 to Contains 60 carbon atoms per molecule and a number average molecular weight of about 3,000 to approximately 60,000 contains.

Desirably is the number average molecular weight of the second copolymer in the range of | 4,000 to 20,000, for example 5,000 to 15,000, and the The number average molecular weight of the first copolymer is suitably in the range from 1,500 to 2,500.

At least one of the copolymers is suitable a copolymer of ethylene and an olefinically unsaturated one Light hydrocarbon monomer of 3 to 21, suitably 3 to 8 carbon atoms per molecule

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10988A / ÖÖS3 bad original

It is preferred that at least one of the copolymers a copolymer of ethylene and an olefinically unsaturated non-hydrocarbon-aliphatic monomer is.

Copolymers of ethylene and are particularly suitable a vinyl (or hydrocarbyl substituted vinyl · -) ester a monocarboxylic acid. ■

If desired, at least one of the. Copolymers a copolymer of ethylene, at least one other ot-olefin and be the monomer »-The preferred others 06-olefins are ethylene, 3? Ropylene, setradeoea, butene, isobutene or mixtures, for example a gauite fraction of ethylene and a smaller proportion (e.g. up to 10 f &) propylene *

Suitable olefinically unsaturated Mcht-hydrocarbon monomers are, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, vinyl hexanoate , vinyl heptanoate, vinyl octanoate, vinyl nonanoate, vinyl decanoate, vinyl laurate, vinyl stearate, vinyl dodecanoate, vinyl ether acrylate, vinyl dodecanoate, methyl acrylate, methyl acetate, methyl acrylate, methyl acetate, methyl acrylate, methyl acrylate, methyl acrylate, methyl acrylate, methyl acrylate, methyl acrylate, methyl acrylate, methyl acrylate, methyl butyl butyrate, vinyl butyrate, vinyl butyrate, vinyl valerate, vinyl butyrate, vinyl , Acrylonitrile, vinyl acetonitrile.

It v.'irö in the blends of this invention that. the erel'.e liisclipolymerisat a total of .99 to 40 $>

preferably 90 to 50 G-ewe ^ S o £. -olefins, which are preferably Ethylene alone or ethylene and propylene contains. It is further desirable that the second copolymer is one Total amount from $ 99 to $ 40, preferably $ 90 Ms 50 G-each o6-olefins, preferably ethylene alone or ethylene and Propylene are included

usually in the G-emic the weight ratio is the two copolymers from 20: 1 to 1:20, preferably 3: 1 to 1: 3.

Although the separate interpolymer ingredients can be mixed as such, it is generally desirable to make a concentrate. This can be done by combining each with a separate solvent, but most conveniently by dissolving each in a common solvent. It can therefore be the g

(first) copolymer with the low molecular weight in kerosene or cyolohexane and the second in a kerosene extract or G-atsch, (a wax obtained from a lubricating oil dewaxing process without purification or refining). The use of an aromatic solvent, for example mineral spirit, is preferred as the usual solvent for both copolymers. Suitable concentrates can be used as active ingredients 5 to 95 $> first copolymer and 95 to 5 $ '

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! 09804/0993 bad original

second copolymer (based on the total weight of the existing copolymer) contain »

The copolymers with the lower number average des Molecular weight can be determined by normal methods using free radical catalysts, preferably organic Peroxide Compounds That Are Made »Suitable processes are in some of the UK prefixed Patent specifications described.

Suitably, (particularly for ethylene-propylene copolymers or ethylene with vinyl acetate or other Vinylestern), polymerization temperatures can be used up to 130 ⁰ C and pressures from 35 to 141 ata psig (500-2000) of the 100th While any free radical catalyst can be used effectively under such conditions, it is often convenient to use lauroyl peroxide.

The copolymers with a higher number average molecular weight can be prepared as described in British patent specification 1 147 904

Under "number average molecular weight" is the molecular weight to understand this by means of vapor phase osmometry (using a "Mechrolab Vapor Phase Osmometer 301Δ ") or by means of membrane osmometry (under

109884/0993

- * 7 ~

Turn of a ¹¹ Me chro lab Membrane Osmometer 501 *) is measured.

The Torliegende invention provides a liquid hydrocarbon composition having improved fluidity is available in a further aspect, said one main part (1) a petroleum distillate fuel or fuel with a boiling range of 100 to 45O ⁰ G or (2) Petrol distillate fuel or fuel and a flash distillate fuel or fuel. Fuel and a smaller proportion, sufficient to improve the fluidity of the hydrocarbon preparation of a first copolymer and a second copolymer, contains, each copolymer corresponding to the preceding definitions of the invention

Suitably a total of 0.001 to 5 wt Copolymers, based on the weight of the fuel (heating oil) present, usually the required Total weight between 0.005 and 5, for example 0.005 to 0.5 or 0.005 to 0.1 / 0.2

If the fuel contains a portion of flash distillate fuel (heating oil), it is preferred that it be less than 60% V0I.9S and can usually be less than 4-0 or 30 56. Under "Flash distillate Bremistoff" is to adjust a distillate fuel or heating oil, the by flash distillation at verri-

109884/0993

• rtc · _: '■ ·.' ·: ■?! ■ - ■ SOUTH δ en -3- BUILDING Original

t 1

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from the normal distillation of crude oil "at atmospheric Refining residues obtained under pressure is recovered.

In terms of atmospheric pressure, such flash distillate fuels have often a boiling range in the range from 350 to 625 ° C.

It should be noted that the terms "petroleum distillate fuel" and "flash distillate fuel" like that be used that including such individual fuels or mixtures of different distillate fuels and mixtures of different KLash distillate fuels are to be understood. It follows that a mixture of distillate and flash distillate fuels is more than one May contain representatives of each individual fuel.

It should also be noted that the liquid hydrocarbon preparations according to the invention are those which contain two copolymers ©, regardless of whether they supplied to the preparations as a mixture or separately became.

The'Polyiaerisatgemisoh the invention can, as far as appropriate, a variety of other additives used in distillate and flash ·? Distillate fuel in the context of the present invention

—9— * '■ ORIGINAL INSPECTED

1 0900 ^ / 0093

used, included. I ¹ Such additives are typically food inhibitors, demulsifiers, corrosion inhibitors, anti-oxidants, dispersants, dyes, color stabilizers, haze inhibitors, antistatic agents, other flow improvers or pour point depressants.

Optionally or in addition, further additives can be added separately to the fuel or heating oil »

The following example explains the invention.

Bin ethylene / vinyl acetate copolymer having a low number average molecular weight The catalyst used was prepared by "conversion of ethylene and vinyl acetate prepared in an autoclave. Was lauroyl peroxide, the temperature was maintained psig (1050) at about 105 ⁰ C at a pressure of about 73 ata Cyclohexane was used as the solvent.

The product was recovered in a known manner and had a number average molecular weight of approximately 2,100 (by vapor phase osmometry) and a vinyl acetate content of 38 grains. This copolymer was referred to as copolymer A.

Am ethylene / vinyl acetate copolymer with a high number average of the molecular weight was prepared by a reaction as described in Example 3 «J of the Britisohen patent

1038Ö4 / 0 $ i3 ORIGINAL INSPECTED

- ίο -

document 1 147 904 is described. The product had one Numerical mean value of the molecular weight (vapor phase osmo-

, metry) of 10,000 and a vinyl acetate content of 26 wt. #.

This copolymer was referred to as copolymer B.

Two fuels (heating oils) were used. Fuel 1 was obtained a petroleum distillate having a boiling point in the range of 193 bia 353 ⁰ Oj and it was crystallized from a Oman crude oil. Bs had a specific gravity of 15/4 ° 0 of 0.8319, a kinematic viscosity at 37.8 ⁰ G (100 ⁰ F) of 2.93 cS, an aniline point of 71 »9 ° 0 and a sulfur content of 0, 68

Fuel 2 was a petroleum distillate with a boiling range of 167 to 364 ° 0, it being obtained from a mixture of Kirkuk and Arzew Eohölen. Bs had a specific weight of 60/6 ⁰ O of 0.8247, a kinematic viscosity at 37 | 8 ° 0 (10O ⁰ I ¹ ) of 2.46 cS, an aniline point of 70.6 ⁰ O and a sulfur content of O ₉ 23 wt.

These two fuels were tested to determine the low temperature utility of certain fuels, particularly diesel fuel. This test is known as the "Cold Filter Plug Point" (Ci ¹ PP) test. The procedure is detailed in Journal Inst. Pet. Vol. 52, Hr. 510, pages 173 to 185, in particular

109884/0093 original inspected

- 11 of them on pages 184 and 185, "described"

1 ο,

^{The Ci 1} PP in ( ⁰ O) was measured for each of the two fuels, with (1) no additive, (2) each copolymer separately and (3) the two copolymers being used together.

The results are summarized in the table below «

It should be noted that the copolymer A was used as a preparation containing 50% by weight of active ingredient in Contained kerosene. The copolymer B was used as a preparation containing 25% by weight of active ingredient in kerosene extract contained. The weights in column 2 of the table therefore relate to the weights of the preparations used.

ORIGINAL INSPECTED __ ₁₂ __

109884/0993

Encore
Saw. # - 12 -
Tabel preparation
Mixed poly
merisat B Preparation
Mixing preparation
polymer A and
Mixing preparation
polymer B
(Weight ratio, o1: 1) Brenn
material ' preparation
Mixed poly
merisat I CTPP ( ⁰ O) 0FPP ( ⁰ C) no GFPP ( ⁰ O) -6 -6 0.01 -6 -10 -12 1 0.03 -8th -11 -13 0.06 -8th -13 -19 no -8th -6 -6 0.01 -6 -10 -15 2 0.03 -6 -11 -17 0.06 -7 ' -12 -21 -7

The results clearly show the synergistic results obtained using the two additives.

109884/0993

Claims (1)

Patent claims: ^ -1 / polymer mixture, suitable for 'use as a flow improver in a hydrocarbon fuel preparation characterized in that it is a first copolymer of ethylene and an olefinically unsaturated one Wicht hydrocarbon monomer, with 3 to 30 Carbon atoms per molecule and a number average molecular weight of 700 to 3,000 and a second Copolymer of ethylene and an olefinically unsaturated Kicht hydrocarbon monomer, with 3 to 60 Carbon atoms per molecule and with a number average yvert the molecular weight of over 3,000 to 60,000. 2. Polyiuerisate mixture according to claim 1, characterized in that that the number average molecular weight of the second copolymer is in the range from 4,000 to 20,000, for example 5,000 to 15,000. 3. Polyuiörisatgemisoh according to one of the preceding claims characterized in that the number mean the molecular weight of the first copolymer is in the range from 1,500 to 2,500. 4. Polymer mixture according to one of the preceding claims characterized in that at least one of the Copolymers a copolymer of ethylene and 109884/0993 »14» an olefinically unsaturated Sioht ~ Kohlenwasaeratoffmonomer with 3 to 21, suitably J Ms 8 carbon atoms per molecule is 5. Polymeric admixture according to one of the preceding claims, characterized in that at least one of the copolymers is a copolymer <a »i ethylene and
is an olefinically unsaturated high-SCol & hydrogen aliphatic monomer » 6 »Palymerisatgemiaali according to the preceding claims thereby geteiiasaioiia®tt "cHaü ?i@B.iggtens © ines der Misohpolym © risate a Miachpolymei? Isat from ethylene "raid one Vinyl «- {oÄ (ir H; rir © oas ^; jl substituted em Yiayl-) Bster is a monooarlionic acid. 7r- Polymetieatgemisoh according to Anaprucli 6 iaöimch net that one of the Miselipolyiiei »isate ®1b Meohpcilymerisat of XthyleB with Yinylaoetat * 8 · Palymeyieatgemiach, genii eiaeis äer vorgelitaänen Insprehe daduroh gekemiseiohiittj, ate at least one of them MiBchpolymerioate a copolymer of ethylene, at least another od-olefin and the monomer is 9 · Polymerissate mixture gQEiäS -ilnsp ^ ucii 8 thereby gek (§anseich net that des anier © db-Ole ^ tu '"SsO ^ yIm is _o - lßiS84 / 6iii 10. Polymer mixture according to one of the preceding claims characterized in that the first copolymer has a total amount of 99 "to 40, preferably 90 Ms Contains 50% by weight of 6-olefins. 11. Polymer mixture according to one of the preceding claims, characterized in that the second copolymer a total of 99 "to 40, preferably 90 to ', Contains 50 wt. $ O ^ -olefins. 12. Polymer mixture according to one of the preceding claims, characterized in that the weight ratio of the two copolymers is 20i1 to 1:20. 13. Polymer mixture according to claim 12, characterized in that the weight ratio is 3 * 1 to 1 * 3. 14 · Polymer mixture essentially as under reference described on the example. 15 · flow improving additive concentrate characterized in that it contains as active ingredients 5 to 95 Gew.jG first copolymer and 95 ft * bia $ wt. Second copolymer, wherein the two itLschpolymerisate were explained in the preceding claims. 16. Concentrate according to claim 15, characterized in that that there is still one or more solvents for the . -16- 109884/0993 original inspected - Contains 16 copolymers. 17o liquid hydrocarbon composition in having improved fluidity in that it comprises a major proportion of (1) a ietrol distillate fuel having a boiling range of 100 to 45O ⁰ G or (2) the designated petroleum Lestillat fuel and a flash Contains distillate fuel and a minor proportion sufficient to improve the fluidity of the hydrocarbon preparation, a first copolymer and a second copolymer, each copolymer being defined in the preceding claims. 18. Preparation according to claim 17, characterized in that that it contains a total of 0.001 to 5% by weight of copolymers, based on the weight of the fuel. 19. Preparation according to claim 18, characterized in that it has a total amount of 0.005 to 5 $> preferably 0.005 to 0.5 wt. ^ Copolymers contains. 20. Preparation according to one of the preceding claims 17 to 19, characterized in that the fuel (2) contains up to 60 YoI.fo flash distillate fuel. 21. Preparation according to claim 20, characterized in that the fuel contains up to 40 <fo _r suitably below 30 $ plash distillate fuel. 109884/0993