DE2017493A1 - Process for separating paraffin from petroleum - Google Patents

Description

Bsso Research and Engineering (US 818 380 - prio 22.4öl969 Company _69o6)

Linden trees. NJ. V.St.A. Hamburg, April 9, 1970

zum Abjrennen_yonBaraf | 'in, from petroleum

The invention relates to a method for separating paraffin from petroleum using dewaxing agents, in particular from C., - bia Co ^ -ot mono olefin-containing polymers of the Ziegler type _o

Various methods are known for separating paraffin from petroleum. One of these methods consists for example, that the paraffin-containing oil cools and the solid paraffin is filtered off. One of the most widely used methods of dewaxing of oils is this as solvent dewaxing (solvent dewaxing) known process »In this process, the oil is diluted with a solvent and heated it until completely dissolved and then cool it down. until the desired amount of paraffin has crystallized out »The paraffin crystals formed in this way are removed from the Slurry filtered off »The paraffin is then further purified while the solvent is recovered for reuse and the deparaf » refined oil is passed on to further refining processes

009846/1573

Although this Luaungenlttel deparing other The process for separating paraffin from hydrocarbon oils has largely replaced »is filtration the wax crystals from the one during dewaxing obtained slurry difficult «so that the rate of piltraction of the slurry is often the The performance of the overall process limited the rate of filtration the slurry depends mainly on the size and shape of those in the KUhI stage The wax crystals formed during the process are determined. Very fine crystals tend to have that Filters quickly clog, reducing the rate of ionization is reduced and finally a shutdown of the filter to remove the accumulated Paraffins are required «Very large crystals, on the other hand, tend to be gel-like, coherent To form masses which do not result in a solid filter cake and a large amount of oil and solvent hold back and are difficult to wash »

To eliminate these difficulties, a general move has been made to paraffin-containing petroleum to put with substances that change the size and shape of the Paraffinkriatalle in such a way that a rapid separation of the paraffin in the dewaxing stages mögllda is «. These substances are as

009846/1573

Dewaxing agents known. In the case of HSA patent publication 3 355 379, a dewaxing process was observed in which one a poly-cc -olefin with a molecular weight of 10 million or more as all dewaxing agents used «In dleaer Fatentachritt is also checked, The molecular weight is critical because there are polymers with lower molecular weight have proven to be practically ineffective.

Contrary to this, it has now been found that it was troubled Folyners of ^ monoolefins are extremely effective dewaxing agents even at relatively low molecular weights.

Accordingly, the present invention proposes a method for separating paraffin from petroleum, in which aan daa oil to form feater paraffin criatalle cools and the paraffin criatalle is removed and which is characterized in that one did daa oil to form paraffin criatalle, based on daa to be dewaxed oil, ßew with about 0.001 to about 5.0 wt. £, preferably 0.005 bia 2.0. £, a nindeatena to 30 wt «^ aua ..- C to 24 ~ ^ ~ ^Λ monoolefin Bllöelichen existing polymers having an" average Molecular weight after

Number of funds from about 1,000 to 200,000 staggered

0098A6 / 157 3

, .. ■: ■ -, -_ © AD ORIGINAL

2017 433

According to a preferred embodiment of the invention, said polymer is used in a mixture with a Friedel-Crafts condensation product of a halogenated paraffin hydrocarbon with an aromatic hydrocarbon, e.g. naphthalene, which synergistically improves the separation of paraffin from briquettes.

The dewaxing agents preferred for the process according to the invention are polymers of at least two different α-monoolefins with about 14 to 24 and preferably 14 to 20 carbon atoms in the molecule or mixtures of at least two different homopolymers from C ₁ to C 10 monoolefins and preferably C ₁₄ - ^ta * ^a Cp ₀ - ^ - monoolefins "Particularly preferred is a copolymer of 15 to 35 Tew ,,?" n-hexadecene-1, 15 to 30 wt.% n-0ctadecen ~ 1 _t 10 to 20 wt. # n-eicosene-1 and 25 to 45 wt. $ c.- Mo Cq ct, mono-olefin, for example, n-hexene -1o

The ο Preferably C. .- used to prepare the Entpäraffinierungamittels for the present invention to C ₂ I ^"06", "mono-olefin can be represented by the general formula Hp, wherein R is a substantially straight-chain hydrocarbon residue having 12 to 22 carbon atoms, R is a

0098Α6 / 1 5 73

§AD ORIGINAL

General Form Group! CBL- (CHg) _n - ^CH 2 - » ^wor * ⁿ η is an integer from about 10 to about 20, and preferably from about 12 to 16. In the present description, "essentially straight-chain» ¹ · hydrocarbon radicals are understood to mean aliphatic chains which contain at most one side chain in the form of a lower alkyl group such as methyl, ethyl, etc. and in which this side chain, if present, is located at such a point, 'that H has a straight-chain part with at least 12 carbon atoms »Suitable monomers include, for example, n-tetradecene-1, n-hexadecene-1, 3-methylhexadecene-1, n-octadecene-1, n-eicosene-1, 4- Methyl eicosen-i, n-docosen-1 and the like.

In general, the polymer used as a dewaxing agent for the process according to the invention contains at least 3% by weight and preferably from 10 to 100% by weight of the said Cj- to C "* - OC-monoolefin". ^ contain other polymerisable monomers such as C 1 to C ₁₂ <.- olefin monomers · When polymerising these lower comonomers with known C ^ .- to ° 24 "CL monoolefins, a copolymer is obtained which is easier to prepare and more economically attractive .

■ ■: - 6 -

0 0 9 8 A 6/1 5 7 3 ° ^{m ®NAL}

_{The C 1 -C 2} -Ql-olefins polymerized with said C ^ .- to C ₂ ^ -et-monoolefins can be represented by the general formula H ₂ CaCHR ', in which R ^{1 is} a hydrocarbon radical having 1 to 10 carbon atoms is · The configuration of the remainder R * does not seem to be critical. R * can therefore consist of an alkyl, aralkyl, aryl or alkylaryl group or a cyoloaliphatic group. Suitable monomers of this type are, for example, propylene, butene-f _t hexene-1, octene-1, decene-1, 3-methyldecene-i, and 3tyrol 3tyrolderivate such as p-methylstyrene, p-isopropylstyrene, "-Hethylstyrol and the like. The mentioned C * .- to Cg.-Ql monoolefins can also be polymerized with various other monomers. For example, effective copolymers can consist of 30 to 100% by weight of said Q - * - to C ₂ oil olefin and 0 to 70% by weight of a polymerizable C ₅ - to Cjg -dolefin polymers used in the process according to the invention to 30 to 100 wt. ^ of the said C * .- to C ₂₄ -CL monoolefin, to 0 to 70 wt. # of the said C to C ₁₂ -OL olefin and to 0 up to 70 wt. 76 of a polymerizable • Cr to C ^ diolefin. These olefins, which can be polymerized with the named QC olefins, include, among others

ORIGINAL INSPEGTED ₁

009846/1573

Blcyeliiohen, alioyclic and aliphatic diolefins with et «· 5 here etna 12 and preferably about 6 to 12 carbon atoms.Suitable monomers of this type are, for example, ivS-cycloootadiene, methylennorbornene, dimethylennorbornene, 1,5-hexadiene, dicyclopentadiene, 5-vinyl-2- norbornene, 1,5-cyclodecadiene, 2,4-dimethyl-2 _t 7-octadiene, 3 (2-methyl-1-propenyl) cyclopentene, 1,5-octadecadiene and the like.

The copolymer preferred for the present invention consists of at least two different straight-chain C ₁ .- to CgQ - ^ "monoolefins, at least two of these oc-monoolefins each in an amount of 10 to 90 wt. ^ And preferably 30 to 60 wt. ^ Of interest is a copolymer which is made from at least two different straight-chain Ο ..- to Cg ₀ -Ot-monoolefins and essentially from 0 to 60%. for example 1-butene or 1-hexene, 0 to 70% by weight of tetradecene-1, 0 to 70% by weight of hexadecene-1, 0 to 70% by weight of octadecene-1

and 0 to 70% by weight of eicosen-1. Of particular interest is a copolyeree which is composed of 15 to 60, preferably 25 to 45, oew. <Hexene-1, 10 to 50, preferably 13 to 35ι wt. ^ N-hexadecene-1 _f 10 to 40,

do ' -

preferably 15 to 30% by weight of octadecene-1 and 5 to P, preferably 10 to 20% by weight of n-eicosen-1.

0098-4671573

According to another preferred embodiment of the invention, the oil waxing agent consists of a mixture of at least two different _{homopolymers produced from the above-mentioned C 1} J to CgQ - ^ - monoolefins, none of the homopolymers being more than 80% by weight, preferably not more than 60 Gewo ^, of the polymer mixture. A particularly effective mixture consists of 0 to 70 wt _o $, for example, 40 Custom #, polyhexadecene, 0 to 70 wt. #, For example, "30 wt. #, PoIyoctadecen and O to 70 wt. ^ _1, for example 30 wt. ^, PoIyeioses.

The polymers for the present invention generally have an average molecular weight according to the numerical average in the range from 1000 to 200,000, preferably from about 1,500 to about 100,000 and more preferably from 2,000 to 30,000. The average Number average molecular weights up to about 30,000 are determined by vapor phase osmometry, e.g. using a vapor phase oemometera model 310A, measured while the higher molecular weights can be measured by membrane geometry.

The polymers for the present invention can in the usual way by polymerizing the monomers

INSPECTED 009846/1573 ™ ^lw " ^vnJN

under relatively mild temperature and pressure conditions in the presence of the catalysts commonly known as coordination catalysts. These Catalysts are made from two components of different types, namely compounds of the heavy Transition metals of groups IV, V and VI of the periodic table, starting with titanium, vanadium and chromium, and organometallic compounds and hydrides of metals of groups I, II and III of the periodic System, the compounds of the metals from groups IV to VI in amounts of 0.01 to 2.0 mol each Mol of the organometallic compound can be present

The compounds of the first type are preferably halides, oxyhalides and mixtures thereof, with titanium and vanadium being preferred as metals. The second component is preferably an organometallic compound of lithium, sodium, magnesium or aluminum, in which the organic part preferably consists of _; consists of an alkylreat. In these organometallic compounds, the valence of the metal may be partially saturated by halogens or alkoxyls, provided, of course, that at least one bond has the metal directly on a carbon atom

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009846/15 73

binds. Often, mixtures of two or more of the connections of the type described above with Advantage can be used.

To »polymerize the inventive monomers The following combinations, among others, are suitable as catalysts: aluminum triisobutyl and vanadium trichloride, aluminum triisobutyl, aluminum chloride and . Vanadium trichloride, vanadium tetrachloride and aluminum trihexyl, vanadium trichloride and aluminum trihexyl, Titanium tetrachloride and Aluroiniumtrihexyl, Vanadiumtrichloriä and Aluminumtrihexyl, Titanium trihexyl and Aluminum trihexyl, titandichlorld and aluminum trihexyl and the same.

To carry out the polymerization, the catalyst components are generally mixed into an inert diluent such as a hydrocarbon solvent, * for example hexane, benzene, toluene, xylene, heptane or the like, and then the monomers at atmospheric pressure or elevated pressure and temperatures in the range of about 10 ° to 82 ⁰ C, the catalyst mixture ssu added. In general, when polymerizing monomers having more than 4 carbon atoms in the molecule at atmospheric pressure and when polymerizing

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009 846/1573

ORIGIN * '. INSPECTED

the more volatile G ₃ - to C ₄ -Oi-olefins worked under increased pressure. The reaction time depends on and is related to the reaction temperature, the choice of catalyst, the pressure used and the desired conversion of the monomers. In general, however, the reaction is over after t / 2 to 5 hours.

In general, one uses for the polymerization, based on the weight of the polymer to be produced, about 120 to 100,000 parts by weight of solvent and about 0.05 to 5 parts by weight of catalyst.

The polymers according to the invention are very effective dewaxing agents and pilgrim aids in dewaxing processes, in which the oil is cooled to form solid wax crystals and the wax crystals are then removed in an analogous manner. Particularly good results have been achieved in the processes known as solution dewaxing. It has been found that in these processes the removal of ¹ % of paraffin that has been deposited from an oil by adding τοπ about 0.001 to about 5 wt.} *, For example 0.01 to 0.06 wt Oils) of the polymers or mixtures according to the invention the same can be substantially improved.

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The polymeric additives according to the invention can be used to remove paraffin from a wide variety of petroleum products such as residual oils, middle distillates and the like, but they have proven to be particularly advantageous for paraffin-containing distillate and residual lubricating oil fractions, such as solvent-neutral oils and bright stocks. " fractions generally have boiling points in the range of about 200 ° bia about 60O ⁰ C and contain from about 5 to about 30 G3W "# paraffins

The wax crystal modifier, the wax-containing oil and, if used, the dewaxing solvent can be mixed together in a number of ways. Thus, for example, can mix or Paraffinkriatallmodifikator and the waxy oil prior to adding the Entparaffinierungalösungsmittels each other but the dewaxing W löaungsmittel with the oil before adding the paraffin mix crystal modifier. The mixing temperature should be higher than the cloud point of the paraffinic petroleum. For example, mixing temperatures of about 5O ⁰ C to about 12O ⁰ C suitable

However, the mixing temperature is preferably in the

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Range from about 70 ° to 95 ⁰ C.

009846/1573

INSPECTiO

- 13 - ⁴ 201749

Particularly good results are achieved when the polymer additive according to the invention is used in a conventional dewaxing process. " For example, mixtures of the polymer described, the dewaxing solvent and the paraffin-containing oil can be worked up by cooling the mixture in a suitable manner to a temperature at which the paraffin precipitates. The paraffin can then by centrifugation or are preferably removed by filtration "The dewaxing is preferably carried out at a temperature in the range of about -40 ° to about -6 ⁰ C and in particular in the range of about -35 ° to about ⁰ -9 C. Dewaxing solvents, which can also be used with advantage for the process according to the invention, are known in large numbers to the person skilled in the art, «Β» benzene, toluene, acetone, methyl ethyl ketone, methyl isobutyl ketone, propane, hexane,)! thyroid chloride, aliphatic alcohols, naphtha and mixtures thereof, for example a mixture of methyl ethyl ketone and toluene in the ratio 45-55, a mixture of methyl ethyl ketone and benzene in the ratio 30-170, and the like. The solvent is ^s per volume generally used in an amount of 0.5 to 3 »5 parts by volume to entparaffinierendem oil.

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0098 4 6/1573 ⁰ ^ iNAL INSPECTED

As has already been said above, the separation of paraffin from petroleum is synergistically improved by using the above-described polyolefins in a mixture with the known paraffin ring modifiers obtained by Priedel-Crafts condensation of a halogenated paraffin with an aromatic hydrocarbon. The halogenated paraffinic hydrocarbon can contain, for example, from about 8 to about 60, preferably from about 16 to about 44, carbon atoms and from about 5 to about 25% by weight, preferably from about 10 to about 18% by weight, of chlorine. The halogenlerten paraffins used in preparing these known Paraffinmodifikatoren be prepared by chlorinating a paraffin wax having a melting point in the range of about 40 ° to 88 ⁰ C until referred to achieve See Chlorierungegrades. The aromatic hydrocarbons used contain a maximum of three substitution groups and / or condensed hinge and can consist, for example, of a hydroxy compound such as phenol, Krespl or IyIθno1 or an amine such as aniline, but naphthalene, phenanthrene or anthraea are preferred. The Priedel-Crafts condensation products which can be used for the invention are prepared by known processes, as described, for example, in British Patents 511,207 and 562,714.

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009846/1573

ORIGINAL INSPECTED

201749

The aynergy pool which can be used as a paraffin crystal modifier according to the invention can contain various amounts of the polyolefins and Friedel-Crafta condensation products mentioned. In general, a Oeeiβch is used which, for example ionaprodukt 25 to 75 wt. ^ 50 wt. ^, Kbnd Ensat and 25 bie dew 75 ·, SB 50 0EW. ^ _T polyolefin contains.

For easier handling, the invention counterfoot can be used PolyjDare additive to be used in fora a Konaentratee. So can nan the polymer to facilitate storage and the Traneportee beiepielaweiee old of a Kbhlenwaaeeratofflöeuneiittel, like one Mineral oil, heptane, toluene and the like, see one below Dissolve the concentrate, which is about 20 to about 80 ßew. £ hydrocarbon solvent and about 20 to Contains 80 wt. ^ C polymeric Zieataetoff.

The polymeric Zuaattatoff of the present invention is compatible ait and other additives can be mineral oils old νemisent which small amounts of agents for improving the Yiskositatsindexes, Roatachutsnitteln, means for Terbeaserung the 3ohaierfahigkeit _t Oxydationaschutznltteln and the like with good success "

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0 0 9 8 4 6/1 5 7 3

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The following examples serve to provide a more detailed explanation the inventionρ

example 1

Ee became a homopolymer of n-tetradecene-1 manufactured in the following way

In a four-shark flask of 500 ml content, which is equipped with a mechanical stirrer, heating mantle, thermometer _t cooler) and. Gas feed line was equipped were _t under waaa erfrei en conditions 0.11 g cokristalliaierter titanium trichloride of aluminum trichloride Katalygator (TiCl ^ .1 / 3AlOl _3), 75 ml of xylene and 0.41 g ala solvent Triäthylaluminiu © given This mixture of catalyst and solvent was stirred for about 30 minutes at room temperature and then ^{heated to about 75 °} C. under nitrogen and mixed with 19 g of n-tetradecene-1. After the addition of the ^ olefin was complete, the reaction mixture was heated for about 2 hours at 70 ° to 80 ⁰ C, after which to stop the reaction 1 ml of isopropyl alcohol was added. The resulting mixture was cooled to room temperature and then mixed with about 10 parts by volume of methanol in order to precipitate the solid tetradecene homopolymer, which was then filtered off and ^{kept in an oven kept at about 60 °} C. and 120 mm pressure for about 12 hours

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·. . 009846/15 73

2017A93

was dried. The finished polymer weighed 13 g and had a number average molecular weight1 measured by Gaaphaaen oamometry (OPO), from about 5GOO.

Example 2

According to the same general procedure as in Example 1, various homopolymers and copolymers of normal C ^ - his "C ^ O /""° ^ ~ ^{Μοηοο1βί} inen were prepared. The properties of these oils, which are referred to below as test oil A and test oil B, are shown in Table I below.

Table I Properties of the tea oils

Testai A (1) Tea oil B (2)

Viscosity, ASTM, 3U5 at 99 ° C 27.9 160 Density, API 31f76 26.7

Pour Point, ASTM, ⁰ C 49 51.5 Paraffin content, wt, ^ 23.9 15

(1) Texas Panhandle Crude Distilled Lube Stock

(2) Louisiana crude residual lube stick

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009846/15 73

For dewaxing, Testttl A was diluted with a solvent of 55 Vol.jt MathylathyIketoη and 45 Vol. £ toluene in a ratio of solvent to oil of 3.111 and then at a rate of 1.5 to 3 ⁰ C per minute from a feed temperature of 60 ° cooled to a Piltertemperatur of -18 ⁰ C. The cooled mixture was continuously filtered through a cooled round leaf filter at a pressure gradient of 560 eh Hg. The filtration cycle consisted of a filtration time of 28 seconds, a drying time of 5 seconds, a washing time of 22 seconds and a second drying time of 8 seconds.

Similarly, the Teetöl B was diluted for dewaxing with hexane in a ratio of solvent to oil of 3 '1 and then at a rate of 1.5 to 3 ⁰ C per minute from a Zuftihrtemperatur of 60 ⁰ C to a Piltertemperatur of - 34 ⁰ C "cooled The cooled mixture was then continuously filtered through a cooled round leaf filter at a pressure gradient of 508 mm Hg. The filtration cycle consisted of a filtration time of 36 seconds, a drying time of 9 seconds, a washing time of 27 seconds and a second drying time of 8 seconds.

^the ° - 19 -

009846/1573

ORIGINAL INSPECTED

Furthermore, the test sheets were made in the same manner dewaxed as above, but one each Sample before cooling with 0.02 to 0.12 wt. # (based on the weight of the paraffinic oil) one of the homopolymers listed below, Copolyiaeren or homopolymer mixtures was added. The blends containing the polymers or polymer blends were then individually among the same dewaxing conditions as above Treated mixtures described without dewaxing agents.

The results obtained on dewaxing test oil A are shown in Tables and below those obtained from dewaxing test oil B. Results are shown in Table III below.

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009846/1673

Table II Dewaxing of TeBt Bl ₁₁ A Used relative Dewaxing agent filtration

- - - gea.chylndigke it (1)

without .1.00

0.06 wt. # N-tetradecene-1-

Homopoly egg (2) 1.91

0.06 wt. 56 n-hexadecene-t-

Homopolymer O) 3 »56

0.06 GeWo ^ n-Ootadecen-1-

Homopolymers (4) 2 * 09

0.03 Gewoji n-tetradecene-1-

Homopolymer a (2) plus

0.03 ßew. t n-octadecene-1-

Honopolyneres (4) 4.23

0.03 0ew #? I n-hexadecene-i-

HoDopolymers (3) plus

0.03 oew.ji n-octadecene-1-

HoiDDpolymers8 (4) 4.46

(1) Ratio of the filtration speed of the oils with dewaxing agent for filtration The oil is speedy without dewaxing agents

(2) Homopolyiieree according to Example 1

(3) Average molecular weight according to the Numbers around 6 800 (DFO)

(4) Number average molecular weight about 7,300 (DFO)

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0 0.9 8 4 6 /1.5 7 3 originally inspected

Table III Dewaxing of tea oil B

Used relative Dewaxing agent filtration

- ·· ■. ·. gea CHWI nä igkei t

without 1 "ÖO

0.05 wt. # N-tetradecene-1-

Homopolymer (i) 1.91

0.05 Gewo # n-Hexadecen-1-

Homopolymers (2) 1.98

0.05% by weight of n-octadecene-1-

Homopolymer (3) 1.81 _V

0.05 wt. # N-tetradecene-i / n-octadecene-1 copolymer (4) 2.67

0.05 wt. # N-hexadecene-1 / n-Octadecene-1 ~ copolymer (5) S, 86

0.05 wt. 5i n-butene-t /

n-Hexadecene-1 copolymer (6) 2j 53

0.05% by weight n-hexene-1 /

(7) 2.92

(1) Homopolymer according to Example 1

(2) average molecular weight after Number average about 6 600 (DPO>

(3) Number average molecular weight about 4,900 (DR)>

(4) Copolymer of 38% by weight of tetradecene and 62% by weight Octadecene with a number average molecular weight of about 2450 (DPO)

(5) Copolymer of 40% by weight of hexadecene and 60% by weight Octadecene with a number average molecular weight of about 2350 (DK))

(6) Copolymer of 40% by weight of butene and 60% by weight Hexadecene with a number average molecular weight of about 9200 (DPO)

(7) interpolymer aua 38 wt _o $ hexene, 26 wt »^ n-hexadecene-ic 21 wt« ^ n-octadecene-1 xmä 15 Gsw ^ n-Eicoasn-i with eins® average mol © k \ alarms weight ' according to the numerical average of about 28,000 (JDH))

2017

As can be seen from the values in the above tables, the polymers of the present invention made from the oil-olefins are extremely effective in improving the oil leakage rate in a conventional solvent dewaxing process. Furthermore, the values show that copolymers of C ₁ ^ - to Cg ₀ -otitonoolefins and mixtures of different homopolymers of these monoolefins are more effective than equal amounts of homopolymers from only one of the monoolefins mentioned.

Example 3

With this example the influence of the molecular " weight of the polymeric dewaxing agent its ability to reduce the oil filtration speed in to improve a dewaxing process will.

A copolymer was obtained in the same manner as in Example 1 by polymerizing a monomeric odor of 38 wt. 56 Hexeh-1, 26 wt. 56 Hexadecen-1, 21 6ew. ^ Octadecen-1 and 15 & ew. ^ Biooaen-1 produced, being different fractions with different molecular weights by fractional precipitation with addition obtained from methanol to a polymar benzene solution

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· Each polymer fraction was used in a concentration of 0.06% by weight (absorbed on the oil) different samples of the test oils E mixed and after the same procedure as in example 2 on your Dewaxing effect checked. The in Table IV The reported results of these experiments show that the more effective polymers have relatively low molecular weights.

Table IV Dewaxing of Testttl B

Average relative. Molecular weight filtration

the polymer fraction speed

(DPO) TD

13,000 2.13

28,000 2.28

37,000 1.35

(1) Ratio of the filtration speed of the oil old anti-paraffination agent for Filtration rate of the oil without dewaxing agent

Example 4 *

This example shows the eynergietic effect between a) a commercially available paraffin wax

f ■■■■■■ ■

Bodifier from the dasae of Friedel Grafts condensate products (condensation product of 4 mol of chlorinated paraffin wax bit 12 wt.) C chlorine and a «

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INSPECTgD 009846/1573 * "■

Melting point of 5O ⁰ C and 1 mole of naphthalene) and b) a Honopolymeren prepared as described in Example 1 of n-octadecene-1 having an average molecular weight to number average of about 8600 (DR)).

The wax-naphthalene cord denaation product, the polyootadecene and a mixture of these two substances were each mixed with a sample of tea oil A and after dewaxed according to the test procedure described in Example 2. The results given in Table V below show that the combination the additives an improvement is achieved,

which are much larger than those with the same amounts the two additives alone achieved improvements is.

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GRfQINAL JNSPECTED

009846/1573

Table V Dewaxing of tea oil A Used relative Dewaxing agent piltration

' "_ Speedy (1)

without 1.00

0.06 wt. # Wax naphthalene

Condensation product 1.71

0.06 wt. ^ Folyoctadecene, 2 »52

0.03 wt. Ii wax naphthalene

Condensation product plus

0.03 wt. ^ Folyoctadecene 3t16

(1) Ratio of the piltration speed of the

Oil with dewaxing agent for the filtration speed of the oil without dewaxing agent.

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Claims (1)

Claims 1 · procedure sub separation of paraffin from petroleum, in which the oil cools down to form solid wax crystals and removes the wax crystals, characterized in that the oil is first Formation of Faraffin crystals, hexogenic on the oil, with about 0.001 to about 5.0% by weight of at least 30% by weight of essentially straight-chain C - * - to Cg .- «.- Mbnoolefin existing polymers: added with a number average molecular weight of at most 200,000. 2. Process for separating paraffin from petroleum, in which the oil is treated with a dewaxing · Solvent mixed, the oil-solvent mixture cools to form solid wax crystals and the wax crystals are removed, thereby characterized in that the oil before formation of the paraffin crystals, based on the oil, with about 0.001 to 5.0 wt. # One of at least 30 wt. ^ made of essentially straight-grained C ..-- to Cg.- - 27 - 009846/157 3 ORIGINAL INSPECTED, in λ η /. ο 201749 ° ol monoolefin existing polymers with a Average molecular weight based on the number ■ average of the highest Ee 200,000. 3. The method according to claim 1 or 2, characterized in that an α-monoolefin of the formula HgCeCH-CH ₂ - (CHg) _n -CHw, where η is an integer from about 10 to 16, containing a polymer bit having an average molecular weight used according to the number average from 1300 to 100,000. 4 «Process according to claims 1 to 3», characterized in that a polymer is used which contains at least two different c <-olefins of the formula H ₂ CeCH-ClI ₂ - (CHg) _n -CH, and in which at least two diener - Monoolefins are each present in an amount of 10 to 90 wt. ^ Of the polymer, 5. The method according to claims 1 to 4, characterized characterized in that one has a polymer with an average Kblekularge weight after Number average from 2OG0 to 30,000 used. - 28 - COPV 0 9 8 4 6/1573 ORIGINAL INSPECTED β "process according to claims 1 to 5 _t characterized in that one uses a polymer" which up to about 70 percent of _e $ G ^ 0 to -. -C «« - cn, monoolefin and au 30 "to about 100. Gew-o. $ Jaua_. C ₁₄ -bie Cg ₀ -fci-monoolefin consists » To method according to - claims 1 Ma 5, characterized in that a polymer is used «which consists essentially of 0 Me about 60 C ₄ = to Cg-Ot-monoolefin, 0 to about 70 tetradecene-1, 0 to 70 wt. # Hexadeoen-1, 0 to 70 Gewe # Octadecen-1 and 0 to 70 Gew. ^ Eicosen ~ 1 consists. 8ο method according to claims 1 to 5 »thereby characterized in that a polymer is used, which consists essentially of 15 to 60 wt = $ Hexene-1, 1θ "to 50 wt <, # n-hexadecene-1, 10 to Gewo $ n-Octadecen-1 and 5 to 30 GeWo # n ~ Eicosen-1 exists o 9ο process for separating paraffin from petroleum, in which the oil is mixed with a dewaxing solvent, the oil-solvent mixture for the formation of solid wax crystals - 29 - 009.846 / 1573 cools wa & 4: it Psraffinkpistall ^ ant, £ erjit _p «5a- - ■ characterized in that, before the paraffin crystals are formed, the oil is mixed with a synergistic mixture of a polymer according to claims 1 to 8 and a Friedel graft -Conensation product of a halogenated paraffin hydrocarbon mixed with an aromatic hydrocarbon » 10 «The method according to claim 9.« characterized ₉ that a dewaxing agent from a synergistic Gemiach of a polymer according to claim 1 Ms 8 and a Friedel-Crafts ~ Kbndensationsprodukt from naphthalene and a paraffin wax with a melting point of 49 ° Ms 88 ⁰ C and a degree of chlorination of 5 Ms 25 wt. chlorine is used hbthto 0QI846 / U73