FR2528051A1 - NITROGEN ADDITIVES FOR USE AS HYDROCARBON MOISTURE DISTILLATE DISORDER DISORDERS AND HYDROCARBON MEAL DISTILLATE COMPOSITIONS COMPRISING THE SAME - Google Patents

Abstract

NEW NITROGEN ADDITIVES FOR USE AS A BLOOD POINT REDUCTION AGENTS OF MEDIUM DISTILLATES, IN PARTICULAR GASOLES, AND THE COMPOSITIONS OF MEDIUM DISTILLATES CONTAINING SUCH ADDITIVES, ARE DESCRIBED. THE ADDITIVES CONSIDERED RESULT FROM THE CONDENSATION OF COMPOUNDS CONTAINING A PRIMARY AMINE FUNCTION, SUCH AS FAT AMINES, POLYAMINES DERIVED FROM FATTY AMINES, POLYAMINES CONTAINING A PRIMARY AMINE FUNCTION AND A TERTIARY AMINE FUNCTION, AMINO-ALHERS OR OF FATTY AMINES ON COPOLYMERS OBTAINED FROM VINYL ESTERS AND MALE COMPOUNDS (DIACIDS, DIESTERS OR ANHYDRIDES). A SENSITIVE EFFECT OF LOWERING THE TROUBLE POINT OF THE MEDIUM DISTILLATES TREATED BY THESE ADDITIVES IS OBSERVED FOR CONCENTRATIONS OF 0.001 TO 1 BY WEIGHT OF ADDITIVES. THESE ADDITIVES ALSO IMPROVE THE LIMIT TEMPERATURE OF FILTRABILITY AND THE OUTPUT POINT OF THE MEDIUM DISTILLATES; THEY ALSO DELAY THE SEDIMENTATION OF FORMED PARAFFINS AND DECREASE CORROSION OF METAL SURFACES IN CONTACT WITH MEDIUM DISTILLATES.

Description

The invention relates to new nitrogen additives which can be used as

  cloud point lowering agents for middle distillates of hydro-

  carbides (fuel oils, diesel) and the compositions of the distillates

  the means containing said additives.

  The petroleum distillates concerned by the invention consist of

  middle distillates (fuel oils, diesel fuels) whose distillate

  (ASTM D 86-67) is between 1500 C and 450 C

  the more particularly considered have a distillation range from an initial temperature between 160 C and 190 C at a final temperature between 350 C and 390 C. There are on the market a large number of products recommended for

  improve the filterability limit temperature and the flow point

  paraffin-rich oil cuts, such as, for example,

  ple: polymers based on long-chain olefins copolymers based on alpha-olefins; ethylene-vinyl acetate copolymers Nacylaminoethyl esters of polymers containing acids or

halocarbon compounds.

  These products act on the kinetic phenomena of crystallization

  and modify the size of the crystals, allowing the use of the sus-

  lower temperature pension without clogging of pipes and filters The products mentioned above do not change the

  temperature at which the first paraffin crystals appear.

  Indeed, it has been considered until now that this temperature was

  a data dependent on the molecular weight and the formula of the paraf-

fine and the nature of the solvent.

  The lowering of the cloud point of middle distillates (in particular gas oils) by an additive would be of great interest to refiners because it would allow, without modifying the distillation scheme, to comply with the specifications currently evolving in the direction

of greater severity.

  It has now been discovered that certain chemical compounds, including one

  definition is given below, have, when added to

  average tillats, the property of not letting appear first

  paraffin crystals at a lower temperature than that

  what these crystals would appear in the absence of such additives This

  property is all the more unexpected since it can be preserved after

  reheating and cooling cycles and manifests itself

  by a mechanism that is not yet explained.

  This class of chemical compounds also has an effect on other properties of middle distillates (especially gas oils),

  modifying the behavior of the medium that contains the paraffins

pitées.

  Thus, the compounds recommended in the invention have an important action

  the filterability limit temperature and the temperature of

  coulement. When paraffin crystals whose formation is caused by cooling appeared, their natural tendency is to gather by gravity in the lower part This phenomenon, generally

  known as sedimentation, causes the clogging of

  and filters and is detrimental to the proper use of

  middle distillates, and in particular gas oils The chemical compounds

  in the invention can significantly reduce the sedimentation rate of paraffins formed by cooling gas oils and

other middle distillates.

  Finally, the products recommended for their properties mentioned above.

  above also give gas oils and other middle distillates

  which are added, anti-corrosion properties on metal surfaces. In general, the additives of the present invention consist of polymeric products having a number average molecular weight.

  about 2,000 to 10,000, resulting from the condensation of a compound with

  primary amine, which will be defined below, on a copolymer formed between: (A) at least one vinyl carboxylate and (B) at least one unsaturated aa-dicarboxylic compound which may be a

  dicarboxylic acid, a diester of such an acid or an anhydride.

  The proportions in the copolymer of the units corresponding to the mono-

  (A) and (B) will preferably be around 50% -50%, the units corresponding to the monomers (A) and (B) being then, in the

  copolymer, distributed alternately.

  The vinyl carboxylates (A) used in the constitution of the copo-

  basic polymers, for example, correspond to the general formula:

R CO CH = CH 2

  in which R represents a monohydric aliphatic hydrocarbon radical

  valent containing, for example, from 1 to 30 carbon atoms, preferably

from I to 21.

  Examples of vinyl carboxylates include acetate, propionate and butyrate or stearate and behenate; we

  will most often use vinyl acetate.

  The unsaturated E-dicarboxylic compounds (B) used in the composition

  The copolymers considered in the invention may be selected from maleic acid, alkyl maleic acids (in particular methyl maleic or citraconic acid), the alkyl diesters thereof.

  acids (in particular methyl, ethyl or propylene diesters).

  In the context of the invention, the anhydrides will be preferred, and more particularly maleic anhydride. j

  The primary amine compound which is condensed with the

  The polymers described above, to form the additives of the invention, can meet one of the following two general formulas (I) and (II): ## STR2 ## "H (I) 2 2 (l

  In the formula (I), R represents a monohydrated saturated aliphatic radical

  valent, comprising from 1 to 30 carbon atoms, Z may, depending on the

  L O case, be an oxygen atom or represent a divalent group NR'-

  R 'being either a hydrogen atom or an aliphatic radical

  monovalent, preferably linear, comprising from 1 to 30 carbon atoms

  bone and, preferably, from 12 to 24 carbon atoms; N is a

  integer from 2 to 4, and m can be zero or be a name

whole number from 1 to 4.

  The compounds of formula (I) above may consist of amines

  of formula R NH 2 (in this case, in formula (I), Z

  present the group -NH; the value of m is zero) Preferably,

  the radical R is linear and contains from 12 to 24 carbon atoms.

  As specific examples of these amines, mention may be made of: dodecyl

  lamine, tetradecylamine, hexadecylamine, octadecylamine,

cosylamine and docosylamine.

  The compounds of formula (I) can also consist of polyamines derived from saturated aliphatic amines corresponding to the formula: ## STR1 ## corresponding to the general formula (I) in which Z represents

  the group NH -, m can have a value of 1 to 4, and N a value of

  from 2 to 4, preferably 3. Preferably, the radical R is linearly

  area and contains from 12 to 24 carbon atoms.

  include: N-dodecyl-1,3-diaminopropane, N-tetra-

  decyl 1,3-diaminopropane, N-hexadecyl-1,3-diaminopropane, Noctadecyl-1,3-diaminopropane, N-eicosyl-1,3-diaminopropane,

  N-docosyl 1,3-diaminopropane, N-hexad 4 cyl dipropylene triacethane

  mine, N-octadecyl dipropylene triamine, N-eicosyl dipropylene

  triamine and N-docosyl dipropylene triamine.

  The compounds of formula (I) may also consist of polyamines corresponding to the formula: RN-1 -CH 2) n NH IH corresponding to the general formula (I) where Z represents NR 'and o R and R', identical or different, are each an alkyl radical having

  from 1 to 24 and preferably from 8 to 24 carbon atoms, R and R '

  preferably together they contain from 16 to 32 carbon atoms; N / A

  a value of 2 to 4 and m a value of 1 to 4 As specific compounds

  include: N, N-diethyl-1,2-diaminoethane, N, N-diiso-

  propyl-1,2-diaminoethane, N, N-dibutyldiamino-1,2-ethane, N, N-

  1,4-diethyl 1,4-butanediyl, N, N-dimethyl-1,3-diaminopropane, N, N-diethyl 1,3-diaminopropane, N, N-dioctyl-1,3-diaminopropane,

  N, N-didecyl-1,3-diaminopropane, N, N-didodecyl-1,3-diaminopropane

  N, N-diketadecyl-1,3-diaminopropane, N, N-dihexadecyl dia-

  1,3-propane, N, N-dioctadecyl-1,3-diamine, propane, N, N-butodine

  cyl dipropylene triamine, N, N-ditetradecyl dipropylenetriamine, N, N-dihexadecyl dipropylene triamine and N, N-dioctadecyl dipropylene triamine. Finally, the compounds of formula (I) considered in the invention may consist of amine ethers more particularly corresponding to the formula: ## STR2 ## which corresponds to the general formula (I) in which Z is an oxygen atom; preferably the radical R is linear and contains from 12 to 24 carbon atoms, m is an integer of 1 to 4 and N is a

  integer from 1 to 4, preferably 2 or 3.

  Among the etheramines, mention may be made, as specific compounds:

  2-methoxyethylamine, 3-methoxypropylamine, 4-methoxybutyl-

  amine, 3-ethoxypropylamine, 3-octyloxypropylamine, 3-decyloxypropylamine, 3-hexadecyloxypropylamine, 3-eicosyloxypropylamine, 3-docosylpropylamine, N- (3-octyloxypropylamine) 1,3-diaminopropane, N- (3-decyloxypropyl) 1,3-diaminopropane, (2,4-trimethyl-6,6-decyl) -3-oxypropylamine, and N (2,4-trimethyl, The primary amino-functional compound involved in the preparation of the additives of the invention may also consist of an aminoalcohol of general formula (II): ## STR1 ##

HO CH 2 R NH 2 (II)

  o R "'represents a linear divalent saturated aliphatic radical or

  mified, preferably linear, containing from 1 to 18 and preferably from

at 18 carbon atoms.

  Specific examples include:

  monoethanolamine, 1-amino-3-propanol, 1-butanol-4-butanol,

  mino-1-pentanol-5, 1-amino-6-hexanol, 1-amino-7-heptanol, amino

  I-octanol-8, 1-amino-10-decanol, 1-amino-11-undecanol, 1-amino-13-tridecanol, 1-amino-14-tetradecanol, 1-amino-16-hexadecanol ,

  2-amino-2-methyl-1-propanol, 2-amino-1-butanol and 2-amino-1

  tanol-1 It should be understood that, without departing from the scope of the invention, it is

  possible to use one or more compounds that meet the

  mule (I) and / or one or more compounds of formula (II).

  The preparation of the additives of the invention generally comprises two

  steps: the preparation of the mono-

  dicarboxylic acid, and then condensation on the polymer formed of at least one compound of formula (I) or (1 D. The preparation of the base copolymers is carried out in the first

  step by conventional methods of radical polymerization.

  for example in the presence of an initiator of the azobisisobutyronitrile type.

  or peroxide (such as lauroyl peroxide) in solution in n

  hydrocarbon derivative, such as, for example, cyclohexane, isooctane, dodecane, benzene, toluene, xylene, diisopropylbenzene or

  tetrahydrofuran or dioxane is still advantageous.

  relatively high boiling point hydrocarbon cuts,

  such as kerosene or diesel.

  The amount of solvent used will generally be such that the concentration

  weight of dry matter is between 25 and 70% and preferably

around 50%.

  The copolymerization reaction in the presence of the radical initiator is carried out at a temperature of 40 to 100 ° C. and preferably of 50 to 70 ° C. Depending on the operating conditions, the reaction time can range from 2 to 10 hours, the most often 3 to 5 hours

  a copolymer solution in the form of a viscous liquid.

  According to a particular method of preparation of the basic copolymers considered

  in the invention, it is possible firstly to carry out the copolymerization

  radicalization of vinyl acetate with the β-dicarboxylic compound

  unsaturated under the conditions already described above, and then

  transacidolysis of acetyl groups by a monocarboxylic acid

  long chain aliphatic xyl, for example linear and saturated

  for example, the number of carbon atoms can range up to 22.

  For the preparation of the additives of the invention, in the second

  step, the condensation of the compound of formula (I) or (II) on the

  polymer formed in the first step, according to any conventional method.

  To the copolymer solution obtained as described above, add

  In general, the compound of formula (I) and / or (II) in a proportion

  molar corresponding substantially to the proportion of diacid, di-

  ester or unsaturated anhydride involved in the preparation of the copo-

  This proportion may be, for example, from 0.9 to 1.1 mole of

  (I) or (II) per mole of dicarboxylic compound.

  The reaction is carried out by heating the mixture to a temperature of

  between 75 and 130 ° C., preferably between 80 and 100 ° C., the duration of the reaction being between approximately 1 and 6 hours, a duration of 1 hour.

  The order of 2 hours is generally sufficient.

  compounds of formula (I) or (II) on the units (B) of the copolymer,

  to imide groups (succinimides), this reaction being

  accompanied by the formation of water or alcohol according to the nature of the dicarboxylic units (B) (diacid, anhydride or diester), it is possible, if it is

  desire, evacuate the volatiles formed, out of the reaction mixture

  nel, either by entrainment with an inert gas such as nitrogen

  or argon, either by azeotropic distillation with the chosen solvent.

  According to another particular mode of preparation of the additives which are the subject of the invention, it is also possible firstly to prepare the vinyl acetate-maleic anhydride copolymers, and then to condense

  these copolymers the products of formula (I) or (II), and finally

  transacidolysis of the acetyl groups contained in the

  polymer with another long-chain aliphatic monocarboxylic acid

  Such a reaction is preferably carried out

  at temperatures between 150 and 220 C, in the ab-

  a solvent, allowing the formed acetic acid to be removed from the reaction mixture; the reaction time is between

2 and 6 hours.

  Another particular mode of synthesis of the additives considered in

  In some cases, the invention may consist in producing the copolymer

  radicalization of one or more carboxylates of vinyl and

  N-substituted leimides, the latter being obtained by prior reaction

  compounds of formula (I) or (II) on maleic anhydride or a

  ie its aforementioned derivatives One can then proceed or not to the transaci-

  dolysis according to the procedure described above.

  The additives are obtained in solution in the chosen solvent, and may

  can be used in this form directly in the distillates

  yen of oil (especially in gas oils) which we wish to improve

the cloud point.

  Although the mechanism of action of these additives on the application temperature

  Since the paraffin crystals in the middle diests have not yet been clearly elucidated, there is a clear improvement in the cloud point of the middle distillates treated with these additives, when they are added at concentrations of, for example, 0.degree. Q 1

  at 1% by weight and preferably from 0.01 to 0.2% by weight.

  It is remarkable to note that the additives considered in the

  tion, which are effective in improving the cloud point of the

  middle distillates, on the other hand, have the property of inhibiting sediment

  tion of n-paraffins in middle distillates at rest, to improve

  the filterability limit temperature and the flow temperature

  and to inhibit the corrosion of metal surfaces in contact with

  these distillates The lowering of the cloud point can go for example

  up to 4 C or more In addition, it is possible to observe a-

  lowering of the filterability temperature, for example up to 4 C or more, a pour point depression being

  go for example up to 9 C or more, and a decrease in

  portion of sedimented paraffins.

  The following examples illustrate the invention without limiting it:

EXAMPLE 1

  a / In a thermostated double-jacketed reactor, 1 liter of

  capacity, equipped with an efficient mechanical stirring system,

  43 g (0.5 mole) of vinyl acetate, 49 g (0.5 mole) of anhydride

  350 ml of toluene and 2.8 g of azobisisobutyronitrile.

  The mixture is stirred for 6 hours at 70 ° C., the resulting copolymer is filtered, rinsed with toluene and then dried under vacuum at 80 ° C. 18.4 g of the copolymer thus obtained are added 14 g (0.05 g). molar equivalent of primary amine) of a commercial mixture of fatty amines containing about 1% of 14 carbon amine, 28% of C 16 amine and 71% of C 18 amine. heptane so that the percentage of dry matter is close to 60%,

then reflux for 3 hours.

  This gives the additive I in solution in heptane, and the concen-

  The final product is adjusted to 50% by weight.

EXAMPLE 2

  Additive II is prepared under conditions identical to those described in

  b / of Example 1, starting from 9.2 g of the copolymer prepared in

  1-a and 8.1 g (or 0.027 molar equivalents of primary amine) of a

  primary chain fatty amine containing about 1% of

  C 14 mine, 5% C 16 amine, 42% C 18 amine, 12% C 20 amine,

and 40% amine C 22.

EXAMPLE 3-

  Additive III is obtained under conditions similar to those described in

  b) in Example 1 by condensation of 16.96 g, that is to say 0.053 equivalents.

  primary amine molar amine mixture having 5% C 16 amine, 15% C 18 amine, 40% C 20 amine.

  and 40% amine C 22, 18.4 g of copolymer obtained according 1-a.

EXAMPLES 4 and 5 -

  In these examples, the transacidification of the copolymer is carried out

  vinyl acetate / N-alkyl succinimide obtained according to bl of Example 1.

EXAMPLE 4

  31.5 g of a copolymer obtained according to 1 b are added with 15 g of stearic acid; the restless set is worn 3 hours to 180 in a

  balloon by allowing the formed acetic acid to be discharged out of the

  The product obtained is, after cooling, dried under vacuum at 80 ° C. to rid it of residual acetic acid.

thus obtains additive IV.

EXAMPLE 5

  Operating in a manner similar to Example 4, and using

  identical molar portions, the transacidolysis of the copolo-

  lymere obtained according to b / of Example 1 using a cross-section of

  fats containing about 1% C 14 acid, 5% C 16 acid, 44% C 18 acid, 10% C 20 acid and 40% C 22 acid The product of this reaction constitutes the additive V.

EXAMPLES 6 to 8 -

  In these examples, a copolymer obtained according to

  Example 1, and following the procedure described for 1b,

  yields, respecting the molar proportions indicated in lb, to the condensation of: Example 6: (2,4,6-trimethyl-3-decyl) -oxy-propylamine,

which provides the VI additive.

Example 7: 1-amino hexadecanol-16,

which leads to additive VII.

  Example 8 N, N-Didodecyl Diamino-1,3 Propane

which supplies the additive VIII.

  Additives I to III are used as 50% solutions of

  dry matter in heptane, additives IV to VIII in the form of

  lutions of the same content in toluene.

  The activity of the additives described in these examples was tested on two cuts of diesel fuels of ARAMCO origin, designated hereinafter G 1 and G 2, the characteristics of which are given in the following Table I:

TABLE I -

  Additives I to VIII were incorporated at 0.1% by weight

  in the diesel fuel cuts G 1 and G 2 described above.

  For each of the compositions thus formed, three determinations were made: the cloud point by the method AFNOR T 60-105

  the filterability limit temperature (TLF) by the method AFNOR M-

07-042.

  the pour point by the method AFNOR T 60-105.

  The results of these determinations are summarized in Table II below:

TABLE II -

  Additives Cloud point (C) TLF (C) Pour point (c) Gl G 2 Gl G 2 G 1 G 2 without + 2 6 O 6 3 0.1% i -1 + 2 4 O -'12 - 15

0.1% II O + 3 4 O 9 -_

* 0,1 i% III 1 + 2 _ 3 1 12 -12

0.10, V + 2 12

  Gasolines -Distillation ASTM% Distilled Mass Volume P.I (C) P F (C) at 350 C to 15 in Kg / 1 l

G 1181 382 89 0.846

G 2 186 385 87 0.847

0.1% IV

  + 2 1 z TABLE II (continued) Additives Cloud point (C) T L F (C) Pour point (c)

G 1 G 2 G 1 G 2 G 1 G 2

0.1% V O + 3 3 1 9 12

O, 1% VI O + 3 3 O 9 9 '

0.1% VII 1 + 2 3 I 12 9

0.1% VIII 1 + 2 4 1 12 9

EXAMPLE 9

  In this example, the anti-corrosion effect of

example 1.

  Product I was used in both gas oils G 1

  previously, at the concentration of 0.01% by weight.

  the additive I of 1 'and G 2 already described The corrosion test consists of studying corrosion by synthetic seawater, cylindrical specimens made of steel or polished iron, according to ASTM D 665 modified in the manner next:

  The temperature is 32.2 C and the duration: 20 hours.

  The two non-additive G 1 and G 2 gas oils give rusty test pieces

  100% of their surface and the two gas oils containing 0.01% by weight

  Additive weights give test specimens intact at 0% rust.

Claims (12)

A product usable especially as an additive for lowering the cloud point of middle distillates), characterized in that it has a molecular weight of 2,000 to 10,000 and results from the reaction on a copolymer containing: (A) units derived from at least one vinyl carboxylate and (B) units derived from at least one unsaturated dicarboxylic compound in the form of a diacid, a light alkyl diester or an anhydride, at least one primary amine function corresponding to one of the general formulas RZ + {H 2, Ni H (1) and HO-CH NH 2 (II) · R represents a monovalent saturated aliphatic radical of 1 to 30 carbon atoms, Z is chosen among the NR 'groups in which R' represents a hydrogen atom or a monovalent saturated aliphatic radical of 1 to 30 carbon atoms, and the oxygen-O- atom ,. n is an integer of 2 to 4; m is zero or an integer from 1 to 4; and R "represents a divalent saturated aliphatic radical of 1 to. 18 carbon atoms.   Product according to claim 1, characterized in that said copolymer contains about 50 mole% of units (A) about 50 mole% of units (B)   3 Product according to one of claims 1 and 2, characterized in that   in said copolymer, the units (A) come from vinyl acetate.   4 Product according to one of claims I and 2, characterized in that   in said copolymer, the units (A) are derived from a carboxy   vinyl acetate whose carboxylic acid part contains a chain   linear aliphatic having up to 22 carbon atoms.   Product according to one of Claims 1 to 4, characterized in that   that the unsaturated O -dicarboxylic compound from which the units originated   (B) consists of at least one maleic or alkyl maleic acid, a dies-   Methyl, ethyl or propyl ether of a telacid, or maleic anhydride or alkyl malgic acid.   6 Product according to one of claims 1 to 5 characterized in that   the amine-functional compound (I) consists of at least one primary monoamine   linear mayor of 12 to 24 carbon atoms.   7 Product according to one of claims 1 to 5, characterized in that   the amine-functional compound (I) consists of at least one polyamine of formula R NH L 2) n H   R represents a linear alkyl radical of 12 to 24 carbon atoms;   ne, n is an integer from 2 to 4 and m is an integer from I to 4.   8 Product according to one of claims 1 to 5 characterized in that   the amine-functional compound (I) consists of at least one polyamine of formula R NR 'CH 2) n N H H R and R' each represent a linear alkyl radical of 8 to 24 carbon atoms R and R 'contain together from 16 to 32 carbon atoms, n is an integer of 2 to 4 and m is an integer of 1 at 4.   9 Product according to one of claims 1 to 5 characterized in that   the amine-functional compound (I) consists of at least one ether-amine of the formula ## STR2 ##   R represents a linear alkyl radical of 12 to 24 carbon atoms;   nen is an integer from 2 to 4 and m an integer from 1 to 4.   Product according to one of Claims 1 to 5, characterized in that   the amine-functional compound (II) consists of at least one amino alcohol of formula: HO CH 2 R "-NH 2   R "'represents a linear alkylene radical of 1 to 18 carbon atoms.   11 Medium distillate composition characterized by the fact that it   takes a major proportion of middle distillate having a distillation range of between 150 and 450 C and / or a minor proportion, sufficient to lower the troubling point of at least one product according to one of claims from 1 to 10.   Middle distillate composition according to claim 11, characterized   characterized in that said middle distillate consists of a cut of gas   having a distillation range from an initial temperature   from 160 to 190 C at a final temperature of 350 to 390 C.   Middle distillate composition according to one of claims 11   and 12, characterized in that the proportion of said product is 0, COI at 1% by weight.   Middle distillate composition according to claim 13, characterized   in that the proportion of said product is from 0.01% to 0.2% weight.