LU80675A1 - PROCESS FOR THE PREPARATION OF PARAFFINIC SOLVENTS - Google Patents

Description

L-2365

8 Λ 71— “T rCRAND-DUCHË DE LUXEMBOURG

..... M ........ 0 ........ I V

j of __________________Mister the Minister of National Economy and the Middle Classes

Title issued: ....................................... · œr g ^ gjjf Service de la Industrial property

LUXEMBOURG

Invention Patent Application I. LABOFINA SA request, rue de la Loi 33, B-1040 BRUSSELS, ja ^ p ^^^ dd ^ 'g "'" by '"' Tean" '' Wxw§xler7iT “25” lSXISel ..... ScEëFfer ..................................

...... Luxembourgy-acting ..... in "-qualit'é'-de" -ma'n'âa'ta '± re ............... ......-........................................... ...............

.................................................. .................................................. .................................................. .................................................. .................................................. ....................... (2) * deposits this December one thousand nine hundred and seventy-eight at 9.9.1.9.9 ....... ..hours, at the Ministry of National Economy and the Middle Classes, in Luxembourg: 1. this request for obtaining a patent for an invention concerning:., ........... .................................................. .................................................. .................................................. .................................................. .................................................. .................. (4) .Process ..... of .... px.ép.aratl.Qn .... de .... s.Qlmn.ts .... paraffiniq.uas ...................................... ...........................

declares, assuming responsibility for this declaration, that the inventor (s) is (are): ........................... .................................................. .................................................. .................................................. .................................................. .................................................. .. (5)

Jacques Grootjans, F.JNeerijsesteenweg 39, B-3061 Leefdaal 2. the delegation of power, dated _____ B.Î..UXellCS -------------------- le --- --------. 4 ..... December ..... 19.7 8 ^ 3. description in language -------- ££ .é.B.Ç.S.ï ..§.§ .------------------------------ of the invention in two copies; 4 .......... j .................... drawing boards, in two copies; 5. the receipt of the taxes paid to the Luxembourg Registration Office on ....... d.ixr.nCuf ..... déc.embr.e .... iiiil ..... ueuf ..... cen.t .... so ± xan.te ..... eighteen ------------------------- ------------------. claims for the above patent application the priority of one (s) request (s) from (6) _________________________ l .___________________________________________________________ filed in (7) ...............— / ...----------------------------------------------- ---------------------------------------------------------- the ------------------------------------------------- ---------------------------------------------------------- ----------------------- (8) ------------------------ ---------------------------------------------------------- ------------- · / ·· --------------------------------- ---------------------------------------------------------- ---------------------------------------------------------- ------------ on behalf of ----------------------------------- ---------------------------------------------------------- ---------------------------------------------------------- ---------------------------- (9) elect domicile for him / her and, if appointed, for their proxy, in Luxembourg. ...................................

• î Jean Waxweiler, 21-25 Allée ..... 5.che.ff.er, .LuXémb.0.ur.g .................... .................................................. .. (io) requests the issue of a patent for the invention for the subject described and represented in the abovementioned appendices, - with postponement of this issue to ................ 1.8 ........................ months.

^ ^ r ^ jxdatair ^ ’> II. Procès-verbal de Dépôt \ The above application for a patent for invention has been filed with the Ministry of National Economy and the Middle Classes, Industrial Property Service in Luxembourg, dated: 19.12.1978

Pr. The Minister ^ 15.00 hours / ^ \ National Economy and the Middle Classes, ff jgpL \ y \ p. d.

Co 'k Mwl, A 68007 W SVf! g- 2353-

DESCRIPTIVE MEMORY FILED IN SUPPORT OF A PATENT INVENTION APPLICATION IN THE GRAND DUCHY OF LUXEMBOURG

LABOFINA S.A.

PROCESS FOR THE PREPARATION OF PARAFFINIC SOLVENTS.

ί c- * · ♦ ι i MEMORY DESCRIPTION filed in support of a

PATENT INVENTION APPLICATION

formed by the so-called Company: LABOFINA S.A.

for PROCESS OF PREPARING PARAFFINIC SOLVENTS Inventor: Mr. Jacques Grootjans.

The present invention relates to a process for the preparation of paraffinic solvents by hydrogenation of a charge consisting of a mixture comprising optional residual monomers and olefin oligomers having 3 to 6 carbon atoms, originating from the polymerization of these olefins in products ranging from light liquids to highly viscous liquids.

f

Paraffinic solvents have many uses, in particular as diluents for paints and insecticides, constituents of waxes and cleaning products or even as solvents for the manufacture of cosmetic products, Generally, paraffinic solvents are prepared by hydrogenation of petroleum fractions containing hydrocarbons aromatic, but the: products thus obtained are not completely free of aromatlqi hydrocarbons and other impurities such as sulfur derivatives. However, for certain uses, it is necessary to remove all of the aromatic hydrocarbons, and the sulfur content must be less than 10 ppm.

In order to eliminate a maximum of aromatic compounds, it has already been proposed to use nickel or a sulfurized nickel as hydrogenation catalysts, but these catalysts require either desulfurization of the feed to be hydrogenated, or very severe operating conditions.

The Applicant has already proposed a process for the preparation of paraffinic solvents free of aromatic compounds and of sulfurized compounds, by hydrogenating a particular charge originating from the distillation of the naphtha fraction of petroleum and consisting mainly of paraffinic hydrocarbons having <5 to 7 carbon atoms accompanied by a lesser amount of aromatic hydrocarbons, sulfur derivatives, nitrogen derivatives and other impurities. This charge can be hydrogenated directly, therefore without prior desulfuratiot treatment thanks to the use of a particular catalyst and under well specified operating conditions such as in particular a partial pressure of hydrogen comprised between 15 and 75 kg / cm 2 and more often between 50 and 70 kg / cm2.

It would therefore be advantageous to be able to apply a process in which the operating conditions would be less severe, and in particular where the partial pressure of hydrogen would be less than approximately 15 kg / cm 2,

The Applicant has now found a new process for the preparation of paraffinic solvents which overcomes these drawbacks.

The present invention particularly relates to a preparation process.

_) operating conditions significantly less severe than in existing processes.

Another object of the invention resides in a process for the preparation of paraffinic solvents completely free of aromatic compounds and of sulfur compounds.

The process of the present invention for preparing final paraffinic solvents essentially consists in subjecting a charge consisting of a mixture comprising optional residual monomers and olefin oligomers having di 3 to 6 carbon atoms and resulting from the polymerization of these olefins in products ranging from light liquids to viscous liquids, to a hydrogenation treatment in which the partial hydrogen pressure is between 6 and 15 kg / cm 2 and the temperature is between 170 and 325 ° C.

i

One of the characteristics of the process of the present invention lies in the particular choice of the charge to be hydrogenated. In fact, the feedstock used in the process of the present invention consists of a mixture comprising optional residual monomers and olefin oligomers having 3 to 6 carbon atoms, which result from the polymerization of these olefins into products ranging from light liquids to viscous liquids, that is to say polymers having a relatively low molecular weight.

Indeed, during the polymerization of olefins having 3 to 6 carbon atoms, and in particular olefins having 4 carbon atoms such as n-but or isobutylene to form polymers with low molecular weight generally between 250 and 5000, there is formation of a mixture consisting of possible residual monomers and of different oligomers, the constituents of this mixture having a number of carbon atoms generally between 4 and 24. However the proportion of the different oligomers is very variable and depends in particular on - polymerization conditions.

This mixture of optional residual monomers and oligomers constitutes a completely suitable filler for preparing paraffinic solvents completely free of aromatic comDOs and sulfurized comoos.

When a charge of optional residual monomers and oligomers originating from the manufacture of low molecular weight butene polymers is used more particularly, the constituents of this charge have a number of carbon atoms generally varying between 4 and 24.

In addition, in this particular charge, a greater proportion of oligomers having 8 and 12 carbon atoms has been observed, this proportion possibly representing up to 70% by weight of the total weight of the charge.

The Applicant has also found that it is possible to hydrogenate a charge of olefin oligomers as defined in the present invention, under significantly less severe conditions than in the usual hydrogenation processes for preparing paraffinic solvents. Indeed, it is possible to carry out the hydrogenation under a partial pressure of hydrogen generally between 6 and 15 kg / cm 2 and preferably between 8 and 13 kg / cm 2.

It is well known that the hydrogenation of olefinic feedstocks can be carried out at temperatures as high as 600 ° C. However, although relatively low hydrogen partial pressures are used, the hydrogenation is carried out under conditions of moderate Turkish tempera. Indeed, the temperature is generally between 170 and 325 ^ 0. and preferably between 200 and 260 ° C,

It was then quite unexpected to obtain such complete hydrogenation of the charge, the product obtained having an iodine index of approximately 0.2, with such a low partial pressure of hydrogen and moderate temperature conditions. s.

The hourly space velocity is generally between about 0.5 and about 5 vol./vol/hour and preferably between about 1 and about 3 • vol / vol / hour, and the hydrogen: oligomers ratio is usually between about 100 and approximately 3000 Nm3 / m3 and preferably between approximately 150 and approximately 500 Nm3 / m3, the ratio being all the higher as the narfielle pressure of hvdrocrpne e> c; t nlnc f, qih1e.

usual hydrogenation, and as such, include the metals of Group VIII of the Periodic Table of Elements, such as platinum, palladium, nickel and cobalt, used alone or deposited on a suitable support. The supported catalysts usually used contain from 0.1 to 27% by weight of metal. Mention may also be made of bimetallic catalysts on a support, such as for example platinum-rhenium, platinum-germanium, platinum-tin or else platinum-irridium deposited on an appropriate support. Examples of suitable supports that may be mentioned include alumina, either monomodal or bimodal, silica-alumina, kieselguhr or even activated carbon. The processes for the preparation of such catalysts are well known to those skilled in the art. An advantageous process consists in impregnating the support with a solution of a compound of a platinum group metal, and in particular chloroplatinic acid when it is desired. deposit the platinum, then evaporate the solution, dry and calcinate at around 400 ° C. Examples of catalysts that may be mentioned include those which contain from 0.1 to 27% by weight of platinum on a support consisting mainly in silica and alumina, the silica being the major constituent and the platinum being distributed for at least 30%, on the surface of the support. Mention may also be made of those which contain 0.1 to 1% of platinum deposited on an alyan alumina support a total volume of pores of at least 0.25 ml / g and of which 90 to 98 Ί-. of this total volume! are distributed around an average dimension of less than 100 A, mention may also be made of those which contain from 0.25 to 1.5% by weight of palladium deposited on an alumina support having a total volume of pores of at least 0.25 ml / g and of which 35 to 50% of this total volume is distributed around an average dimension less than .300 + 50 A and of which 25 to 35 7 of this total volume are distributed around a - average dimension greater than 300 + 50 A, the latter average dimension being at least 1.5 times larger than the former.

According to an advantageous embodiment of the process of the invention, γ \ ύλ offûY't'uâ 1 t * i Λη H * i in o rnncl * i fnoo Ho mnnnmorPG rpc <3 or d * isobutylene of low molecular weight, according to the operating conditions described above. Next, the debutanization of the hydrogenated products is carried out and finally the products obtained after debutanization are subjected to fractional distillation in a distillation column having from 15 to 25 plates, the temperature at the inlet of the column being between 100 and 150 ' C and the etar reflux rate "· between 1 and 2. This fractional distillation makes it possible to obtain paraffinic solvars having different boiling ranges.

The present invention is also described with the aid of the examples below, given by way of illustration and without any limiting character.

Example l

A paraffinic solvent was prepared by hydrogenating a charge consisting of residual monomers and oligomers from the manufacture of polybutene. This charge had the following weight composition:

Residual monomers in C,: 6.29 4

C oligomers: 1.86 C? : 1.65 c8: Z4.84 C,: 1.92 C10: ° '53 C11 5 · 18 C12; 35'78 C13; 9 · 97 C ,,: 0.80 c15: 2.02 C16: 3.88 C17: 0.44 C18: °> 9 ° C19: 0.53 C ...: 1.75 ~ / **

In addition, the ASTM D 86 distillation gave 38 ° C as an initial point and 307 ° C as an end point.

The bromine index for this charge was 89.5.

The operating conditions of the hydrogenation operation were as follows:

* - temperature: 260 ° C

- hourly space velocity: 2.0 vol / vol / hour - partial hydrogen pressure: 12.9 kg / cm2 - hydrogen ratio; oligomers: 120 Nl / 1 The hydrogenation was carried out in the presence of a commercial catalyst constituted by alumina in the form of spheres of 1.5 mm in diameter containing 0.36 7. by weight of platinum.

The hydrogenated products were subjected to debutanization and then to fractional distillation. We thus obtained 2 paraffinic solvents whose boiling ranges go for the first from the initial point to 160cC, for the second from 160 to 2600C. These different boiling ranges have been chosen according to the boiling ranges of commercial paraffinic solvents.

The paraffinic solvents obtained had the following properties

Solvents 1 2

Density 15 / 4eC 0.710 0.779

Color Saybolt +30 +30

Aromatic content 0 t 0%

Flash point Abel <. 15 ° C 55.5 ^ 0

Kauri butanol index 30.1 27.3 * Aniline point 70.54C 83 ^

Iodine index 0.3 0.5

Example 2

The charee of residual monomers and of ialomers - s - whose composition is described in Example 1 was hvdroaéné.

The operating conditions for the hydrogenation reaction were as follows:

- temperature: 205 ° C

- hourly space velocity: 1 vol / vol / hour - partial hydrogen pressure: 7 kg / cm2 - hydrogen ratio: oligomers: 450 Nl / 1 The hydrogenation was carried out in the presence of a hydrogenation catalyst whose support is an alumina in the form of extrudates of 1.5 mm in diameter with a specific surface of 174 m2 / g. The total pore volume is 0.81 ml / g. The pore volume is distributed as follows: ♦ 0.37 ml / g, ie 45.7% of the total pore volume is distributed around a with an average dimension of 65 A.

0.25 ml / g, i.e. 30.9 7, of the total pore volume is distributed around an average dimension of 6,000 A.

This bimodal alumina was impregnated with a solution of palladium chloride to finally deposit therein 0.77 by weight of palladium.

The hydrogenated products were subjected to debutanization and then to fractional distillation, and 2 solvents with different boiling ranges were finally obtained.

The properties of these solvents are as follows:

Solvents ,, »

Boiling range

PI 160 ° C

to to

160 ° C 260 ° C

Density 15 / 4’C 0.721 0.782. ’Color Saybolt +30 +30

Aromatic content 0 7 0%

Flash point Abel <153C 59.7 ° C

- Ο -

Example 3

A charge of oligomers originating from the polymerization of propylene, and having the following composition, was hydrogenated:

Oligomers in: 12.1% C5: 0.08% c 1.60 t - o C? : 1.75%

Cg: 1.94% C9: 63.4%

Cu: 18.1% C1Ç: 1.03% # 15

In addition, the ASTM D 86 distillation gave an initial point 23 and an end point 202 ° C.

The operating conditions for the hydrogenation reaction were as follows:

- temperature: 230 ° C

- hourly space velocity: 3 vol / vol / hour - partial pressure of hydrogen: 10 kg / cm2 - hydrogen ratio J oligomers: 300 Nl / 1 The hydrogenation was carried out in the presence of a catalyst whose support consists of silica and alumina, the proportion of silica being 68.7%. This support was impregnated with a chloro-platinic acid solution so as to deposit 0.74% by weight of platinum therein.

The hydrogenated products were subjected to debutanization and then to fractional distillation and finally 2 paraffinic solvents were obtained having different boiling ranges.

- 10 -

The properties of the solvents obtained were as follows:

Solvents

Boiling range

50 ° C 160 ° C

to to

260 ° C 260 ° C

Density 15/4 ° C 0.715 0.773

Color Saybolt +30 +30

Aromatic content 0% 0%

Flash point Abel 15 ° C 49.7 ° C

Kauri butanol index 33 29.2

Aniline point 65.7 ° C 74.7 ° C

’Iodine index 0.2 0.3

Example 4

The charge of residual monomers and of oligomers, the composition of which is described in Example 1, was hydrogenated.

The operating conditions for the hydrogenation reaction were as follows:

- temperature: 205nC

- hourly space velocity: 2 vol / vol / hour - partial pressure of hjd'ogene: 13 kg / cm2 - hydrogen ratio: oligomers: 130 NI / 1 The hydrogenation was carried out in the presence of a bimetallic hydrogenation catalyst consisting of platinum and rhenium on a support; consisting of an alumina having a specific surface of 178 m2 / g.

The support was impregnated by a known method to deposit 0.35% by weight of platinum and 0.40% by weight of rhenium.

, * The hydrogenated products were subjected to debutanization and then to fractional distillation and finally 2 paraffinic solvents were obtained having different boiling ranges.

Claims (10)

1. A process for the preparation of paraffinic solvents, characterized in that it essentially consists in subjecting a charge consisting of a mixture comprising optional residual monomers and olefin oligomers having 3 to 6 carbon atoms and originating from the polymerization of these olefins in products ranging from light liquids to viscous liquids, to a catalytic hydrogenation treatment in which the partial hydrogen pressure is between 6 and 15 kg / cm 2 and the temperature is between 170 and 325 ° C. ".J- 2. Method according to claim 1 characterized in that the filler consists of a mixture comprising optional residual monomers of olefins having 3 to 6 carbon atoms and oligomers of these olefins, the constituents of this filler having a number of atoms carbon generally between 4 and 24, ’3) A method according to claim 1 characterized in that the charge has a boiling range between 20 and 350eC. '- the' - 4. Method according to claim 1 and 2, characterized in that the charge comprises n-butene and / or isobutylene and oligomers of these olefins, the constituents of this charge having a number of carbon atoms between 4 and 24, 5. Method according to claims 1 to 4 characterized in that one carries out the hydrogenation treatment at a partial pressure of hydrogen preferably between 8 and 13 kg / cm2 and at a temperature preferably between 200 and 260 ° vs. 6. Method according to claim 1, characterized in that the hydrogenation catalyst consists of 0.1 to 2% by weight of a Group VIII metal having a hydrogenating activity and deposited on a support, * 7. Method according to claim 1, characterized in that the catalyst contains two metals including platinum and another metal selected from the group comprising rhenium, germanium, tin and irridium, deposited on a support. 8. Method according to claims 6 and 7, characterized in that the support is chosen from the group comprising alumina, silica-alumina, kieselguhr and activated carbon, 9. Method according to claim 1 to 8, characterized in that the hydrogenated products have an iodine index of between 0.2 and 0.4. 10. Paraffinic solvents obtained according to the process described in any one of the preceding claims. * w "*