DE1057098B - Process for the preparation of higher alkenes - Google Patents

Abstract

Alkenes containing at least 5 carbon atoms per molecule are obtained by submitting to thermal cracking, in the vapour phase, heavy cycle oil boiling above 300 DEG C. which has been separated by fractional distillation from the products of the catalytic cracking of hydrocarbon oils, and has been substantially wholly freed from aromatics by solvent extraction. The heavy cycle oil may be used in admixture with the residual oil drawn off as bottoms in the fractional distillation. Suitable solvents are: furfural, liquidsulphur dioxide and mixtures of phenol and water. The cracking is effected by heating the vapours of the raffinate, together with an inert diluent such as steam, at a temperature between 500 DEG and about 700 DEG C. for a short period, e.g. a few seconds. In an example, the starting material was a mixture of heavy cycle oil of B.R. 300-500 DEG C., obtained by fractionation of the product obtained by cat. cracking a mineral oil distillate of B.R. 300-500 DEG C., and of the oil withdrawn as bottoms in this fractionation; this mixture contained 55 per cent of aromatics. The mixture was extracted with furfural at between 60 DEG and 70 DEG C. in a rotating disc extraction column, the volume ratio of solvent to oil being about 3 : 1. The raffinate, which contained only 1.5 per cent aromatics, was vaporized rapidly at a maximum temperature of about 470 DEG C., together with a fraction of the resulting cracked product boiling above 300 DEG C., which was recycled in a weight-ratio of 2.9:1 with reference to the raffinate. The vapours, after separation of unvaporized material still present, were passed through a furnace at a maximum temperature of about 550 DEG C. for a period of 3.6 seconds, together with 6.5 per cent by weight of steam. The portion of the cracked product boiling above 300 DEG C. was recycled to the supply of fresh raffinate, while the portion boiling below 300 DEG C. was separated by fractional distillation into a fraction containing gaseous alkenes, a C5-alkene fraction, a C6-C8 alkene fraction, a C9-C13 alkene fraction, and a C14-C18 alkene fraction. The alkene content of these fractions was 85 to 90 per cent by weight. Specification 659,241 is referred to.ALSO:Alkenes containing at least 5 carbon atoms per molecule are obtained by submitting to thermal cracking, in the vapour phase, heavy cycle oil boiling above 300 DEG C. which has been separated by fractional distillation from the products of the catalytic cracking of hydrocarbon oils, and has been substantially wholly freed from aromatics by solvent extraction. In an example, a C12-C16 fraction having an alkene content of 88 per cent was separated from the thermally cracked products, and was used to alkylate benzene at 30 DEG C. employing liquid HF as catalyst. The crude alkylate was separated from the non-acid phase, and then distilled under reduced pressure to yield purified alkylate having an average M.W. of 271. This alkylate was converted with oleum and caustic soda into an alkylaryl sulphonate, which had good detergent properties. In another example, a C6-C8 alkene fraction was treated with sulphuric acid to remove dienes, and was then converted into aldehydes by treatment with water gas in the presence of cobalt-on-kieselguhr as catalyst, the maximum temperature and pressure being 140 DEG C. and 250 atm. respectively. The product was freed from cobalt carbonyl compounds by cooling, releasing the pressure, introducing hydrogen up to a pressure of 50 atm., heating for 2 hours at 160 DEG C., and then, after cooling, releasing the gas and adding further hydrogen under pressure. The resulting aldehydes were then converted into alcohols by heating with hydrogen at 185 DEG C. under 140 atm. in the presence of nickel-on-kieselguhr catalyst. After filtering off the catalyst the resulting alcohols were distilled to separate the fraction boiling between 161 DEG and 221 DEG C. which comprised the C7-C9 alcohols. In order to remove formates, the C7-C9 alcohols were subjected to treatment with hydrogen at 250 DEG C. and 140 atm. in the presence of copper chromite catalyst. After filtering off the catalyst, the alcohols were re-distilled, and recovered as a colourless fraction boiling between 161 DEG and 199 DEG C. In a further example, the C7-C9 alcohols were converted into the corresponding phthalates; and the crude esters were purified by heating with 1 per cent lime and 0.02 per cent potassium permanganate (as a 1 per cent aqueous solution) with strong agitation for 45 minutes at about 110 DEG C., and subsequently heating with activated carbon for some hours at 80 DEG C. Esters of adipic, methyladipic, and sebacic acids are also referred to; these may be used as synthetic lubricating oils. A further example, describes the preparation of sodium alkyl sulphates from a C8-C18 alkene fraction. Calcium alkyl salicylates, and the calcium salts of alkyl aromatic sulphonic acids, are also referred to. Specification 659,241, [Group III], is referred to.

Description

GERMAN

kl 12 ο 19/01

INTERNAT. KL. C 07 C

PATENT OFFICE

N10793 IVb / 12 ο

REGISTRATION DATE: JUNE 14, 1955

NOTICE THE REGISTRATION AND ISSUE OF THE AUS LE GE S CHRIFT:

MAY 14, 1959

Applicant:

N.V. De Bataafsche

Petroleum Maatschappij,

The hague

Representative: Dr. K. Schwarzhans, patent attorney, Munich 19, Romanplatz 9

Claimed priority: The Netherlands, June 16, 1954 and May 13, 1955

HanHoog and Albert Schaafsma, The Hague, have been named as inventors

Method of manufacture

It is already known to use higher alkenes by cracking such hydrocarbon mixtures in the Produce vapor phase rich in paraffinic hydrocarbons, such as solid paraffins, and subjecting the liquid products thus obtained to fractional distillation.

It is also known that hydrocarbon material, io
which contains both aromatics and solid paraffins,
as a starting material for the production of such
Alkenes or their derivatives can be used.
The prerequisite for this is that the aromatics are whole
or for the most part before the cracking process 15
be removed, for example by extraction
with selective solvents. Suitable starting 'materials for this known process are below
other solid raw paraffins, oil resulting from the paraffin sweating process, tar oils and paraffinic 20
Lignite oils and mineral oil distillates or residues containing solid paraffin and aromatics ^:

for example, high-paraffin distillates of aroma- «".

rich petroleum. - - -

It has now been found that an oil with a 25 functions under the influence of the catalyst boiling point used above about 300 ° C, a so-called tor takes place, including isomerization reactions, Heavy oil, which is a by-product in the case of the fractional- the composition of this pronounced differs Distillation of the liquid cracked product is very important - from the previous one for this one tes from the catalytic cracking of hydrocarbons - purpose used paraffinic hydrocarbon oils is obtained, a very suitable starting 30 material materials of natural origin. In particular material for the production of higher alkenes and would have been due to the high naphthous content Represents derivatives. As such it can use hydrocarbons and aliphatic ones or is combined with the residual oil. Hydrocarbons with a branched structure in the mixes, which can be expected as soil product from the described non-ornamental part of the same, benen distillation accrues and sludge oil called 35 that the heavy oil is not at all or very little than will. The heavy oil is used to produce the starting material for the production of higher Alkenes used after the alkenes and alkene derivatives contained therein were suitable. In contrast to Aromatics wholly or for the most part by Extrak- this assumption, however, has been found that the tion were removed with selective solvents. Heavy oil is an excellent starting material for In the method according to the invention, 4.0 is therefore this purpose and that, starting from the raffinate described heavy oil or mixtures of the same going, which by means of the selective solvent

is obtained, high yields of higher alkenes are achieved can be, these yields are not lower and in some cases even higher than they with the aid of hydrocarbons rich in paraffin, for example solid paraffins, as starting material be achieved.

One already has return gas oils from the catalytic cracking of hydrocarbons

with the residual oil subjected to extraction with selective solvents and then in the Vapor phase cracked the aromatic-free or almost aromatic-free raffinate obtained in this way.

It is extremely surprising that the heavy oil, which was previously only used as heating oil found if it wasn't the catalytic cracking process was fed back into circulation, dealing with Vor

part as a starting material for the production of 50 thermal cleavage at a pressure of about

higher alkenes and alkene derivatives can be used. Due to the special nature of the procedure, out which the heavy oil comes from and in which, in addition to the actual cracking, several other reac-

46 at in the heater and 28 at in the reactor. Under these conditions, however, the hydrocarbon oil lies partially during the cracking in the form of the liquid phase before, and with -a sol-

909 510/473

Claims (3)

3 4 The process in the "mixed phase" is mainly facilitated. Since it was found that the corpse Hydrocarbons of petrol character, the other components of heavy oil in the case of the Extrakgeg'en no high quality olefins. treatment treatment for the most part in the extract In contrast to this well-known thermal transition, there is a previous topping of the rest Splitting process for the purpose of gasoline production: if heavy fuel oil is not absolutely necessary, in the process according to the invention completely in the The aromatic extract, which in the extract Vapor phase worked, and also the heavy oil tion must be maintained and mainly Starting material · be dearomatized beforehand, from polycyclic compounds, for example while using a return gas oil in naphthalene derivatives and the like, can be used as fuel oil mixed-phase methods such a measure can be used. But he can also, for example not applicable. as a heat transfer medium or as a com- The invention is of particular practical importance in herbicide use tion because it makes it possible to do this in the case of catalytic. Find. Cracking in large quantities of heavy oil, which The process according to the invention is carried out by the ches was previously a by-product of little value, 15 the following examples are explained in more detail, if not for economic reasons in the district _. . Run was returned for the production of ice cream valuable higher alkenes and their derivatives. A mixture of for which there is a steadily growing need for heavy fuel oil, which is between about 300 and 500 ° C is available. This also applies to heavy oil, boiled 20 and when fractionating a liquid one which in the catalytic cracking of a cracked product from the catalytic cleavage of a Sulfur-rich mineral oils is obtained, for example Middle East petroleum distillate with a boiling point between wisely from certain Middle Eastern oils, and therefore see 300 and 500 ° C, and an oil, has a relatively high sulfur content, for example as the bottom liquid in this fractionation wise 2 to 3%. In the extraction of a heavy oil 25 was withdrawn, used. This mixture had of this kind, the sulfur compounds become largest - an index of refraction. of n ™ = 1.5278 and a partly removed together with the aromatics, so that a specific gravity d ⁷ ° of 0.9102 existed practically sulfur-free raffinate is obtained. 55 percent by weight from aromatics, while the rest Extraction of the heavy oil, which given paraffins and naphthenes. if mixed with a mud oil, this mixture was mixed with furfural at 60 'up by means of the usual selective solvents for 70 ° C in an extraction column with rotating Aromatics carried out, for example furfural, flüs- disks extracted,. Which of the type described siges sulfur dioxide, mixtures of phenol and was and had five theoretical extraction stages, Water and the like, the treatment preferably being 13 l of the oil mixture and 45 l of furfural per were fed in countercurrent in at least three extraction stages for 35 hours. That way were he follows. Furfural and mixtures of phenol and 41.7 percent by weight. Raffinate based on the Water are particularly suitable for this purpose, as the starting mixture is obtained, which is 63.5% off with them in a simple way a practically aromatic naphthene and isoparaffins, 35% from n-paraffin free raffinate is obtained, even if small amounts and only 1.5% consisted of aromatics. Solvent ratios exist, for example 40 This raffinate was then in the steam between 2.0 and 3.5. phase cracked For this purpose, a Although the extraction treatment at a slightly maximum temperature of about 470 ° C together higher temperature, e.g. B. between 50 and 80 ° C, with the over 300 ° C boiling fraction of the georack can be carried out, is the one in the German th product, which in the weight ratio 2.9 ': 1, Patent specification 877136 described extraction column 45 based on the raffinate, recycled particularly advantageous for this purpose. The column was evaporated as completely as possible. To has a rotating shaft with a number of disks separating the remaining unevaporated material on, and on the inner wall of the same are in places where these vapors together with 6.5 weight which are located in the middle between the panes, percent water vapor passed through a crack oven, Rings attached whose inner diameter is about 50 with the maximum temperature about 550 ° C and the larger than the diameter of these disks. Contact time was 3.6 seconds. The proportion of so The thermal cracking, which the raffinate in the obtained cracked product, which is above 300 ^! ° C is subjected to the process according to the invention, boiled, was added to the freshly fed raffinate in the vapor phase, the vapors of the mixed. The fraction boiling below 300 ° C. was raffinate together with an inert diluent by fractional distillation into a fraction with medium, preferably steam, during a short gaseous alkenes, a C ₅ -alkene fraction, a period of time, e.g. B. a few seconds, a high temperature C ₆ -C ₈ alkene fraction, a Cg-C - ^ - alkene fraction and temperature of for example 500 to 560 ° C exposed to a C ₁₄ -C ₁₈ alkene fraction, these being separated. The cracked product obtained in this way can fractions in amounts of 24.8 percent by weight, after separation of the normally gaseous 60 4.3 percent by weight, 14.4 percent by weight, 22.8 percent by weight by fractional distillation into the percent by weight and 22.8 percent by weight, based on the desired Higher alkenes fractions and a raffinate supplied were obtained. The high-boiling alkene bottom product can be separated, which content of these fractions was 85 to 90 weight in the circulation of the cracking zone. percent. Although the heavy oil in its entirety of the 65 patent claims
Extraction treatment can be subjected is In some cases it is advantageous to use the small amounts 1. Process for the preparation of higher alkenes such products by distillation to remove that. by cracking paraffinic hydrocarbons boil below 350 ° C, as this is the later separation of mixtures of substances in the vapor phase from which of the high-boiling alkenes from the cracked product, the aromatics present therein have been completely or largely removed by extraction with selective solvents, characterized in that a heavy oil is used as the paraffin-containing starting material, which occurs in the fractional distillation of a cracked product from the catalytic Cracking of hydrocarbon oils is obtained, optionally mixed with the residual oil, which is withdrawn as the bottom product in such a distillation. 2. The method according to claim 1, characterized in that that a heavy oil is used from which all components boiling below 350 ° C are away. 3. The method according to claim 1 or 2, characterized in that the extraction by means of Performs furfural or phenol-water mixtures. Considered publications:
Petroleum and Coal, 3 (1950), p. 132;
Petroleum Refiner, April 1949, pp. 111-116;
AN Sachanen, Conversion of Petroleum, 1948, p. 219. © 909 510/473 5.59