DE2360980A1 - PROCESS FOR PRODUCING AN ALKYLATE GASOLINE - Google Patents

Description

Patent assessor . Hamburg, December 5, 1973

Dr. Gerhard Schupfner -547 / ik

German Texaco A.G.

2000 Hamburg 76 T 73 093 (D 72,071-F)

Sextuple gate 2

TEXACO DEVELOPMENT CORPORATION

135 -East 42nd Street New York, N.Y. 10017

UNITED STATES. '

Process for the production of an alkyl benzine

The invention "relates to" a method of manufacture an alkyl petrol. More precisely, "it concerns them Conversion of components of a light paraffinic Gasoline in alkylate and light olefins.

As is known to those skilled in the art, the continuous improvement in the quality of gasoline engines, particularly automobiles, has led to the demand for better fuels octane numbers permit. It was always desired to work up crude oil feedstocks and standing at your disposal F.affinerieströme so that ihrä VSSR ^T e »DMIG ER in the gasoline pool

becomes possible; and that need is compounded by the continued demand for high octane unleaded gasoline " reinforced.

The invention is therefore based on the object of a method for the production of alkylate gasoline from paraffinic starting compounds. Through the procedure components of lighter paraffinic gasoline mixtures are to be converted into fractions that can be mixed in in unleaded gasoline.

The object is achieved by a method for production an alkylate gasoline from a material containing paraffinic components as a feed stream, which characterized in that the feed stream under isomerization and cracking conditions in the presence of Brings hydrogen into contact with an isomerization and cracking catalyst,

from the isobutane formed and light and heavy Stream containing paraffins separates an isobutane-containing stream,

the deisobutanized stream thus obtained in the presence of steam to form a C ^ -olefin fraction containing product stream thermally cracks, the isobutane-containing stream with the C ^ -olefin fraction containing product stream is alkylated and the resulting alkylate fraction wins.

The invention will now be explained in more detail. The paraffinic Gasoline blend components that can be treated by the method of the present invention can, for example, be a Electricity that is available in a refinery. Most of the time it is a stream, the light paraffinic one Contains components. Examples of such streams are those that contain predominantly low paraffins, including butanes, pentenes, etc., e.g. light top distillate, various condensates and raffinates

409828/0 9 74

from which the aromatics have been extracted.

Although the feedstock can be a pure C ₇ - or (/, - paraffin - ', it is usually a mixture containing CL-co-paraffins. The paraffin content can be 60 - "100 % ", preferably it is 70 - 90%, for example about 80%. The feed material can also contain naphthenes in amounts of 5 - 30%, preferably 5 - 20 %, for example 8%, and other components such as aromatics in amounts of 2 - 15 %, for example 12%, Minor amounts of other components, including aromatics and the like, may be present.

Usually the octane rating is EOZ (EON Clear) of the viewing material below about .60, for example between 30 and 50, about 45.

A typical feed stream may be a light TJdex eaffinate from which the aromatics have been extracted, and has the following composition?

TTdex Baffinat

Volume% ■

at SD ι el 80 .7% '■' ■ ?. ,8th 11 , 5

Component · · Area

Paraffins 70-90.

Naphthenes. 5-20 "aromatics 2-15

100.0

This' eaffinate has an octane number EOZ of 4-5., A boiling point at 88 ° C, an end of boiling at 135 ° C and an API density of 70.1 °.

Another exemplary feed stream is a light one Top distillate (obtained from the debutanization of a ■ Interest rate) of the following composition: ·

409828/0974

Ready ch example 80 - 99 9 ^, 0 0 - 8th 5.0 - 0 - 15th 5.0

Light top distillate

- volume%

Component

Paraffin Naphthene Aromatics

This distillate has an octane number BOZ of 60.8, a Beginning of boiling at 55 G, an end of boiling at 149 C and one API density of 79.2 °.

The paraffinic component-containing feed stream is passed through an isomerization and cracking stage, in which he comes into contact with an isomerization cracking catalyst subjected to isomerization and cracking conditions becomes an isomerized, cracked stream that Contains isobutane, light and heavy paraffins.

The isomerization and cracking catalyst is a catalyst which is characterized by its ability to process hydrocarbons, e.g. feedstock containing paraffins, like paraffins from the CV - Co area, to a product that e.g. contains C and CL paraffins and at the same time isomerizing the product and / or the feedstock, / e.g. by isomerization of butane to form significant amounts of isobutane.

A typical catalyst is an activated alumina as disclosed in commonly assigned US Pat. No. 5,689,434. (Other suitable catalysts are disclosed in commonly assigned U.S. Patents 3,607,959, 3,567,796, and 3,523,142 disclosed).

The catalysts described in the aforesaid patent can be made by combining alumina with an activator system consisting of (a) chlorine or bromine and (b) an inorganic sulfur compound which

40 9 828/0974

Hydrogen sulfide or SX ^ where m is 1 or 2 or X is chlorine or bromine. The activation is effected at 177 "40O ⁰ C. The preferred ratio of chlorine or bromine to the inorganic sulfur compound is 0.1: 1 to 4: 1; and the finished. Catalyst contains 3-15% by weight of chlorine" or bromine »

The catalyst preferably also contains 0.01-5% by weight Platinum, palladium, rhodium or ruthenium "

A preferred catalyst can be prepared by the process described in US Pat. No. 3,689,434, Example 1. It is a chlorinated platinum on alumina catalyst ₀

The isomerization and cracking of the feed stream, which contains the paraffinic components, is brought about when the process according to the invention is carried out in that 100 parts by volume (this number serves as the basis for the following numbers) in the liquid phase (with the exception of the hydrogen, "which itself) is in the gas phase at 149-204 ⁰ C, preferably 154 -'190 ⁰ C, eg 163 ° C and a pressure of 7 _S 3 ° --70 * 3 atmospheres, preferably 21.1 49 ₅ 2 atü, ZoBo 21.1 atü pass through an isomerization and cracking stage «

Through this isomerization and cracking stage. is also hydrogen in an amount of 0.1-5, preferably 0.2 3.0, ZoB. 1.5 moles, per mole of hydrocarbon feed passed through o This corresponds to a hydrogen flow rate of 50.7-2 5355, preferably 101 ₁ 4 - I 690, ZoB ₃ 845 Nm ⁵ Zm ^ (300-15,000, preferably 600-10 000, - ZoBo 5,000 SCFB) ₀ The purity of the hydrogen is 50 - 100% by volume, preferably 80 -. .100 Volo -%, eg 95 ■ Voio -% ρ The space velocity (LHSV) of the total feed through the catalyst bed is 0.5 - 8, preferably 1 - 3 _{9 0} Z ₀ B 2, v-FÜssigkeit

409828/0974

per volume catalyst per hour.

During contact with the catalyst in the isomerization and the cracking stage converts the paraffins into an isomerized cracked product stream which Contains isobutane and light and heavy hydrocarbons. In a "preferred embodiment of the invention In the process, paraffins, e.g. those containing butane, are converted into a product, isobutane contains.

This product stream can be withdrawn and passed through a high pressure separator in which 50-100 parts, preferably? 0-98 {pillars, e.g. 95 parts of the hydrogen at 21.1-49.2 atu, e.g. 34.5 atu, by flash distillation withdrawn and returned to the isomerization and cracking zone.

The product stream from which the hydrogen has been separated contains (a) light paraffins, ie paraffins with boiling points below that of isobutene υτκ! which include, for example, C ₅ and C "2 paraffins (b) isobutane and (c) heavy paraffins, ie paraffins which have a higher boiling point than isobutane and the η-butane, C _n - and (/,. paraffins lock in.

In a preferred embodiment of the invention, this product stream is passed to a fractionation or separation stage in which light paraffins, isobutane and heavy. Paraffins and hydrogen are separated from each other. However, it is preferred that the hydrogen, at least the major amount thereof, prior to the fractionation stage, in which the other three components are separated _$ is removed. Thus, the preferred fractionation product comprises (a) a light paraffins stream, (b) an isobutane-containing stream, and Cc) "a heavy paraffins stream.

How it turns out to the skilled person depends on the type of

409828/0 97 4

! Separation from the proportions in which the various components exist relative to one another. For example, it may be expedient to separate isobutane and a lighter fraction as overhead product from a heavier soil fraction in a first fractionation stage, after which the isobutane sediment is separated from a lighter, second animal head fraction in a second fractionation stage in the fractionation in a first stage a lighter fraction than overhead prodtikt and isobutane xmü a heavier fraction than soil, the latter soil is further fractionated, with isobutane as overhead product and a heavier fraction is obtained as second soil. '

In a further embodiment of the process according to the invention, the separation is carried out in a single fractionation tower, light paraffins being obtained as the overhead product, the heavier paraffins as bottom bodies and an isobutane fraction as a side cut; This Seitenscimitt is stripped $ to obtain a pure isobutane.

The product streams obtained in the fractionation can contain the following components?

Stream of liquid heavy paraffins -, -. -. Volume%

Part of the wide area . Example paraffins 15-70- 43.2

Caphthenes 60-50 28.1

Aromatics below 5 0

RON clear 60-80 71

This liquid stream can e.g. in a "Henge of 50 -

80 parts, preferably 60-75 parts, e.g. 68.3 parts won werelen.

4DS8 28/097

Stream, in the form of a vapor, with light paraffins

Volume%,

Bestandtei l range Example

Methane .0-4- O

Ethsn 0-5 O

Propane 0-15 6

n-butane 0-15 2.5

n-pentane 0-10 .0.4

i-pentane 0-25 4.8

The isobutane fraction can, for example, be 10-70 parts, preferably 15-65 'parts, e.g. Make up 23.3 parts.

When carrying out the method according to the invention the light paraffin fraction and the heavier fraction Paraffins combined to form a isomerized and cracked stream.

This stream, a total of 30-95 parts, preferably 35 parts, e.g. 82 parts, can be sent to a thermal cracking stage in which the reaction is controlled so that maximum amounts of C -, - and C-olefins. can be obtained.

The thermal cracking is preferably carried out in a non-catalytic tube furnace or an oil heater in the presence of steam. The temperature of the hot thermal steam cracking is 54-3 - 93O ⁰ C, preferably 650 870 ⁰ C, for example at 760 ⁰ C, at a pressure from 0 to 7.03 atm, preferably C, 21 - 3.52 atm, for example, 1.76 atmospheres, and a Mo! Ratio of vapor to hydrocarbon of: 0.1-10, preferably 0.2-8, for example 5.

The product stream coming from thermal cracking, containing an olefin fraction is preferably fractionally distilled to (a) a light olefinic Distillate fraction, (b) a heavy gasoline fraction (thermal naphtha fraction), and (c) a C ^ -C ^ olefin fraction

409828/0974

to win. 5-95 parts, preferably 15-85 parts, e.g. 61.2 parts of the light olefinic distillate fraction may contain components with a boiling point below that of propylene. This stream can be, for example, the following Components contain (based on the "in the case of thermal Cracking used "material):

Volume% '

component area hydrogen 5-20 methane 10-40 acetylene 0-5 Ethylene 20-70 Ethane 2-12

■. example

12.5 28.5 0.4 27.6 • 5.7

With the fractional distillation of the thermal Cracking the coming stream you get a heavy gasoline (thermal naphtha) or Dripolette (which is a heavier one Fraction is) in an amount of, for example, 5-50 Parts, preferably 7-40 parts, e.g. 13.8 parts.

The C ~ - C ^ olefin fraction obtained in the fractionated Distillation of the product stream coming from the thermal cracking can be obtained by the following listed composition, based on the material used in thermal cracking

be: .

■ Volume% '_

Example ■ 1.8 12.5

· ■■■ · "2.3

5.3

■. 3.2 0.2

This C, C, - olefin stream, a total of 5-, 45 parts, preferably 7-40 parts, e.g. 12.4 parts, is sent to the alkylation stage in which it is used for alkylation. of

409828/097 4

component area propane 0-8 Propylene 5-30 Butadiene 0-8. Butene. . . 2-15 n-butane 1-10 Isobutane 0-4

isobutane-containing stream obtained from fractionation of the isomerized and cracked stream is used. The alkylation may be at from 4.4 to 21.1 ⁰ C, preferably from 7.2 to 15.6 ⁰ C, eg 12, S ⁰ C in the presence of 85 - 89 '- 7 preferably 90 - 97 ° p- eg 95 acid at a space velocity (Gal G-allone acid in the contactor) of 0.1-0.6, preferably 0.15-0.40, for example 0.25. The internal molar ratio of isobutane to olefin is 100-700, preferably 150-55O, for example 250; the external molar ratio is 2-40, preferably 4-30, for example 10.

The alkylate gasoline fraction obtained, which in a total of 10-60 parts, preferably 15-50 parts, E.g. 31 j5 parts is obtained by an octane number ROZ (RON Clear) from 91 - 102, e.g. 95.0.

It should also be noted that the alkylate gasoline product can be obtained in amounts of 10-60 parts, preferably 15-50 parts, eg 31.5 parts per 100 parts of the material fed to the isomerization and cracking stages. "this amount can d \ irch hydrogenating the Dripolens or heavy gasoline can be increased hydrogenation of this current can, for example, at 260 -. x 400 ⁰ C, preferably 274-385 ° C, eg 343 ^O C, and from 7.03 to 70.3 atm , preferably -10.5-56.2 atmospheres, for example 35.2 atmospheres, using a nickel-molybdenum on aluminum oxide catalyst, as is commercially available under the name American Cyamid EDS-3 catalyst from hydrogen to heavy gasoline can be 33.8-845 ImVm, preferably 5Q7-338 Nm ^ per m ^, e.g. 169 Nm ^ per nr; the space velocity is 0.2-10, preferably 0.4-8, e.g. 2.0 V / h / V. ·

The hydrogenated heavy gasoline product (a gasoline cut) used in an amount of 5-50 parts, preferably 7-40 parts Dividing, e.g., I3-9 dividing, can be obtained as follows

409828/0974

example 0 98 0 86 0 50,

be marked ι

Eigensc way. - Area

Ε! O Z (EON clear) 90-102

ROZC * ⁿ ■> ■ ^: 82-92. Aromatics, Vo 1-% 30-80

The following is the description of a "preferred embodiment of the implementation of the method according to the invention, which are made in "connection with the figure attached here" will. All parts mean volume parts, unless otherwise stated.

The figure shows a flow sheet according to which, the inventive Procedure can be carried out. The feed introduced into the process through line 10 can

1 590 m ^ / iDap- light Udex raffinate of a 4-5 RON, which contains 80.7% paraffins, 7.8 % naphthenes and 11.5% & 'omats. This feed is mixed in the liquid phase with 845 Nur / et pure hydrogen introduced through line 11 and the mixture passed through line 12 to the isomerization and cracking stage 13.

The catalyst used in step 13 is prepared according to Example 1 of US Pat. No. 3,689,434 and is a chloride-activated platinized alumina. In level 13 ^ the following conditions prevail: a temperature of 163 C, a pressure of 21.1 atmospheres and a space velocity of

2 V / h / V. The effluent leaves stage 1J through line 14 and passes stage 15, in which a temperature of 163 C and a pressure of 26., 7 atmospheres prevail., with one in circulation guided hydrogen stream is obtained, which is withdrawn through line 11. ~ ■

The separation stage 15 also becomes a hydrogen-free one Stream withdrawn through line 16. This stream is passed to fractionation stage 17 as shown schematically.

409828/0974

-12- 7 360980

In line 17, an isobutene-containing stream is separated off, isobutane is removed from 370.5 ^m ' r ^r ' ° Teg and discharged through line 18 '. A light paraffin stream is also obtained which contains protons every hour (93.81 rr 'per day) and n-But ^ n (35.75 ^. ^ ^ Ro Tan :) and is subtracted by durc.ji lOitur.7 .v / ird - and a stream of heavy paraffins, the naphthenes and paraffins of a molecular weight above that of the C j, .- Kohl exv -?;? χ s he-F.tof? ej η meters of 1086 πι per Ta «τ contains mid by conduction; ? O deducted.

The light paraffin stream in line 19 and the heavy paraffin stream in line 20 are combined in line 21 and passed to the thermal steam cracking stage 22, which operates at 760 ° C. and 1.76 atmospheres with a steam / hydrocarbon molar ratio of 5.

In thermal steam cracking, the feed stream is converted into a thermally cracked product stream, the one Contains olefin fraction. This stream that is withdrawn through line 23, wed st the following composition on:

Stock 1 -. ϊ © ΐ.1.9.

Hydrogen '12.5

Methane '' 28.5

Acetylene 0.4

Ethylene 27.6

Ithane 5.7

Propylene. 12.5

Propane 1.8

Butadiene 2.3

Butene 5.3

η-butane - ■ 3.2

iso-butane 0.2

C ₅₊ Λ 7.9

The thermally recycled product that is an olefin fraction contains, is fractionally distilled in stage 2Λ to a

409828/097 4 _{ÖAD 0RlGINAL}

. - 13 -? 3 6 Π 9 8

To obtain light olefin distillate (which is withdrawn by Loitunr 25.-) _t , which contains ethylene, as the main olefin in an amount of 61.2 parts, as well as a heavy gasoline (heavier thermal naphtha) or Dripolen, which in an amount from 218.6 irr -per tar is subtracted through line 26. This stream, which contains pentane and higher hydrocarbons, is partially hyd-n "e ^ t in stage 28 (with 169 NmVm" hydrogen, which is fed through line 2?) At 34-3 C and 35 »5 atm in the presence of a Hydrogenation catalyst, namely nickel-molybdenum · on aluminum oxide. (HDS-3 from American Cyanamid), and the hydrogenated heavy gasoline is fed through line 29 to a gasoline pool in quantities of 220.8 m per day. The product in line 29 has an octane rating RON of 98.0.

The one obtained in the fractional distillation in stage 24 Olefin cut, the 58.8 nr per day C, olefins,

7.. Ty ^

39.7 m per day η-butane and 138.0 nr per day propylene is contained by, line 30 (together with 370 * 5 Ή " Isobutane, which is brought in through line 18) to the alkylation stage 3> 1.

The alkylation is carried out at 12.8 ⁰ C in the presence of 95% sulfuric acid at a space velocity of 0, .25-V / Hr / V. The internal oil ratio of isobutane to olefin is 250, the external oil ratio is 10.

The alkylate gasoline product is used in an amount of 500.8 m " subtracted per day through line 32 and has an octane number RON of 95.0. . ■.

As the person skilled in the art can see from the above, the process according to the invention leads to excellent results. It makes it possible to achieve maximum alkylate yields and to obtain valuable olefin by-products from a less valuable refinery stream. Process created to increase gasoline production and, at the same time, a process for

- " - · - - ** 409828/0974 '.

- ή - '7360980

Consumption of paraffinic products - because of their low potencies Otherwise, the octane number is not mixed with unleaded gasoline v / could ground.

BAD ORIGtNAL 09828/0974

Claims (1)

-, - · ■ "■■ '. ■ .., ■ I ^ IX. ^ 1 Λ. Process "for the production of an alkylate rate from a material containing paraffinic components as a feed stream, because the feed stream is subjected to isomixing and cracking conditions in the presence of hydrogen with an isonizing and cracking - brings catalyst into contact, from the isobutane formed and glow and a stream containing heavy paraffins Separates isobutane-containing electricity, the deisobutanized stream obtained in this way in Presence of steam forming an a G ^ - Olefin fraction containing product stream thermally crackt, the isobutane-containing stream with which the C ^ - The product stream containing the olefin fraction is alkylated and the resulting alkylate gasoline fraction is recovered, 2. The method according to claim 1, characterized , that you have a C ^, to co-paraffins as the feed stream containing -stream begins, 5, method according to claim 1,. characterized, that a raffinate stream is used as the feed stream uses, from which the aromatics are removed by extraction. . . "'^ 4, method-according to claim 1, characterized, that a stream containing at least 60% paraffins is used as the feed stream. 0 9 8 2 8/0 9 7 k \ BAD ORIGINAL 5. The method according to any one of the preceding claims, . characterized in that an activated aluminum oxide is used as isomerization and cracking catalyst is used. 6. The method according to any one of the preceding claims, characterized in that the isomerization and cracking catalyst used is platinum, palladium, rhodium or ruthenium on an aluminum oxide, which with (a) chlorine or bromine and (b) hydrogen sulfide or S Xp (in which m is 1 or and X is chlorine or bromine) has ^{been activated at a temperature of 175-40O 0} C, is used. 7. The method according to any one of the preceding claims, characterized. marked, that the hydrogen is separated from the isomerized and cracked stream before further processing * 8. The method according to claim 7? characterized in that the stream obtained after isomerization and cracking is converted into a stream of light paraffins (a), separating an isobutane-containing stream (b) and a heavy paraffins stream (c). 9. The method according to claim 8, characterized, that the currents (a). and (c) united and 409828/097 4 thermally cracks. . 10. The method according to any one of claims 1-7. characterized , that the effluent of thermal cracking: one subjected to fractional distillation while at least one CL-olefin fraction and one thermal the heavy gasoline fraction obtained is separated off. 11. Method according to claim 10,
_{characterized:} in that the hydrogenated naphtha fraction to obtain a gasoline cut .. 12. The method according to claim 11,
characterized in that the hydrogenated heavy gasoline is added to the alkylate gasoline fraction. 13. The method according to any one of the preceding claims, characterized , that one comes from isomerization and cracking Stream into a stream of light paraffins (a), an isobutane-containing stream (b) and a stream heavier Paraffins (c) separates; unites streams (a) and (c), thermally cracks to form a G ^ olefin fraction to win containing product stream, with which one the isobutane-containing stream is alkylated and the resulting alkylate-gasoline fraction is recovered. 14-, method according to claim 15, characterized, -that one contains a C. olefin fraction, thermally cracked product stream. in a light olefinic distillate fraction, a heavy gasoline fraction and a C ^ olefin fraction separates the Isobutane-containing stream with the C. olefin fraction alkylated to form an alkylate gasoline fraction 40 98287 097 4 and the alkylate gasoline fraction wins. Method according to claim, characterized in that the heavy gasoline is hydrogenated and the hydrogenated directs thermal naphtha to a gasoline pool. 409828/0974