RU2312849C2 - Olefin stock hydrogenation process - Google Patents

Abstract

FIELD: petrochemical processes.

SUBSTANCE: volume hydrogenation of complex-composition olefin stock involves catalytic distillation thereof within catalytic distillation zone incorporating hydrogenation catalyst in presence of hydrogen resulting in hydrogenation of about 30 to about 100% of olefins containing in feedstock into corresponding saturated compounds. Hydrogenate is then withdrawn from catalytic distillation zone and subjected to separation of unhydrogenated olefins including most light olefins and separation of unhydrogenated olefins including most heavy olefins therefrom.

EFFECT: simplified technology.

8 cl, 2 dwg, 11 tbl, 13 ex

Description

Field of Invention

The present invention relates to the hydrogenation of an olefin feed, in particular, it relates to a method for the hydrogenation of an olefin feed containing many different unsaturated olefinic hydrocarbon compounds.

SUMMARY OF THE INVENTION

The invention provides a method for hydrogenating an olefin-containing feed comprising many different unsaturated olefinic hydrocarbon compounds, which comprises: bulk hydrogenating the olefin feed by means of catalytic distillation in a catalytic distillation zone containing a hydrogenation catalyst and in the presence of hydrogen, resulting in unsaturated olefinic hydrocarbon compounds present in the feed hydrogenated to the corresponding saturated compounds; and withdrawing saturated compounds from the catalytic distillation zone.

Catalytic distillation in a catalytic distillation zone includes the implementation of hydrogenation reactions under the influence of a hydrogenation catalyst simultaneously with or in combination with distillation in the same zone. In other words, hydrogenation and separation by distillation are carried out simultaneously in one zone.

By “bulk” hydrogenation is meant that a number of different unsaturated olefinic hydrocarbon compounds are present that are present in the olefin feedstock. In one embodiment of the invention, practically all unsaturated olefinic hydrocarbon compounds of the feed can be hydrogenated. The method may then include feeding saturated compounds to a separation step and separating lighter saturated compounds or paraffins from heavier saturated compounds or paraffins.

In another embodiment of the invention, however, the number of different unsaturated olefinic hydrocarbon compounds that are hydrogenated may be less than the total number of different unsaturated olefinic hydrocarbon compounds that are present in the feed. The method may then include withdrawing at least one unreacted unsaturated olefinic hydrocarbon compound from the catalytic reaction zone.

Brief Description of the Drawings

Figure 1 shows a simplified schematic diagram of a process for the hydrogenation of olefin feedstock according to the first embodiment of the invention.

Figure 2 shows a simplified schematic diagram of a process for the hydrogenation of an olefin feed according to a second embodiment of the invention.

DETAILED DESCRIPTION OF THE INVENTION

The invention is characterized in that during bulk hydrogenation a number of different hydrocarbon compounds are hydrogenated, and not only one single unsaturated hydrocarbon compound or one single category of unsaturated hydrocarbon compounds, such as dienes and / or acetylene compounds, is hydrogenated.

The feed may include from 60 wt.% To 100 wt.% Unsaturated olefinic hydrocarbon compounds, usually from 80 to 100 wt.% Of such compounds. If the feed contains less than 100 wt.% Unsaturated olefinic hydrocarbon compounds, the rest of the feed may consist of branched and normal paraffins, such as octane and / or 2-methylheptane; oxygenates such as alcohols; aromatic hydrocarbons such as benzene; and saturated and unsaturated cyclic compounds other than aromatic hydrocarbons, such as cyclohexane. Any aromatic compounds present in the feed will be hydrogenated to the corresponding saturated cyclic compounds, however, any oxygenated compounds present in the feed will usually not be hydrogenated by bulk hydrogenation of the feed.

In one embodiment of the invention, the feed may be a C ₇ -C ₁₃ naphtha fraction, i.e. it may contain a number of different unsaturated olefinic hydrocarbon compounds having from 7 to 13 carbon atoms. However, in another embodiment of the invention, the feed can include oligomers derived from C ₃ -C ₇ unsaturated olefinic hydrocarbons, i.e. it may contain a number of different unsaturated olefin oligomers.

The feed can be derived from the Fischer-Tropsch process, i.e. it can be obtained in the so-called Fischer-Tropsch process. In other words, it can be obtained by reacting synthesis gas comprising carbon monoxide and hydrogen in the presence of a suitable Fischer-Tropsch catalyst, usually a cobalt, iron or cobalt-iron Fischer-Tropsch catalyst, at elevated temperatures and in a suitable reactor, which is usually a fixed or suspended bed reactor, resulting in a series of products, including a number of olefinic unsaturated hydrocarbon compounds suitable for use as raw materials in this invention. The products of the Fischer-Tropsch process usually must then be processed to obtain an olefin fraction. Thus, as described hereinabove, the feed will then contain, in addition to unsaturated olefinic hydrocarbon compounds, also branched and normal paraffins, such as octane and / or 2-methylheptane; oxygenates such as alcohols; aromatic hydrocarbons such as benzene; and saturated and unsaturated cyclic compounds other than aromatic hydrocarbons such as cyclohexane.

From 30 to about 100% of unsaturated olefinic hydrocarbon compounds can be hydrogenated in the catalytic distillation zone.

When an individual unsaturated olefin compound can, at least in principle, remain unhydrogenated or unreacted in the catalytic distillation zone, two or more different unsaturated olefinic hydrocarbon compounds will usually remain unhydrogenated or unreacted. Such unhydrogenated or unreacted compounds are usually either the lightest compounds in the feed or the heaviest compounds in the feed, and in the process of the invention thus leading to these compounds, they are separated in the catalytic distillation zone from the hydrogenated compounds.

The catalytic distillation zone is usually a column. The catalyst may be in the form of particles and may be provided as a packing layer. The feed and hydrogen must then, of course, be introduced continuously into the column, the product being continuously withdrawn from the column as a product stream. Raw materials and hydrogen can enter the column at the same level or at different levels. Preferably, however, hydrogen may enter the column below the level at which the feed enters the column. Suitable distillation devices, for example a bulk nozzle, structured nozzle, trays or any other distillation apparatus or device, are introduced into the column below and / or above the catalytic bed.

The particulate hydrogenation catalyst in the packing layer provides good contact between unsaturated olefinic hydrocarbon compounds and hydrogen, while also providing the required separation of the gas and liquid phases. The hydrogenation catalyst may preferably be a heterogeneous catalyst. Usually it has a particle size of from 0.79 to 6.35 mm and can be in any desired shape, for example, spherical, elongated or the like. Typically, such catalysts contain as their active component one or more of metals, such as nickel, copper, cobalt, chromium, zinc, iron and platinum group metals, i.e. platinum, palladium, rhodium and ruthenium.

Although the column can, at least in principle, operate at elevated pressures up to 1500 kPa (g), it is envisaged that it will operate normally at approximately atmospheric pressure or at a pressure only slightly above atmospheric pressure, which is an advantage of the method of the invention. Thus, the working pressure in the column can usually be in the range from about 50 kPa (g) to about 200 kPa (g).

The temperature in the column will depend, inter alia, on the composition of the feedstock, the pressure in the column and on unsaturated olefinic hydrocarbon compounds that have not been hydrogenated, i.e. which should be separated from hydrogenated hydrocarbon compounds. So, if the raw material is a C ₇ -C ₁₃ naphtha fraction and the column working pressure is 100-200 kPa (g), the temperature of the catalyst layer can be about 120-140 ° C, and the product stream is then removed as a bottoms stream, and the unreacted olefinic hydrocarbon compounds, which are lighter compounds, are withdrawn in the form of a distillate stream. If the raw material is a C ₇ -C ₁₃ naphtha fraction and the column working pressure is about 100 kPa (g), the temperature of the catalyst layer can be about 150 ° C, the product stream being discharged as a distillate stream, and unreacted olefinic hydrocarbon compounds being more heavy compounds, withdrawn in the form of a bottoms stream. If the feed includes unsaturated olefin oligomers derived from C ₃ -C ₇ olefins and the column working pressure is about 50-200 kPa (g), the temperature of the catalyst layer may be about 160 ° C-200 ° C, and the product stream is withdrawn as distillate stream, and unreacted olefinic hydrocarbon compounds, which are heavier compounds, are discharged as bottoms.

The invention will now be described by way of example with reference to the accompanying drawings.

1, the numeral 10 generally designates a process for hydrogenating an olefin feed according to a first embodiment of the invention.

The process 10 includes a catalytic distillation column 12 containing a bed of particles 14 from the hydrogenation catalyst in the form of particles, as well as a plurality of distillation plates 16 in the distillation zone 20 above the bed of the catalyst nozzle 14.

The feed line 20 leads to the distillation zone 18, while the hydrogen feed line 22 leads to the column 12 below the catalyst packing layer 14.

An output line of bottoms product 24 leads from the cube of the column 12. It is divided into a line of reboil 26 and a line of output of the product 28. The line of reboil 26 is connected to the reboiler 30 and returns part of the bottled product to the column 12.

The helmet line 32 leads from the top of the column 12 to the condenser 34 and from it to the reflux tank 36. The liquid line 38 leads from the reflux tank 36 and is divided into a return line 40 to the top of the column 12 and a distillate product output line 42. The hydrogen output line 44 leads from a reflux tank 36 to a hydrogen recycle compressor 46 with a line 48 leading from the compressor 46 to the hydrogen supply line 22. The hydrogen feed line 50 also leads to the hydrogen supply line 22.

When using an olefin feed, such as a naphtha fraction obtained by the Fischer-Tropsch process, is fed into the distillation zone 18 via a feed line 20, while hydrogen is simultaneously introduced into the cube of the column via line 22. Column 12 is maintained at a pressure slightly above atmospheric pressure, usually at 100-200 kPa (g), and the temperature of the catalyst layer is usually maintained at 120-165 ° C. The heavier unsaturated olefinic hydrocarbon compounds of the Fischer-Tropsch naphtha fraction are hydrogenated to paraffins, the paraffins being discharged via line 24 as a bottoms stream or product. Part of the bottoms product is returned to evaporation through line 26 and reboiler 30, and the remainder is withdrawn via line 28. Lighter unreacted or unhydrogenated unsaturated olefinic hydrocarbon products are withdrawn through line 32 and condensed in a condenser 34 before passing to reflux tank 36. Their liquid component is discharged along line 38, with part of it being supplied for irrigation along line 40 to the top of column 12, while the residue is withdrawn as a distillate product or stream through line 42. Hydrogen is fed to the column as recycle using line 44 leading from the reflux tank 36, compressor 46 and line 48.

Thus, through process 10, volumetric hydrogenation of the naphtha fraction obtained in the Fischer-Tropsch process can be carried out. With such bulk hydrogenation, the heavier unsaturated olefinic hydrocarbon compounds are hydrogenated to paraffins, which are removed via line 28 as a bottoms product. Undesirable lighter unsaturated olefinic hydrocarbon compounds are withdrawn via line 42 as a distillate product.

It should be clear that other types of raw materials can be processed in a process having the same configuration as in FIG.

Thus, in another embodiment of this embodiment of the invention, process 10 can be used to bulk hydrogenate olefin feeds, including unsaturated olefin oligomers (i.e. polymers derived from 2, 3 or 4 monomer units) derived from C ₃ -C ₇ olefins. Unsaturated oligomers are hydrogenated to paraffins, with paraffins being withdrawn as bottoms, and unwanted light non-hydrogenated or unsaturated olefin oligomers and olefins being removed as a distillate product.

In process 10, the degree of hydrogenation is determined by the supply of hydrogen through line 22 and the operating conditions in column 12. Hydrogenation does not have to be complete. The hydrogen recycle compressor 46 provides the required partial pressure of hydrogen in the catalyst bed 14.

Process 10 is presented in examples 1 and 2 hereinafter. In examples 1 and 2, as well as in examples 3 and 4, also described hereinafter, a catalytic distillation column 12 was used with a height of 10 m and a diameter of 2 inches (approximately 5 cm), consisting of four 2.5 m sections. In each of Examples 1-4, the column was loaded with an available industrial hydrogenation catalyst, as indicated. The catalyst particles were packed in bags made of stainless steel woven mesh wrapped in a demister wire mesh. The column had power entry points in the upper flanges of all 2.5 m sections in order to make process optimization possible. Hydrogenated components could be removed either as a distillate stream or as a bottoms stream.

In general, in Examples 1 and 2, hereinafter, the process configuration was as shown in FIG. 1, except that the hydrogen recycle lines 44, 48 and the hydrogen compressor 46 are omitted, instead, the hydrogen purge line leads from the reflux tank 36. No distillation trays are provided either above or below the catalyst bed, and the catalyst packing thus also acts as distillation trays.

In examples 1 and 2, the C ₇ -C ₁₃ naphtha fraction of the Fischer-Tropsch process with an olefin content of 84 wt% was introduced equally above the catalytic layer 14 at a rate of 0.5-1 kg / h. Hydrogen was introduced into the cube of column 12 along line 22, i.e. below the catalytic layer 14, with a speed of 1.0-2.5 nm ³ / hour. The column pressure was varied in the range of 100-200 kPa (g), which gave the temperature of the catalyst layer in the range of 120-140 ° C. The conversion of raw olefins was 60-80%. Hydrogenated compounds were removed as bottoms.

It was found that results similar to those obtained in Examples 1 and 2 can also be achieved by using a larger scale catalytic distillation column 12, also having a length of 10 m but having a diameter of 4 inches (approximately 100 mm), and using the same affordable industrial hydrogenation catalyst.

Example 1

A 10 m and 2 inch column was loaded with a commercially available hydrogenation catalyst obtained from Kats Leuna GmbH Catalyst of Am-Hauptor, Geb. 8322, D-06237, Leuna, Germany, under the designation Leuna Catalyst 6564TL 1.2. The C ₇ -C ₁₃ naphtha fraction obtained by the Fischer-Tropsch process, with an olefin content between 42 and 72 wt.%, Was fed above the catalyst bed at a rate of 1 kg / h. The composition of the raw materials is given in table 1.1.

Table 1.1
The composition of hydrocarbons and the characteristics of the raw materials Raw material component  wt.% C5 0.23 C6 2.18 C7 17.78 C8 27.39 C9 23.78 C10 17.49 C11 9.46 > C11 1,69 Total one hundred Characteristics of raw materials Bromine number (g Br / 100 g) 81.6 Acid number (mg KOH / g) 15.4 Carbonyls (% IEC) 5.9 Alcohols (% C ₇ ) 6.5 Esters (mg KOH / g) 2,3

Hydrogen was supplied below the catalyst bed at a rate of 89 g / h. The column pressure was 100 kPa (g), which resulted in a catalyst layer temperature of 117 ° C. The reboiler temperature was 164 ° C. Hydrogenated compounds were removed as bottoms. 798 g / h of cubic product and 200 g / h of distillate product were taken. The conversion of raw olefins was 57%. An analysis of the distillate and bottoms products is given in table 1.2 below.

Table 1.2
Product analysis Distillates Bromine number (g Br / 100 g) 15.77 Acid number (mg KOH / g) 18.90 Carbonyls (% IEC) 6.30 Alcohols (% C ₇ ) 10.50 Esters (mg KOH / g) 2.20 VAT residue (hydrogenated
product) Bromine number (g Br / 100 g) 40.25 Acid number (mg KOH / g) 5.90 Carbonyls (% IEC) 4,50 Alcohols (% C ₇ ) 3.10 Esters (mg KOH / g) 10.30

Example 2

A 10 m and 2 inch column was loaded with the same commercially available hydrogenation catalyst as used in Example 1. The same Fischer-Tropsch feed as used in Example 1 was fed above the catalyst bed at a rate of 748 g / hr. Hydrogen was supplied below the catalyst bed at a rate of 224 g / h. The pressure in the column was 212 kPa (g), which resulted in a temperature of the catalyst layer of 140 ° C. The reboiler temperature was 197 ° C. Hydrogenated products were withdrawn as bottoms. 544 g / h of bottoms product and 216 g / h of distillate product were taken. The conversion of raw olefins was 78%. Analyzes of distillate and bottoms products are given in table 2.1 below.

Table 2.1
Product analysis Distillates Bromine number (g Br / 100 g) 10.25 Acid number (mg KOH / g) 19.40 Carbonyls (% IEC) 3.60 Alcohols (% C ₇ ) 14.80 Esters (mg KOH / g) 2.40 VAT residue
(hydrogenated product) Bromine number (g Br / 100 g) 20.82 Acid number (mg KOH / g) 1,50 Carbonyls (% IEC) 2.70 Alcohols (% C ₇ ) 4.10 Esters (mg KOH / g) 18.30

In FIG. 2, the numeral 100 generally designates a process for hydrogenating an olefin feed according to a second embodiment of the invention.

In process 100, components that are the same or similar to components of process 10 of FIG. 1 are denoted by the same numerical designations.

The catalytic distillation column 12 of process 100 is similar to the column of process 10, except that the distillation zone 18 is provided below the packing layer of the catalyst 14. The feed line 20 still leads to the distillation zone 18 and is thus also located below the packing layer of the catalyst 14 .

In process 100, bulk hydrogenation of an olefin feed, such as a naphtha fraction obtained by the Fischer-Tropsch process, where the unsaturated hydrocarbon feed compounds are converted to paraffins, can be carried out. Hydrogenated Compounds, i.e. paraffins are withdrawn via line 42 as a distillate product, and undesirable heavier unsaturated hydrocarbon compounds, i.e. raw oligomers are withdrawn via line 28 as a still product.

It should be clear that other types of raw materials can be processed in a process having the same configuration as in FIG.

Thus, in another embodiment of the invention, the hydrogenation of a mixture of oligomers derived from C ₃ -C ₇ unsaturated or olefinic hydrocarbon compounds can be carried out in process 100. Unsaturated oligomers are hydrogenated to paraffins. Paraffins are removed as a distillate product, and unwanted unsaturated heavier components in the form of heavier olefins and / or oligomers are removed as bottoms. As previously, the degree of hydrogenation is determined by the supply of hydrogen and the operating conditions in the catalytic distillation column 12, and the hydrogenation need not be complete. The hydrogen recycle compressor 46 provides the required partial pressure of hydrogen in the catalytic layer 14 of the catalytic distillation column 12.

As in figure 1, the degree of hydrogenation is determined by the supply of hydrogen and operating conditions in the column 12; hydrogenation does not have to be complete; and a hydrogen recycle compressor 46 provides the required partial pressure of hydrogen in the catalyst bed 14.

In Examples 3-9, hereinafter, process 100 was used, except that instead of hydrogen recycle through line 44, compressor 46 and line 48 was used to purge hydrogen from reflux tank 36.

In examples 3 and 4, the C ₇ -C ₁₃ naphtha fraction obtained by the Fischer-Tropsch process with an olefin content of 84 wt.% Was introduced into the catalytic distillation column 12 below the catalytic layer 14 at a rate of 2 kg / h. Hydrogen was introduced into column 12 at a speed of 2 nm ³ / h below the catalytic layer 14. The pressure in the column was maintained at 100 kPa (g), which resulted in a catalyst layer temperature of about 150 ° C. The conversion of the olefins of the feed was 80-85%.

Example 3

A 10 m and 2 inch column was loaded with the same commercially available hydrogenation catalyst as used in Example 1. The C ₇ -C ₁₃ naphtha fraction obtained by the Fischer-Tropsch process with olefins between 42 and 72 wt.% Was fed below the bed catalyst at a rate of 2 kg / h. The composition of the raw materials is given in table 3.1.

Table 3.1
The composition of hydrocarbons and the characteristics of the raw materials Raw material component  wt.% C8 1.00 C9 49.43 C10 33.13 C11 15.73 C12 0.71 > C12 0.00 Total one hundred Characteristics of raw materials Bromine number (g Br / 100 g) 82.5 Acid number (mg KOH / g) 0.2 Carbonyls (% IEC) 5.9 Alcohols (% C ₇ ) 6.2 Esters (mg KOH / g) 2.6

Hydrogen was supplied below the catalyst bed at a rate of 179 g / h. The pressure in the column was 100 kPa (g), which resulted in a temperature of the catalyst layer of 143 ° C. The reboiler temperature was 219 ° C. A reflux ratio of 2 was maintained. Hydrogenated compounds were removed as a distillate stream. 486 g / h of bottoms product and 1497 g / h of distillate product were taken. Excess hydrogen was flushed. The conversion of raw olefins was 83%. Analyzes of distillate and bottoms products are given in table 3.2 below.

Table 3.2
Product analysis Distillates (hydrogenated product) Bromine number (g Br / 100 g) 3.25 Acid number (mg KOH / g) 0.02 Carbonyls (% IEC) 5.05 Alcohols (% C ₇ ) 5.70 Esters (mg KOH / g) 2,50 VAT residue Bromine number (g Br / 100 g) 47.18 Acid number (mg KOH / g) 0.09 Carbonyls (% IEC) 3.85 Alcohols (% C ₇ ) 1.85 Esters (mg KOH / g) 4,50

Example 4

A 10 m and 2 inch column was loaded with the same commercially available hydrogenation catalyst as that used in Example 1. The same Fischer-Tropsch feed as used in Example 3 was fed below the catalyst bed at a rate of 2 kg / hr.

Hydrogen was supplied below the catalyst bed at a rate of 179 g / h. The pressure in the column was 100 kPa (g), which resulted in a temperature of the catalyst layer of 148 ° C. The reboiler temperature was 236 ° C. A reflux ratio of 2 was maintained. Hydrogenated compounds were removed as a distillate stream. 102 g / h of bottoms product and 1897 g / h of distillate product were taken. Excess hydrogen was flushed. The conversion of raw olefins was 75%. Analyzes of distillate and bottoms products are given in table 4.1 below.

Table 4.1
Product analysis Distillates (hydrogenated product) Bromine number (g Br / 100 g) 20.14 Acid number (mg KOH / g) 0.11 Carbonyls (% IEC) 5.60 Alcohols (% C ₇ ) 5.70 Esters (mg KOH / g) 2.25 VAT residue Bromine number (g Br / 100 g) 21.83 Acid number (mg KOH / g) 0.13 Carbonyls (% IEC) 4.95 Alcohols (% C ₇ ) 0.40 Esters (mg KOH / g) 5.45

In Examples 5-9, a 10 m catalytic distillation column 12 with a diameter of 4 inches (approximately 100 mm) consisting of ten 1 m sections was used. In each of the examples, it was loaded with a packed bed 14 of a commercially available hydrogenation catalyst, which was specified. The catalyst was loaded in the form of a proprietary catalytic packing obtained from Catalytic Distillation Technologies 10100 Bay Area Boulevard, Pasadena, Texaz 77507, USA, described in US Pat. . Hydrogenated compounds were removed as bottoms.

Example 5

A 10 m and 4 inch column was loaded with a commercially available hydrogenation catalyst obtained from Kats Leuna GmbH Catalyst of Am-Hauptor, Geb. 8322, D-06237, Leuna, Germany under the designation Leuna Catalyst 7762K. The Fischer-Tropsch C ₇ -C ₁₃ naphtha fraction with an olefin content of between 45 and 80 wt.% Was fed below the catalyst bed at a rate of 14.251 kg / h. The composition of the raw materials is given in table 5.1.

Table 5.1
The composition of hydrocarbons and the characteristics of the raw materials Raw material component  wt.% C6 0.42 C7 15.73 C8 27.48 C9 24.50 C10 17.68 C11 11.30 C12 2.03 > C12 0.06 Total one hundred Characteristics of raw materials Bromine number (g Br / 100 g) 90.0 Acid number (mg KOH / g) 17,2 Carbonyls (% IEC) 6.4 Alcohols (% C ₇ ) 6.3 Esters (mg KOH / g) 4.3

Hydrogen was supplied below the catalyst bed at a rate of 396 g / h. The pressure in the column was 102 kPa (g), which resulted in a temperature of the catalyst layer of 172 ° C. The reboiler temperature was 203 ° C. A reflux number of 6 was maintained. Hydrogenated compounds were removed as a distillate stream. 2.789 kg / h of bottoms and 11.463 kg / h of distillate products were taken. Excess hydrogen was flushed. The conversion of raw olefins was 87%. Analyzes of distillate and bottoms products are given in table 5.2 below.

Table 5.2
Product analysis Distillates (hydrogenated product) Bromine number (g Br / 100 g) 10.12 Acid number (mg KOH / g) 16.30 Carbonyls (% IEC) 5.30 Alcohols (% C ₇ ) 6.80 Esters (mg KOH / g) 3.70 VAT residue Bromine number (g Br / 100 g) 17.55 Acid number (mg KOH / g) 1.30 Carbonyls (% IEC) 3.00 Alcohols (% C ₇ ) 0.60 Esters (mg KOH / g) 32.00

Example 6

A 10 m and 4 inch column was loaded with the same commercially available hydrogenation catalyst as used in Example 5. The same Fischer-Tropsch feed as used in Example 5 was fed below the catalyst bed at a rate of 18.016 kg / h.

Hydrogen was supplied below the catalyst bed at a rate of 434 g / h. The column pressure was 300 kPa (g), which resulted in a temperature of the catalyst layer of 208 ° C. The reboiler temperature was 244 ° C. A reflux ratio of 4 was maintained. Hydrogenated compounds, i.e. paraffins were withdrawn as a distillate stream. 2.727 kg / hr of cubic product and 15.648 kg / hr of distillate were taken. Excess hydrogen was flushed. The conversion of raw olefins was 95%. Analyzes of distillate and bottoms products are given in table 6.1 below.

Table 6.1
Product analysis Distillates (hydrogenated product) Bromine number (g Br / 100 g) 2.18 Acid number (mg KOH / g) 15.25 Carbonyls (% IEC) 4.95 Alcohols (% C ₇ ) 6.45 Esters (mg KOH / g) 2,55 VAT residue Bromine number (g Br / 100 g) 14.76 Acid number (mg KOH / g) 0.47 Carbonyls (% IEC) 2.70 Alcohols (% C ₇ ) 0.58 Esters (mg KOH / g) 40,45

In general, in Examples 7-9, olefin feeds, including a mixture of unsaturated oligomers, were introduced below the catalyst bed at a rate of between 5-15 kg / h. Hydrogen was supplied at a rate of 1-9 nm ³ / h below the catalyst bed. The pressure in the column was varied between 50-200 kPa (g), which led to temperatures of the catalyst layer in the range of 160-200 ° C. The conversion of raw olefins was 60-99%.

Example 7

A 10 m and 4 inch column was loaded with the same commercially available hydrogenation catalyst as used in Example 5. A mixture of oligomers with an olefin content of between 45 and 80 wt.% Was fed as olefin feed below the catalyst bed at a rate of 15.02 kg / h . The composition of the raw materials is given in table 7.1 below.

Table 7.1
The composition of hydrocarbons and the characteristics of the raw materials Raw material component  wt.% Propane 0.01 Isobutane 0.27 1-Butene + Isobutene 0.54 Butane 5.62 trans-2-butene 3.43 cis-2-butene 2,32 C5 paraffins 1.31 Olefins C5 2,57 C6 paraffins 0.28 Olefins C6 3.83 C ₇ and heavier hydrocarbons 79.83 C ₄ and lighter hydrocarbons 6.29 Total one hundred Characteristics of raw materials Bromine number (g Br / 100 g) 90.0 Sample 1 RVP 66 kPa Sample 2 RVP 65 kPa

Hydrogen was supplied below the catalyst bed at a rate of 0.79 kg / h. The pressure in the column was 163 kPa (g), which resulted in a temperature of the catalyst layer of 193 ° C. The reboiler temperature was 234 ° C. The reflux stream was maintained at 55 kg / h. The hydrogenated product was removed as a distillate stream. 14.62 kg / h of distillate were collected. Excess hydrogen was flushed. The conversion of raw olefins was 99.9%. The bromine number of the distillate (hydrogenated) product was 0.05.

Example 8

A 10 m and 4 inch column was loaded with the same commercially available hydrogenation catalyst as used in Example 5. The same feed as that used in Example 7 was fed below the catalyst bed at a rate of 15.00 kg / h.

Hydrogen was supplied below the catalyst bed at a rate of 0.18 kg / h. The pressure in the column was 133 kPa (g), which resulted in a temperature of the catalyst layer of 202 ° C. The reboiler temperature was 229 ° C. The reflux stream was maintained at 40 kg / h. Hydrogenated compounds were removed as a distillate stream. 14.80 kg / hr of distillate were collected. Excess hydrogen was flushed. The conversion of raw olefins was 39.0%. The bromine number of the distillate (hydrogenated) product was 54.92.

Example 9

A 10 m and 4 inch column was loaded with the same commercially available hydrogenation catalyst as was used in Example 5. The same feed as was used in Example 7 was fed below the catalyst bed at a rate of 10.02 kg / h.

Hydrogen was supplied below the catalyst bed at a rate of 0.33 kg / h. The column pressure was 52 kPa (g), which resulted in a temperature of the catalyst layer of 177 ° C. The reboiler temperature was 214 ° C. The reflux stream was maintained at 35 kg / h. The hydrogenated product was removed as a distillate stream. 10.22 kg / h of distillate were collected. Excess hydrogen was flushed. The conversion of raw olefins was 99.4%. The bromine number of the distillate (hydrogenated) product was 0.56.

Examples 10-13

Examples 10-13 were carried out identically to examples 7-9, using the same raw materials, catalyst, etc., but having different feed rates, feed rates of hydrogen and other operating parameters. Flow costs, operating parameters, product analyzes and results are shown in Table 8.1. For completeness, Examples 7-9 are included in Table 8.1.

Table 8.1 Period No. 7 10 eleven 8 12 13 9 FLOW SPEED Raw materials Catpoli kg / hour 15.02 14,99 15.01 15.00 10.00 10.00 10.02 Hydrogen kg / hour 0.79 0.22 0.29 0.18 0.79 0.79 0.33 Products VAT residues kg / hour 0.56 * 1,02 0.16 * 0.30 * Distillates kg / hour 14.62 15,20 14.02 14.80 10.14 9.78 10.22 Blowdown - hydrogen kg / hour 0.62 0.12 0.14 0.11 0.68 0.68 0.22 OPERATION Column pressure kPa (huts) 163 136 153 133 56 55 52 Catalyst bed temperature ° C 193 201 200 202 159 164 177 Reboiler temperature ° C 234 229 230 229 211 215 214 Phlegm flow kg / hour 55 45 45 40 35 35 35 ANALYSIS  wt.% Products raw materials Distillates Bromine number g Br / 100 g 90.00 0.05 35.42 9.45 54.92 2.11 1.15 0.56 RESULTS CONVERSION TO PARAFFINS % Total olefins based on Br number 99.9 60.6 89.5 39.0 97.7 98.7 99,4 * In these examples, the formation of bottoms was neglected

The authors believe that the method according to the invention has, among others, the following advantages.

A lower pressure can be used in the catalytic distillation column 12 compared to the fixed bed / fluid bed hydrogenation technologies to achieve the same conversion / productivity potential, which results in less expensive equipment.

Hydrogenation is an exothermic reaction, so that a significant amount of heat is produced. In process 10, removal of such significant amounts of in situ heat of reaction can be achieved. Large fluid recycling or the use of inter-coolers is not required, potentially leading to a simplified process.

Thanks to the excellent heat dissipation of the reaction, i.e. the absence of “hot spots”, less catalyst poisoning occurs due to the formation of oligomers, which results in an increased catalyst life compared to the same catalyst used in a fixed bed hydrogenation reactor.

The acidity of the feed, which can lead to the formation of heavy components / oligomers, does not adversely affect the activity of the catalyst, since heavy components are continuously washed off the surface of the catalyst particles.

Additionally, the method according to the invention has general advantages over conventional methods for the hydrogenation of olefin feedstocks, including a hydrogenation reactor followed by a distillation column, such as:

- it is expected that the equilibrium threshold will be overcome, since the products are continuously removed from the reaction zone, which will lead to increased productivity;

- an increased catalyst life is expected due to the removal of products from the catalyst surface as a result of the washing action of irrigation in the catalytic distillation column;

- Increased selectivity is expected because local high temperatures are limited, which can lead to the formation of by-products;

- a reasonable choice of the location of the input points of the feed into the catalytic distillation column may limit the harmful effects of poisons and / or inhibitors in the feed;

- the method can be applied to azeotropic systems;

- the method makes it possible to remove large amounts of reaction heat, while maintaining a stable temperature of the catalyst, since the temperature in the column is set by the pressure in the column, provided that the column operates in a mode above the minimum required load;

- the general scheme of the process can be simplified, since two operations of known processes are now carried out in one apparatus.

Claims (8)

1. The method of hydrogenation of olefin-containing raw materials, consisting of many different unsaturated olefinic hydrocarbon compounds, including bulk hydrogenation of the olefin feed by catalytic distillation in a catalytic distillation zone containing a hydrogenation catalyst and in the presence of hydrogen, whereby from 30 to about 100% of the unsaturated olefinic hydrocarbon compounds present in the feed are hydrogenated to their corresponding saturated compounds; and withdrawal of saturated compounds from the catalytic distillation zone; recovering non-hydrogenated olefinic hydrocarbon compounds, including the lightest olefinic hydrocarbon compounds of the feed, from said hydrogenate; and recovering non-hydrogenated olefinic hydrocarbon compounds, including the heaviest olefinic hydrocarbon compounds of the feed, from said hydrogenate. 2. The method according to claim 1, in which the specified volumetric hydrogenation is carried out under pressure up to 1500 kPa (g.). 3. The method according to claim 2, in which the specified volumetric hydrogenation is carried out under pressure in the range from 50 to 200 kPa (g.). 4. The method according to claims 1, 2, or 3, wherein said feedstock comprises C ₇ -C ₁₃ naphtha. 5. The method according to claims 1, 2, or 3, wherein said feedstock comprises oligomers obtained by oligomerization of unsaturated C ₃ -C ₇ olefinic hydrocarbons. 6. The method according to claims 1, 2, or 3, in which the specified feedstock includes unsaturated hydrocarbon compounds obtained by the Fischer-Tropsch reaction. 7. The method according to claim 4, wherein said feedstock comprises C ₇ -C ₁₃ naphtha, said bulk hydrogenation is carried out under pressure in the range of 100-200 kPa (g) in the catalyst bed, which is at a temperature in the range of about 120-140 ° C, and the product stream includes saturated compounds, removed as a bottoms stream, and a distillate stream, includes unreacted unsaturated olefinic hydrocarbon compounds, which are lighter compounds. 8. The method according to claim 2, in which the specified raw material includes unsaturated olefin oligomers derived from C ₃ -C ₇ olefins, the specified volume hydrogenation is carried out under pressure in the range of 50-200 kPa (g) in the catalyst layer, which is at a temperature in the range of about 160-200 ° C, and the product stream includes saturated compounds that are removed as a distillate stream, and bottoms, includes unreacted unsaturated olefinic hydrocarbon compounds, which are heavier compounds.

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