Method of producing pure 1-butene from c4-fractions

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing pure 1-butene from C4 hydrocarbon fractions primarily containing 1-butene, 2-butene, and butane(s) with a 1,3-butadiene and isobutene impurity, involving preparation of a mixture primarily containing 2-butenes via rectification, catalytic isomerisation of 2-butenes into 1-butene and extraction of 1-butene via rectification, characterised by that at least catalysed isomerisation of 1-butene into 2-butene in said fraction is carried out at temperature lower than 120°C, as well as rectification with continuous removal of isobutane, isobutene and 1,3-butadiene in the distillate and obtaining a residual stream primarily containing 2-butene and n-butane, in which rectification conditions are maintained such that concentration of 1,3-butadiene and isobutene with respect to the sum of 2-butene is not higher than standard limits in the desired 1-butene. A large portion of n-butane is separated from the residual stream via extractive rectification with a polar agent and catalysed isomerisation of 2-butenes to 1-butene is carried out at temperature higher than 120°C, while continuously extracting the formed 1-butene via rectification.

EFFECT: high efficiency of the method.

14 cl, 5 ex, 4 tbl, 2 dwg

 

The invention relates to the field of obtaining pure 1-butene. More specifically the invention relates to the field of obtaining pure 1-butene from hydrocarbon fractions C4containing predominantly n-butenes, butanes and as additives isobutene and 1,3-butadiene.

For polymerization to poly-1-butene necessary concentrated 1-butene (~99%), which is harmful for the polymerization of impurities does not exceed: 1,3-butadiene 0,001-0,002%, isobutene of 0.1%. In the original hydrocarbon With4-fractions typically contain 1-butene and 2-butenes in a ratio of 1-butene to 2-butenes ~1:1, n-butane, isobutane and harmful for the polymerization of 1-butene impurities: 1,3-butadiene (usually 1-2%) and isobutane (usually 1-1 .5%).

Known methods [US-pat No. 4144146, 1984, US-pat No. 4718986, 1988] isolation and purification of 1-butene present in4-faction. They include removing isobutane catalyzed by interaction with methanol, removing butadiene catalytic hydrogenation and distillation remove isobutane as a distillate and the mixture of 2-butenes and n-butane as VAT residue. Feature of the method according to US-4144146, unlike US-4718986, is that the hydrogenation of butadiene is carried out in a dedicated rectification 1-butene and then spend additional rectification of 1-butene from 2-butenes.

The disadvantages of this method is:

- is the application already contained in C 4fractions of 1-butene and not using it to gain 1-butene contained in C4fractions of 2-butenes;

-treatment of 1-butene from butadiene by deep hydrogenation, paired with the loss of part of the n-butenes;

a very difficult separation by distillation of 1-butene from isobutane (the coefficient of relative volatility (α) pairs isobutane-1-butene is at the top of the distillation column only 1.05), combined with the loss of a significant part of 1-butene. The degree of extraction of 1-butene is just 80-83%, the usage amount of n-butenes to produce 1-butene ~47%.

The known method [US-pat No. 5955640, 1999 produce 1-butene from C4fractions containing predominantly n-butenes and n-butane with impurities - 1,3-butadiene and isobutene. The method includes removing isobutene and 1,3-butadiene by their chemical transformations and then rectification of 1-butene from isobutane displayed in conjunction with part 1-butene in the distillate and the rectification of 2-butenes and n-butane output from part 1-butene in the VAT residue (sequence rectification may be above or reverse: first from 2-butenes and n-butane and isobutane), then the flow of isobutane with part 1-butene and thread 2-butenes and n-butane with part 1-butene connect, spend the separation of butane from n-butenes using adsorption on molecular sieves and n is current n-butenes, which is dominated by the 2-butenes and is 1-butene, is subjected to catalytic isomerization, in which part of the 2-butenes is transformed into a 1-butene. Stream after isomerization connect with the original4-faction and with it is subjected to the above processing. Receive (in the example) to 86% of 1-butene from the original amount of 1-butene and 2-butenes.

In fact, 1-butene partially recognized as a part of the present in4-a fraction of 1-butene and partially receive as a result of isomerization of 2-butenes to 1-butene. The disadvantages of the method are:

- the complexity and inevitable high energy intensity;

- the need for deep cleaning of the stream fed to the distillation, chemical methods, in particular by hydrogenation of 1,3-butadiene;

- not a high yield of 1-butene in relation to the amount coming from With4the fraction of n-butenes.

Also known [US Pat. Application No. 2007/0055088, 2007] a method of obtaining a 1-butene-based dehydrogenation of n-butane. Contact gas dehydrogenation allocate4the fraction containing predominantly n-butane and n-butenes (including 1-butene) by extractive distillation with a polar extractant, n-butane returned to the dehydrogenation zone, and in a mixture of n-butenes (1-butene and 2-butenes) hydronaut 1,3-butadiene and then spend the allocation of 1-butene in the node rectification connected to the area(s) of the isomerization of 2-bout the new 1-butene.

The disadvantages of the method:

- complexity and high energy consumption associated with the use of high-temperature dehydrogenation of n-butane;

- complexity and high energy extractive distillation in which it is necessary to separate the distillate relatively high-boiling n-butane (norm. TKip=- 0.5°C) from the relatively low-boiling 1-butene (norm. TKip=-6,5°C)and leave it in a VAT product (decorate);

in the process it turns out not sufficiently concentrated (95,9%) and lack of clean (0.9% isobutene and ~0.01% of 1,3-butadiene 1-butene.

Also known from U.S. Pat. Ru # 2304134, register. 10.08.2007,, way to obtain pure 1-butene, possibly with an admixture of n-butane from a mixture predominantly of hydrocarbons4according to which the initial mixture is subjected to one or two rectification preferably with previous and/or concurrent, and/or intermediate isomerization to 1-butene to 2-butenes, deduce the composition of the distillate hydrocarbons with normal temperature below minus 4°C and the remaining stream containing mainly 2-butenes and n-butane are isomerization to 2-butenes 1-butene and was isolated by distillation as distillate 1-butene, possibly with an admixture of n-butane.

A serious drawback of the method according to EN No. 2304134 is an extremely high energy intensity, especially when rectification 1-butene is t 2-butenes and n-butane (more 9,0 Gcal/t 1-butene), extremely large distillation columns to obtain pure 1-butene (over 150 plates and more than 7 m in diameter) and the accumulation of n-butane in the system. The main reason is the extremely low coefficient of relative volatility (α) pair of 1-butene n-butane (α≈1.1) and azeotrope in a mixture of n-butane - 2-butenes.

We have found a way free from the disadvantages of the above methods. It is based on:

virtually complete isomerization in the source4-a fraction of 1-butene in a more high-boiling 2-butenes, quite easily purified by distillation from isobutane, isobutene and 1,3-butadiene;

- joint removal by distillation of relatively low-boiling impurities: isobutane (TKip=-11,7°C), isobutene (TKip=-6,9°C) and 1,3-butadiene (TKip=-4,4°C) from relatively high-boiling hydrocarbons: 2-butenes (TKip=+0,9°C and +3,7°C) and n-butane (TKip=- 0.5°C), which separated the impurities do not form azeotropes;

the Department relative to non-energy-intensive extractive rectification more low-boiling n-butane from the more high-boiling 2-butenes, which greatly facilitates the subsequent separation of the pure 1-butene after isomerization to 2-butenes to 1-butene;

- hydrogenation ò parts of 1,3-butadiene in C4-faction is achieved together with the hydroisomerization of 1-butene to 2-butenes.

The equilibrium of reaction(s) 1-butene 2-butenes is strongly temperature dependent. At relatively low temperatures in the equilibrium mixture is strongly dominated by the 2-butenes (at 50°C ~96%at 100°C ~93,4%); at high temperatures, the content of 1-butene increases (at 150°C ~9.9%, and at 350°C ~22%). Therefore, at the stage of conversion of 1-butene to 2-butenes need less high temperature (<120°C)stage 2-butenes → 1-butene - higher (>>120°C).

We say:

1. The way to obtain pure 1-butene from hydrocarbon With4fractions containing mainly 1-butene, 2-butenes and butane(s) with a mixture of 1,3-butadiene and isobutene, including the production of a mixture containing predominantly 2-butenes, with distillation, catalytic isomerization to 2-butenes 1-butene and isolation of 1-butene by distillation, characterized in that spend at least catalyzed isomerization of 1-butene to 2-butenes in a specified fraction at a temperature less than 120°C and rectification with continuous removal of the distillate isobutane, isobutene and 1,3-butadiene and receiving VAT stream containing mostly 2-butenes and n-butane, in which the conditions of rectification support so that the concentration of 1,3-butadiene and isobutene in relation to the amount of 2-butenes is not above regulatory limits in the target 1-butene, from the specified VAT stream is separated most n-butane extractive rectification of the polar agent and spend catalyzed isomerization of 2-butenes to 1-butene at temperatures over 120°C under continuous removal of the formed 1 - butene rectification.

As methods that increase the efficiency of the method according to claim 1, we declare the methods characterized in that:

- catalyzed positional isomerization of n-butenes in hydrocarbon mixtures is carried out in liquid, gas-liquid or gas phase(Ah) mode hydroisomerization and/or positional isomerization;

as catalysts hydroisomerization use deposited on a solid carrier of metals selected from the group including Nickel, palladium and other platinum group metals of the periodic table, or their hydroisomerization-active compounds;

- as catalysts for the isomerization of alkenes in the absence of hydrogen using acid, acidic ion exchangers, acidic zeolites, isomerization-active metal oxides, alkali metals, or a combination of some of these catalysts;

the isomerization of 1-butene to 2-butenes in the original hydrocarbon mixture is carried out in the mode hydroisomerization with simultaneous hydrogenation of butadiene(s);

- carried out initially liquid (hydro)isomerization ò part contained in a mixture of 1-butene to 2-butenes, and then spend additional isomerization, combined with the specified rectification, in the catalyst zone, located in the middle part of the strengthening of the distillation zone;

- from the decree of the tion of the cubic flow distillation, extractive distillation with a polar extractant deduce distillate, containing predominantly n-butane, and the extractant is desorbed concentrated mixture of 2-butenes containing not more than 3%, preferably not more than 0.5% n-butane, which is fed to the isomerization of 1-butene;

as the polar solvent use solvent selected from the group comprising N,N-dimethylformamide, N-organic, N,N-dimethylacetamide, N-formylmorpholine, sulfolan, β-methoxypropionitrile, acetonitrile, methyl ethyl ketone, mixtures of solvents among themselves and/or water and/or hydrocarbons5-C6;

- isomerization to 2-butenes 1-butene and its secretion is carried out at a temperature of from 120 to 400°C in a flow of the gas, gas-liquid or liquid reactor, followed by distillation of 1-butene and/or in the United reactive distillation system;

- when using the combined reactive distillation system catalyst include within the reactive distillation column in the middle or comprehensive parts or/and external flow reaction zone, both ends of which are connected with a distillation column;

at least part neprivrednih 1-butene to 2-butenes return from the bottom of the distillation column or cube in the reaction zone to the isomerization of 2-butenes to 1-butene;

in the upper part of the distillation or reactive distillation is the column serves alkane(s) 5-C6;

- dedicated 1-butene addition rectificat from n-butane in the presence of alkane(s)5-C6;

- part neprivrednih 1-butene to 2-butenes with an admixture of n-butane is withdrawn from the lower part of the distillation or reactive distillation column, remove and systems.

In the claims, and then in the text the term "rectification" is used, as is customary in international practice, to refer to "simple" rectification carried out in the absence of specially introduce polar extractant. The separation process in the presence of high-boiling polar agent referred to as "extractive distillation".

The application of the invention is illustrated in Fig. 1 and 2 and examples. These drawings and examples do not exclude the possibility of using other methods, subject to all of the signs of paragraph 1 of the claims.

According to figure 1 source4-fraction fed into the process in line 1, is heated and sent to the reaction zone with a catalyst hydroisomerization (zone 10), where line 2 serves hydrogen (or hydrogen-rich gas). The residual stream of hydrogen and light impurities output line 3.

Leaving the area 10 liquid flow of the hydrocarbons fed to the zone with a catalyst usual positional isomerization (zone 20), from line 5 (hereinafter referred to as line 6) stream is fed into the column 30, or from areas of the 10 liquid flow directly served by line 4 (hereinafter the line 6 in column 30.

Column 30 may be a distillation, but preferably in its "upper" (firming) parts have additional isomerization zone or hydroisomerization. If hydroisomerization in column 30 serves a secondary stream containing hydrogen, 2A.

On top of the column 30 through line 7 output distillate containing predominantly isobutane and impurities. From the bottom of the column 30 output lines 8 stream mainly containing 2-butenes and n-butane.

Stream 8 is distilled off from the heavy impurities (dimers and the like) in the evaporator 40. From the bottom of the evaporator 40 output line 9 a small stream containing heavy impurities. Main (evaporated) stream is available on line 11 in column extractive distillation (ER) 50.

In the upper part of the column ER serves on line 12 polar extractant (e). In the lower part of the column of ER and/or the boiler serves the flow of intermediate desorbent (PD)coming on line 13.

On top of the column 50 output line 14 distillate containing predominantly n-butane. From the bottom of the column 50 through line 15 output stream containing e, PD and a mixture of 2-butenes, which are served in the desorption zone of high pressure (zone 60). Possibly on the line 16 in the lower portion of zone 60 serves stream DD.

Top zone 60 output line 17 desorbed (LW), containing mainly a mixture of 2-butenes entering the reactor 80 reverse isomerization of 2-BU is ENES 1-butene. Bottom zone 60 through line 18 liquid stream containing predominantly e and DD, served in the middle part of the desorption zone of low pressure (area 70).

Top zone 70 output line 19 to a stream containing predominantly PD. It condense and recycle line 13 in column 50 and/or line 16 in zone 60. Bottom zone 70 output lines 21 a stream containing predominantly e, which recycle line 12 in column 50.

In the reactor 80 together with the flow line 17 serves also recirculated flow line 27 containing nesamierinamais 2-butenes and possibly solvent - alkane(s)5-C6. The mixture is heated and/or fully or partially vaporized and injected into the reactor 80 through line 22. From the reactor 80 deduce gaseous, liquid or liquid stream, which is on line 24 serves in a distillation column 90.

On top of the column 90 output as a distillate of pure 1-butene. From the bottom of the column 90 output line 26 stream mainly containing 2-butenes and/or alkane(s)5-C6. Thread 2-butenes on line 27 (then 22) recycle to the reactor 80. Probably from the lower part of the column 90 output line 28, the stream containing 2-butenes, which recycle lines 27 and 22 in the reactor 80.

At the conclusion of the cube column 90 flow predominantly alkanes C5-C6part of it may recycle through line 31 into the upper part (n is also the top selection) column 90. Perhaps part of the flow is predominantly alkanes on line 29 recycle in the evaporator 40 and further along the line 11 in column 50.

The diagram in figure 2 differs from the scheme in figure 1 the organization of the site reverse isomerization to 2-butenes 1-butene and distillation (rectification) of pure 1-butene. To do this, use column (system) catalytic distillation (column 100), in the middle part which is the isomerization catalyst or hydroisomerization. The flow line 17 is fed in the middle part of the column 100. When using it hydroisomerization catalyst in the lower part of the column 100 is available on line 23 hydrogen-rich stream.

On top of the column 100 by line 24 deduce distillate containing pure 1-butene. From the bottom of the column 100 output line 25 a stream containing predominantly alkane(s)5-C6that recycle line 26 to the evaporator 40 (hereinafter referred to as line 11 in column 50) and/or on line 27 in the upper part of the column 100 and/or removed from the system through line 28.

The use of the invention is illustrated by examples.

The examples use the following notation:

F - hydrocarbon meals, t/h; D - distillate, t/h; - cubic residue, t/h; LW - desorbed, t/h; N the practice.- a number of practical (valve) plates; R - reflux number; ER - extractive rectification; GHIS - hydroisomerization; isomerization.

Example 1

The process really is : according to figure 1. When using butane-butenova fractions from C4-pyrolysis fractions (little butane gases) zone 20 is not used. Column 30 (in this example) does not contain catalyst. Line 2A is not used.

Zone 10 is the catalyst Ni on solid media (possible "Pd on the media"), the temperature of 50-60°C.

In extractive distillation is used N,N-dimethylformamide (DMF) as a solvent e, and n-pentane as an intermediate desorbent DD.

In the reactor 80 is used catalyst Ni on the media can be "Pd on the media"); the temperature of 145-150°C. At the outlet of the reactor 80 ratio of 1-butene/∑ 2-butenes ~10/90.

Characteristics of streams and the main technological parameters are given in table and 1B.

Example 2

The process is similar to the process in example 1. In contrast, in zones 10 and 20 are placed catalysts, which hydroisomerization-active compounds, sulfonic cation exchanger and palladium. In zone 10, the content of Pd in the catalyst 5 wt.% and temperature of 80-90°C. in the zone 20, the content of Pd in the catalyst 2.5 wt.% and the temperature of 50-60°C. In the column 30 is fed a mixture that is output from the bottom of zone 30.

Obtained in the process streams according to the quantity and composition is almost the same as the streams of example 1 (including stream 6).

Example 3

The process is similar to that shown in example 1. In contrast, in the upper zone to the pubic 30 is selfactivity isomerization catalyst, with large passages for steam flow, for additional conversion of 1-butene to 2-butenes.

The concentration of 1-butene in the distillate of the column 30 is reduced from ~21% (as in example 1) to 2.5-3.0%. The number of pure 1-butene (distillate column 90) increases from 11.9 t/h up to 12.4 t/h

Example 4

The process is carried out as described in figure 2. Difference from examples 1 and 2 is that the hydroisomerization of 2-butenes and isolation of 1-butene are held in column (system) catalytic distillation (No. 100), containing hydroisomerized the catalyst in the middle part.

The quantity and quality of 1-butene on line 24 is practically the same as obtained by the line 25 in the form of a distillate of the column 90 in example 1.

From the cube column 100 by line 25 displays a small amount (<0.1 to 0.2 t/h), containing mainly 2-butenes, n-butane and 5-20 wt.% dimers of n-butenes.

Example 5

Is similar to options 1 and 2, but for the transformation of 2-butenes to 1-butene in the reactor 80 is a high-temperature gas-phase isomerization at 350-370°C. At the outlet of the reactor 80 ratio of 1-butene/Σ 2-butenes ~20/80.

The material balance and the main parameters are given in tables 2A and 2B.

Table 1A
Material balance With4-hydrocarbons and parameters to note is ru 1
With4-hydrocarbons and technology. optionsGUISE of butene-1 in the butenes-2 (zone 10)Rectification in the column 30Extractive rectification ER and desorption of high pressure
BBF (L.1)From the zone 10 in Col (L.4 and 6)D, L.7In, L.8D Col, L.14LW zone 60 (L.17)
wt.%wt.%wt.%wt.%wt.%wt.%
Isobutane3,53,527,8---
N-butane8,59,812,39,497,620,33
Isobutan1,91,915,4 0,00170,0070,001
Butene-148,0a 3.930,80,0150,040,013
TRANS-Butene-220,256,6a 12.762,92,2869,1
CIS-Butene-216,024,20,327,70,0530,5
Butadiene-1,31,90,0870,70,0004~<0,001
Flow, t/h15,0015,001,89~13,11~1,23~11,89
Technology. parameters
Temp., °C
50-60
Coal-water/katal., t/t·h1,0
N the practice.170 (111 theory. tar.)13050-60
The extractant/F, t/t-5,1
Pressure (top), ATA4,84,54,0
The pace.(cube), °C62,2110-120145-150
The steam flow, t/h (Gcal/h)9,5 (4,9)9,2 (4,8)

Table 1A (continued)
With4-hydrocarbons and technology. optionsGUISE of butenes-2 to butene-1 (reactor 80)Rectif. butene-1 from the butenes-2 (No. 90)∑ (incl. ER and desorption)
Food, L.22 (LW zone 60 + recycling In from Col)From the reactor 80 in No. 90, L.24D, L.25 (pure butene-1)In, L.26 (recycling WR)
wt.%wt.%wt.%wt.%
Isobutane----
n-butane0,470,470,400,49
Isobutan0,000120,000120,001~
Butene-10,02 10,099,200,02
TRANS-Butene-268.2061,30,4068,10
CIS-Butene-231,3128,2-0,00131,40
Butadiene-1,30,000050,00005<0,001-
Flow, t/h~118,5~118,5~11,9106,66
Technology. parameters:
The pace. in the reactor, °C
145-150
Coal-water/katal., t/t·h2-3
N the practice. 140-150
Pressure (top), ATA4,5
The pace. rectif. (cube)60-65
The steam flow, t/h (G cal/h) [t/t product]78,9(41,0)97,6 (50,8) [8,2]

Table 1B
The material balance and the parameters for the extractant and intermediate desorbent (n-pentane) is for example 1
ComponentsE. in Col, L.12PD in Col, L.13In zone 60 zone 70, L.18D zone 70, L.13In zone 70, l
wt.%wt.%wt.%wt.%wt.%
n-Pentane0,2 94,06,194,00,2
The solvent (DMF)99,86,093,96,099,8
Flow, t/h66,64,5071,104,5066,6
Technology. parameters:
N the practice.
10-20
R~0,1
Pressure top, ATA1,0-1,1
Temp., Cuba, °C155-165
The steam flow, t/h (Gcal/h)0,5 (0,23)

Table 2AMaterial balance With4-hydrocarbons and parameters for example 5With4-hydrocarbons and technology. optionsGHIS in BBF butene-1 in the butenes-2 (zone 10)Rectification in the column 30ER and desorption of high pressureBBF,L.1From the zone 10 in No. 30, L.4 and 6D, L.7In, L.8D Col, L.14LW zone 60, L.17wt.%wt.%wt.%wt.%wt.%wt.%Isobutane3,53,527,8---n-butane8,59,812,39,497,62 0,33Isobutan1,91,915,40,00170,0070,001Butene-148,0a 3.930,80,0150,040,013TRANS-Butene-220,256,6a 12.762,92,2869,1CIS-Butene-216,024,20,327,70,0530,5Butadiene-1,31.90,0870,70,0004~<0,001Flow, t/h15,0015,001,89~13,11~1,23Technology. parameters:
Temp., °C50-60Coal-water/katal., t/t·h1.0N the practice.170 (111 theory. tar.)13050-60The extractant/F, t/t-5,1Pressure (top), ATA4,84,54,0The pace.(cube), °C62,2110-120145-150The steam flow t/h (Gcal/h) 9,4 (4,9)9,2 (4,8)

Table 2A (continued)
With4-hydrocarbons and technology. optionsFrom butenes-2 to butene-1 (reactor 80)Rectif. butene-1 from the butenes-2 (No. 90)∑ (incl. ER and desorption)
Food, L.22 (LW zone 60 + recycling of Col)From the reactor 80 in Col, L.24D, L.25 (pure butene-1)In, L.26 (Retz. in R)
wt.%wt.%wt.%wt.%
Isobutane----
N-butane0,890,890,331,02
Isobutan0,000230,00023 0,0012-
Butene-10,0418,999,480,05
TRANS-Butene-266,3753,30,1965,73
CIS-Butene-232,7026,90,00133,21
Butadiene-1,30,000090,00009~0,001~
Flow, t/h62,862,811,950,92
Technology. parameters:
The pace. in the reactor, °C
300-350
Coal-water/katal., t/t·h2-3
N the practice.140-150
Pressure (top), ATA4,1
The pace. rectif. (cube)65-69
The steam flow, t/h (Gcal/h) [t/t product]49 (25,5)67,6 (35,2) [5,7]

Table 2B
The material balance and the parameters for the extractant and intermediate desorbent - for example 5
ComponentsE in No. 50, L.12PD in Col, L.13In zone 60 zone 70, L.18D zone 70, L.13In zone 70, l
wt.%wt.%m is S.% wt.%wt.%
n-Pentane0,294,07,594,00,2
The solvent(DMF)99,86,092,56,099,8
Flow, t/h66,64,5071,104,5066,6
Technology. parameters: N the practice.10-20
R≤0,1
Pressure top, ATA1,0-1,1
Temp., Cuba, °C155-165
The steam flow, t/h (Gcal/h)0,5 (0,23)

1. The way to obtain pure 1-butene from hydrocarbon With4fractions containing mainly 1-butene, 2-butenes and butane(s) with a mixture of 1,3-butadiene and isobutene, including the production of a mixture containing predominantly 2-butenes, with distillation, catalytic isomerization to 2-butenes 1-butene and isolation of 1-butene by distillation, characterized in that spend at least catalyzed isomerization of 1-butene to 2-butenes in a specified fraction at a temperature less than 120°C and rectification with continuous removal of the distillate isobutane, isobutene and 1,3-butadiene and receiving VAT stream containing mostly 2-butenes and nbutane in which conditions rectification support so that the concentration of 1,3-butadiene and isobutene in relation to the amount of 2-butenes is not above regulatory limits in the target 1-butene, from the specified VAT stream to separate a large part of nbutane extractive distillation with a polar agent and spend catalyzed isomerization of 2-butenes to 1-butene at temperatures over 120°C, with continuous removal of the formed 1-butene by distillation.

2. The method according to claim 1, characterized in that catalyzed position from which merisalu nbutanol in hydrocarbon mixtures is carried out in liquid, gas-liquid or gas phase(Ah) mode hydroisomerization and/or positional isomerization.

3. The method according to claim 1, characterized in that the catalysts of hydroisomerization use deposited on a solid carrier of metals selected from the group including Nickel, palladium and other platinum group metals of the periodic table, or their hydroisomerization-active compounds.

4. The method according to claim 1, characterized in that as catalysts for the isomerization of alkenes in the absence of hydrogen using acid, acidic ion exchangers, acidic zeolites, isomerization-active metal oxides, alkali metals, or a combination of some of these catalysts.

5. The method according to claim 1, characterized in that the isomerization of 1-butene to 2-butenes in the original hydrocarbon mixture is carried out in the mode hydroisomerization with simultaneous hydrogenation of butadiene(s).

6. The method according to claim 1, characterized in that the initially conducting liquid (hydro)isomerization mostly contained in a mixture of 1-butene to 2-butenes, and then spend additional isomerization, combined with the specified rectification, in the catalyst zone, located in the middle part of the strengthening of the distillation zone.

7. The method according to claim 1, characterized in that the specified VAT stream of the extractive distillation rectify the ing with a polar extractant deduce distillate, containing mainly nbutane, and was stripped extractant concentrated mixture of 2-butenes containing not more than 3%, preferably not more than 0.5% nbutane, which is fed to the isomerization of 1-butene.

8. The method according to claim 7, characterized in that the polar solvent use solvent selected from the group comprising N,N-dimethylformamide, N-organic, N,N-dimethylacetamide, N-formylmorpholine, sulfolan, β-methoxypropionitrile, acetonitrile, methyl ethyl ketone, mixtures of solvents among themselves and/or water and/or hydrocarbons5-C6.

9. The method according to claim 1, characterized in that the isomerization to 2-butenes 1-butene and its secretion is carried out at a temperature of from 120 to 400°C in a flow of the gas, gas-liquid or liquid reactor, followed by distillation of 1-butene and/or in the United reactive distillation system.

10. The method according to claim 9, characterized in that when using a combined reactive distillation system catalyst include within the reactive distillation column in the middle or comprehensive parts or/and external flow reaction zone, both ends of which are connected with a distillation column.

11. The method according to claim 1, characterized in that at least part neprivrednih 1-butene to 2-butenes return from the bottom or the cube rect Picatinny column in the reaction zone to the isomerization of 2-butenes to 1-butene.

12. The method according to claim 1, characterized in that the upper part of the distillation or reactive distillation column serves alkane(s)5-C6.

13. The method according to claim 1, characterized in that the selected 1-butene addition rectificat from nbutane in the presence of alkane(s)5-C6.

14. The method according to claim 1, characterized in that the part neprivrednih 1-butene to 2-butenes with an impurity nbutane drawn from the lower part of the distillation or reactive distillation column, is removed from the system.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: C10+ fraction of alpha-olefins contaminated with aromatic C9+ compounds is extracted from the main product stream and fed into a conversion reactor where C10+ alpha olefins and aromatic C9+ components react in the presence of a Friedel-Crafts alkylation catalyst to form aromatic C19+ compounds, and the obtained aromatic C19+ compounds are separated from unreacted C10+ alpha olefins in or after the conversion reactor.

EFFECT: method simplifies removal of by-products.

10 cl, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a method of extracting isobutylene from an isobutylene containing fraction through hydration of the isobutylene containing fraction, obtaining a tert-butanol containing fraction and its subsequent dehydration. The method is characterised by that, dehydration is done in two stages. At the first stage, temperature is kept at 90-120°C and pressure at 1-3 kgf/cm2 and concentrated isobutylene and an aqueous solution of tert-butyl and sec-butyl alcohol are extracted, from which concentrated sec-butyl alcohol and an isobutylene containing fraction, which is taken for hydration, are extracted at the second stage. Process at the second stage is carried out at temperature 100-130°C and pressure 2-6 kgf/cm2.

EFFECT: use of the given method allows for extracting isobutylene without butene or butadiene impurities, and reduction of tert-butyl alcohol loss.

1 cl, 1 tbl, 8 ex, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention refers to the method of purification of paraffin hydrocarbons from methanol admixtures. The said purification is carried out in the presence of hydrogen on the catalyst containing one of the metal selected from Ni and Pd applied on the inert carrier at temperature 30-100°C, mole excess hydrogen : methanol in the range (5-50): 1 and volume hydrocarbons feed rate 1-6 hrs.-1.

EFFECT: simplifying and cheapening of the process.

1 cl, 9 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention is referred to the area of hydrocarbons preparation by catalytical hydrodeoxygenation of products of fast pyrolysis of a biomass and working out of the catalyst for this process. The catalyst of oxygen-organic products hydrodeoxygenation of fast pyrolysis of lignocellulose biomasses, containing either precious metal in amount of no more 5.0 wt % or containing nickel, or copper; either iron, or their combination in a non-sulphide restored shape in amount of not more than 40 wt % and transitive metals in a non-sulphide shape in amount of not more than 40 wt %, carrying agent - the rest, is described. Three variants of the catalyst preparation method, providing application of transition metals on the carrying agent by a method of impregnation of the carrying agent solutions of metal compounds are described, or simultaneous sedimentation of hydroxides or carbonates of transition metals in the presence of the stabilising carrier, or the catalyst is formed by joint alloying/decomposition of crystalline hydrate nitrates of transition metals together with stabilising components of zirconium nitrate type. The process of oxygen-organic products hydrodeoxygenation of a biomass fast pyrolysis is performed using the above described catalyst in one stage at pressure of hydrogen less than 3.0 MPa, temperature 250-320°C.

EFFECT: increase stability in processing processes of oxygen-containing organic raw materials with the low content of sulphur, and also soft conditions of process realisation.

10 cl, 12 ex, 2 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to method of oxidising alkane from C2 to C4 with the obtaining of corresponding alkene and carboxylic acids. The method includes the following stages: (a) contact in the oxidation reaction zone of the alkane, which contains molecular oxygen gas, not necessarily corresponding to the alkene and not necessarily water in the presence of at least one catalyst, effective with the oxidation of the alkane to the corresponding alkene and carboxylic acid, alkane, oxygen and water; (b) separation in the first separating agent at least part of the first stream of products in a gaseous stream, which includes alkene, alkane and oxygen, and a liquid stream, which includes carboxylic acid; (c) contact of the mentioned gaseous stream with the solution of a salt of metal, capable of selectively chemically absorbing alkene, with the formation of a liquid stream rich in chemically absorbed alkene; (d) isolation from the flow of the solution of salt of the metal. The invention also relates to combined methods of obtaining alkyl-carboxylate or alkenyl-carboxylate (for example vinyl acetate), moreover these methods include oxidising of alkane from C2 to C4 with the obtaining of corresponding alkene and carboxylic acid, isolation of alkene from the mixture of alkene, alkane and oxygen by absorption using the solution of the salt of metal and extraction of the stream rich in alkene from the solution of the salt from metal for using when obtaining alkyl-carboxylate and alkenyl-carboxylate.

EFFECT: improved method of oxidising alkane from C2 to C4 with the obtaining of corresponding alkene and carboxylic acids.

46 cl, 1 dwg

FIELD: organic chemistry.

SUBSTANCE: invention refers to enhanced method of propane and/or butanes flow separation from original hydrocarbons containing alkylmercaptan impurities by means of fractional distillation resulted in liquid phase and separated flow from column head at pressure providing that separated flow from column head containing propane and/or butanes has temperature within 50 to 100°C, including (i) addition to specified origin hydrocarbons an amount of oxygen sufficient for mercaptan oxidation, (ii) fractional distillation of produced mixture containing at least one catalyst layer oxidising mercaptans to sulphur compounds with higher boiling temperatures and (iii) separation of sulphur compounds with higher boiling temperatures as portion of distillation liquid phase.

EFFECT: improved method of propane and/or butanes flow separation from of original hydrocarbons by means of fractional distillation resulted in liquid phase and separated flow.

8 cl, 2 tbl, 1 dwg, 1 ex

FIELD: petrochemical processes.

SUBSTANCE: invention relates to treatment of C5-hydrocarbons in order to remove cyclopentadiene impurities, which process may be, in particular, used in rubber production industry when producing hydrocarbon monomers applicable in stereospecific polymerization processes. Treatment of hydrocarbons is accomplished with cyclohexane in presence of organic solvent and alkali catalyst, after which C5-hydrocarbons are separated from reaction products via rectification. Organic solvent is selected from alkylene glycol monoalkyl ethers including their mixtures taken in amounts 0.5 to 5.0 wt % based on C5-hydrocarbons.

EFFECT: increased degree of cyclopentadiene extraction at lower reagent consumption.

8 cl, 1 tbl, 23 ex

FIELD: petroleum chemistry, chemical technology.

SUBSTANCE: crude alpha-olefin is heated, raw vinylidene olefins are isomerized in the presence of catalyst and alpha-olefin is separated from isomerized vinylidene olefin by rectification. Separation of alpha-olefin is carried out for at least two successive steps at similar temperatures on top of vat and reducing pressure of rectifying column at each following step. Condensed phase removing from top of the rectifying column at previous step is fed to feeding zone of the following step and the rectifying column at top and vat section is sprayed. For spraying the top section of column the condensed phase removing from the top of rectifying column at the same step is used and for spraying the vat section of column the vat liquid of rectifying column at the same step is used. Separated alpha-olefin is purified additionally from oxygen-containing impurities by adsorption up to polymerization degree of purity. Raw heating, isomerization, separation and adsorption are carried out in atmosphere in inert gas. The unit used for treatment of alpha-olefin includes reactor for isomerization of vinylidene olefins in raw, rectifying column wherein feeding zone is joined with reactor outlet and wherein alpha-olefin of high purity degree is removed from the column top. The unit includes also at least one rectifying column for additional treatment of alpha-olefin of high purity from isomerized vinylidene olefins and adsorption column for separation of oxygen-containing impurities in alpha-olefin of high purity wherein the column inlet is joined with the top outlet of the last rectifying column used for additional treatment of alpha-olefin of high purity and outlet is used for removing alpha-olefin of the polymerization purity degree. Invention provides enhancing quality of the end product.

EFFECT: improved method for treatment.

8 cl, 1 dwg, 1 ex

The invention relates to petrochemistry, namely the production of oligomers of propylene by oligomerization of propylene in phosphoroclastic catalysts and the method of purification of oligomers of propylene

FIELD: chemistry.

SUBSTANCE: invention relates to a method of separating isopentane-isoamylene-isoprene-containing hydrocarbon fractions or butane-butylene-divinyl hydrocarbon fractions obtained at the first step of two-step dehydrogenation of corresponding paraffin hydrocarbons, involving separation of paraffin-olefin-diene fraction obtained at the first dehydrogenation step through extraction rectification, and is characterised by that a vapour stream is extracted from a desorber via lateral collection, where the said vapour stream contains large amount of diene, and after condensation, said stream is taken for extraction of the diene end product at the second extraction rectification step, and an olefin fraction which does not contain diene is collected from the top of the desorber and taken to the second dehydrogenation step.

EFFECT: use of said method increases output of the end product.

1 cl, 2 ex, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to peptides which originate from an antigen recognised by autoantibodies used for diagnosing rheumatoid arthritis. The peptides are filaggrin molecule fragments which contain modified residues of arginine and having amino acid sequences given in the formula of invention. The invention discloses a method of diagnosing rheumatoid arthritis by detecting autoimmune antibodies using the said peptide(s) through reaction of the latter with the blood serum of patients suffering from rheumatoid arthritis. Presence of autoimmune antibodies in the analysed sample is indicated by presence of peptide complexes formed with the antibody.

EFFECT: disclosed peptide has high specificity and sensitivity.

4 cl, 1 dwg, 3 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to a method of extracting benzene from mixtures with non-aromatic hydrocarbons, simultaneously obtaining distillate through extractive rectification, characterised by that the selective solvent used is in form of mixtures containing 14.7-48.5 wt % sulfolane or N-formylmorpholine and 48.5-83.3 wt % methylpyrrolidone, containing 2-3 wt % water.

EFFECT: use of given method allows for obtaining benzene, toluene and distillate containing not more than 1-1,5 vol. % benzene, which can be used as a component of motor car fuel or as raw material for pyrolysis process.

1 cl, 1 ex, 4 tbl, 2 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a method of separating alkane and alkene fractions, possibly containing alkadiene impurities, using extraction rectification in the presence of polar extraction agent(s), wherein the basic amount of alkanes comes out in a distillate stream, and the basic amount of alkenes comes out in a strippant stream distilled from the extraction agent. The method is characterised by that before extraction rectification, the larger part of 1-alkene(s) in the alkane and alkene fractions is isomerised and/or hydroisomerised to 2-alkene(s) at temperature not above 100°C in the presence of heterogeneous catalyst(s) with activity during positional isomerisation of alkene, and possibly a small amount of polar substance which does not deactivate the catalyst(s).

EFFECT: more efficient separation of alkane and alkene mixtures through extraction rectification.

11 cl, 13 ex, 1 dwg

FIELD: chemistry.

SUBSTANCE: method includes supply of initial mixture and dimethylsulfoxide (DMSO) as separating agent, taken in ratio 7-7.5:1 to initial mixture, into extraction rectification column (1) efficiency 50 t.t., initial mixture being supplied on 30 t.t., separating agent on 10 t.t. of column (plate numeration from top of column), phlegm number in column constitutes 1.5-2, taking of benzol in distillate and mixture benzol-perfluorobenzol (PFB) - tertiary amyl alcohol (TAA)-DMSO from column (1) cube , supply of mixture PFB-TA-DMSO on 25 t.t. of column of separating agent regeneration (2) with efficiency 50 t.t., phlegm number in column being 1-3, removal separating agent from column cube and its supply to column (1), supply of column (2) distillate, representing aseotropic mixture PFB-TAA, for separation into complex of two columns (3) and (4) with efficiency 35 t.t., with removal from column cubes of TAA and PFB, respectively, aesotropic mixture being supplied on 18 t.t. of column (3), phlegm numbers of columns (3) and (4) being equal 0.5-1.5 and 1-2 respectively, re-cycle of aseotrope PFB-TAA, which is separated in distillate of column (4) into column(3) feeding, ratio of re-cycle of column (4) and feeding of column (3) being (1-1.1):0.66, pressure in columns (1)-(3) is 300 mm of mercury, pressure in column (4) - 760 mm of mercury.

EFFECT: simplification of technology, increase of ecological compatibility of process and quality of obtained products.

1 tbl, 1 dwg, 1 ex

FIELD: chemistry.

SUBSTANCE: described is the method of obtaining unrefined 1, 3-butadiene with the help of extractive distillation from C4-fractions, which contain C4-acetylenes as the secondary components, with the use of a selective solvent. The method is achieved in a column with dividing partitions, which contains in the bottom part an evaporator, in which lengthwise there is a dividing partition, which forms the first zone, the second zone and the underlying combined zone of the column, connected along the upper flow with the extractive washing column. Supply of energy to the column with the dividing partition through the lower evaporator is regulated such that from the column with the dividing partition draw off the lower stream, which contains the solvent, saturated with C4-acetylenes, in which the portion of 1, 3-butadiene is limited with the estimation that the 1, 3-butadiene lost is economically acceptable. In this case the lower stream is submitted into the decontaminator for acetylenes, from which C4-acetylenes are removed and the purified solvent is removed from it from the lower stream.

EFFECT: increase in the periods of the operation of the device between the cleaning cycles.

11 cl, 1 tbl, 1dwg, 1ex

FIELD: chemistry.

SUBSTANCE: method of separation of starting mixture (A) consisting of two or more constituents, by extractive distillation with the selective solvent (S) within dividing wall column (TKW), is proposed. The separation is performed in the dividing wall column (TKW) having a dividing wall aligned in a longitudinal direction (TW) and extending to an upper end of the column and dividing an interior of the column into first region (1), second region (2), and lower combined column region (3). The starting mixture is fed into first region (1), first top stream (B) is taken off from first region (1), and second top stream (C) is taken off from second region (2), with each of the streams having a prescribed specification. The selective solvent (S) is introduced in an upper part of first region (1) and/or in an upper part of second region (2), and flow of solvent (S1) into the first region (1) and/or flow of solvent (S2) into second region (2) are set so that each of the prescribed specifications for top streams (B, C) are met.

EFFECT: invented method of dividing mixtures is more efficient in terms of energy and solvent consumption.

6 cl, 7 dwg, 1 tbl

FIELD: petrochemical processes.

SUBSTANCE: invention relates to a method for continuously separating C4-fraction by extractive distillation using selective solvent on extractive distillation column, which method is characterized by a separation barrier disposed in extractive distillation column in longitudinal direction extending to the very top of the column to form first zone, second zone, and underlying common zone. Butanes (C4H10)-containing top stream is withdrawn from the first zone, butenes (C4H8)-containing top stream is withdrawn from the second zone, and C4H6 stream containing C4-fraction hydrocarbons, which are more soluble in selective solvent than butanes and butenes, is withdrawn from underlying common zone of column.

EFFECT: reduced power consumption and expenses.

15 cl, 2 dwg, 2 ex

FIELD: petrochemical processes.

SUBSTANCE: hydrocarbon mixture obtained by extractive distillation of C4-fraction using selective solvent, which mixture contains those C4-hydrocarbons, which are better soluble in selective solvent than butanes and butenes, is subjected to continuous separation. Mixture is supplied to first distillation column, wherein it is separated into top stream, containing 1,3-butadiene, propine, and, if necessary, other low-boiling components and, if necessary, water, and bottom stream containing 1,3-butadiene, 1,2-butadiene, acetylenes, and, if necessary, other high-boiling components. Proportion of 1,3-butadiene in bottom stream of the first distillation column is controlled in such a way as to be high enough to dilute acetylenes beyond the range wherein acetylenes can spontaneously decompose. Top stream from the first distillation column is passed to second distillation column, wherein it is separated into top stream, containing propine, and, if necessary, other low-boiling components and, if necessary, water, and bottom stream containing pure 1,3-butadiene.

EFFECT: simplified process and reduced power consumption.

4 cl

FIELD: petroleum processing and petrochemistry.

SUBSTANCE: in particular, invention aims at producing extraction dearomatized component from reformat of gasoline fraction, which component may be used in production of petroleum solvents such as hexane solvents. Process comprising countercurrent extraction of aromatic hydrocarbons with liquid selective extractant to separate dearomatized component (raffinate) and subsequent extractive rectification of resulting extract phase by distilling off aromatic hydrocarbons is characterized by that liquid selective extractant is diethylene glycol or triethylene glycol, countercurrent extraction is carried out at 125-140°C, extractive rectification is carried out using process steam in presence of saturated selective extractant wherein evaporation of water is performed with the aid of energetic steam, unsaturated selective extractant after extractive rectification and recycled gasoline are sent to extraction stage preliminarily using unsaturated selective extractant as heat carrier to generate process steam, and energetic steam condensate is used to heat recycled gasoline to 80-130°C.

EFFECT: enhanced process efficiency.

3 cl, 1 dwg, 1 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of copolymerising olefins, according to which a) a first starting olefin material is prepared, mainly consisting of Cn-olefins, and a second starting olefin material, mainly consisting of Cm-olefins, where n and m independently denote different integers from 2 to 12, and where the second starting olefin material is characterised by degree of branching of olefins defined in form of an ISO index ranging from 0 to 18, and is obtained via dimerisation of raffinate II, mainly consisting of isomeric n-butenes and n-butane, in the presence of a nickel-containing oligomerisation catalyst, and b) the first and second starting olefin materials react on a heterogeneous olefin oligomerisation catalyst based on sheet and/or framework silicates. The invention also relates to codimers obtained using said method, a method of producing alcohols according to which said olefin codimers undergo hydroformylation followed by hydrogenation of mixtures of alcohols obtained using said method.

EFFECT: high efficiency of the method.

18 cl, 2 tbl, 1 ex

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