The method of obtaining alkyltin-butyl esters and the method of simultaneous receipt of such esters and 1-butene

 

(57) Abstract:

United way for the simultaneous production alkyltin-butyl ester and 1-butene, including the introduction of flow C4hydrocarbons in the node for the esterification and recycling the residual flow in the same node after a possible separation of 1-butene, and the processing section isomerization to convert the rest of butenes in isobutene, the node separation by molecular sieves, separating the hydrocarbons in the vapor phase, is included in the cycle. 3 S. and 14 C.p. f-crystals, 4 tab., 5 Il.

The invention relates to a combined method of manufacturing alkyltin-butyl esters and possibly 1-butene.

More specifically the invention relates to a combined method for the production of tert-butyl methyl ether (methyltetr-butyl ether MTBE) or estiltrat-butyl ether (methyl tert butyl ether ETBE) and possibly 1-butene. More specifically, the invention relates to maximize the use of butenova faction in the combined cycle for the production of MTBE or ETBE and possibly 1-butene. Known processes which include processes of synthesis alitretinoin ether in contact C4carbon-containing isobut hiromasa hydrocarbons, separation of butenes from butane, the flow of butane on surprisely, direction isomerizing stream into the synthesis reactor [8]

Known methods make it possible to subject isobutene, in principle, full conversion, leaving the other components are virtually unchanged from their subsequent enrichment and extraction.

The prior art processes for the separation of butane-butylene mixtures using adsorption, in particular the allocation of butylenes from these fractions using zeolite NaX (ed. St. USSR 701982, class C 07 C 7/13, 1979). The process is carried out in the vapor phase.

Disclosed separation of saturated and unsaturated hydrocarbons, including C4using zeolite X and Y in [9] and [7] However, ed. St. 701982 separation of hydrocarbons occurs in the liquid phase. The advantage of the invention compared with [8] is that stage extracoronal distillation is replaced by a phase separation on a molecular sieve, which works in the stream of hydrocarbon in the vapor phase.

All processes receive alkyltin-butyl ether, known from the literature, have the disadvantage that the necessary work sections fraktsionirovanija or extracoronal distillation, which skillremodeling esters eliminates these drawbacks.

The method comprises the following process stages:

a) introducing a stream of C4hydrocarbons consisting mainly of isobutene, linear butenes and possibly traces of butadiene, because he comes from, for example, from node gidrogenizirovanii butadiene, in section synthesis alkyltin-butyl ether together with a stream of aliphatic alcohol;

b) separating the obtained ether and any unreacted alcohol from a stream of hydrocarbons;

c) introduction of a residual flow of hydrocarbons or part thereof in the vapor phase section of the separation on a molecular sieve for separation of butenes and retrieval of butenes;

d) introduction of a stream of hydrocarbons containing the extracted butenes, along with a faction, you may not introduced in the stage (c), section skeletal isomerization for conversion of linear butenes in isobutene;

e) recycling isomerizing stream into the synthesis reactor alkyltrimethylenedi ether after mixing with the input stream C4of hydrocarbons.

Alternative flow C4hydrocarbons can be practically free from isobutene because it comes from an existing installation synthesis alkyltrimethylenedi ether. In this case, the flow of C4hydrocarbons Woda obtained ether, the output stream is introduced into the separation Assembly of saturated hydrocarbons, recyclery fraction of butenes in section isomerization. Next, the combined method of manufacturing alkyltin-butyl esters may include

a) introducing a stream of C4hydrocarbons consisting mainly of isobutene, linear butenes and butane and possibly traces of butadiene, because he comes from, for example, from node gidrogenizirovanii butadiene in section synthesis alkyltin-butyl ether together with a stream of aliphatic alcohol.

b) separating the produced ether and any unreacted alcohol from a stream of hydrocarbons;

c) introduction of a residual flow of hydrocarbons in the frame section isomerization for conversion of linear butenes in isobutene;

d) introducing a flow of isomerized hydrocarbons coming from c), or their fractions in the gas phase, in the section separation on a molecular sieve for the separation of butane and butenes and retrieval of butenes;

e) recycling isomerizing stream containing the extracted butenes, possibly together with a part that is not entered in stage d), in the synthesis reactor, alkyltin-butyl ether after mixing with the input stream C4of hydrocarbons.

This distance is meters from isobutene, because it comes from an existing installation of synthesis alkyltin-butyl ether. In this case, the flow of C4hydrocarbons are injected directly into the section isomerization, and then in section separation on a molecular sieve.

In the combined method for the simultaneous production alkyltrimethyl esters and 1-butene this method includes:

a) the introduction of fresh input stream C4hydrocarbons consisting mainly of isobutene, linear butenes and butane plus recycled stream containing, possibly, traces of butadiene, in section synthesis alkyltin-butyl ether together with a stream of aliphatic alcohol;

b) Department of industrial air and any unreacted alcohol from a stream of hydrocarbons;

c) introduction of a residual flow of hydrocarbons or its fractions (first pass), in the vapor phase, in the section separation on a molecular sieve for the separation of paraffins (consisting mainly of butane) from butenes, removing the butenes and reset paraffins;

d) introducing the thus treated stream of hydrocarbons in site selective gidrogenizirovanii butadiene;

e) introducing a flow of hydrocarbons from a node hydrogenation of butadiene or its fracchia thread containing mainly residual isobutane and 1-butene (the flow of isobutane), and stream containing mainly 2-butenes, 1-butene, and the residual n-butane (butene stream);

f) introducing a stream of butene from stage e) in the frame section isomerization for conversion of linear butenes in isobutene;

g) introducing a stream of isobutane from stage e) or in section separation on a molecular sieve, either directly in the section isomerization;

h) recycling isomerizing stream into the synthesis reactor alkyltrimethylenedi ether after mixing with the input stream C4of hydrocarbons.

For the alternative embodiment of the combined method for the simultaneous production alkyltin-butyl ester and 1-butadiene rubber of this invention the input stream C4hydrocarbons may contain traces of butadiene and be practically free from Isobutanol as it comes, for example, from an existing installation of synthesis alkyltin-butyl ether. In this case, the flow of C4injected directly before the site selective hydrogenation of butadiene and after the section of the separation of the molecular sieve.

In a further alternative embodiment of the combined method for the simultaneous deposition is after the section of the separation of the molecular sieve, and after bypass. Again in this second alternative embodiment of this method the flow of C4hydrocarbons may contain traces of butadiene and be practically free from isobutene. In this case, the flow of C4hydrocarbons injected before the site selective hydrogenization and after the section of esterification.

Stream C4hydrocarbons used in the method of the invention comprises isobutane, isobutene, n-butane, 1-butene, TRANS - or CIS-2 - butene and possibly small quantities of C3or C5hydrocarbons, and is largely free from butadiene, because he comes from a node hydrogenation or removal of butadiene. In particular, the flow of C4hydrocarbons may contain the following, in addition to a small number of C3and C5for example, between 0 and 5 wt. 0.5 to 45 wt. isobutane, 1-20% n-butane, 5-55 wt. isobutene, the remainder to 100% is a linear butenes.

Any aliphatic alcohol can be used in the method of the invention, although methyl and ethyl alcohol are preferred for the production of tert-butyl methyl ether (MTBE) and estiltrat-butyl ether (ETBE), respectively.

The reaction eterization preferably carried out in WOD, 4039590 and 4071567, 4447653 and 4465870. As an alternative to traditional technology, the ether can be synthesized through the reactor in the form of columns on the principle of catalytic distillation described, for example, in U.S. patent 4475005 and published in the application for the European patent 470655.

The flow of hydrocarbons leaving the site of esterification, introduced in section separation to extract the received broadcast and any unreacted alcohol. The remaining part of C4separated from the air in a normal distillation column bottom product which mainly contains ether. C4hydrocarbons extracted from the head of the column in azeotropic mixture with unreacted alcohol. The alcohol is then removed by known methods, for example, by extraction with water.

The residual fraction C4hydrocarbons, free of ether and alcohol, or part thereof, in excess of 5 wt. from the total available flow is injected into a section of the separation on a molecular sieve to remove inert aliphatic hydrocarbons consisting mainly of n-butane and isobutane.

Any zeolite molecular sieve selective with respect to the unsaturated double bond, can be used in this way izaberete is)xMe2O3(SiO2)y,

where Cat represents a cation with a valence of "n" capable of exchange for calcium (Ca), such as sodium, lithium, potassium, magnesium, etc.

x is a number between 0,7 and 1,5;

Me is boron or aluminum;

y is a number between 0.8 and 200, preferably between 1.3 and 4.

The preferred zeolites are those of type X and Y, with a particle size between 0.1 and 3 mm, These zeolites allow to obtain the selectivity olefin/paraffin between 3 and 12, the selectivity is defined as:

< / BR>
where G0and Gpare adsorbed quantities of moles of olefins (o) and paraffins (p) in equilibrium with their respective partial pressures Poand Pp.

Aliphatic hydrocarbons are separated in the vapor phase at a temperature between 20 and 180oC, preferably between 70 and 140oC, at an absolute pressure of between 1 and 10 bar, preferably between 1 and 5. To ensure continuity of the process of this invention is the preferred use of the system, including at least two sections that are installed in parallel, so that while one section is adsorbing, the other is desorbitadamente, for example aliphatic hydrocarbons such as pentane, hexane, heptane, octane, and so on in the vapor phase, followed by distillation of the mixture for the extraction of olefins.

The method of this invention enables to obtain a stream of aliphatic hydrocarbons, which is practically free from olefins or olefin content of up to 5 wt.

A stream of olefins, leaving a section of the separation on a molecular sieve consisting mainly of residual fraction of butane and 1-butene and CIS - and TRANS-2-butene, introduced in section isomerization to convert 1-butene and CIS - and TRANS-2-butene in isobutane.

In the case of a combined process for the simultaneous alkyltrimethyl esters and 1-butene olefin stream, leaving a section of the separation on a molecular sieve consisting mainly of residual fraction of butane, 1-butene and CIS - and TRANS-2-butene, introducing section for selective hydrogenation of butadiene, which can be created in a subsequent frame section isomerization.

The hydrogenated stream C4free of butadiene is injected into a section of the separation of 1-butene.

Considering that during the hydrogenation of butadiene can OBRAZOVATEL in the cycle, preferably before section division 1-butadiene and before the second pass.

1-Butene can be separated by known methods such as distillation, extractive distillation or adsorption on molecular sieves. Separation by distillation is preferred for this invention and, as a rule, is carried out in two distillation columns arranged in series. In a typical arrangement, the isobutane stream of isobutane), still present in the input stream is separated in the head the first column, the head product of the second column is 1-butene with a purity exceeding 99% grassroots product is a stream enriched in residual n-butane, CIS - and TRANS-2-butene and traces of n-butene (butene stream). Operating conditions are described in U.S. patent 4718986 and in canadian patent 1232919.

In an alternative arrangement for separating 1-butene using distillation, the butene stream exits the bottom of the first column, the second column gives as a grassroots product 1-butene high purity with Isobutanol (stream isobutene) leaving the head of the column.

In addition to isobutene flow isobutene contains a certain amount of 1-butene and can therefore be rezi the AI. In this second case is not possible to include in the loop section to be removed C3-hydrocarbons formed during hydrogenation of butadiene, since these are removed in the subsequent frame section isomerization.

The butene stream is introduced into the section of isomerization for conversion of linear butenes in isobutene.

The isomerization reaction can be conducted, for example, using the method described in U.S. patent 4038337, using as catalyst sililirovany product aluminum oxide described in U.S. patent 4013589 and 4013590, or using zeolite catalysts, such as those described, for example, in published applications to the European patent 523838 and 501577.

The output section isomerization get enriched Isobutanol stream that can be recycled in the synthesis alkyltin-butyl ether. Any C3-and C5+the hydrocarbons formed at this stage are removed, for example by distillation.

United way of production alkyltin-butyl esters of the present invention is illustrated in Fig.1 to 4, which represent three embodiments of a non-limiting example, and in Fig.5, which represents the approximate voprosam-butyl ether, partition separating molecular sieve aliphatic hydrocarbons and a frame section isomerization. Input stream 2, consisting of the sum of fractions of C4hydrocarbons 1 and recycled fractions 8 and from the site isomerization of C, introduced in section A, together with the aliphatic alcohol 3. Having extracted the produced ether 4 using conventional systems, not shown in the figure, the remaining fraction 5 is introduced entirely or partially in section of division B. If using a partial separation of the said residual fraction bypasses the section of division B (dashed line).

Thread 7 of section division B, consisting mainly of 1-butene and CIS - and TRANS-2-butene, plus residual butane, is included in section isomerization C. it is enriched with Isobutanol stream 8 is extracted and recyclery in section A. Any C3-or C5+the hydrocarbons formed during isomerization, go through 9 and 9'.

In Fig. 2 hydrocarbon fraction 1 is virtually free from isobutene because it assumes, for example, from an existing installation of synthesis alkyltin-butyl ether. Subsequently, the flow is injected through the pipe 10 directly to the section isomerization with the flow 7 of section separation.

From section division B receive the stream 5, which consists mainly of butane, practically free from olefins and out of the loop, and the thread 6, consisting mainly of 1-butene and CIS - and TRANS-2-butene plus residual butane. Because this thread may contain butadiene, it is introduced in section hydrogenation H together with a stream of hydrogen 6'.

Get two output stream, namely the flow of exhaust gas 6 and hydrogenated stream 7.

Hydrogenated stream 7 is administered wholly or partly in section separated by the new line 7').

In this case, a partition separating 1-butene works by distillation and includes two distillation columns. The first R', which enter the stream 7, produces as the head product stream consisting mainly of isobutane and 1-butene 7' (stream of isobutane). This stream may be recycled in section separation on a molecular sieve in either before or after bypass 5', or can be entered directly into the section isomerization C. the Second column of R, which is injected downstream product 8' of the columns of R', produces as head of product 1-butene 8 with the required properties (purity exceeding 90%) and as a grassroots product stream (8"), which, together with the possible flows (7') and/or (7") enter in section isomerization of C via (9). Stream (10), which is enriched with Isobutanol and contains the possible traces of butadiene, extracted from this section and recycle in section A. Any C3-or C5+the hydrocarbons formed during isomerization, or those that are injected in series with the input stream 1, go through 9' and 9".

Considering that during the selective hydrogenation of butadiene may be formed of light C3-hydrocarbons, the diagram of a method may include the node removal, for example, a node distillation, for Tokenization and before section division 1-butene, before the bypass, i.e. in the pipe 7" before will join the thread 5.

In an alternative arrangement, the section of the distillation extraction of 1-butene stream of butene 8" is taken from the bottom of the first R columns'. Because the thread 8 is taken from the bottom of the second column R, the flow of isobutane 7" is coming out of her head.

Section division B includes the site of adsorption/desorption of D and two distillation columns E and F (Fig.5).

For continuous operation two node D can be provided as working in different ways, one in the adsorption phase and the other in desorption.

Two streams D1 and D2 is extracted from node D.

Stream D are extracted during an adsorption practically free from olefins and is introduced into distillation column E to extract recycled desorbent E2 of the discharged fraction of butane E1.

Olefinic fraction D2 is extracted during desorption and injected into the distillation column F to extract the fraction of butene F1 (return cycle) from desorbent F2, which recyclery.

All locations shown in Fig.1 4, the method allows the discharge of almost free from olefins, paraffin stream in the United way productions is m maximizing the production alkyltin-butyl ether. It also provides an opportunity to reduce the concentration of paraffins in the cycle, thereby reducing costs and energy consumption.

Example 1. Referring to the circuit of Fig.1 and the associated table.1, representing the number of substances in the method for capacity in 0,2471 kg/m2in a reactor for the production of MTBE enter the stream C4hydrocarbons with speed 99,6 g/h having the following composition, wt.

C30,10

n-Butenes 24,26

Butane 5,46

in connection with recyclorama flow 8 speed 217,3 g/h, to 45.4 g/h of methanol (tube 3) is also injected into the reactor.

Performance MTBE 4 125 g/h, which corresponds to the conversion of isobutene 99.5%

237,3 g/h and a residual fraction C4hydrocarbons containing about 16 wt. aliphatic hydrocarbons, is removed from section A synthesis through 5. Approximately 75% of this fraction passes through the bypass, the residue is introduced into a section of the separation on a molecular sieve, operating at 130oC and a pressure of 4 bar. 100 cm3zeolite X in the form of pellets, extruded through a sieve 1/16", used as an adsorbent, n-hexane in the vapor phase (approximately 120 g/h) is used as desorbent for adsorbed olefins. After OTDEL paraffins approximately 96.7% of the shed. In the stream 7 contents aliphatic hydrocarbons is reduced to 14.2 wt. after separation of desorbent by distillation.

Stream 7 is introduced into the section of isomerization of C, in which the n-butenes are converted to isobutene and other related products, mainly falling in the category of C3-and C5+of hydrocarbons. These co-products are removed (streams 9 and 9'), and the resulting fraction 8 is recycled in section synthesis of MTBE (see table.1).

Example 2. Referring to the circuit of Fig.2 and the associated table.2, representing the number of substances in the method for capacity in 0,2471 kg/m2enter the stream C4hydrocarbons 1 from an existing installation MTBE, not shown in the figure in section isomerization. This flow speed 113,6 kg/h, and contains approximately 11% butane add to the thread 7 of their separation Assembly of Bhutan, and introduce in section isomerization, where n-butenes are converted to isobutene. Related products (streams 9 and 9') is removed, and the remaining olefins stream 8 is introduced into the section of esterification, where by adding to 45.5 g/h of methanol to produce 125 g/h of MTBE 4. Part (25%) of the residual stream 5 is introduced into the section separation (100 cm3zeolite X in example 1), from which discharge 96.7% of butane with a speed of 11.5 g/h (disbabled to the input stream 1 and introduced in section isomerization (see table. 2).

Example 3. Referring to the circuit of Fig.3 and the associated table.3, in the reactor for the production of MTBE enter the stream C4hydrocarbons in example 1 (1), but with a speed of 100 g/h in conjunction with the recycled stream (7) with a speed of about 226 g/h

Methanol with a velocity of 45.7 g/h is also injected into the reactor (tube 3). Performance MTBE 4 is 125,7 g/h when the degree of conversion of isobutene 99.5%

246,1 g/h the remaining fraction C4hydrocarbons containing about 19 wt. aliphatic hydrocarbons, is removed from section A synthesis through 10. This stream is introduced into the host isomerization C. After removal related products 9 and 9' residual stream 5 is introduced into separation unit B. Approximately 84% of this fraction passing through the bypass, the residue is introduced in section divisions, operating at 130oC and a pressure of 4 bar. 100 cm3zeolite X is used as the adsorbent of example 1. Stream 6 containing mainly 4.4 g/h aliphatic hydrocarbons with a paraffin content of approximately 96.7% of the dump.

Thread 7 add to the thread 91), and then injected into a section of esterification (see tab. 3).

Example 4. Referring to the circuit of Fig.4 and the accompanying table. 4, representing La simultaneous production of MTBE and 1-butene at a rate of 100 g/h and with the following composition, wt.

C3-0,45

Isobutan 23,57

1-Butene 36,67

2-Butenes 34,13

Isobutane 1,50

p-Butene 2,85

Butadiene 0,74

C5+0,10

in connection with the recycled stream 10 speed 147,8 g/h and 36.2 g of methanol also introduce (trumpet 3) in the reactor A.

Performance MTBE (4) is to 98.4 g/h, which is equivalent to the degree of conversion of isobutene 99.9%

185,5 g/h and a residual fraction C4hydrocarbons containing about 11 wt. aliphatic hydrocarbons, is removed from section A synthesis through 5. Approximately 60% of this fraction passing through the bypass, the residue is introduced in section separation on a molecular sieve, operating at 130oC and a pressure of 4 bar. 100 cm3zeolite X in the form of beads, extruded through a sieve 1/16", used as an adsorbent, n-hexane in the vapor phase (approximately 120 g/h) is used as desorbent for adsorbed olefins. After separation of desorbent by distillation stream 5 containing mainly 5,2 g/h aliphatic hydrocarbons with a paraffin content of approximately 96,2% (96.7% of the sum of butenes + butane) are displayed. In the stream 6 contents aliphatic hydrocarbons decreases to 8.8 wt. after separation of desorbent by distillation. thew in linear butenes, and a small part is converted to isobutane. Gidrogenizirovannye stream 7 is introduced into the extraction section 1-butene R. In this arrangement of Fig. 4 stream 7 is introduced into the first distillation column R', from the head which receives a stream of isobutane 7" speed 30,8 g/h, consisting mostly of just isobutane and all C3hydrocarbons contained in the stream 7, plus 1-butene. In this location the stream 7" injected into the frame section isomerization C.

Thread 8' (148,2 g/h), a free, mostly from isobutane, enter in column R, which receive of 18.45 g/h of 1-butene as the major product with a purity exceeding 99% (8). Thread 8" (129,75 g/h) are added to a thread 7", forming the thread 9 (160,5 g/h). The last stream is introduced into the section of isomerization of C, in which the n-butenes are converted to isobutene and other related products, usually falling in the category of C3-and C5+. These co-products are removed (streams 9 and 9'), and the resulting fraction 10 recycle in section synthesis of MTBE (see table. 4).

Example 5. Samples of zeolite of type X in the form of balls 1/16" heated in a muffle furnace to 400oC for 5 h in a stream of nitrogen. 4 g of zeolite treated in this way is loaded into a steel column AISI 316 what it is, through a column of flowing vaporous n-hexane for approximately 1000 to saturate the active sites of the zeolite. Then the flow of vaporous C4hydrocarbon passes through the column with a velocity of 7.6 l/h

Stream C4hydrocarbon has the following composition, wt.

Isobutane 3,8

Isobutan 4,4

n-butane 11,2

n-Butenes 80,0

1,3-Butadiene 0,6

Stream C4hydrocarbon passes through the column for approximately 1100 C.

The thread then stop, and then enter the flow preobrazovannogo n-hexane with a speed of 0.6 cm3/min for approximately 1800 C. Outflow from the system condense in a glass heat exchanger at -15oC.

The extracted mixture consists of the sum of the adsorbed amount of C4hydrocarbons and the amount enclosed in the volume of system, not occupied by the zeolite.

The extracted mixture of C4hydrocarbons at the outlet of the column has the following composition wt.

Isobutane 1,15

Isobutan 4,78

n-butane of 3.46

n-Butenes 88,77

1,3-Butadiene 1,84

Experimental data and analysis of the condensed liquid by gas chromatography shows the following selectivity si is an 4,13

The selectivity of Si is defined as the following ratio:

< / BR>
where A and R are molar fractions of C4hydrocarbons at the inlet and in the extracted solution, respectively;

i and o are signs binding component and the component comparison (n-butane), respectively.

Example 6. The method according to example 4 is repeated except that instead of zeolite X using zeolite Y. the flow Rate of C4hydrocarbon is 0.5 cm3/min. the Mixture of C4hydrocarbons extracted at the outlet of the column has the following composition wt.

Isobutane 1,00

Isobutan 6,44

n-butane a 3.87

n-Butenes 87,38

1,3-Butadiene 1,31

Experimental data and analysis of the condensed liquid by gas chromatography shows the following selectivity system, wt.

Isobutene/n-butane 4,33

1-Butene/n-butane 3,00

t-2-Butene/n-butane 3,22

c-2-Butene/n-butane 5,30

Example 7 (comparative). The method according to example 5 is repeated except that a mixture of C4hydrocarbons and hexane is used in the liquid phase. To achieve this, the working pressure inside the system is 14 bar.

A mixture of C4hydrocarbons extracted at the output of the 80,62

1,3-Butadiene 0,64

Experimental data and analysis of the condensed liquid by gas chromatography shows the following selectivity system, wt.

Isobutene/n-butane 1,8

1-Butene/n-butane 1,05

t-2-Butene/n-butane 1,06

c-2-Butene/n-butane 1,116

1. The method of obtaining alkyltin-butyl esters comprising contacting the stream WITH an4-hydrocarbons containing isobutene, linear butenes and butanes, in section synthesis alkyltin-butyl ether with a stream of aliphatic alcohol, separating the obtained ether and unreacted alcohol from the residual stream of hydrocarbons, the separation of the residual flow of hydrocarbons or part of section division for the Department of butane from butenes with receiving a stream of hydrocarbons containing the extracted butenes, the introduction of this latest thread in the section of skeletal isomerization for the conversion of linear butenes in isobutan obtaining isomerizing flow and management isomerizing flow in the section of the synthesis alkyltin-butyl ether, characterized in that the separation of the residual stream of hydrocarbons and its parts in section of the separation is carried out in the vapor phase molecular sieve with a coefficient of elevadorados, not entered in the section of the separation.

2. The method of obtaining alkyltin-butyl esters comprising contacting the stream WITH an4-hydrocarbons containing isobutene, linear butenes and butanes, in section synthesis alkyltin-butyl ether with a stream of aliphatic alcohol, separating the obtained ether and unreacted alcohol from the residual stream of hydrocarbons, the separation section of the separation to separate butane from butenes with receiving a stream of hydrocarbons containing the extracted butenes, isomerization for the conversion of linear butenes in isobutene in section skeletal isomerization of obtaining isomerizing flow, the management section of the synthesis alkyltin-butyl ether, characterized in that the isomerization is subjected to a residual stream of hydrocarbons, separation serves isomerized stream or part thereof, the separation is carried out in the vapor phase molecular sieve with a coefficient of selectivity olefin/paraffin 3 12 and received a stream of hydrocarbons containing the extracted butenes and possibly part isomerizing flow not included in the section separation, recyclist in section synthesis alkyltin-butyl ether.

3. The method according to p. 1 or 2, characterized in that the about under item 1 or 2, characterized in that original thread WITH4-hydrocarbons that do not contain isobutene, introduced in section isomerization.

5. Way to simultaneously obtain alkyltin-butyl ester and 1-butene by contacting the stream WITH an4hydrocarbons consisting mainly of isobutene, linear butenes and butane, in section synthesis alkyltin-butyl ether with a stream of aliphatic alcohol, separating the resulting alkyltin-butyl ether and unreacted alcohol from the residual stream of hydrocarbons, including the separation section of the separation to separate butane from butenes with receiving a stream of hydrocarbons containing the extracted butenes, and reset butane, processing node in the selective hydrogenation of butadiene, the flow in the section of skeletal isomerization for the conversion of linear butenes in isobutene and management isomerizing flow in the section of the synthesis alkyltin-butyl ether, characterized in that that separation is subjected to a residual flow of hydrocarbons or part thereof, the separation is carried out in the vapor phase molecular sieve feed resulting stream of hydrocarbons containing the extracted butenes, processing in the node selective hydrogenation of part b in the node separation of 1-butene to obtain a stream of 1-butene with purity, greater than 99% of the isobutane stream, containing mainly residual isobutane and 1-butene and butene stream containing mainly 2-butenes, 1-butene, and the residual n-butane, with subsequent supply section of skeletal isomerization of butene stream and a feed stream of isobutane or section division or section of skeletal isomerization.

6. The method according to p. 5, characterized in that original thread WITH4hydrocarbons consisting mainly of isobutene, linear butenes and butane, is introduced into the section of the synthesis alkyltin-butyl ether after pre-mixing with recyclization samaritanism stream.

7. The method according to p. 4, characterized in that original thread WITH4-hydrocarbons containing traces of butadiene and practically free from isobutene, injected directly before the site selective hydrogenation of butadiene and after the section of the separation of the molecular sieve.

8. The method according to PP. 1 to 7, characterized in that aliphatic alcohol use methyl or ethyl alcohol.

9. The method according to PP.1 to 8, characterized in that the remaining part of the flow of hydrocarbons, partial in section, division of molecular sieve exceeds 5% of total residual is m-type zeolite, able to demonstrate the selectivity to unsaturated double bond and having the General formula

(Cat2/nO)xMe2O3(SiO2)y,

where Cat cation with valence n, are able to exchange for calcium, such as sodium, lithium, potassium, magnesium and others;

x 0,7 1,5;

Me is boron or aluminum;

y 0,8 200,0, preferably 1,3 4,0.

11. The method according to p. 10, characterized in that the molecular sieve is a zeolite of type X or Y with a particle size of 0.1 to 3.0 mm

12. The method according to PP.1 to 11, characterized in that the ratio of selectivity of zeolite olefin paraffin is 3 to 12.

13. The method according to PP.1 to 12, characterized in that the separation is performed in the vapor phase at 20 180oWith 1 and 10 bar.

14. The method according to PP. 1 to 13, characterized in that the butenes is extracted by elution of olefins adsorbed on the molecular sieve, aliphatic hydrocarbons, followed by distillation of the mixture.

15. The method according to p. 4, wherein 1-butene is separated by distillation, extractive distillation or adsorption on a molecular sieve.

16. The method according to p. 15, wherein 1-butene is separated with high frequency using two distillation columns, raspoloen), separated as the head product and the second of which is entered as a cubic product of the first column 1-butene is obtained as the head product with a purity of greater than 99% of CBM product is a stream enriched in residual n-butane, CIS - and TRANS-2-butene and traces of 1-butene (butene stream).

17. The method according to p. 15, wherein 1-butene is separated with high purity using two distillation columns arranged in series, displaying of the first column a stream of butene in the form of the cubic product with the filing of the head product of the second column, from which in the form of the cubic product output 1-butene with a purity exceeding 99% and a stream of isobutane as head of product.

Priority points:

11.02.94 under item 1.

24.11.94 on PP.2 and 5.

 

Same patents:

The invention relates to the field of high octane components of gasoline, namely tert-alkyl esters alilovic

The invention relates to an improved method for producing a C1-C4tert-alkyl (C4-C5alilovic ethers, which are used as high-octane additives to motor fuels

The invention relates to the production of high-octane components

The invention relates to the production of high-octane oxygen-containing components of gasoline, namely tert-alkyl esters alilovic

The invention relates to improved methods of producing high-octane organic compounds, namely, to obtain high octane gasoline additives

The invention relates to the field of petrochemicals, in particular, to obtain methyl-tricalcium esters, which are used as high-octane additives to motor fuels

The invention relates to the United way of getting isobutene and alkyl tert-butyl ethers, such as methyl tert-butyl ether (MTBE), ethyl tert-butyl ether (ETBE), and so on
The invention relates to petrochemistry, and more particularly to methods of producing methyl tertiary butyl ether by etherification of the isobutene-isobutilene fractions of methanol in the presence of catalysts selfactivity
The invention relates to the field of production of alkyl tert-alilovic esters, used as high-octane components of motor fuels or are intermediates in the processes of extraction of isoolefine used as monomers for synthetic rubber

The invention relates to the field of high octane components of gasoline, namely tert-alkyl esters alilovic

The invention relates to an improved method for producing a C1-C4tert-alkyl (C4-C5alilovic ethers, which are used as high-octane additives to motor fuels

The invention relates to the field of high octane components of gasoline containing tert-alkalemia alcohol and tert-alkyl esters alkalemia

The invention relates to a previously undescribed perchlorates of diphenylethylenediamine General formula (I)

< / BR>
where n= 0,1; R1, R6the atom of hydrogen or halogen, C1-C6alkyl, C1-C6alkoxy or di(C1-C6)alkylamino; R2, R5= a hydrogen atom or halogen, C1-C6- alkoxy - or actigraphy; R3, R4the atom of hydrogen or C1-C6alkoxygroup; R7=R8=R9a hydrogen atom, or R7+R9=(CH2)1-3and R8=H; if n=0 have the General formula (Ia-C):

< / BR>
(perchlorate 1,5-diphenyl-3-ethoxymethyleneamino), and when n=1 have the General formula (I-R):

< / BR>
(perchlorate 1,7-diphenyl-3,5-diethoxymethylsilane) and which can be used as a promising synthons in organic synthesis, and in particular in the synthesis of fluorescent dyes (Durder J. A

The invention relates to the production of high-octane components

The invention relates to the production of high-octane oxygen-containing components of gasoline, namely tert-alkyl esters alilovic

The invention relates to improved methods of producing high-octane organic compounds, namely, to obtain high octane gasoline additives

The invention relates to the field of petrochemicals, in particular, to obtain methyl-tricalcium esters, which are used as high-octane additives to motor fuels

The invention relates to the United way of getting isobutene and alkyl tert-butyl ethers, such as methyl tert-butyl ether (MTBE), ethyl tert-butyl ether (ETBE), and so on
The invention relates to petrochemistry, and more particularly to methods of producing methyl tertiary butyl ether by etherification of the isobutene-isobutilene fractions of methanol in the presence of catalysts selfactivity

FIELD: organic chemistry, petroleum chemistry, chemical technology.

SUBSTANCE: the parent mixture consisting of preferably from C4-hydrocarbons comprising n-butenes, impurities of isobutene and/or butadienes and, possibly, butanes is subjected for a single or two-fold rectification with preliminary and/or simultaneous, and/or intermediate isomerization of 1-butene to 2-butenes preferably. From the distillate composition hydrocarbons with normal boiling points below -4°C and, possibly, n-butane in a remained flow containing 2-butenes preferably and, possibly, other part of n-butane are removed, and isomerization of 2-butanes to 1-butene is carried out, and 1-butene is isolated as a distillate, possibly, with impurity of n-butane. Invention provides simplifying technology of the process.

EFFECT: improved preparing method.

13 cl, 3 dwg, 2 tbl, 9 ex

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