The allocation method tert-alkenes c4-c5

 

(57) Abstract:

Usage: petrochemistry. The inventive hydrocarbon mixture is contacted with a mixture containing predominantly non-tertiary(e) alcohol(s) with the number of carbon atoms is not less than 2 and water at a concentration of 0.5 to 90 wt.% in the presence of high acid cationite catalyst is distilled off unreacted hydrocarbons, conduct catalytic decomposition of the formed compounds in the presence of high acid cationite catalyst and distilled tert-alkenes WITH4-C5. The technical result is an increase in the yield of the target product and service life of the catalyst. 7 C.p. f-crystals, 2 tab., 2 Il.

The invention relates to the selection of tert-alkenes from hydrocarbon mixtures.

More specifically the invention relates to the extraction of tert-alkenes C4-C5from hydrocarbon mixtures by connecting them with hydroxyl-containing substances, separating the resulting solids from unreacted hydrocarbons and their subsequent separation by distillation tert-alkenes.

Known methods for isolating tert-alkenes from hydrocarbon mixtures by interaction with water or non-tertiary alcohols in the presence of Ki further decomposition of the resulting tertiary alcohol or ether in the presence of an acidic catalyst and distillation of the tert-alkene(s). Contact with water is carried out in liquid phase (contacting two liquid phases) devices with a co-current or countercurrent reactive substances /S. Y. Pavlov. Isolation and purification of monomers for synthetic rubber, L.: Chemistry, 1987, S. 128 - 142/.

The disadvantage of this method based on the interaction with water, is the low rate of reaction(s) due to negligible mutual solubility of hydrocarbons and water.

To overcome this drawback, it was proposed to maintain in the water 2 to 20 wt.% the resulting tertiary alcohol. This, however, leads to substantial restriction of the conversion of tert-alkenes due to the introduction of the product in conditions of equilibrium reactions /EN 2076091, 27.03.97/.

The method for extracting tert-alkenes from hydrocarbon mixtures by contact with aliphatic alcohols C1-C4in the presence of ion exchangers molded catalyst in the apparatus of the reactive distillation type with subsequent decomposition forming(them)by tert-alkyl Olkiluoto(s) ether(s) in the second reactive distillation apparatus containing molded sulphidity catalyst /EN 20057710, 15.01.94/.

This method is most similar to that proposed is in, which leads to the loss of the tert-alkenes, reduced service life of the catalyst, but also to the accumulation of dimers and oligomers in the aliphatic alcohol when reusing (recycling) for contact with the partial hydrocarbon mixture.

We offer a selection of tert-alkenes C4-C5from hydrocarbon mixtures comprising at least their catalytic contacting the hydroxyl-containing compounds in the presence of high acid cationite catalyst, distillation of the unreacted hydrocarbons, catalytic decomposition of the formed compounds in the presence of high acid cationite catalyst and the Stripping stream containing predominantly tert-alkene(s), namely, that the hydrocarbon mixture is contacted with a mixture containing predominantly non-tertiary(e) alcohol(s) with the number of carbon atoms is not less than 2 and water in a concentration of from 0.5 to 90 wt.%.

As one of the variants of the proposed method lies in the fact that the catalytic contacting and Stripping unreacted hydrocarbons is carried out in the system reactive distillation comprising series-connected counter flows zhidkostyu zone, moreover, the partial hydrocarbon mixture is fed to the lower part of the reaction zone and/or the upper part of the comprehensive area, and in the upper part of the reaction zone and/or the lower part of the firming zone serves alcohol mixture, which support the water concentration of 0.5 - 5.0 wt.%.

As a variant of the proposed method lies in the fact that the contacting is carried out in liquid phase(s) flow(s) or/and counter-current(s) unit(s) or/and direct-flow apparatus with partial evaporation of the reaction mixture and supplied to the mixture maintain the concentration of 5 - 92% of water relative to its total weight with alcohol(s).

As a variant of the proposed method lies in the fact that after separation of the reaction mixture at least part of the return water layer, preferably after cooling, the entrance to the catalytic zone contact, and the organic layer is distilled hydrocarbon, C3-C4and the rest served in the area of decomposition formed(their)SJ ether(s) and tertiary alcohol.

As a variant of the proposed method lies in the fact that the catalytic decomposition of the formed ester(s) and the tertiary alcohol is carried out with continuous distillation of the tert-alkene(s) and CBM is.

As a variant of the proposed method lies in the fact that in the areas of catalytic probe and catalytic decomposition using selfactivity(e) the catalyst(s) with a particle size of 2 to 40 mm and/or fine-grained sulfonic with a particle size of 0.3 - 2 mm, is loaded in the device(s) in the form of microcontainers with mesh or permeable membrane so that the proportion of free cross section in the device(s) is not less than 30%.

As a variant of the proposed method lies in the fact that in the liquid phase(s) device(s) contacting asleep, you may posando, fine-grained catalyst with a size of 0.3 to 2 mm, and in the rest of the reactor using the catalyst according to p. 6.

As a variant of the proposed method lies in the fact that when the distillation tert-alkene(s) from the zone of the catalytic decomposition of conduct partial condensation of the distilled stream and the condensed part of the return as phlegmy, and the rest is subjected to rectification and CBM product mainly containing alcohol(s) and/or ether(s), return to the zone of the catalytic decomposition and/or the area of catalytic contact with tert-alcantarea mixture.

The term liquid phase(s) device(s) in the PV condensed state.

Can be used various design options reactors and methods of heat removal in the device contact and the heat supply in the decomposition reactor.

When conducting the probe in the flow(s) within the reactor(s) supply of reagents can be carried out both top-down and bottom-up.

In the presence of two liquid phases, a solid phase can serve as a hydrocarbon phase, and distributed - water-alcohol, or a continuous phase of a water-alcohol, and distributed - hydrocarbon. Settling zone may be located within the contact apparatus, and beyond - in a separate tank.

The implementation of the invention is illustrated in Fig. 1 to 2 and examples 1 to 4.

These drawings and examples do not exclude the possible implementation of the invention and other possible technical solutions, while respecting the essence of the invention set forth in the claims.

According Fig. 1, the partial hydrocarbon mixture F (stream 1) is fed under a layer or between layers trail of catalyst in the reaction-distillation apparatus PP-1. Above the layer of catalyst is fed stream 2 containing alcohol(s) and water (together referred to as "R" - reagents).

On top of PP-1 in the.

Bottom-PP-1 output stream 4 containing predominantly formed ether(s) and tertiary alcohol, and possibly incompletely reacted non-tertiary(e) alcohol and water.

Stream 4 is fed into the apparatus PP-2 over layer and/or between the layers and/or under a layer of cationite catalyst.

Top-PP-2 output stream 5 containing predominantly tert-alkene(s) and the lower stream 6 containing predominantly non-tertiary(e) alcohol(s) and water.

Stream 6 is preferably returned to the apparatus PP-1, possibly after purification from accumulating impurities (zone cleaning "0" shown by the dotted line).

According Fig. 2, a partial hydrocarbon mixture F and a mixture of R containing predominantly non-tertiary(e) alcohol(s) and water, is fed into reactor R-1, respectively, flows 1 and 2. Upon exit from the zone of contact of the mixture (in the presence of heterogeneity) is subjected to delamination.

A mixture containing mainly unreacted hydrocarbons, the resulting ester(s) and tert-alcohol and possibly unreacted(e) non-tertiary alcohol and water, direct flow 3 in a distillation column K-1. Aqueous-alcoholic layer can be recycled (preferably through the fridge) for entry into the reactor R-is the natural enemy of unreacted hydrocarbons, and the lower stream 6 containing predominantly formed ether(s) and tert-butyl alcohol, and possibly non-tertiary alcohol and water.

Stream 6 is sent to the decomposition apparatus (apparatus P-2). On top of the unit P-2 output stream 7 containing predominantly tert-alkene(s), and the bottom stream 8 containing predominantly non-tertiary alcohol(s) and water, which is returned to the reactor R-1 and/or removed from the system.

Thread 7 can be routed to the secondary site for the Department carried alcohols and/or ethers, for example by rectification (Fig. 2 - in column K-2) or water washing.

As examples of ways to extract isobutene of isamuanoguchi C4-hydrocarbon mixtures and extraction tert-pentanol (2-methyl-2-butene and 2-methyl-1-butene) from isopentenyladenosine C5-hydrocarbon mixtures.

Key indicators are given in table. 1 and 2. Specified in the examples, the catalysts of the essence: "sulfonation with polyethylene and sulfonation with polypropylene" - molded from polyethylene and polypropylene sulfonate catalysts containing as sulfonated matrix is a copolymer of styrene with divinylbenzene (particle size catalysts 4 to 10 mm).

Catalisano particles 0.3 - 1 mm All the catalysts were used in the H+form.

In all experiments did not include formation of dimers and oligomers tert-alkenes and was not observed decrease of the catalyst activity during the hours of the experiment.

1. The allocation method tert-alkenes WITH4-C5from hydrocarbon mixtures comprising at least their catalytic contacting the hydroxyl-containing compounds in the presence of high acid cationite catalyst, distillation of the unreacted hydrocarbons, catalytic decomposition of the formed compounds in the presence of high acid cationite catalyst and the Stripping stream containing predominantly tert-alkene(s), wherein the hydrocarbon mixture is contacted with a mixture containing predominantly non-tertiary(e) alcohol(s) with the number of carbon atoms is not less than 2 and water at a concentration of 0.5 to 90 wt.%.

2. The method according to p. 1, characterized in that the catalytic contacting and Stripping unreacted hydrocarbons is carried out in the system reactive distillation comprising series-connected counter flows of liquid and vapor comprehensive reaction zolotorudnuju the mixture is fed to the lower part of the reaction zone and/or the upper part of the comprehensive area, and in the upper part of the reaction zone and/or the lower part of the firming zone serves alcohol mixture, which support the water concentration of 0.5 - 5.0 wt.%.

3. The method according to p. 1, characterized in that the catalytic contacting is carried out in liquid phase(s) flow(s) or/and counter-current(s) unit(s) or/and direct-flow apparatus with partial evaporation of the reaction mixture and supplied to the mixture maintain the concentration of 5 - 92% of water relative to its total weight with alcohol(s).

4 the Method according to PP.1 to 3, characterized in that after separation of the reaction mixture at least part of the return water layer, preferably after cooling, the entrance to the catalytic zone contact, and the organic layer is distilled hydrocarbons WITH3-C4and the rest served in the area of decomposition formed(their)SJ ether(s) and tertiary alcohol.

5. The method according to PP.1 to 4, characterized in that the catalytic decomposition of the formed ester(s) and the tertiary alcohol is carried out with continuous distillation of the tert-alkene(s) and VAT residue preferably return to the zone(s) catalytic contact with tert-alcantarea mixture.

6. The method according to PP.1 to 5, characterized in that catalysator(s) with a particle size of 2 - 40 mm and/or fine-grained sulfonic with a particle size of 0.3 - 2 mm, is loaded in the device(s) in the form of microcontainers with mesh or permeable membrane so that the proportion of free cross section in the device(s) is not less than 30%.

7. The method according to PP.1 - 6, characterized in that the liquid-phase(e), the device(s) contacting asleep, you may posando, fine-grained catalyst with a particle size of 0.3 to 2 mm, and in the rest of the reactor using the catalyst according to p. 6.

8. The method according to PP.1 to 7, characterized in that the distillation tert-alkene(s) from the zone of the catalytic decomposition of conduct partial condensation of the distilled stream and the condensed part of the return as phlegmy, and the rest is subjected to rectification and CBM product mainly containing alcohol(s) and/or ether(s), return to the zone of the catalytic decomposition and/or the area of catalytic contact with tert-alcantarea mixture.

 

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