RU2574060C1 - Method of producing methyl ethyl ketone and butadiene-1,3 - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: methyl ethyl ketone is used as a solvent for different paint materials, adhesives and for dewaxing lubricating oils and wax deoiling. Butadiene-1,3 is one of the basic monomers used to produce synthetic rubber. The method includes the catalytic dehydration of oxo-derivatives of butane, selected from butanediol-1,2, butanediol-2,3, butanediol-1,3, butanediol-1,4, epoxybutane-2,3, epoxybutane-1,2 or a mixture of the said compounds. The catalyst used is solid-phase catalysts selected from: aluminosilicates with a zeolite structure, mesoporous or micro-mesoporous aluminosilicates, crystalline metallo-aluminophosphate molecular sieves, crystalline metallosilicates with a zeolite structure of the formula T₂O₃*(10-1000)SiO₂, where T represents elements selected from a group of p-elements of group III or d-elements of groups IV-VIII, phosphates of p-elements of group III or d-elements of groups TV-V; dehydration is carried out at 130-400°C and atmospheric pressure, and the obtained products are separated after dehydration.

EFFECT: providing high selectivity for one of the desired products with high overall selectivity for the desired products, high degree of conversion of raw materials with high stability of catalyst operation over time.

8 cl, 1 tbl, 46 ex

Description

The present invention relates to a catalytic method for producing methyl ethyl ketone and butadiene-1,3 in one process from oxygen-containing derivatives of butane.

Methyl ethyl ketone (MEK) is used as a solvent for various paints and varnishes, glues, as well as for dewaxing of lubricating oils and de-oiling of paraffins. In addition, methyl ethyl ketone is an intermediate in the production of methyl ethyl ketone peroxide. Methyl ethyl ketone in industry is obtained by the following methods: 1) in a three-stage process from butenes of the C4 pyrolysis fraction, 2) by dehydrogenation of 2-butanol, 3) by oxidative dehydrogenation of 2-butanol.

Butadiene-1,3 is one of the main monomers used for the production of synthetic rubbers. In recent years, the demand for butadiene has been increasing, and currently there is a shortage of this product on the world market. Currently, the following methods for producing butadiene are used in industry: 1) extraction of butadiene from the C4 fraction of pyrolysis of oil products, 2) dehydrogenation of butanes, 3) oxidative dehydrogenation of n-butane and n-butenes. Earlier in the industry, methods for producing butadiene from oxygen-containing compounds were common: 1) synthesis of butadiene-1,3 from ethanol, 2) aldol method for the synthesis of butadiene from acetylene, 3) pyrolysis of 2,3-butylene glycol diacetate (glycol method).

Recently, methods for the conversion of butanedyls and some other oxo derivatives of C4 to MEK and butadiene have been gaining popularity.

For example, a known method for producing MEK using enzymatic catalysis (US 2011/0008858, 01/13/2011).

There is also a method of producing butadiene-1,3 in the presence of microorganisms (US 8715957, 05/06/2014.)

However, enzymatic catalysis is characterized by the non-renewability of the catalysts used and the multi-stage synthesis process.

Known catalytic methods for the individual production of the products of interest to us (methyl ethyl ketone and butadiene-1,3) when using oxygen-containing derivatives of butanes as raw materials.

A known method of producing methyl ethyl ketone by dehydration of 1,3-butanediol at 150-270 ° C in the presence of a catalyst containing a mixture of oxides of copper, zinc, chromium and aluminum (SU 782297, 02/07/1984).

However, this method does not provide for the possibility of producing butadiene-1,3. As by-products, acetone and butyraldehyde are formed in the process.

Methods for producing methyl ethyl ketone by dehydration of 2,3-butanediol in the presence of strong acids as a catalyst, in particular sulfuric acid (Richard R. Emerson "Kinetics of Dehydration of Aqueous 2,3-Butanediol to Methyl Ethyl Keton", Ind. Eng. Chem, are described). (Prod. Res. Dev. 1982, 21, 473-477).

The main reaction product is methyl ethyl ketone, butadiene formation does not occur in this process. In addition, in the case of homogeneous catalysis, the catalyst is difficult to separate from the resulting mixture of products, which complicates the process of isolating the target product.

A known method involving the dehydration of diols in the presence of solid phase catalysts - oxides of various metals (mainly rare earths). In the known method, the dehydration of diols is not completely targeted (with the removal of only one water molecule) to unsaturated compounds (WO 2007/083736, 07.26.2007).

Also known are solid-phase catalysts based on phosphates of certain alkali and alkaline earth metals used in diol dehydration processes (SU 555832, 06/28/1977, SU 5788383, 11/10/1977).

However, the dehydration of diols used as raw materials in the above patents does not provide the products of interest to us, namely, MEK and butadiene-1,3.

Regarding the production capabilities of 1,3-butadiene as the target product, the following can be noted.

In Industrial and Engineering Chemistry 37 (1945), No. 9, 877-884 describes the production of butadiene-1,3 in high yield during the pyrolysis of butylene glycol diacetate. This method has good performance. The process is non-catalytic and is carried out at sufficiently high temperatures (400-600 ° C). In order to carry out the process, it is first necessary to obtain butylene glycol diacetate, and then to remove acetic acid in the second stage. Thus, in addition to the target butadiene, an acid is present in the mixture of the obtained products, the presence of which leads to corrosion of the equipment and complicates the process of butadiene isolation.

The most promising is the development of a method for the simultaneous synthesis of MEK and 1,3-butadiene from oxane derivatives of butane.

A known method for the catalytic dehydration of 2,3-butanediol at 325-375 ° C using solid-phase catalysts selected from oxides of zirconium, titanium, aluminum, iron. During dehydration, depending on the choice of a particular catalyst, the conversion of 2,3-butanediol from 60 to 100%, the content of the resulting mixture of methyl ethyl ketone in the amount of 30-40 mol%, and butadiene-1.3 in the amount of 20-40 mol% is ensured (Hailind Duan et all "Dehydration of 2,3-butanediol into 3-buten-2-ol catalyzed by ZrO ₂ ", Catalysis Communications 48,2014,1-4 - see table 1).

The main disadvantage of this method is the large spectrum of the resulting substances and low selectivity for the target reaction products - MEK and butadiene-1,3. The formation of a large number of by-products greatly complicates the further isolation of MEK and butadiene-1,3 from the reaction mixture. Also in this method, a number of catalytic systems are unstable in the process under study and lose activity (conversion drop by 15%) after 5 hours of operation.

The objective of the present invention is to develop a catalytic method for the synthesis of methyl ethyl ketone and butadiene-1,3 in one process, providing high selectivity for one of the target products with high total selectivity for the target products and a high degree of conversion of the feedstock with high stability of the catalyst over time.

The problem is solved by the described method for the simultaneous production of methyl ethyl ketone and butadiene-1,3. The method consists in the fact that catalytic dehydration of a feedstock selected from butanediol-1,2, butanediol-2,3, butanediol-1,3, butanediol-1,4, epoxybutane-2,3, epoxybutane-1,2 or mixtures is carried out of the mentioned compounds, solid-phase catalysts from the series are used as a catalyst in the process: aluminosilicates with a zeolite structure, mesoporous or micromesoporous aluminosilicates, crystalline metal silicates with a zeolite structure of the composition T ₂ O ₃ * (10-1000) SiO ₂ , where T elements are selected from the group p-elements of group III or d-elements IV-VIII gr pp crystalline metalloaluminophosphate molecular sieve, phosphates, p-elements group III or d-elements of groups IV-V. Dehydration is carried out at 130-400 ° C and atmospheric pressure, and after dehydration of the raw materials, the products obtained are separated.

The method of dehydration of the feed also involves the use of a composition of two or three of the mentioned catalysts.

When used as catalysts, phosphates selected from the group of p-elements of group III and d-elements of IV-V groups, they are used in composition with these oxides.

The method provides that the catalysts used may contain silica or alumina binder.

Preferably, the dehydration is carried out at a feed rate of from 0.5-1000 g / g · hour.

According to the method, dehydration is carried out in a flow-type reactor with a fixed catalyst bed.

According to the method, dehydration is also carried out under static conditions when the amount of catalyst is from 0.5 to 20% by weight of the reaction mixture.

The method provides that the resulting mixture of products is separated into liquid and gaseous by cooling the gas mixture to liquefy methyl ethyl ketone.

The technical result of the implementation of the method within the scope of the independent claim is the high selectivity for one of the target products with high selectivity for the sum of products and high stability of the catalyst

As the zeolite catalysts in the claimed process, narrow-porous zeolites of the CHA, LTA, RHO type, medium-porous zeolites of the MFI, FER, MEL, TON type, wide-porous zeolites of the FAU, BEA, MOR, MTW, MAZ type, mesoporous aluminosilicates SBA-type MCM-MC were tested. -15 or micromesoporous aluminosilicates having a mesopore fraction of 0.4-0.9 and characterized by a Si / Al ratio of 2 to 1000

In addition, crystalline metalaluminophosphate molecular sieves with the structure of zeolites such as AFI, CHA, AEI, AEL, AEN, AET, AFN, AFO, AFR, AFX were also tested. With all of the above catalysts, the claimed technical result was achieved.

An advantage of the proposed method is also the ability to control the composition of the synthesis products by selecting one or another catalyst from a number of declared.

The possibility of implementing the method with the achievement of the claimed technical result is confirmed by the data given in table 1. The table includes the most promising of the tested catalysts.

The proposed method for the dehydration of butanediols and epoxybutanes in general is as follows.

The feed is fed to a flow-type reactor with a fixed catalyst bed. At the outlet of the reactor, the resulting mixture of products is divided into liquid and gaseous

phase. The component composition of the substances is determined by chromatographic method. Butadiene is separated from methyl ethyl ketone by cooling the gas mixture of the resulting products to a MEK liquefaction temperature (60 ° C).

The following examples illustrate the implementation of the invention and demonstrate the achievement of a technical result in comparison with known methods for producing methyl ethyl ketone and butadiene-1,3.

Example 1

As a catalyst, zirconium phosphate Zr (HPO ₄ ) _{2 is used} . The catalyst is placed in a flow reactor, purged with nitrogen at a temperature of 350 ° C for 1 hour, then the temperature is reduced to 250 ° C and butadiene-2,3 is fed at a rate of 2.4 g / g · hour at atmospheric pressure. The reaction is carried out for 3 hours. Chromatographic analysis of the reaction mixture showed the formation of methyl ethyl ketone in 72% yield and 1,3-butadiene in 8% yield. The conversion of butanediol-2,3 was 95%. The conversion products are cooled to completely transfer the MEK to the liquid phase. The results are presented in table 1.

Example 2

The process is conducted as in example 1, the difference is that the measurement of the process parameters occurs 10 hours after the start of the reaction. Process indicators are presented in table 1.

Example 3 (comparative).

The process in the conditions of example 1, however, as the catalyst used, the catalyst of the prototype is zirconium oxide ZrO ₂ . The process indicators are presented in table 1. This example is characterized by the formation of a large number of by-products.

Example 4 (comparative).

The process is conducted under the conditions of example 1, the difference is that they use the prototype catalyst - zirconium oxide ZrO ₂ - and the process parameters are measured 10 hours after the start of the reaction. Process indicators are presented in table 1.

Analysis of the results obtained in examples 1-4, shows the advantages of the method of producing ketone and diene on the proposed catalysts (zirconium phosphate) compared with known catalysts with the same process parameters. Compared with the catalyst of the prototype, the proposed catalyst exhibits higher activity, selectivity and stability.

The following examples show the possibility of carrying out processes with some catalysts from a number of declared under different process conditions.

Example 5

The process is carried out as in example 1, the difference is that ferrierite FER in the H-form with a ratio of Si / Al = 40 is used as a catalyst. Process indicators are presented in table 1.

Example 6

The process is conducted as in example 1, the difference is that the catalyst used is MFI zeolite in the H-form, calcined at 500 ° C with a Si / Al ratio of 27.5. Process indicators are presented in table 1.

Example 7

The process is conducted as in example 1, the difference is that the catalyst used is MFI zeolite in the H-form, calcined at 500 ° C with a ratio of Si / Al = 40. Process indicators are presented in table 1.

Example 8

The process is carried out as in example 1, the difference is that the catalyst used is MFI zeolite in the H-form, calcined at 500 ° C with a ratio of Si / Al = 140. Process indicators are presented in table 1.

Example 9

The process is carried out as in example 1, the difference is that FAU zeolite in the H form calcined at 500 ° C with a Si / Al ratio of 30 is used as a catalyst. Process indicators are presented in table 1.

Example 10

The process is carried out as in example 1, the difference is that FAU zeolite in the H form calcined at 500 ° C with a Si / Al ratio of 40 is used as a catalyst. Process indicators are presented in table 1.

Example 11

The process is carried out as in example 1, the difference is that the catalyst used is BEA zeolite in the H-form, calcined at 500 ° C with a ratio of Si / Al = 37.5. Process indicators are presented in table 1.

Example 12

The process is carried out as in example 1, the difference is that the Sn-BEA zeolite calcined at 500 ° C with a ratio of Si / Sn = 100 is used as a catalyst. Process indicators are presented in table 1.

Example 13

The process is carried out as in example 1, the difference is that the catalyst is Zr-BEA zeolite calcined at 500 ° C with a Si / Zr ratio of 200. Process indicators are presented in table 1.

Example 14

The process is carried out as in example 1, the difference is that the catalyst used is Ga-BEA zeolite calcined at 500 ° C with a ratio of Si / Ga = 100. Process indicators are presented in table 1.

Example 15

The process is carried out as in example 1, the difference is that the catalyst used is Fe-BEA zeolite calcined at 500 ° C with a ratio of Si / Fe = 100. Process indicators are presented in table 1.

Example 16

The process is carried out as in example 1, the difference is that the catalyst used is the mesoporous material MCM-41 with an aluminum content of 3% and a pore size of 2.5-3 nm. Process indicators are presented in table 1.

Example 17

The process is conducted as in example 1, the difference lies in the fact that the catalyst is used micromezoporous material (MMM), obtained by recrystallization of zeolite MFI. Process indicators are presented in table 1.

Example 18

The process is carried out as in example 1, the difference is that the catalyst is used aluminophosphate material SAPO-34 with a structure of the CHA type zeolite with a ratio of Al ₂ O ₃ : 1.06 P ₂ O ₅ : 1.08 SiO ₂ . Process indicators are presented in table 1.

Example 19

The process is carried out as in example 1, the difference is that the metal-substituted aluminophosphate material CoAlPO-18 with an AEI type zeolite structure is used as a catalyst. Process indicators are presented in table 1.

Thus, examples 5-19 illustrate the dependence of the process indicators on changes in the surface characteristics of the catalyst, as well as on the number of Brønsted and Lewis acid centers, which allows the selection of a specific catalyst from a number of declared ones, which makes it possible to obtain a mixture of conversion products of a given composition.

Example 20

The process is carried out as in example 1, the difference is that the catalyst obtained as follows is used as a catalyst. Silicon oxide SiO ₂ in an amount of 10 g is impregnated in terms of moisture capacity with an aqueous solution of phosphoric acid in an amount of 1.5 g (85%). The resulting catalyst was dried at 110 ° C and calcined in air at a temperature of 400 ° C. Process indicators are presented in table 1.

Example 21

The process is carried out as in example 1, the difference is that the catalyst used is a niobium phosphate catalyst NbOPO ₄ . Process indicators are presented in table 1.

Example 22

The process is carried out as in example 1, the difference is that the catalyst used is aluminum phosphate catalyst AlPO _4. The process indicators are presented in table 1.

Example 23

The process is carried out as in example 1, the difference is that titanium phosphate is used as a catalyst. Process indicators are presented in table 1.

Example 24

The process is carried out as in example 1, the difference is that boron phosphate is used as a catalyst. Process indicators are presented in table 1.

Example 25

The process is carried out as in example 1, the difference is that an oxophosphate material based on phosphate and niobium oxide with an oxide phase content of 15% is used as a catalyst. Process indicators are presented in table 1.

Examples 20-25 illustrate the possibility of varying the composition of the catalyst and the deposition of the active component on the carrier.

Example 26

The process is carried out as in example 1, the difference is that the catalyst used is MFI zeolite in the H-form with a ratio of Si / Al = 140, granulated with Al ₂ O ₃ (content of 20% by weight of the catalyst), acting as a binder . Process indicators are presented in table 1.

Example 27

The process is conducted as in example 1, the difference is that the zirconium phosphate from example 1 is used as a catalyst, granulated with silica (content of 20% by weight of the catalyst) acting as a binder. Process indicators are presented in table 1.

As can be seen from examples 26-27, there is a dependence of the activity of the catalyst on changes in the content of the active phase of the system.

Example 28

Similar to example 1, the difference is that epoxybutane-2,3 is used as a raw material for the synthesis of methyl ethyl ketone and butadiene-1,3. Process indicators are presented in table 1.

Example 29

Similar to example 28, the difference is that the niobium phosphate catalyst of example 21 is used. The process indicators are presented in table 1.

Example 30

Similar to example 1, the difference is that epoxybutane-1,2 is used as a raw material for the synthesis of methyl ethyl ketone and butadiene-1,3. Process indicators are presented in table 1.

Example 31

Similar to example 28, the difference is that as a raw material for the synthesis of methyl ethyl ketone and butadiene-1,3, a mixture of epoxybutane-1,2 and epoxybutane-2,3 is used. Process indicators are presented in table 1.

Example 32

Similar to example 1, the difference lies in the fact that butanediol-1,2 is used as a raw material for the synthesis of methyl ethyl ketone and butadiene-1,3. Process indicators are presented in table 1.

Example 33

Similar to example 1, the difference is that butanediol-1,3 is used as a raw material for the synthesis of methyl ethyl ketone and butadiene-1,3. Process indicators are presented in table 1.

Example 34

Similar to example 1, the difference is that as a raw material for the synthesis of methyl ethyl ketone and butadiene-1,3, a mixture of butanediol-1,4 and butanediol-2,3 is used. Process indicators are presented in table 1.

Example 35

Similar to example 1, the difference is that as a raw material for the synthesis of methyl ethyl ketone and butadiene-1,3, a mixture of butanediol-1,2 and butanediol-2,3 is used. Process indicators are presented in table 1.

Example 36

Similar to example 35, the difference is that the niobium phosphate catalyst of example 21 is used. The process indicators are presented in table 1.

Example 37

Similar to example 35, the difference is that the aluminum phosphate catalyst from example 22 is used. The process indicators are presented in table 1.

Examples 28-37 illustrate the possibility of implementing a method for producing MEK and butadiene-1,3 in a wide range of variation in the composition of the feedstock.

Example 38

Similar to example 1, the difference is that the dehydration is carried out at a temperature of 200 ° C. Process indicators are presented in table 1.

Example 39

Similar to example 1, the difference is that the dehydration is carried out at a temperature of 300 ° C. Process indicators are presented in table 1.

Example 40

Similar to example 1, the difference is that dehydration is carried out at a temperature of 400 ° C. Process indicators are presented in table 1.

Example 41

Similar to example 1, the difference is that the feed rate of the feed is 0.5 g / g · hour. Process indicators are presented in table 1.

Example 42

Similar to example 1, the difference is that I use aluminum phosphate from example 22 as a catalyst and the feed rate of the feed is 1.1 g / g · hour. Process indicators are presented in table 1.

Example 43

Similar to example 1, the difference is that the feed rate of the raw material is 1000 g / g · hour. For this example, a characteristic low degree of conversion, which is reflected in low yields of products. However, the selectivity of MEK and butadiene-1.3 was 59 and 8.3%, respectively. Process indicators are presented in table 1.

Example 44

Similar to example 40, the difference is that epokibutane-2,3 is used as raw material. Process indicators are presented in table 1.

Example 45

Similar to example 1, the difference is that the process is carried out in a static reactor with a volume of 100 ml, 250 ° C and a mass content of catalyst equal to 0.5% (by weight of the reaction mixture). The reaction was carried out for 10 hours. Process indicators are presented in table 1.

Example 46

Similar to example 1, the difference is that the process is carried out in a static reactor with a volume of 100 ml, 130 ° C and a mass content of catalyst equal to 20% (by weight of the reaction mixture). The process indicators are presented in table 1. The formation of a large number of heavy products (C8-C12) was observed.

Examples 38-46 illustrate the possibility of implementing a method for producing MEK and butadiene in a wide range of variation of reaction conditions.

Thus, all the examples presented indicate that the implementation of the method in the presence of the claimed solid phase catalysts allows to achieve high selectivities for the formation of methyl ethyl ketone and butadiene-1,3 with high system activity and stable operation over time. For the used catalysts, the time of stable operation in the process is more than 3 times higher than the time of stable operation of the catalyst of the prototype.

Claims (8)

1. The method of producing methyl ethyl ketone and butadiene-1,3 in one process, comprising the catalytic dehydration of oxo derivatives of butane, characterized in that the dehydration is subjected to oxo derivatives selected from butanediol-1,2, butanediol-2,3, butanediol-1,3, butanediol -1,4 epoxybutane-2,3, epoxybutane-1,2, or mixtures of the above compounds, while solid-phase catalysts from the series are used as catalyst: aluminosilicates with a zeolite structure, mesoporous or micromesoporous aluminosilicates, crystalline metalaluminophosphate molecular sieves, crystalline metal silicates with a zeolite structure of the composition T ₂ O ₃ * (10-1000) SiO ₂ , where the T elements are selected from the group of p-elements of group III or d-elements of IV-VIII groups, phosphates of p-elements of group III or d-elements of the TV-V groups, dehydration is carried out at 130-400 ° C and atmospheric pressure, and after dehydration, the products obtained are separated. 2. The method according to p. 1, characterized in that during dehydration use a composition of two or three of the mentioned catalysts. 3. The method according to p. 1, characterized in that the phosphates from the group of p-elements of group III and d-elements of IV-V groups are used in composition with oxides of the same elements. 4. The method according to p. 1, characterized in that the used catalysts contain a binder based on silicon oxide or aluminum. 5. The method according to p. 1, characterized in that the dehydration is carried out at a feed rate of from 0.5-1000 g / g · hour. 6. The method according to p. 1, characterized in that the dehydration is carried out in a flow-type reactor with a fixed catalyst bed. 7. The method according to p. 1, characterized in that the dehydration is carried out under static conditions when the amount of catalyst is from 0.5 to 20% by weight of the reaction mixture. 8. The method according to p. 1, characterized in that the resulting products are separated into liquid and gaseous by cooling the gas mixture to liquefy methyl ethyl ketone.