Method for hydrogenation of acetone to isopropanol

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of isopropanol of high purity by hydrogenation reaction of acetone. Hydrogenation of acetone is carried out in liquid phase for at least two stages at temperature from 60oC to 140oC and under pressure from 20 to 50 bars. In hydrogenation nickel-containing catalyst on neutral carrier, preferably on a carrier made of α-form of aluminum oxide is used. The molar ratio hydrogen : acetone = (1.5-1):1. Reactor of the first stage can be circulation reaction, and at the second stage - tube reactor. For hydrogenation reaction acetone containing 1.0 wt.-% of water, not less, is used. Invention provides carrying out the process with high selectivity to yield isopropanol containing impurities in the concentration less 300 mole fr., preferably, less 100 mole fr.

EFFECT: improved hydrogenation method.

6 cl, 2 dwg, 1 ex

 

The present invention relates to a method of hydrogenation of acetone, to be more precise method of hydrogenation of acetone to isopropanol.

Acetone is a product that finds wide application and can be the target order is received, for example, by oxidation of propene or as the reaction product of the coupling in the synthesis of phenol on the hook.

In the synthesis of phenol on the hook for one molecule of phenol get one molecule of acetone. Variants of the consumption of phenol and acetone are very different; for example, in the synthesis of bisphenol a And phenol and acetone are spent in the ratio 2:1.

Possible product obtained from acetone, is isopropanol, with a much wider range of applications. A significant part of the isopropanol is converted into ethers, in particular isopropyl and tert-utilizability esters.

The conversion of acetone to isopropanol is generally accomplished using catalytic hydrogenation. For the production of simple isopropanolic esters in most cases use a combined method of hydrogenation and esterification. For example, applications for European patents EP 0694518, EP 0665207, EP 0652200 and EP 0661257 disclose methods of obtaining various simple isopropyl esters. Common in these patent applications is the following diagram of a method:

(a) to triticeae hydrogenation of the liquid phase, containing acetone,

(b) etherification thus obtained in acidic isopropanol catalyst systems.

Stage (a) and (b) follow each other immediately, i.e. without separation of the mixture of products obtained in stage (a).

In addition, the application for the European patent EP 0665207 reported a single-stage process, in which stage (a) and (b) are performed at a special catalyst in a single reactor.

The allocation of isopropanol after reaction stage (a) is due to the formation of by-products (methods designed to obtain simple isopropyl esters) is very complicated.

The closest analogue of the invention is a method for the hydrogenation of acetone to isopropanol, described in European patent EP 0379323, in which acetone is subjected to catalytic hydrogenation with mandatory use of the reactor irrigation type at a temperature in the range from 20 to 200°C. and at a pressure in the range from 1 to 80 bar. Reactors irrigation type are used to create a large surface for mass transfer between liquid and gas. Therefore, they must have a large surface area of irrigation. The quality of the resulting isopropanol, i.e. the number of products is not considered.

For many applications, isopropanol should not contain such products as isopropyl ether or traces of solvents, introduced from the stage hydrogenation. In particular, for use in medicine or cosmetics, or to receive future products isopropanol must have a very high degree of purity. The high degree of purity can be achieved in a wide industrial scale only with the help of expensive cleanup operations. For example, generated upon receipt of isopropanol the addition of water to propene, sulfur-containing compounds may prevent its use in cosmetic or pharmaceutical industries. The separation of these components is only possible with the help of post-processing isopropanol carbon dioxide aluminum or metals such as copper or Nickel.

The present invention is a method effective for the hydrogenation of acetone to isopropanol of high purity.

The problem is solved by a method of hydrogenation of acetone with hydrogen in the liquid phase in the presence of a hydrogenation catalyst in a neutral medium, and the hydrogenation of acetone in the liquid phase carried out at least in two stages.

The method according to the invention can be used for the production of isopropanol from acetone in large technical scale (more than 100 kilotons per year). The formation of by-products is almost completely eliminated, the result is f without the need for costly separation.

Therefore, the object of the present invention is a method for the hydrogenation of acetone to isopropanol, and the hydrogenation in the liquid phase is not less than two-stage.

When the hydrogenation of acetone can occur following reaction:

After aldol condensation and acetone to diacetone alcohol (DAS), carried out at an alkaline catalyst, the removal of water leads to the formation of 4-methyl-3-penten-2-he (oxide mesityl, MD). Hydrogenation of this intermediate component Ω leads to the formation of 4-methyl-2-pentanol (MP) in 4-methyl-2-pentanone (isobutyl ketone, MIBK). But DAS can be gidrirovanny also directly and to hexyleneglycol (GG). Target product (IE) may further during dehydration b) continue to respond to undesirable simple diisopropyl ether (DIPE).

Used catalyst should be neutral so as not to have a catalytic action on the undesirable side reaction of the target product PI, aldorino condensation and subsequent dehydration.

Some of the above side reactions occur during dehydration.

Therefore, to prevent these reactions, that is, to increase the selectivity, it is supposed to supply small quantities of water, which, being regulatel is the first for the special cases of the use of isopropanol, remains in the mix of products and, if necessary, should be removed.

The present invention, in contrast, enables the hydrogenation of acetone in the presence of very small amounts of water. In the earlier sources indicated that water flow into the primary flow is necessary to increase the selectivity, that is, to suppress the formation of by-products.

Using the inventive method acetone can be gidrirovanny to isopropanol when the content of water, equal to 1.0% wt. or less, preferably 0.5 wt.%. or less, and particularly preferably equal to 0.2% wt.

Required for large-scale industrial processes large degree of conversion can be achieved in the proposed case, or through the use of the circulation reactors, or for the account of reactors connected in series in a cascade configuration.

Thanks declared multistage method acetone can be gidrirovanny to isopropanol of high purity. An individual working as a parallel and/or cascade stage method can be made in the form of circulation or tubular reactors.

Reaction conditions can vary within wide limits; the hydrogenation in the liquid phase can be carried out at temperatures in the range from 60 to 140, preferably from 70 to 130°C and PR is the pressure in the range from 20 to 50, preferably from 25 to 35 bar. Conditions for temperature and pressure can at different stages differ.

Usually work with an excess of hydrogen: the molar ratio of hydrogen to acetone may be in the range from 1.5: 1 to 1:1.

If special modifications of the claimed method uses two stages, the first stage reactor can be designed as a circulating, and the reactor of the second stage - like tubular.

A simplified schematic diagram of the inventive method presents some of the possible nodes in figure 1.

A large part of the desired conversion is achieved in the circulation reactor And recycle the product. This reactor operates at a high level of concentration and can hold mode with low frequency circulation. The reaction product withdrawn from circulation reactor may be subjected to intermediate cooling (B). Finally, the process of hydrogenation is carried out in a shaft furnace (In)operating in mode a tubular reactor without recycle of the product. The sign "(a)" denotes a supply pipe and removal of hydrogen, the sign "p) - product pipeline. Both reactors a and b of figure 1) is designed as adiabatic.

The initial temperature of the first stage of the process is usually in the range from 50 to 90°C and a total pressure of from 10 to 30 bar. At high initial activity of the catalyst may be the sludge is reduced initial temperature, or increased the rate of circulation in the first reactor and thus set the desired outlet temperature, which may correspond to the temperature at the inlet of the second reactor.

The reactor of the first stage of the process can work as a circulation reactor with multiplicity circulation from 6 to 10. The content of acetone in securityuser the flow is reduced in the range from 8 to 20 wt.%, and the content of isopropanol increased accordingly. The process of hydrogenation is exothermic, so that in the reactor or after it it is necessary to provide for cooling. The hydrogenation in the liquid phase of the first stage of the process may be carried out at a temperature in the range from 60 to 130°C., preferably from 80 to 120°C. and at a pressure of from 20 to 50 bar, preferably from 25 to 35 bar.

The second stage of the process running on the characteristics of the tubular reactor may be carried out at a temperature in the range from 60 to 140°C., preferably from 70 to 130°C. and at a pressure in the range from 20 to 50 bar.

At both stages of the process can be used the same hydrogenation catalysts. The use of conventional hydrogenation catalysts based on such active components, such as copper, chromium, ruthenium or Nickel deposited on materials such as aluminum oxide, titanium dioxide or titanium dioxide qi is Konya. In the proposed method proved to be good catalysts based on Nickel - for example, with a Nickel content of about 10% wt. - on a neutral carrier. The material of the catalyst carrier in any case should be neutral. Neutral materials carriers are, for example, α -aluminum oxide, titanium dioxide, zirconium dioxide or mullite.

According to the claimed method are the high purity isopropanol. The total concentration of such by-products formed during the hydrogenation, as 4-methyl-3-penten-2-it, 4-methyl-2-pentanol, datetoday alcohol, hexyleneglycol and simple diisopropyl esters may be less than 300, preferably less than 200 and particularly preferably less than 100 ppm

Multi-concept reactor equipment provides other benefits due to the high technological flexibility: in the reactors can be installed independently from each other, the ratio of circulation, pressure and temperature. By reducing the activity of the catalyst in the same reactor can be, for example, correspondingly increased temperature in the subsequent reactor.

When choosing reactors it is necessary to pay attention to the good distribution of the liquid and/or the presence of a large surface gas exchange that can be achieved through the use of special switchgear, is for example, Raschig rings, nozzles in the form of wire mesh or structured packing of Sulzer, and also due to relatively high flow rate, amounting to at least 30 m3/m2·PM

The example below describes in more detail the present invention without limiting, however, the scope of its use.

Example

Using the experimental setup of figure 2.

When periodic process raw material f is placed in the separation tank and is injected into the recirculation loop reactor. Then, the display apparatus at the desired reaction conditions. At the beginning of the reaction circulation switch on the reactor R. after About 5 minutes, fixed values of temperature and pressure, and at this time produce the first sampling. Supply and drainage of hydrogen is produced via pipelines G and X. the result of pumping the product through appropriate amount of catalyst in a single pass through the layer thickness will have different conversion rates. In addition, provide isothermal flow mode, enabling simplification of the kinetic evaluation of the experiments. By sampling at different times of the experiment can be composed of a graph of the dependence of concentration on time of contact. These experiments are consistent with the model periodically acts the irradiation reactor with a stirrer or a tubular reactor.

Using Nickel-containing catalyst (10% wt. Nickel) on a neutral carrier of α -aluminum oxide.

The results of the experiments:

The circulation reactor of the type used in the first stage:

Inlet temperature: 70°C

Outlet temperature: 115°C

The multiplicity of circulation: 1:8

Volumetric speed: 220 m3/m2·h

Mass fraction of input:

acetone 22,2

isopropanol 77,8

Mass fraction of output:

acetone 12,5

isopropanol is 87.5

The tubular reactor used in the second stage:

Inlet temperature: 70°C

Outlet temperature: 126°C

The volumetric rate: 38 m3/m2·h

Mass fraction of input:

acetone 12,5

isopropanol is 87.5

Mass fraction of output:

acetone 0,54

isopropanol 99,45

By-products: less than 100 ppm

By-products are: methyl isobutyl ketone, 4-methyl-2-pentanol, hexyleneglycol and other certain high-boiling compounds.

1. The method of hydrogenation of acetone to isopropanol hydrogen in the liquid phase in the presence of a hydrogenation catalyst at neutral medium, characterized in that the hydrogenation of acetone in the liquid phase is at least two-stage.

2. The method according to claim 1, characterized in that the hydrogenation in the liquid phase is carried out at a temperature of from 60 to 140°is, at a pressure of from 20 to 50 bar and a molar ratio of hydrogen : acetone equal to (1.5 to 1): 1.

3. The method according to claim 1 or 2, characterized in that the total concentration of by-products formed during the hydrogenation, does not exceed 300 ppm

4. The method according to one of claims 1 to 3, characterized in that the hydrogenation is subjected to acetone with a water content of less than 1.0 wt.%.

5. The method according to one of claims 1 to 4, characterized in that the hydrogenation in the liquid phase is carried out in the presence of a Nickel catalyst on a neutral carrier.

6. The method according to claim 5, characterized in that the use of Nickel-containing catalyst on a carrier of α-aluminum oxide.



 

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FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of isopropanol of high purity by hydrogenation reaction of acetone. Hydrogenation of acetone is carried out in liquid phase for at least two stages at temperature from 60oC to 140oC and under pressure from 20 to 50 bars. In hydrogenation nickel-containing catalyst on neutral carrier, preferably on a carrier made of α-form of aluminum oxide is used. The molar ratio hydrogen : acetone = (1.5-1):1. Reactor of the first stage can be circulation reaction, and at the second stage - tube reactor. For hydrogenation reaction acetone containing 1.0 wt.-% of water, not less, is used. Invention provides carrying out the process with high selectivity to yield isopropanol containing impurities in the concentration less 300 mole fr., preferably, less 100 mole fr.

EFFECT: improved hydrogenation method.

6 cl, 2 dwg, 1 ex

FIELD: chemical technology.

SUBSTANCE: invention relates to a method for hydrogenation of acetone to yield isopropyl alcohol as an intermediate compound widely used in organic synthesis and an important industrial solvent. Method involves the hydrogenation reaction that is carried out in multitube reactor wherein nickel-base catalyst is used and reactor works in small reagents flow feeding into reactor. Based on using multitube reactor the method provides carrying out the regulated and controlled elimination of heat formed in the reaction carrying out. Method shows economy as it doesn't require recycle of the valuable end reaction product.

EFFECT: improved method of hydrogenation.

9 cl, 1 tbl, 1 dwg

FIELD: industrial organic synthesis.

SUBSTANCE: isopropyl alcohol production process comprises hydrogenation of starting acetone including from 0.01 to 10000 ppm benzene in presence of hydrogen and catalyst to give isopropyl alcohol and benzene hydrogenation products, acetone and benzene contained in feedstock being hydrogenated simultaneously. In its second embodiment, isopropyl alcohol production process comprises product separation stage. Process of producing phenol and isopropyl alcohol containing benzene hydrogenation products comprises stages: alkylation of benzene with isopropyl alcohol and/or propylene to form cumene, oxidation of resulting cumene into cumene hydroperoxide, acid cleavage of cumene hydroperoxide to produce phenol and acetone including from 0.01 to 10000 ppm benzene, preferably concentration of produced benzene-polluted acetone, and catalytic hydrogenation of benzene-polluted acetone into isopropyl alcohol containing benzene hydrogenation products, hydrogenation of benzene and acetone proceeding simultaneously.

EFFECT: enhanced process efficiency.

3 cl, 1 dwg, 1 tbl

FIELD: chemistry.

SUBSTANCE: method involves a stage of interaction of one or more α-halogenketones with general formula I , where each of "X" independently represents a halogen atom, except fluorine, a hydrogen atom and "Z" represents a halogen atom, except fluorine; with molecular hydrogen in the presence of heterogeneous catalyst, containing a transition metal, where the catalyst is a metallic salt, which is saturated with the catalyst carrier, where the metal consist of iridium, ruthenium or their mixture. The metal catalyses hydrogenation of all carbonyl groups of α-halogenketons to alcohol groups, at temperature from 1° to 200°C and pressure of at least 14 abs. pound/square inch with formation of one or more α-halogenspirits with general formula II . The invention also relates to the method of obtaining epoxides (alternatives), to the method of obtaining epi-halogenhydrine (alternatives) and to the method of obtaining propylene oxide (alternatives).

EFFECT: improved activity of the catalyst.

3 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: alkylarylketon hydration method involves contacting of raw material containing alkylarylketons and 1.3 to 30% (wt) of phenol compounds with hydrogen in the presence of heterogeneous hydration catalyst.

EFFECT: higher output of aryl alcohols due to positive influence of a phenol compound on catalytic activity.

6 cl, 2 ex

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