JPS59501263A - Method for producing methyl formate and methanol in liquid phase - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Process for producing methyl formate and methanol in liquid phase The present invention is directed to the production of methyl formate and methanol -Process for producing methyl formate and methanol from so-called synthesis gas- It is something to do.

The production of methyl formate and methanol is carried out in one step and alkali or by a catalyst system consisting of alkaline earth metal alcoholates and heterogeneous Cu, Cr catalysts. Reactions that are catalyzed occur in the liquid phase.

Methanol and methyl formate are combined with carbon monoxide and hydrogen chemistry according to the total reaction below. Produced by reaction: 1, Co + 2H2CHaOH -Carbon oxide, hydrogen, methanol I1. 2CO+ 2H2HCOOCHa-carbon oxide hydrogen methyl formate Methanol and monoacid in the presence of alkali or alkaline earth metal alcoholates It has been known that methyl formate can be produced from carbon dioxide (German public announcement). Specification 1,147,214. (see Norwegian specification 135749), and methanol It is also known that methyl formate can be prepared by hydrogenolysis of methyl formate. i.e. German Patent Specification 902375 describes methyl formate and hydrogen in a catalytic gas phase reaction. This shows a method for producing methanol by reacting

Additionally, methyl formate and methanol can be produced at high temperatures in a catalytic gas phase reaction. However, it has not been used on a large scale for industrial manufacturing.

It has also been suggested that one reactor and ■ be carried out at the same stage (German patent 8098039), which describes the production of methanol. This person The method is not suitable for industrial use because the above catalyst systems have low productivity and are deactivated by rapid freezing. It is hardly used. Current industrial production of metal is heterogeneous. It is carried out by a catalytic gas phase reaction of carbon monoxide and hydrogen using a metal catalyst.

The reaction occurs at a pressure of about 100 atmospheres and a temperature of about 250°C. The gas phase reaction , a relatively large amount of gas must be recompressed and recycled to the reactor; It has the disadvantage that the conversion rate in each pass through is relatively low. This drawback is energy This is strongly amplified by the fact that energy costs are rapidly increasing.

The object of the invention has the characteristics specified in claim 1.

Regarding the present invention, it is surprising that the product methyl formate is present in the liquid phase. At the same time as their production by chemical reactions involving methanol, air is removed from the reaction zone. It has been found that the removal is advantageous in physical form. This fact shows that methanol is It is produced without methyl formate as an intermediate product as expected, and the reaction machine The structure is unknown, but it is shown that it is produced by a reaction unrelated to the concentration of methyl formate. ing.

The principle of removing methanol/methyl formate from the reactor has several technical advantages. and they are important for making the method technically/economically competitive. .

The chemical reaction that produces methyl formate and methanol involves the liberation of a significant amount of heat. There is. Since the method requires constant temperature in the reactor, heat can be removed from the reactor section. have to leave. The reaction takes place in the liquid phase, which is a simple process compared to gas phase reactors. can be implemented in an effective manner. Further product is expelled from the liquid phase and removed from the reactor. As the unreacted carbon oxides and hydrogen are removed, the heat of reaction is transferred to the reaction products. It will gradually be compensated for by heat loss due to evaporation of the material. Regarding thermoeconomics, The amount of energy that would otherwise be required for cooling in the reactor is thus saved. This is very advantageous because it reduces The temperature of the reactor can be controlled in this way. indirect heat regulation of the process through product evaporation by varying the amount of product removed. It can be done economically and advantageously.

By removing the products in gaseous form, the technical benefits of the catalytic process and the catalytic activity can be improved. The technical advantages of the method with respect to its durability and longevity and its handling in the method are can get. substances suspended in the reaction medium and dissolved m(alcoholate); The catalyst present in the reactor is not removed; on the contrary, the product is removed in the reactor. remains. This means that if the product is removed from the reactor in the liquid phase, refers to the omission of the separation necessary to remove the catalyst from the product. Therefore, the catalyst is fresh processing via the desired separation process stream, either feed or spent catalyst regeneration. can be done.

According to the invention, the lifetime of the catalyst and the removal of products from the reaction medium are surprisingly It was also found that there is a relationship between the use of principles. Therefore, methane formate is removed from the reaction medium. The removal principle of methyl formate minimizes the concentration of methyl formate in the reservoir, increasing the lifetime of the catalyst. It can be used appropriately for

The reaction according to the invention comprises an alkali or alkaline earth alcoholate in a liquid reaction phase; Alcoholate preferably prepared from methanol and suspended in the liquid reaction mixture. carried out in the presence of a heterogeneous catalyst consisting of a cloudy Cu-Cr oxide compound. . The reaction pressure and temperature can be varied within a wide range. Preferably 10-100% pressure is used. The temperature is chosen to provide a practical rate of reaction.

Suitably the reaction is carried out at a temperature within the range of 50<0>C to 240<0>C.

A chemical compound with the approximate composition Cu (OH)’ (NH4)Cro4 is placed in the presence of air. by calcination at a temperature of about 350° C. and then reduction of the product with hydrogen. It is known to produce [copper chromate] catalysts. This kind of copper chromate catalyst is However, according to the invention, the above-mentioned calcination in air can be replaced by an inert atmosphere, such as argon, helium-11, nitrogen or similar inert gases; and then reduced with hydrogen according to known methods. The use of special Cu--Cr oxide catalysts has proven particularly suitable.

What chemistry does the catalyst have during pyrolysis in an inert atmosphere compared to known calcining methods? The details of why the change occurred are not known. Cu(OH)(N H4) Thermal decomposition of Cro4 is carried out within the range of 250-500°C, most suitably at 270°C. It can be carried out at temperatures within the range of -320<0>C.

In addition to the above-mentioned Cu-Cr oxide components, catalyst systems as well as heterogeneous hydrogenation catalysts are Other components or carriers conventionally used as ,Fe,,o3,Mn01Mg0. Cab, BaO1Si02. activated carbon etc. , can also be included.

The reaction is carried out in known technical reactors for solid/liquid/gas systems.

Preferably, a type of reactor is selected which is characterized by good gas/liquid/solid mixing. selected. Methyl formate as well as methanol are produced during the reaction and The ratios between the components can be varied within a wide range by varying process conditions and catalyst composition. available.

Methanol originally acts as a solvent for the reaction. Other organic solvents, e.g. Alcohols, ethers, saturated hydrocarbons and aromatics can also be used. Book , sulfur and CO2 free and varying the molar ratio of carbon monoxide and hydrogen Synthesis gas that can be used is used in this method.

For reasons of conversion rate and selectivity with respect to the conversion to the desired products, the reaction It is essential that the reaction be carried out in a nearly anhydrous reaction medium.

Methyl formate and methanol were separated into separate columns as the top and bottom products, respectively. Collected during the process. A portion of the methanol production is suitably returned to the reactor. Living The methanol produced has a particularly high purity (anhydrous) and is therefore specially suited for this purpose. well suited for A sketch of an embodiment of the method is shown in FIG.

The present invention is advantageous and highly flexible for the joint production of methyl formate and methanol. It provides a certain method. The composition of the product ranges from pure methyl formate to pure Can be varied to range up to methanol, and manufactured according to the actual situation of the market can be adjusted at any time. As is known, methanol and methyl formate The forecast for the market is very promising. The characteristics of methanol are its ability as an energy carrier. Future uses of methanol are being studied. For this reason, the expected production Due to the substantial increase, the need for additional plants with relatively high production volumes has been anticipated.

Namely, a new and improved process for the production of methanol on an industrial scale. There should be demand and good opportunities for the application of advanced technology.

Methyl formate has a reasonable value for use as a raw material for a series of essential petrochemical products. It appears to be an essential intermediate in C1-based chemistry due to its .

The following examples further illustrate the objects of the invention.

Shigonmasu↓2J -The reaction of carbon oxide and hydrogen was studied in two essentially different reaction systems 1 The reaction consists of an alkali or alkaline earth metal alcoholate and a Cu-catalyst Common to both systems was that they were carried out in one step in the presence of a catalyst system. both systems A small reactor with a capacity of 120 ml was used for this purpose.

One reactor system dissipates the generated methyl formate and methanol into excess carbon monoxide and and hydrogen were removed from the reactor by bubbling through the reactor. In this case generated The substance was removed in gaseous form. The amount of gas is adjusted to maintain a constant liquid standard. Ta. In this case the catalyst remained in the reactor. The results are graphed in Figures 1-9. More shown.

In other reactor systems, the produced methyl formate and methanol are removed from the reactor in the liquid phase. The resulting dissolved and temperature sensitive catalyst is transported from the reactor along with the product stream. It will be revealed. Heterogeneous catalyst is recovered in a hydrocyclone, and then pumped into the reactor. I returned it. Methanol and methyl formate are passed through the separation section by the product stream, and the The homogeneous catalyst recovered was recycled to the reactor. The results are shown in graph II in Figures 1-9. Shown below.

Activity of the catalyst system as a function of time, pressure, temperature and various combinations of catalyst Shown regarding. As a heterogeneous catalyst, nominal composition: 39% Cu, 32% Cr, and Kirdlerschdhemii Katari of Munich with 2.5% Mn. Catalyst commercially available from Zettle GmbH under the trademark rG89J was used in all tests. did. Activity is produced per kg of catalyst (alcoholate) per unit of time. The results are expressed as kg of methanol and the results are shown in the accompanying drawings. The result is that the catalytic activity decreases slowly when the reaction products are removed in the gas phase rather than in the liquid phase. Ru. clearly shows that.

Wense Yuyu tongue A small amount (7) Cu (OH) N H4Cr O (approximately 2 g) was placed in an inert atmosphere (H e) pyrolyzed in Hold the sample at the maximum decomposition temperature shown in Figure 10 for 1 hour. It was. At the same time, 120 ml/min of helium was pumped through the decomposition section. Next 12g 0.75 g of the decomposed product in methanol was heated at 185 °C with a magnetic stirrer. A small autoclave with a volume of 30ml of temperature control and hydrogen pressure of 100 pearls. Pre-reduction was carried out using hydrogen in a vacuum chamber. After 16 hours the mixture was cooled to 20°C and The catalyst was separated from the methanol by centrifugation. the catalyst remained in the autoclave However, methanol was removed. Autoclave then add 1 mol% of catalyst as l 6th order monoxide fed with log dry methanol containing Na methylate Carbon and hydrogen conversion was carried out at 130 °C and 75 bar for 2.5 hours. . After the test, the reaction mixture was cooled to 20 °C and subjected to gas/liquid chromatography ( glc). Methanol and formate as a function of maximum decomposition temperature The production of chill (expressed as % of weight gain) is shown in Figure 1O by graph II. The selectivity to methanol/methyl formate in the reaction of CO and H2 is It was over 95% in all of these tests.

For comparison, Cu (OH) NH4CrO was heated in air according to a known method. calcination and as a catalyst for the reaction of carbon monoxide and hydrogen according to the same method as above. It was tested. The results are shown by graph H in FIG.

The results indicate a significantly more active catalyst compared to that obtained by known calcination methods. The medium is provided by thermal decomposition of Cu(OH)NH4 in an inert atmosphere. It was showing.

Engraving (no changes to the content) gaol case Respect 0 ■) Iku Naeaki 1 Procedure amendment writing method) %formula% 3. Person who makes corrections Relationship to the incident: Patent applicant 6. Subject of correction translation of the drawing 7. Contents of correction March 5, 1982 Mr. Kazuo Wakasugi, Commissioner of the Patent Office 1, %, f appearance display PCT/No. 82100040 2 Name of the invention Process for producing methyl formate and methanol in liquid phase 3, patented by Sa Address: 1-9-15-5 Akasaka, Mukai-ku, Tokyo, Date of submission of auxiliary equipment April 13, 1983 6. Attached Intellectual Catalog fl)　M-positive translation Amended claims Accepted by the International Bureau on April 13, 1983; original claims 1 to 4 as new claim Replace with range 1-7 1. Co-produce methanol and methyl formate in liquid phase in one reaction step, and then characterized in that it is removed from the reaction part in phase form - containing carbon and hydrogen oxides; The presence of a catalytic system consisting of metal alcoholates and copper-chromium oxides A method for producing methyl formate and methanol by reacting as follows.

2. Methyl formate and methanol are separated by fractional distillation, and then methanol is separated. Claim 1, characterized in that the method is recycled in whole or in part to the reaction stage. Method described.

3. A claim characterized in that barium methoxide is used as the metal alcoholate. The method described in item 1 of the scope of the request.

4. In addition to methanol and methyl formate, an organic inert solvent is present in the liquid phase. A method according to claim 1, characterized in that:

5. Cu(OH)(NH4)C in an inert atmosphere as a copper-chromium oxide catalyst Claims characterized in that using a special type provided by the pyrolysis of ro. The method described in paragraph 1.

6. The reaction is carried out at a temperature below 240°C and a pressure below 100 bar. 6. A method according to claims 1-5, characterized in that:

7. Cu(OH)(NH4)C at temperatures below 320°C in an inert atmosphere A copper-chromium oxide catalyst obtained by thermal decomposition of ro.

international search report

Claims (1)

[Claims] 10 The reaction was carried out in a liquid phase consisting mainly of methanol, while methyl formate and meth carried out catalytically, with continuous removal of 7-nol from the reaction part in gaseous form. - from a synthesis gas consisting of carbon oxide and hydrogen to methyl acid and A method for producing methanol in one reaction step. 2. Methyl formate and methanol are separated by fractional distillation, and then methanol is separated. Claim 1xj, characterized in that it is recycled in whole or in part to the reaction stage. The method described in 4. 3. Catalytic reaction with alkali or alkaline earth alcoholate and in an inert atmosphere A special Cu-catalyst provided by the thermal decomposition of Cu(OH)(NH4)Cr04 Claims 1-2, characterized in that the process is carried out in the presence of a catalyst system consisting of a catalyst. Method described. 4. The reaction is carried out at a temperature below 240°C and a pressure below lOOpar 4. A method according to claims 1-3, characterized in that: