JPS6039652B2 - Method for producing lower oxygen-containing organic compounds - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the production of low-grade oxygen organic compounds using a mixed gas of carbon monoxide and hydrogen (hereinafter referred to as synthesis gas) as a raw material.

Lower oxygen-containing organic compounds such as acetic acid, methanol, ethanol, and propanol are valuable industrial products that have traditionally been
It is mainly produced from crude oil.

However, in recent years, with the depletion of petroleum resources and the rising price of naphtha derived from crude oil, there has been a desire to develop a method for producing these petrochemical basic raw materials using synthetic gas obtained from carbon resources other than petroleum. Many studies have been conducted on the production of oxygenated organic compounds from synthesis gas. For example, using iron-based catalysts for ammonia synthesis, synthesis gas is heated at a high space velocity of 8 to 25 atm and a temperature of 190 to 225°C. The ginol (Sy blood 1) method to obtain alcohols by reacting with water, or the iron catalyst with a large amount of alkali added at 10 to 30 atm, 210 to 180 qo, SVIOO ~
The oxyl (○ko 1) method has been known for a long time, in which alcohols are produced by using 50 and other r-1 and combining it with the oxo method. Recently, a methanol synthesis method using a zinc oxide/steel oxide catalyst has also been implemented industrially. However, the products obtained by the dino method and the oxyl method are mixtures of alcohols with a wide range of chain lengths, up to C, 8, and have poor selectivity, and in the methanol synthesis method, the product is limited to methanol, which is valuable. high ethanol and fluoride. . The drawback was that panol was not produced. Furthermore, the above-described method does not allow generation of organic acids such as acetic acid. On the other hand, recently, a method of selectively synthesizing C2 oxygen-containing compounds such as ethanol, acetaldehyde, and acetic acid using a rhodium-based catalyst has been studied.

for example,. Method for producing C2 oxygen-containing compounds using a dium catalyst (Japanese Patent Application Laid-open No. 51-80806), method for producing ethanol using a rhodium-iron catalyst (Special Publication No. 51-80807)
, a method for producing a C2-oxygen compound using a rhodium-mangaso catalyst (Japanese Patent Application Laid-Open No. 52-14706), a method for producing acetic acid using a rhodium/ruthenium catalyst (US Pat. No. 4,101,45)
JP-A-54-13850, a method for producing a C2 oxygen compound using a rhodium/halogen/magnesium catalyst
4) A method for producing ethanol using a rhodium/zirconium oxide/silica catalyst (Japanese Unexamined Patent Publication No. 56-147730) is known, but these methods have the disadvantage of using rhodium, an expensive precious metal that is produced in small quantities. Therefore, there is a wide demand for the development of a catalyst for synthesizing a useful lower oxygen-containing organic compound to replace rhodium. In order to solve the above-mentioned problems found in conventional methods, the present inventors have conducted intensive research on non-rhodium-based catalysts for selectively synthesizing lower oxygen-containing organic compounds from synthesis gas. On the other hand, the present inventors have found that when copper and/or molybdenum is added, the selectivity of oxygen-containing organic compounds is significantly increased, and the present invention has been completed.

That is, the present invention provides a method for producing a lower oxygen-containing organic compound from synthesis gas, in which the catalyst contains [a] nickel and 'b' at least one metal selected from steel and molybdenum as a catalytically active metal component. This method is characterized by using a supported catalyst. The fact that the selectivity of lower oxygen-containing organic compounds is significantly increased by the catalyst described above is truly surprising and unexpected.

This is because nickel is generally known as a catalyst for methane synthesis, copper as a catalyst that usually provides only methanol, and molybdenum was thought to have no effective catalytic ability for synthesis gas reactions. The catalyst used in the present invention is preferably produced by impregnating a catalyst carrier with a solution of a nickel salt, a copper salt and/or a molybdenum salt, and then drying the catalyst carrier.

In this case, these metal salts can be supported simultaneously or sequentially. As metal salts, all soluble nickel, copper and molybdenum salts are used, such as nitrates, halides, organic acid salts, ammonium salts, etc.
The salts mentioned above are dissolved in a suitable solvent. Suitable solvents include, for example, water, aqueous ammonia, and nitric acid. In addition to the impregnation method, an ion exchange method, a precipitation method, a kneading method, etc. can also be used as the supporting method. For example, in the case of the ion exchange method, the catalyst is produced by using a suitable asomine salt as the supported metal, immersing the carrier in this solution for an appropriate time to perform ion exchange, and then drying in an oven. Various porous materials can be used as the carrier. for example,
Silica, alumina, and other low group metal oxides may be used, with silica being most preferred. The dried catalyst is then reduced by a suitable reducing agent, such as hydrogen.

In this case, the appropriate reduction temperature is between 300 and 600 q○. Further, before the catalyst is subjected to the reduction treatment, it may be calcined with a suitable gas such as air, and the temperature at that time is suitably between 300 and 600 pm. The nickel content in the catalyst can vary over a very wide range, for example from 1% to 3% by weight. In the catalyst used in the method of the present invention, the selection and amount of the metal combined with nickel is particularly important.

That is, when producing alcohols and acetic acid (and esters) together, it is effective to combine only copper with nickel, and in this case, the amount of copper added is 0.01 to 1 part nickel by weight. 1 castle office is 0.1 to 5. If there is too little copper, there will be too much hydrocarbon richness. live,
If there is too much copper, the product obtained will be mostly methanol alone. On the other hand, when exclusively producing alcohols, it is effective to use nickel and molybdenum alone or in combination with molybdenum and copper. The amount of molybdenum added is 0.00 to 1 nickel by weight.
1-10, preferably 0.01-5. When molybdenum is added, a significant effect is obtained in that both the reaction activity and the selectivity for alcohols increase. When copper is further added together with molybdenum, the reaction activity decreases, but the effect of suppressing the by-product of hydrocarbons and increasing the selectivity of alcohols is obtained. In this case, the amount of copper added is 0.01 to 10 to 1 nickel in terms of weight ratio.
Preferably it is 0.1-5. The volumetric ratio of carbon monoxide to hydrogen in the raw synthesis gas used in the process of the invention can vary within a wide range, ranging from 20:1 to 1:2.
0, especially 5:1 to 1:5.

The raw material synthesis gas may also contain gases other than carbon monoxide and hydrogen, such as inert gases such as nitrogen, argon, and helium, and gases such as carbon dioxide and methane. The reaction temperature is generally from 100 to 400, preferably from 150 to
It is in the range of 350 qo. The reaction pressure is 1 to 300 k9/c flow, preferably 5 to 200 k9/c flow. A gas phase reaction is preferred for carrying out the reaction, for which a conventional fixed bed flow reactor can be used. The space velocity of the gas at this time can be varied within a wide range, and can vary from 10 to 100.
00 dishes r-1, preferably 50 to 1000 dishes r-1. According to the present invention, valuable products such as methanol, ethanol, n-propanol, and acetic acid (ester) can be produced from synthesis gas with high selectivity using catalysts made of inexpensive metals such as nickel, copper, and molybdenum. The method of manufacturing these products is highly practical, and the present invention can greatly contribute to saving petroleum resources.

Hereinafter, the present invention will be explained in more detail with reference to examples and comparative examples.

In addition, the meanings of the terms in the table are as follows.

C.

Reaction/rate (%)=A 小三×,o. A: Number of moles of carbon monoxide supplied B: Number of moles of carbon monoxide recovered Carbon efficiency (%) = C difference Xloo C: Number of moles of the product D: Number of carbon atoms of the product A, B :Has the same meaning as above.

Further, each symbol shown below means the following.

Me. Day,. ,,． , methanol, Et. Day,. ,...Ethanol, nP (3 days,...n-fu. Ro/Gnol, AC○Me...Methyl acetate, AcOEt.
...Ethyl acetate, CH4...Methane, C20...
...C2 or higher hydrocarbons, C02...carbon dioxide. Example 1 Dissolve nickel nitrate (Nj (N03) 2, clothes 20) 2.97 mm and nitric acid steel (Cu (N03) 2, 20) 0.57 mm in distilled water to make 18 regular customers. Pour the solution into Davison grade 57 silica gel (12-20 mesh) 15
After impregnating the saw and leaving it for 1 hour, it was dried using an evaporator under reduced pressure at 80°C for 1 hour and at 1100C for 1 hour.

After firing this in an air stream at 500 oo for 3 hours,
A supported catalyst containing 4% nickel and 1% copper was prepared by reduction treatment at 400oC in a hydrogen stream for 3 hours. Next, the prepared catalyst was taken in Step 13 and filled into a high pressure flow reactor.
Synthesis gas (carbon monoxide/hydrogen = 0.5) was heated to 6N/Hr.
(SV: 46 or r-1), and the reaction temperature was 28.
The reaction was carried out at a reaction pressure of 20 k9/m. in this case,
The reaction gas was directly introduced into a gas chromatograph through a gas sampler in a gaseous state to perform qualitative and quantitative analysis of the products. The results are shown in Table 1. It should be noted that the values shown in this table are the values at which steady activity was reached after one hour or more had elapsed from the start of the reaction. Free acetic acid, which is not an ester, is also produced with a carbon efficiency of several percent, but it is not shown in the table because the exact value could not be measured (Table 2
~The same applies to Table 4). Examples 2-5, Comparative Examples 1-
2 Using the same procedure as in Example 1, the total supported amount of nickel and copper was set at 5%, and various supported amounts were prepared by changing the ratio of each. Using this catalyst, reactions were carried out in the same manner as in Example 1. The results are shown in Table 1.

For comparison, the reaction results using supported catalysts of nickel alone (Comparative Example 1) and copper alone (Comparative Example 2) are also shown in Table 1. As can be seen from these results, nickel alone does not Most of the products are hydrocarbons, and copper alone is almost exclusively methanol, whereas in the binary nickel-copper system, ethanol, n-propanol,
It can be seen that the selectivity of C2 or higher oxygen-containing organic compounds such as methyl acetate and ethyl acetate is increased. Table-1 Examples 6 to 7 Using the catalyst prepared in Example 1, using the same machine as Example 1, the results were reacted at a reaction temperature of 26,000, Example 6, and the results of reaction at a reaction temperature of 30,000 were shown in Example 7. Table as -
Shown in 2.

The results of Example 1 in which the reaction was carried out at 2800° are also shown in Table-2.

This result shows that the selectivity of acetate ester is better at lower temperatures. Examples 8 to 10 Supported catalysts containing 8% nickel and 2% copper were prepared in the same manner as in Example 1 at various hydrogen reduction temperatures, and reactions were carried out in the same manner as in Example 1 using this catalyst. The results are shown in Table 3.

Table 2 Table 3 Example 11 A catalyst was prepared in the same manner as in Example 1 except that the supported amounts of nickel and copper were 5% and 2.5%, respectively. The reaction was carried out at a rate of 924r-1.

The results are shown in Table-4. Example 12 50 at the time of preparation
A catalyst was prepared in the same manner as in Example 11 except that air calcination was not performed at 0oo, and a reaction was performed using the obtained catalyst.

The results are shown in Table-4. Example 13 Nickel nitrate was weighed to give a weight of 5% nickel, made into an aqueous solution as in Example 1, impregnated into a silica carrier, dried, and air-calcined at 500° C. for 3 hours.

This was immersed in an ammonia aqueous solution of 0.2 hol of nitric acid steel weighed so that the amount of copper supported was 2.5%, left overnight to support the copper through ion exchange, and then passed through an oven and dried. After baking in the air for 3 hours at 400℃,
A catalyst was prepared by performing hydrogen reduction for a period of time in the same manner as in Example 1. Using this catalyst, a reaction was carried out in the same manner as in Example 11, and the results are shown in Table 4. Example 14 Nickel nitrate was weighed so that the amount of nickel supported was 5%, made into an aqueous solution as in Example 1, impregnated into a silica carrier, dried, and air-calcined at 500° C. for 3 hours.

This was impregnated with a nitric acid steel aqueous solution weighed so that the amount of copper supported was 2.5%, dried, air fired at 500 oo for 3 hours, and hydrogen reduction treated at 400 qo to remove nickel and copper. A two-stage supported catalyst was prepared. The results of a reaction carried out in the same manner as in Example 11 using this catalyst are shown below.
4. Example 15 Weighed nickel nitrate so that the amount of nickel supported was 5%, made it into an aqueous solution as in Example 1, impregnated it onto a silica carrier, dried it, and air-calcined it at 500°C.
Hydrogen reduction treatment was performed using 00 to prepare a nickel-supported catalyst.

This was impregnated with a nitric acid steel aqueous solution weighed so that the amount of copper supported was 2.5%, and after drying, hydrogen reduction treatment was performed at 300 oo for 3 hours to prepare a two-stage supported catalyst of nickel and copper. Table 4 shows the results of a reaction carried out in the same manner as in Example 11 using this catalyst. Table-4 Example 16 Nickel nitrate (Ni(N03)2・20) 2.97 hours, ammonium molybdate ((NH4)6Mo70)
Dissolve 0.14% of 24.4 ratio ○) in distilled water to make a constant volume of 18M, and add this solution to Davison Grade 57 silica gel (1
2 to 20 mesh) After soaking in 15 pieces of sawdust and leaving it for 1 hour,
Using an evaporator at 8,000 for 1 hour, at 11,000
It was dried for 1 hour.

This was calcined in an air stream at 50,000 Celsius for 3 hours, and then reduced in a hydrogen stream at 40,000 Celsius for 3 hours to prepare a supported catalyst containing 4% nickel and 0.5% molybdenum. This prepared catalyst was taken from i3 and charged into a high-pressure flow reactor, and 6N of synthesis gas (carbon monoxide/hydrogen = 0.5) was added to the reactor.
The reaction was carried out at a flow rate of 1/hr (SV=46 s/hr), a reaction temperature of 22,000, and a reaction pressure of 20 kg/hr. The results are shown in Table-5. Examples 17 to 19, Comparative Example 3 A catalyst in which nickel and molybdenum were supported in various ratios was prepared in the same manner as in Example 16, and a reaction was carried out in the same manner as in Example 16 using this catalyst. are shown in Table-5.

Table 5 also shows the reaction results using molybdenum as a single catalyst as Comparative Example 3.

Table 5 also shows the results of Comparative Example 1 using the aforementioned nickel-only catalyst. With a nickel-only catalyst, most of the products are hydrocarbons, but when molybdenum is added, the selectivity to alcohols such as methanol, ethanol, and n-propanol is greatly improved, and the reaction activity is also increased. . On the other hand, when using molybdenum alone, most of the products were hydrocarbons and carbon dioxide. Table 5 Example 20 2.97 ml of nickel nitrate, 0.57 ml of copper nitrate, and 0.14 ml of ammonium molybdate were dissolved in distilled water to make 18 [regular solution], and this solution was mixed with Davison grade 57 silica gel (12- 20 mesh) 15 sawdust soaked and left for 1 hour, then soaked at 80oo for 1 hour using an evaporator, 11
000 for 1 hour.

After firing this in an air stream at 500℃ for 3 hours,
Nickel 4
%, 1% copper, and 0.5% molybdenum. Table 6 shows the results of a reaction using this catalyst at a reaction temperature of 24,000, a reaction pressure of 20 kg/earth, and a space velocity of 924 hr-1. From the results shown in Table 6,
It can be seen that alcohols are produced with good selectivity. Examples 21-25 Using the catalyst of Example 20, various temperatures,
The reaction was carried out in the same manner as in Example 20 at the space velocity, and the results are shown in Table 16.

Table 6 Examples 26 to 29 Various amounts of nickel, copper, and molybdenum were prepared by the same method as in Example 20, and the reaction temperature was 2600.
0, and the reaction was carried out at a space velocity of 462 hr-1.

The results are shown in Table-7. Examples 30-31 Catalysts were prepared in the same manner as in Example 20, except that air calcination was not performed at 50,000 ℃ during preparation, and the reaction temperature was 260 ℃.
The reaction was carried out at 0.00.

The results are shown in Table-8. Examples 32 to 33 Using the method of Example 1, a permanent catalyst containing 4% nickel and 1% copper was prepared.

This was impregnated with an aqueous solution of ammonium molybdate of 0.14 μm, and heated to 1100° C. for 1 hour at 8,000° C. using an evaporator.
It was dried at 0 for 1 hour. Thereafter, a reduction treatment was performed at 40,000 ℃ for 3 hours in a hydrogen stream to prepare a two-stage supported molybdenum/nickel-copper catalyst. Using this, a reaction was carried out at 26,000, and the results are shown in Table 8. It can be seen that good alcohol selectivity can be obtained even if the specific support method for nickel, copper, and molybdenum is changed. Table-7 Table-8

Claims (1)

[Claims] 1. In a method for producing lower oxygen-containing compounds from carbon monoxide and hydrogen, (a) nickel and (b)
A method for producing a lower oxygen-containing organic compound, which comprises using a supported catalyst containing at least one metal selected from copper and molybdenum as a catalytically active metal component.