KR20230094327A - Method for producing isopropanol by acetone hydrogenation - Google Patents

Abstract

The present disclosure relates to a method for producing isopropanol through acetone hydrogenation using a catalyst containing nickel. The method for producing isopropanol according to one embodiment includes the step of resupplying a certain amount of reaction products of the acetone hydrogenation reaction to the top of a reactor, thereby enabling effective heat control and producing high purity isopropanol in high yield through an economical process.

Description

Method for producing isopropanol by hydrogenation of acetone {Method for producing isopropanol by acetone hydrogenation}

The present disclosure relates to a method for producing isopropanol through acetone hydrogenation using a catalyst comprising nickel.

Isopropanol is an aliphatic saturated alcohol that is an isomer of propanol. It is volatile and flammable, and is highly soluble in other hydrocarbon solvents, so it is used as a solvent or as a disinfectant, preservative, and antifreezing agent. In addition, isopropanol can also be used as a raw material for producing cumene, isopropylamine, isopropyl ether, and the like, and is widely used in the field of industrial raw materials or organic synthesis.

As a method for producing isopropanol, a method of producing isopropanol by hydrolyzing propylene obtained from petroleum using an acid as a catalyst or producing isopropanol by hydrogenating acetone is known.

Regarding a method for producing isopropanol using acetone, Chinese Patent Publication CN 1027283614 A discloses a method for producing isopropanol through acetone hydrogenation using a catalyst containing nickel, and Chinese Patent Publication CN 113024351 A discloses a nickel- Disclosed is a method for producing isopropanol through acetone hydrogenation using an alumina catalyst, which includes cooling a portion of the reaction product and then reintroducing it into the reactor.

One object of the present invention is to provide a method for producing high purity isopropanol in high yield using a catalyst containing nickel.

In one embodiment, injecting a reactant containing acetone to the top of the reactor in which the inlet temperature is maintained at T ₁ ℃; hydrogenating acetone in the presence of a catalyst loaded into the reactor; Recovering a product containing isopropanol from the bottom of the reactor; resupplying a portion of the recovered product to the top of the reactor at a recycle ratio R defined by the following relational expression 1; and introducing the product into a purification column to purify isopropanol; It provides a method for producing isopropanol comprising a.

In this case, the catalyst may include an alumina-based carrier supported with an active metal including nickel, and the hydrogenation reaction is performed with Weight Hourly Space Velocity (WHSV) V h ^-1 , maximum reaction temperature T _max , and It can be performed at a pressure of 18 kg/cm ² or higher.

In addition, the method for producing isopropanol may satisfy the following relational expression 2.

[Relationship 1]

Recycle ratio (R) = (mass flow rate of resupplied product)/(mass flow rate of acetone input)

[Relationship 2]

{R x (T _max - T ₁ )} / T ₁ ≥ 6.3

The present disclosure relates to a method for producing isopropanol through acetone hydrogenation using a catalyst containing nickel. It is possible to effectively control heat generation by including the step of doing, and it is possible to produce high-purity isopropanol with high yield in an economical process.

Hereinafter, the present invention will be described in detail.

Meanwhile, the embodiments of the present invention may be modified in various forms, and the scope of the present invention is not limited to the embodiments described below. In addition, the embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art. Furthermore, "include" a certain component throughout the specification means that other components may be further included without excluding other components unless otherwise stated.

One embodiment provides a method for producing isopropanol comprising the following steps:

Injecting a reactant containing acetone into the upper part of the reactor where the inlet temperature is maintained at T ₁ °C;

hydrogenating acetone in the presence of a catalyst loaded into the reactor;

Recovering a product containing isopropanol from the bottom of the reactor;

resupplying a portion of the recovered product to the top of the reactor at a recycle ratio R defined by the following relational expression 1; and

[Relationship 1]

Recycle ratio (R) = (mass flow rate of resupplied product)/(mass flow rate of acetone input)

Introducing the product to a purification column to purify isopropanol.

At this time, the catalyst includes an alumina-based carrier on which an active metal containing nickel is supported,

The hydrogenation reaction is carried out at a weight hourly space velocity (WHSV) V h ^-1 , a maximum reaction temperature T _max , and a pressure of 18 kg/cm ² or more,

In addition, the method for producing isopropanol satisfies the following relational expression 2:

[Relationship 2]

{R x (T _max - T ₁ )} / T ₁ ≥ 6.3 .

A method for producing isopropanol according to an embodiment is {R x (T _max - T ₁ )} / T according to the relational expression 2 with inlet temperature (T ₁ ), maximum reaction temperature T _max , and recycle ratio (R) as variables. The value of ₁ is 6.3 or more, and at the same time, the hydrogenation reaction is performed at a pressure of 18 kg/cm ² or more, so it has excellent conversion rate and selectivity.

In one embodiment, the pressure condition is, for example, 20 kg/cm ² or more, 18 kg/cm ² to 50 kg/cm ² , 18 kg/cm ² to 40 kg/cm ² , 20 kg/cm ² to 50 kg/cm ² , 20 kg/cm ² to 40 kg/cm ² , 18 kg/cm ² to 35 kg/cm ² , 20 kg/cm ² to 35 kg/cm ² , or 20 kg/cm ² to 30 kg / cm ² may be, but is not limited to the above range.

In an embodiment, the {R x (T _max - T ₁ )} / T ₁ value according to the relational expression 2 is, for example, 6.3 or more, 6.4 or more, 10.0 or less, 6.3 or more and 9.0 or less, 6.3 or more, 8.5 or less, or 6.3 or more. It may be 8.0 or less, 6.4 or more and 8.5 or less, or 6.4 or more and 8.0 or less, but is not limited to the above range.

In the method for producing isopropanol according to an embodiment, isopropanol can be produced with high conversion and selectivity by introducing reactants for acetone hydrogenation including acetone and hydrogen from the top to the bottom of the reactor.

In one embodiment, the maximum reaction temperature T _max of the hydrogenation reaction may be, for example, 120 °C to 150 °C, 125 °C to 150 °C, or 130 °C to 150 °C, but is not limited thereto.

In one embodiment, the inlet temperature T ₁ may have a value that is not limited within the range according to the relational expression 2, but is, for example, 30 ℃ to 60 ℃, 35 ℃ to 60 ℃, greater than 35 ℃ 60 less than 35 °C, greater than 35 °C and less than 55 °C, 35 °C to 55 °C, or 35 °C to 50 °C. In one embodiment, the inlet temperature may mean the temperature of an upper bed among a plurality of beds constituting the reactor, or a separate device (eg, a pre-heater) is used before injecting the reactant into the reactor It may also mean the temperature of a reactant (eg, acetone, hydrogen, and a product to be resupplied) adjusted by the above process. In one embodiment, the efficiency of the acetone hydrogenation reaction may be increased by controlling the inlet temperature T ₁ .

In one embodiment, the recycling ratio R may have a value that is not limited within the range according to the relational expression 2, but is, for example, 2.0 to 5.0, 2.0 to 4.0, 2.5 to 4.0, or 2.5 to 4.5 days. can An isopropanol production method according to an embodiment includes the step of resupplying a portion of the reaction product to the top of the reactor according to the recycle ratio, thereby effectively controlling heat generation in the reactor.

In one embodiment, the mass space velocity V may have a value that is not limited within the range according to the relational expression 2, but is, for example, 1.0 h ^-1 to 4.0 h ^-1 , or 1.5 h ^-1 to 4.0 h ^-1 , 2.0 h ^-1 to 4.0 h ^-1 , or 2.0 h ^-1 to 3.5 h ^-1 .

In one embodiment, the hydrogenation reaction may be performed by adding hydrogen so that the ratio of the number of moles of hydrogen to the number of moles of acetone is 1.0 to 2.0 or 1.0 to 1.8.

In one embodiment, the content of the active metal in the catalyst may be, for example, 20% to 40% by weight, 20% to 35% by weight, 20% to 30% by weight, or 20% to 25% by weight, , It is not limited to the above range. In addition, in one embodiment, the active metal may further include, in addition to nickel, an active metal commonly used in metal catalysts, for example, one of platinum, palladium, ruthenium, rhodium, and any two or more alloys thereof It may further include more than one.

In one embodiment, purifying the isopropanol may include sequentially introducing the product into a lights column and a heavy column. For example, water (moisture), acetone, diisopropyl ether (DIPE), etc. can be separated and purified through the light column, and 4-methyl-2-pentanol (MPOL), hexylene glycol through the heavy column (HG) and the like can be separated and purified. In the case of purification using two columns according to the above embodiment, moisture and/or impurities can be more effectively removed.

In one embodiment, the water content of the product can be effectively removed through the purification step, and the water content of the purified product is, for example, about 500 ppm (wt / wt) or less, 400 ppm (wt / wt) or less, 300 ppm ( wt/wt) or less or 100 ppm (wt/wt) to 300 ppm (wt/wt), but is not necessarily limited to the above range. In one embodiment, the method for producing isopropanol can lower the water content of about 2000 ppm to 3000 ppm before purification to the water content in the above range by performing a purification step.

In the isopropanol production method according to an embodiment, the conversion rate of acetone to isopropanol may be 95.0% or more, 97.0% or more, 98.0% or more, or 99.0% or more, and/or selectivity for isopropanol is 98.0% or more, or 99.0% may be ideal

Each step included in the isopropanol production method may be performed continuously to produce isopropanol in a continuous manner, or a series of processes may be repeated several times. In addition, the method for producing isopropanol may be performed by further combining conventional steps in the art.

Hereinafter, examples and experimental examples of the present invention will be specifically illustrated and described. However, the examples to be described later are merely illustrative of a part of the present invention, and the present invention is not limited thereto.

< Example >

After filling 58 g of catalyst (Ni 20.7wt%, Al ₂ O ₃ 79.3 wt%) in the second and third beds from the top of a tubular reactor with a diameter of 2.54 cm and a length of 60 cm composed of four beds, After adjusting the temperature of the central part of the first bed in the upper part to the temperature of the reactant inlet in Table 1 below, acetone and hydrogen as reactants were introduced into the upper part of the reactor. At this time, the hydrogenation reaction was performed by setting the injection rate of the reactants (mass space velocity (WHSV)), the maximum temperature of the reactor, the pressure condition, and the molar ratio of acetone and hydrogen as shown in Table 1 below. A product containing isopropanol was recovered from the bottom of the reactor, and a part of the recovered product was re-supplied to the top of the reactor at a recycle ratio according to Table 1. Then, the product recovered from the bottom of the reactor was sequentially introduced into a light column (stage 40) and a heavy column (stage 45) to obtain a final product after purification, which was analyzed by gas chromatography to determine the mass fraction of the product ), isopropanol conversion and selectivity were calculated. The results are shown in Table 2 and Table 3 below.

< comparative example >

The acetone hydrogenation reaction was performed in the same manner as in the above example, but by setting the reaction process conditions as shown in Table 1 below. The final product was obtained and analyzed by gas chromatography in the same manner as in the above example, and the results are shown in Tables 2 and 3 below.

WHSV
(V, h ^-1 ) Hydrogen/acetone molar ratio Recycle Rate (R) enter
(kg/cm ² ) inlet
Temperature (T ₁ , ℃) reaction temperature
(max, ℃) {R x (T _max - T ₁ )} / T ₁ Example 1 2.20 1.50 2.87 20.00 39.41 131.75 6.7 Example 2 3.04 1.50 2.87 20.00 40.00 133.40 6.7 Example 3 2.52 1.51 2.90 20.00 40.50 130.50 6.4 Example 4 2.52 1.11 2.93 20.00 40.40 135.60 6.9 Example 5 2.53 1.11 2.89 20.00 35.00 129.00 7.8 Example 6 2.54 1.10 2.90 30.00 39.67 136.50 7.1 Example 7 3.03 1.10 2.93 20.00 45.17 145.00 6.5 Example 8 3.03 1.10 3.89 20.00 50.75 142.75 7.1 Example 9 3.03 1.10 2.44 20.00 40.67 147.00 6.4 Comparative Example 1 2.52 1.11 2.94 15.00 39.33 134.00 7.1 Comparative Example 2 3.02 1.11 2.95 20.00 49.50 150.25 6.0 Comparative Example 3 3.95 1.13 2.98 20.00 50.00 154.33 6.2

(In Table 1, {R x (T _max - T ₁ )} / T ₁ values are rounded to the second decimal place)

weight% acetone IPA DIPE MPOL HG etc total Example 1 0.38 99.40 0.15 0.01 0.04 0.02 100 Example 2 1.02 98.78 0.11 0.01 0.06 0.01 100 Example 3 1.26 98.51 0.17 0.01 0.05 0.01 100 Example 4 1.29 98.41 0.23 0.01 0.04 0.01 100 Example 5 4.06 95.71 0.14 0.01 0.06 0.01 100 Example 6 1.08 98.49 0.38 0.01 0.03 0.02 100 Example 7 2.09 97.31 0.50 0.01 0.05 0.02 100 Example 8 1.89 97.54 0.49 0.01 0.04 0.02 100 Example 9 2.67 96.67 0.54 0.02 0.06 0.03 100 Comparative Example 1 5.24 94.32 0.30 0.01 0.06 0.06 100 Comparative Example 2 1.84 97.32 0.74 0.02 0.05 0.04 100 Comparative Example 3 2.52 96.58 0.78 0.02 0.05 0.04 100

Conversion rate (%) Selectivity (%) Example 1 99.62 99.67 Example 2 98.98 99.74 Example 3 98.74 99.69 Example 4 98.71 99.60 Example 5 95.94 99.78 Example 6 98.92 99.39 Example 7 97.91 99.21 Example 8 98.12 99.22 Example 9 97.33 99.15 Comparative Example 1 94.76 99.53 Comparative Example 2 98.17 98.87 Comparative Example 3 96.95 98.90

As shown in Table 2 and Table 3, all examples in which the {R x (T _max - T ₁ )} / T ₁ value satisfies 6.3 or more and the reaction pressure is 18 kg/cm ² or more have an isopropanol conversion rate. It was 95.0% or more, and the selectivity was very excellent at 99.0% or more. On the other hand, Comparative Example 1 having {R x (T _max - T ₁ )} / T ₁ value of 6.3 or more but low pressure and Comparative Example 2 and Comparative Example 2 having {R x (T _max - T ₁ )} / T ₁ value of less than 6.3 In the case of Example 3, it was found that the conversion rate and selectivity were lower than those of Examples.

In the above, the present invention has been described in detail through preferred embodiments, but the scope of the present invention is not limited to specific embodiments, and should be interpreted by the appended claims. In addition, those skilled in the art should understand that many modifications and variations are possible without departing from the scope of the present invention.

Claims (12)

Injecting a reactant containing acetone into the upper part of the reactor where the inlet temperature is maintained at T ₁ °C;
hydrogenating acetone in the presence of a catalyst loaded into the reactor;
Recovering a product containing isopropanol from the bottom of the reactor;
resupplying a portion of the recovered product to the top of the reactor at a recycle ratio R defined by the following relational expression 1; and
introducing the product into a purification column to purify isopropanol; including,
The catalyst includes an alumina-based carrier on which an active metal containing nickel is supported,
The hydrogenation reaction is carried out at a weight hourly space velocity (WHSV) V h ^-1 , a maximum reaction temperature T _max , and a pressure of 18 kg/cm ² or more,
A method for producing isopropanol that satisfies the following relational expression 2:
[Relationship 1]
Recycle ratio (R) = (mass flow rate of resupplied product)/(mass flow rate of acetone input)
[Relationship 2]
{R x (T _max - T ₁ )} / T ₁ ≥ 6.3 .
According to claim 1,
The maximum reaction temperature T _max of the hydrogenation reaction is 120 ℃ to 150 ℃, isopropanol production method.
According to claim 1,
The inlet temperature T ₁ is 30 ℃ to 60 ℃, isopropanol production method.
According to claim 1,
The recycle ratio R is 2.0 to 5.0, a method for producing isopropanol.
According to claim 1,
The mass space velocity V is 1.0 h ^-1 to 4.0 h ^-1 , isopropanol production method.
According to claim 1,
The hydrogenation reaction is a method for producing isopropanol, which is reacted by adding hydrogen so that the ratio of the number of moles of hydrogen to the number of moles of acetone is 1.0 to 2.0.
According to claim 1,
The active metal content in the catalyst is 20% to 40% by weight, a method for producing isopropanol.
According to claim 1,
The active metal further comprises at least one metal selected from the group consisting of platinum, palladium, ruthenium and rhodium.
According to claim 1,
Purifying the isopropanol comprises introducing the product into a lights column and a heavy column in sequence.
According to claim 1,
A method for producing isopropanol, wherein the conversion rate of acetone to isopropanol is 95.0% or more.
According to claim 1,
A method for producing isopropanol, wherein the isopropanol selectivity is 98.0% or more.
According to claim 1,
The product purified through the purification step has a water content of 300 ppm (wt / wt) or less, isopropanol production method.