KR20210039216A - Process for producing methacrylic acid and methylmethacylate - Google Patents

Abstract

The present invention relates to a method for producing methacrylic acid and methyl methacrylate. According to the present invention, the lifetime of a catalyst is improved, and methacrylic acid and methyl methacrylate can be obtained in equal yields.

Description

Manufacturing method of (meth)acrylic acid and methyl methacrylate {PROCESS FOR PRODUCING METHACRYLIC ACID AND METHYLMETHACYLATE}

The present invention relates to a method for producing (meth)acrylic acid and methyl methacrylate.

The process of producing unsaturated fatty acids from olefins via unsaturated aldehydes corresponds to a typical catalytic partial oxidation. In the partial oxidation reaction of olefins, molybdenum oxide, bismuth oxide, and transition metal compounds are used to prepare a catalyst, and a process of oxidizing propylene or isobutylene to produce (meth)acrylic acid via (meth)acrolein, naphthalene or orthoxylene ( Ortho-xylene) is oxidized to produce phthalic anhydride, or benzene, butylene, or butadiene is partially oxidized to produce maleic anhydride.

The partial oxidation reaction generally proceeds in two stages. In the first-stage catalytic reaction, propylene or isobutylene is oxidized by oxygen, diluted inert gas, water vapor, and an arbitrary amount of catalyst to mainly produce (meth)acrolein, and the second-stage catalytic reaction is also oxygen, diluted inert gas, water vapor. And (meth)acrolein is oxidized by an arbitrary amount of catalyst to produce (meth)acrylic acid.

The catalyst for producing (meth)acrylic acid based on heteropolyacid is a catalyst with a unique property that simultaneously functions as an acid catalyst and an oxidation catalyst. There are various factors, such as a decrease in the conversion rate of isobutylene in the reaction of the first step, an alkali metal ion exchange method when preparing a heteropolyacid catalyst, and thermal shock due to rapid activity. In particular, since the collapse of the catalyst structure due to long-term operation necessarily accompanies the characteristics of the catalyst, studies such as introduction of various alkali metals have been conducted in order to overcome this and extend the life of the catalyst.

In most process operations, the activity of the heteropolyacid catalyst decreases over time, resulting in an increase in unreacted (meth)acrolein, which is a second-stage catalytic reactor along with the (meth)acrolein produced in the first step reaction after a purification process. Flows into. At this time, due to the decrease in the activity of the second-stage catalyst, the amount of (meth)acrolein reused gradually increases, so that the concentration of (meth)acrolein at the inlet of the second catalyst reactor continuously increases. For the safety of the process operation, if the concentration of (meth)acrolein increases, the reaction conditions get out of the reaction conditions and the explosion limit is approached.Therefore, the excess (meth)acrolein in the process is incinerated to operate in a direction to stabilize the process, which acts as a significant loss. This leads to a decrease in productivity.

In order to minimize the side effects caused by the decrease in catalytic activity as described above, Asahi Caseiwa Evonik (EVONIC) developed a direct oxidative esterification (DOE) technology in which (meth)acrolein was introduced into oxygen and methanol under a noble metal catalyst to operate the commercialization process. However, this process has limitations due to inefficiencies such as high cost and high pressure operation.

Meanwhile, typically, methyl methacrylate is prepared by esterification of (meth)acrylic acid and methanol produced through a two-step partial oxidation reaction of isobutylene. However, in the above method, since the produced (meth)acrylic acid is used as a reactant, and a number of steps are required to prepare methyl methacrylate, the reaction process is inefficient and complicated.

Thus, in the present invention, by providing a method for producing (meth)acrylic acid and methyl methacrylate, it is intended to prevent deterioration of catalytic activity and to efficiently produce methylmethyl methacrylate and (meth)acrylic acid.

Korean Patent Publication No. 10-2018-0055154 Chinese Patent Publication No. 101073776

The present invention is to provide a method for producing (meth)acrylic acid and methylmethacrylate, which can obtain (meth)acrylic acid and methylmethacrylate in an equivalent level of yield while enabling improvement of catalyst life.

The present invention comprises the step of reacting a raw material containing (meth) acrolein, a molecular oxygen-containing gas and methanol in the presence of a metal oxide catalyst represented by the following formula (1), (meth) acrylic acid and methyl methacrylate Provides a manufacturing method:

[Formula 1]

Mo _a A _b B _c C _d D _e E _f O _g

In Formula 1,

Mo is molybdenum,

A is at least one element selected from the group consisting of W and Cr,

B is at least one element selected from the group consisting of P, As and Si,

C is at least one element selected from the group consisting of B, Ce, Pb, Mn, V, Nb and Te,

D is at least one element selected from the group consisting of Al, Zr, Rh, Cu, Ni, Ti, Ag, Sb, Fe, Co, and Sn,

E is one or more elements selected from the group consisting of Na, K, Li, Rb, Cs, Ta, Ca, Mg, Sr and Ba,

a, b, c, d, e, f and g are the atomic ratios of each element,

When a=12, b is 0.01 to 15, c is 0.01 to 15, d is 0 to 20, e is 0.01 to 20, f is 0 to 20, and g is the oxidation state of each element. It is a number that is determined accordingly.

Hereinafter, the present invention will be described in detail.

The terminology used herein is for reference only to specific embodiments and is not intended to limit the invention. In addition, the singular forms used herein also include plural forms unless the phrases clearly represent the opposite meaning.

As used herein, the meaning of'comprising' or'containing' specifies a specific characteristic, region, integer, step, action, element, or component, and of another specific characteristic, region, integer, step, action, element, or component. It does not exclude additions.

In the present specification, terms including ordinal numbers such as'first' and'second' are used for the purpose of distinguishing one component from other components, and are not intended to limit the component by the ordinal number.

Conventional methyl methacrylate was prepared by esterification reaction of (meth)acrylic acid obtained through a two-step partial oxidation reaction of isobutylene with methanol. However, during the two-step oxidation reaction, (meth)acrolein, which is a product of the first step reaction and a reactant of the second step, accumulates in the reactor due to deterioration of catalytic activity in repeated production processes. Accumulated (meth) acrolein can cause an explosion, so excess (meth) acrolein is incinerated to stabilize the process, which causes a significant loss.

However, when the production method of the present invention is applied to the second step of oxidizing (meth)acrolein to (meth)acrylic acid during the two-step partial oxidation reaction, (meth)acrolein is directly used as a reactant for producing methylmethacrylate. As a result, the (meth)acrolein accumulated is minimized, and accordingly, the life of the catalyst used in the reaction is extended, thereby promoting an increase in the yield of the overall process. In addition, methyl methacrylate in addition to (meth)acrylic acid can be obtained in an equivalent level of yield.

Metal oxide catalyst

The metal oxide catalyst of the present invention is used to efficiently produce (meth)acrylic acid by oxidizing (meth)acrolein. In particular, when the catalyst of the present invention is used in the second step of the two-stage partial oxidation reaction of isobutylene, it helps the oxidation of (meth)acrolein to (meth)acrylic acid, and in addition to (meth)acrolein, methanol is used as a reactant. When included, methyl methacrylate can be produced simultaneously with (meth)acrylic acid.

Preferably, the metal oxide catalyst may be represented by the following Formula 1-1:

[Formula 1-1]

Mo _a Sb _h Cs _i A _b B _c C _d D _e E _f O _g

In Formula 1-1,

Mo is molybdenum,

A is at least one element selected from the group consisting of W and Cr,

B is at least one element selected from the group consisting of P, As and Si,

C is at least one element selected from the group consisting of B, Ce, Pb, Mn, V, Nb and Te,

D is one or more elements selected from the group consisting of Al, Zr, Rh, Cu, Ni, Ti, Ag, Fe, Co, and Sn,

E is one or more elements selected from the group consisting of Na, K, Li, Rb, Cs, Ta, Ca, Mg, Sr and Ba,

a, b, c, d, e, f and g are the atomic ratios of each element,

When a=12, b is 0.01 to 15, c is 0.01 to 15, d is 0 to 20, e is 0.01 to 20, f is 0 to 20, and g is the oxidation state of each element. It is a numerical value determined accordingly, h is 0 to 20, and i is 0 to 20.

Preferably, in Formula 1-1, h is 0.01 to 20, and i is 0.01 to 20.

Preferably, the metal oxide catalyst may be represented by the following Formula 1-2:

[Formula 1-2]

Mo ₁₂ W _b P _c V _d Cu _e Sb _h Cs _i O _g

In Formula 1-2,

Mo is molybdenum, W is tungsten, P is phosphorus, V is vanadium, Cu is copper, Sb is antimony, Cs is cesium,

b, c, d, e and g are the atomic ratios of each element,

b is 0.05 to 0.15, c is 1 to 1.5, d is 0 to 0.5, e is 0.01 to 0.5, g is a value determined according to the oxidation state of each element, h is 0.01 to 0.5, i is from 0.5 to 1.5.

More preferably, the metal oxide catalyst represented by Formula 1-2 may have a composition of _{P 1.2} Mo ₁₂ W _0.1 V _0.2 Cu _0.2 Sb _0.1 Cs _{1.0 excluding oxygen.}

Preferably, the metal oxide catalyst may be represented by the following Formula 1-3:

[Formula 1-3]

Mo ₁₂ P _c V _d Cu _e Sb _h Cs _i O _g

In Formula 1-3,

Mo is molybdenum, P is phosphorus, V is vanadium, Cu is copper, Sb is antimony, Cs is cesium,

b, c, d, e and g are the atomic ratios of each element,

c is 1 to 1.5, d is 0.5 to 1.5, e is 0.01 to 1, g is a value determined according to the oxidation state of each element, h is 0.01 to 0.5, and i is 1 to 1.5.

More preferably, the metal oxide catalyst represented by Formula 1-3 may have a composition of _{P 1.3} Mo ₁₂ V _1.0 Cu _0.5 Sb _0.3 Cs _{1.2 excluding oxygen.}

The composition of the metal oxide catalyst can be confirmed through ICP-mass analysis. As an example, the composition of the catalyst can be confirmed through elemental analysis after sample preparation using an Agilent 7500 and a microwave sample pretreatment device.

There is no particular limitation on the raw material compound used in the formation of the metal oxide catalyst, and it may be applied by combining an ammonium salt, nitrate, carbonate, chloride, lactate, hydroxide, organic acid salt, oxide, or mixture thereof of the metal element.

The metal oxide catalyst comprises: preparing a suspension obtained by dissolving or dispersing the raw material compound in water; Drying the suspension to obtain a solid; Molding the solid material into an appropriate shape; And it can be prepared by a method comprising the step of sintering the molded solid.

In addition, the metal oxide catalyst may be used by being supported on an inert carrier. For example, the inert carrier is SiO ₂ , Al ₂ O ₃ , MgO, MgCl ₂ , CaCl ₂ , ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ , SiO ₂ -Al ₂ O ₃ , SiO ₂ -MgO, SiO ₂ -TiO ₂ , SiO ₂ -V ₂ O ₅ , SiO ₂ -CrO ₂ O ₃ , SiO ₂ -TiO ₂ -MgO, and at least one compound selected from the group consisting of zeolite have. When the inert carrier is used, a step of contacting and supporting the suspension with the inert carrier before performing the drying step may be additionally performed.

There is no particular limitation on the shape of the metal oxide catalyst, and a spherical shape, a cylindrical shape, a hollow shape, a ring shape, an irregular shape, and the like may be applied.

As for the size of the metal oxide catalyst, in the case of a cylindrical shape, the ratio (L/D) of the length (L) and the outer diameter (D) of the catalyst is preferably 0.5 to 1.3; In the case of cylindrical and spherical, the outer diameter (D) of the catalyst is preferably 3 to 10 mm.

On the other hand, the metal oxide catalyst of the present invention may be used by being charged in a reactor. The reactor is not particularly limited, but a conventional one having a circular cross-sectional shape may be used. The inner diameter and length of the reactor may be determined within a range capable of filling a catalyst and an inert material and expressing an appropriate reaction efficiency. Preferably, the reactor may have an inner diameter of 15 mm to 100 mm and a length of 0.1 m to 10 m.

Method for producing (meth)acrylic acid and methyl methacrylate

The production method of (meth)acrylic acid and methylmethacrylate of the present invention is a method of simultaneously producing (meth)acrylic acid and methylmethacrylate, and in the presence of the above-described metal oxide catalyst, (meth)acrolein, molecular oxygen It is obtained by reacting the containing gas and methanol.

The molecular oxygen-containing gas refers to a gas composition containing _{oxygen (O 2 ).} In the present invention, the molecular oxygen-containing gas is used to oxidize (meth)acrolein to (meth)acrylic acid and methyl methacrylate, and methanol is used as a reactant for introducing a methoxy substituent into methyl methacrylate. In particular, in the above production method, methyl methacrylate is produced by directly reacting (meth)acrolein and methanol.

When preparing the (meth)acrylic acid and methylmethacrylate, based on the total reactants, (meth)acrolein is 3 to 5 mol%, methanol is 5 to 15 mol%, molecular oxygen (O ₂ ) is 6 to 15 mol %, nitrogen (N ₂ ) 55 to 77 mol%, water vapor (H ₂ O) 5 to 10 mol% may be used.

When preparing the (meth)acrylic acid and methyl methacrylate, the space velocity of (meth)acrolein may be ^{300 to 900 hr -1.}

When preparing the (meth)acrylic acid and methyl methacrylate, the reaction temperature may be 250 to 310 °C.

When preparing the (meth)acrylic acid and methyl methacrylate, the reaction pressure may be 0.1 to 3 kg/cm ² .

Preferably, the molar ratio (m2/m1) of (meth)acrolein (m1) and oxygen (m2) in the molecular oxygen-containing gas may be 2 to 100. Preferably, the molar ratio (m2/m1) of the (meth)acrolein and oxygen in the molecular oxygen-containing gas may be 2 to 50, 2 to 30, 2 to 10, or 2 to 7. When the molar ratio (m2/m1) of oxygen in the (meth)acrolein and molecular oxygen-containing gas is less than 2, the catalytic activity decreases, and the molar ratio of oxygen in the (meth)acrolein and molecular oxygen-containing gas (m2/m1) If the value exceeds 100, the operating condition in the reactor approaches the explosive range, and process safety cannot be maintained.

Preferably, the molar ratio (m3/m1) of (meth)acrolein (m1) and methanol (m3) may be 1 to 100. Preferably, the molar ratio (m3/m1) of the (meth)acrolein and methanol may be 1 to 50, 1 to 30, 1 to 10, or 1 to 7. When the molar ratio (m3/m1) of the (meth)acrolein and methanol is less than 1, the productivity of methylmethacrylate decreases, and when the molar ratio of (meth)acrolein and methanol (m3/m1) exceeds 100, excessive Process operation becomes unstable due to methanol.

The conversion rate of (meth)acrolein and the yield of (meth)acrylic acid and methyl methacrylate prepared according to the preparation method can be calculated by the following Equations 1 to 3.

[Equation 1]

Conversion rate of (meth)acrolein (%) = [(number of moles of reacted (meth)acrolein)/(number of moles of supplied (meth)acrolein)] * 100

[Equation 2]

Yield (%) of (meth)acrylic acid = [(number of moles of (meth)acrylic acid produced)/(number of moles of supplied (meth)acrolein)] * 100

[Equation 3]

The yield of methyl methacrylate (%) = [(number of moles of methyl methacrylate produced) / (number of moles of supplied (meth) acrolein)] * 100

In Equations 1 to 3, the number of moles of each gas can be measured by Gas Chromatography. As an example, the Gas Chromatography can be measured by analyzing with the Agilent 6890 Gas Chromatography System. Specifically, the reaction gas flowing from the bench pilot is supplied to the column through an automatic valve system, and FID: H-1000 capillary, TCD Porapak-Q, It can be analyzed with an MS-5A column.

The yield of the (meth)acrylic acid prepared by the manufacturing method may be 30 to 60%, 30 to 50%, 30 to 40%, or 30 to 37%.

The yield of the methyl methacrylate prepared by the above manufacturing method may be 30 to 60%, 30 to 50%, 30 to 45%, or 35 to 45%.

Preferably, the yield of the (meth)acrylic acid prepared by the manufacturing method is 30 to 60%, 30 to 50%, 30 to 40%, or 30 to 37%, and the yield of methyl methacrylate is 30 To 60%, 30 to 50%, 30 to 45%, or 35 to 45%.

On the other hand, the manufacturing method of (meth)acrylic acid and methyl methacrylate may be applied to the process without particular limitation, may be performed alone, or may be applied as part of other processes. For example, it may be applied to the second step of the two-stage partial oxidation reaction of isobutylene, in which case (meth)acrolein, which is the product of the first step of the second-stage partial oxidation reaction, can be used as the reactant of the second step. have. That is, the (meth)acrolein used in the method for producing (meth)acrylic acid and methylmethacrylate is a gas phase catalytic oxidation reaction of a reactant containing isobutylene with a molecular oxygen-containing gas in the presence of the above-described metal oxide catalyst. It may be obtained by doing.

The production method of (meth)acrylic acid and methylmethacrylate of the present invention directly introduces methanol to the oxidation of (meth)acrolein to improve the life of the catalyst while obtaining (meth)acrylic acid and methylmethacrylate in an equivalent level of yield. Provides a way to do it.

Hereinafter, it will be described in more detail to aid in understanding the present invention. However, the following examples are merely illustrative of the present invention, and the contents of the present invention are not limited by the following examples.

Preparation Example 1: Preparation of catalyst 1

In 3000 mL of ultrapure water, ammonium paramolybdate ((NH ₄ ) ₆ Mo ₇ O ₂₄ 4H ₂ O, 500 g), ammonium tungstate ((NH ₄ ) ₁₀ W ₁₂ O ₄₁ 5H ₂ O, 6.2 g), A first reaction solution was prepared by dissolving ammonium metavanadate (NH ₄ VO ₃ , 5.52 g) and cesium nitrate (CsNO _{3, 46.0 g).}

Meanwhile, a second reaction solution was prepared by dissolving 85% by weight aqueous phosphoric acid solution (32.65 g) and copper nitrate (Cu(NO ₃ ) ₂ ·3H _{2 O, 11.40 g) in 300 mL of ultrapure water.}

_{Antimony trioxide (Sb 2} O ₃ , 6.84 g) was added while mixing and stirring the first and second reaction solutions. The mixture reaction solution thus obtained was heated to 95° C. while continuously stirring, maintained at this temperature for 3 hours, and then cooled naturally.

The slurry containing the catalyst precursor was dried at 120° C. for 15 hours and then pulverized. Polymethacrylate (PMMA; average particle diameter of 40 µm or less) powder was added to the dried pulverized product in an amount of 10 parts by weight based on 100 parts by weight of the dried pulverized product, mixed, and coated on a spherical carrier. The molded material was calcined at 380° C. for 5 hours under air flow to prepare a catalyst 1. The prepared catalyst was confirmed by ICP analysis after sample preparation using an Agilent 7500 and microwave sample pretreatment device, and the composition of Catalyst 1 excluding oxygen is as follows:

P _1.2 Mo ₁₂ W _0.1 V _0.2 Cu _0.2 Sb _0.1 Cs _1.0

Preparation Example 2: Preparation of catalyst 2

A first reaction solution was prepared by dissolving _{molybdenum trioxide (MoO 3} , 500 g), vanadium pentoxide (V ₂ O ₅ , 26.05 g) and cesium nitrate (CsNO ₃ , 20.8 g) in 3000 mL of ultrapure water.

Meanwhile, a second reaction solution was prepared by dissolving an 85% by weight aqueous phosphoric acid solution (42.59 g) and copper carbonate (CuCO ₃ ·Cu(OH) _{2, 16 g) in 300 mL of ultrapure water.}

_{Antimony trioxide (Sb 2} O ₃ , 12.66 g) was added while mixing and stirring the first and second reaction solutions. The mixture reaction solution thus obtained was heated to 100° C. while continuously stirring, maintained at this temperature for 3 hours, and then naturally cooled.

The slurry containing the catalyst precursor was dried at 120° C. for 15 hours and then pulverized. Polymethacrylate (PMMA; average particle diameter of 40 µm or less) powder was added to the dried pulverized product in an amount of 10 parts by weight based on 100 parts by weight of the dried pulverized product, mixed, and coated on a spherical carrier. The molded material was calcined at 380° C. for 5 hours under air flow to prepare a catalyst 2. The prepared catalyst was confirmed by ICP analysis after sample preparation using an Agilent 7500 and microwave sample pretreatment device, and the composition of Catalyst 2 excluding oxygen is as follows:

P _1.3 Mo ₁₂ V _1.0 Cu _0.5 Sb _0.3 Cs _1.2

Comparative Preparation Example 1: Preparation of Catalyst 3

_{Molybdenum trioxide (MoO 3} , 500 g), cesium carbonate (Cs ₂ CO ₃ , 70.73 g) and an 85% by weight aqueous phosphoric acid solution (42.59 g) were dissolved in 3000 mL of ultrapure water. The reaction solution was mixed and heated to 100° C. while stirring, maintained at this temperature for 3 hours, and cooled naturally.

The slurry containing the catalyst precursor was dried at 120° C. for 15 hours and then pulverized. Polymethacrylate (PMMA; average particle diameter of 40 µm or less) powder was added to the dried pulverized product in an amount of 10 parts by weight based on 100 parts by weight of the dried pulverized product, mixed, and coated on a spherical carrier. The molded material was calcined at 380° C. for 5 hours under air flow to prepare a catalyst 2. The prepared catalyst was confirmed by ICP analysis after sample preparation using an Agilent 7500 and microwave sample pretreatment device, and the composition of Catalyst 3 excluding oxygen is as follows:

P _1.3 Mo ₁₂ Cs _1.5

Example 1

(Meth)acrylic acid and methyl methacrylate were prepared by filling a stainless steel reactor with an inner diameter of 16 mm and a length of 350 mm in which the catalyst 1 prepared in Preparation Example 1 was filled in a fixed bed with 300 mm of catalyst. Specifically, 3 mol% of (meth)acrolein, 9 mol% of methanol, 7.08 mol% of molecular oxygen, 71 mol% of nitrogen, and 9.8 mol% of water vapor were supplied to the reactor in which the catalyst was charged in the fixed bed. At this time, the space velocity of (meth)acrolein is 20 to 30 hr ^-1 , and the space velocity of the reaction gas as a whole is 895 hr ^-1 . The reaction temperature was 270 to 310 °C, the reaction pressure was adjusted to ^{0.3 kg / cm 2.}

Example 2

(Meth)acrylic acid and methyl methacrylate were prepared in the same manner as in Example 1, except that the catalyst 2 prepared in Preparation Example 2 was used instead of the catalyst 1.

Comparative Example 1

(Meth)acrylic acid and methyl methacrylate were prepared in the same manner as in Example 1, except that the catalyst 3 prepared in Comparative Preparation Example 1 was used instead of the catalyst 1.

Comparative Example 2

(Meth)acrylic acid and methyl methacrylate were prepared in the same manner as in Example 1 except that methanol was not used.

Experimental example

In Examples 1 and 2 and Comparative Examples 1 and 2, the conversion rate of (meth)acrolein and the yield of (meth)acrylic acid and methyl methacrylate were measured and shown in Table 1 below. The conversion rate and yield were calculated by the following Equations 1 to 3, and the number of moles of each gas was analyzed and measured with an Agilent 6890 Gas Chromatography System. Specifically, the reaction gas flowing from the bench pilot was supplied to the column through an automatic valve system, and analyzed by FID: H-1000 capillary, TCD Porapak-Q, and MS-5A columns.

[Equation 1]

Conversion rate of (meth)acrolein (%) = [(number of moles of reacted (meth)acrolein)/(number of moles of supplied (meth)acrolein)] * 100

[Equation 2]

Yield (%) of (meth)acrylic acid = [(number of moles of (meth)acrylic acid produced)/(number of moles of supplied (meth)acrolein)] * 100

[Equation 3]

The yield of methyl methacrylate (%) = [(number of moles of methyl methacrylate produced) / (number of moles of supplied (meth) acrolein)] * 100

catalyst MACR conversion rate
(%) MAA yield
(%) MMA yield
(%) Example 1 P _1.2 Mo ₁₂ W _0.1 V _0.2 Cu _0.2 Sb _0.1 Cs _1.0 88.14 30.5 40.34 Example 2 P _1.3 Mo ₁₂ V _1.0 Cu _0.5 Sb _0.3 Cs _1.2 87.06 37.84 38.15 Comparative Example 1 P _1.3 Mo ₁₂ Cs _1.5 80.14 37.47 28.60 Comparative Example 2 P _1.2 Mo ₁₂ W _0.1 V _0.2 Cu _0.2 Sb _0.1 Cs _1.0 89.14 68.88 -

MACR: (meth)acrolein

MAA: (meth)acrylic acid

MMA: methylmethacrylate

In the above Table 1, it was confirmed that the example of the present invention using the catalyst containing Sb as a constituent element had a higher conversion rate of (meth)acrolein compared to Comparative Example 1, and (meth)acrylic acid and methylmethacrylic in each example It was confirmed that both the yields of the rates exceeded 30%, so that both products could be obtained at the same level. In addition, by confirming that methyl methacrylate was not prepared because methanol was not used as a reactant in Comparative Example 2, it was found that methanol was an essential reactant in order to simultaneously obtain (meth)acrylic acid and methyl methacrylate.

On the other hand, in Comparative Example 2 in which methanol was not added as a reactant, methyl methacrylate was not prepared at all, whereas in Examples 1 and 2, it was confirmed that methyl methacrylate at the same level as (meth)acrylic acid was prepared. . Therefore, it can be inferred that the number of unreacted (meth)acrolein reused in the reactor would have decreased, and as a result, deterioration of catalytic activity can be prevented, and thus an increase in catalyst life can be expected.

Claims (9)

In the presence of a metal oxide catalyst represented by the following formula (1), comprising the step of reacting a raw material containing (meth) acrolein, a molecular oxygen-containing gas, and methanol,
Method for producing (meth)acrylic acid and methyl methacrylate:
[Formula 1]
Mo _a A _b B _c C _d D _e E _f O _g
In Formula 1,
Mo is molybdenum,
A is at least one element selected from the group consisting of W and Cr,
B is at least one element selected from the group consisting of P, As and Si,
C is at least one element selected from the group consisting of B, Ce, Pb, Mn, V, Nb and Te,
D is one or more elements selected from the group consisting of Al, Zr, Rh, Cu, Ni, Ti, Ag, Sb, Fe, Co, and Sn,
E is one or more elements selected from the group consisting of Na, K, Li, Rb, Cs, Ta, Ca, Mg, Sr and Ba,
a, b, c, d, e, f and g are the atomic ratios of each element,
When a=12, b is 0.01 to 15, c is 0.01 to 15, d is 0 to 20, e is 0.01 to 20, f is 0 to 20, and g is the oxidation state of each element. It is a number that is determined accordingly.
The method of claim 1,
The metal oxide catalyst is represented by the following formula 1-1,
Method for producing (meth)acrylic acid and methyl methacrylate:
[Formula 1-1]
Mo _a Sb _h Cs _i A _b B _c C _d D _e E _f O _g
In Formula 1-1,
Mo is molybdenum, Sb is antimony, Cs is cesium,
A is at least one element selected from the group consisting of W and Cr,
B is one or more elements selected from the group consisting of P, As and Si,
C is at least one element selected from the group consisting of B, Ce, Pb, Mn, V, Nb and Te,
D is one or more elements selected from the group consisting of Al, Zr, Rh, Cu, Ni, Ti, Ag, Fe, Co, and Sn,
E is one or more elements selected from the group consisting of Na, K, Li, Rb, Cs, Ta, Ca, Mg, Sr and Ba,
a, b, c, d, e, f, g, h and i are the atomic ratios of each element,
When a=12, b is 0.01 to 15, c is 0.01 to 15, d is 0 to 20, e is 0.01 to 20, f is 0 to 20, and g is the oxidation state of each element It is a numerical value determined accordingly, h is 0 to 20, and i is 0 to 20.
The method of claim 1,
The metal oxide catalyst is represented by the following formula 1-2,
Method for producing (meth)acrylic acid and methyl methacrylate:
[Formula 1-2]
Mo ₁₂ W _b P _c V _d Cu _e Sb _h Cs _i O _g
In Formula 1-2,
Mo is molybdenum, W is tungsten, P is phosphorus, V is vanadium, Cu is copper, Sb is antimony, Cs is cesium,
b, c, d, e and g are the atomic ratios of each element,
b is 0.05 to 0.15, c is 1 to 1.5, d is 0 to 0.5, e is 0.01 to 0.5, g is a value determined according to the oxidation state of each element, h is 0.01 to 0.5, i is 0.5 to 1.5.
The method of claim 1,
The metal oxide catalyst is represented by the following formula 1-3,
Method for producing (meth)acrylic acid and methyl methacrylate:
[Formula 1-3]
Mo ₁₂ P _c V _d Cu _e Sb _h Cs _i O _g
In Formula 1-3,
Mo is molybdenum, P is phosphorus, V is vanadium, Cu is copper, Sb is antimony, Cs is cesium,
b, c, d, e and g are the atomic ratios of each element,
c is 1 to 1.5, d is 0.5 to 1.5, e is 0.01 to 1, g is a value determined according to the oxidation state of each element, h is 0.01 to 0.5, and i is 1 to 1.5.
The method of claim 1,
The molar ratio (m2/m1) of (meth)acrolein (m1) and oxygen (m2) in the molecular oxygen-containing gas is 2 to 100,
Method for producing (meth)acrylic acid and methyl methacrylate.
The method of claim 1,
The molar ratio (m3/m1) of (meth)acrolein (m1) and methanol (m3) is 1 to 100,
Method for producing (meth)acrylic acid and methyl methacrylate.
The method of claim 1,
The yield of (meth)acrylic acid in the reaction is 30 to 60%,
Method for producing (meth)acrylic acid and methyl methacrylate.
The method of claim 1,
The yield of methyl methacrylate in the reaction is 30 to 60%,
Method for producing (meth)acrylic acid and methyl methacrylate.
The method of claim 1,
The yield of (meth)acrylic acid in the reaction is 30 to 60%, and the yield of methyl methacrylate is 30 to 60%,
Method for producing (meth)acrylic acid and methyl methacrylate.