KR20210096440A - Catalyst for synthesizing trioxane and method of synthesizing trioxane using the same - Google Patents

Abstract

The present invention relates to a catalyst for synthesizing trioxane. The catalyst according to the present invention includes a catalyst material containing phosphorus (P), vanadium (V) and molybdenum (Mo) as constitutional elements, and an inert support on which the catalyst material is supported, wherein the catalyst material is represented by chemical formula 1 of P_xV_yMo_zH_mO_n, wherein, 0 < x <= 1.2, 0 < y <= 2, 0 < y <= 20, 10 <= z/y <= 100, 0 < m < 4, and 0 < n < 70, and accelerates conversion of formaldehyde into trioxane.

Description

Catalyst for trioxane synthesis and trioxane synthesis method using the same

The present invention provides a catalyst for synthesizing trioxane for converting gaseous formaldehyde into trioxane, and a trioxane synthesis method using the same.

Formaldehyde is a chemically reactive reducing agent that is used as a raw material in the process of producing molding materials, preservatives, adhesives, and foaming agents from resins such as phenol, melanin, and urea. Liquid trimerization of liquid formaldehyde is polyoxymethylenes It is an important industrial process used in the production of trioxane, an intermediate in the manufacture of However, in this case, since moisture is included, the tendency of formaldehyde to polymerize increases, leading to catalyst poisoning by polyoxymethylene deposition, causing serious problems in the manufacturing process, and high cost for moisture removal. Therefore, a method for making a high molecular weight substance directly from gaseous formaldehyde has been studied for a long time.

US Patent No. 6,313,323 B1 discloses a catalyst comprising a solid phosphoric acid catalyst material and a support for producing trioxane from gaseous formaldehyde, specifically H ₃ PO ₄ (catalyst material) / SiO ₂ (support), H ₃ PO ₄ / SiO ₂ -Al ₂ O ₃ , H ₃ PO ₄ / TiO ₂ , HPA (Heteropoly acid) / Al ₂ O ₃ and the like are disclosed.

US Patent Publication No. 5,508,448 A discloses a (VO)HPO ₄ ·1/2H ₂ O (Vanadyl hydrogenphosphate hemihydrate) catalyst, but the synthesis process is very complicated, the vanadium content is too high, and the stability is low.

US Patent Publication No. 5,508,449 A discloses a H ₃ PVMo ₁₁ O ₄₀ ·nH ₂ O (11-molybdo-1-vanadophosphoric acid) catalyst (n=0-32), but the STY may be too high.

US Patent Publication No. 6,124,480 A discloses a H ₄ PVMo ₁₁ O ₄₀ catalyst material, but the conversion of formaldehyde to trioxane was less than 30%.

US Registered Patent US 6,313,323 B1 US Patent Publication No. 5,508,448 A US Patent Publication No. 5,508,449 A US Patent Publication No. 6,124,480 A

A catalyst for trioxane synthesis and a trioxane synthesis method using the same according to an embodiment of the present invention is to improve the conversion rate of formaldehyde to trioxane.

In addition to the above problems, the embodiment according to the present invention may be used to achieve other problems not specifically mentioned.

The catalyst for trioxane synthesis according to an embodiment of the present invention includes a catalyst material including phosphorus (P), vanadium (V) and molybdenum (Mo) as constituent elements, and an inert support on which the catalyst material is supported, The catalyst material has the formula

[Formula 1]

P _x V _y Mo _z H _m O _n

In Formula 1, 0<x≤1.2, 0<y≤2, 0<y≤20, 10≤z/y≤100, 0<m<4, 0<n<70.

The inert support may comprise activated carbon.

Based on the total volume of the catalyst for trioxane synthesis, 0.9 to 1.1 mol of phosphorus (P) may be supported.

Trioxane synthesis method using a catalyst for trioxane synthesis according to an embodiment of the present invention, Phosphoric acid (H ₃ PO ₄ ), Vanadium pentoxide (V ₂ O ₅ ) and Molybdenum trioxide (MoO ₃ ) by mixing in water Forming a mixture, stirring the mixture, extracting the filtrate after reduced pressure and drying to prepare a catalyst material, supporting the catalyst material on an inert support to prepare a catalyst for trioxane synthesis, and for trioxane synthesis It includes a conversion reaction step of converting formaldehyde to trioxane by treating formaldehyde using a catalyst.

Here, the catalyst material includes phosphorus (P), vanadium (V) and molybdenum (Mo) as constituent elements, promotes the conversion reaction of formaldehyde to trioxane, and the catalyst material has the following formula.

[Formula 1]

P _x V _y Mo _z H _m O _n

In Formula 1, 0<x≤1.2, 0<y≤2, 0<y≤20, 10≤z/y≤100, 0<m<4, 0<n<70.

In the conversion reaction step, formaldehyde may be treated by a predetermined throughput.

The natural log (ln) value of the amount of formaldehyde treated per mass of the catalyst material supported on the inert support may be 3.4 to 3.6.

The predetermined throughput may be 0.001 to 0.3 kg/h.

In the step of preparing the catalyst material, stirring may be performed at a temperature of 70 to 90° C. for 2 to 4 hours at a speed of 400 to 600 rpm.

In the conversion reaction step, as the reaction pressure of the conversion reaction increases, the conversion rate of formaldehyde to trioxane may increase.

The inert support may comprise activated carbon.

A catalyst for trioxane synthesis and a trioxane synthesis method using the same according to an embodiment of the present invention can improve the conversion rate of formaldehyde to trioxane.

1A to 1C are graphs showing experimental results showing the influence of a support for carrying.
2A and 2B are graphs showing experimental results in the case of trioxane production at a 0.001 kg/h treatment scale.
3A to 3D are graphs showing experimental results in the case of trioxane production at a 0.06 kg/h treatment scale.
4A to 4C are graphs showing experimental results in the case of trioxane production at a 0.3 kg/h treatment scale.
5 is a graph showing the ratio of an appropriate amount of formaldehyde treatment and catalyst material loading for increasing the yield of trioxane.

With reference to the accompanying drawings, the embodiments of the present invention will be described in detail so that those of ordinary skill in the art to which the present invention pertains can easily implement them. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. In order to clearly explain the present invention in the drawings, parts irrelevant to the description are omitted, and the same reference numerals are used for the same or similar components throughout the specification. In addition, in the case of a well-known known technology, a detailed description thereof will be omitted.

In order to clearly express various layers and regions in the drawings, the thicknesses are enlarged. When a part, such as a layer, film, region, plate, etc., is "on" another part, it includes not only the case where it is "directly on" another part, but also the case where there is another part in between. On the other hand, when a part is said to be "just above" another part, it means that there is no other part in the middle. Conversely, when a part, such as a layer, film, region, plate, etc., is "under" another part, it includes not only the case where the other part is "directly under" but also the case where there is another part in between. On the other hand, when a part is said to be "just below" another part, it means that there is no other part in the middle.

Throughout the specification, when a part "includes" a certain element, it means that other elements may be further included, rather than excluding other elements, unless otherwise stated.

The present invention relates to a catalyst for synthesizing trioxane from formaldehyde. The catalyst according to the present invention can significantly improve the conversion rate of formaldehyde to trioxane compared to the prior art, for example, it can exhibit a conversion rate of 30% or more.

A catalyst according to embodiments includes a catalyst material supported on an inert support.

The inert support is made of a material that does not react with the catalyst material, and may include activated carbon. In general, since activated carbon has a relatively very large specific surface area compared to silica, which can be used as an inert support, the activated carbon support can improve the conversion performance of the catalyst into trioxane.

The catalyst material includes phosphorus (P), vanadium (V) and molybdenum (Mo) as constituent elements, and the catalyst material may be represented by the following chemical formula.

[Formula 1]

P _x V _y Mo _z H _m O _n

(In Formula 1, 0<x≤1.2, 0<y≤2, 0<y≤20, 10≤z/y≤100, 0<m<4, 0<n<70)

In Formula 1, the composition ratio (content ratio) (z/y) of molybdenum (Mo) to vanadium (V) may be 10 or more and 100 or less. When the composition ratio (z/y) is less than 10, the relative content of molybdenum is small, so that the reactivity between the catalyst material and formaldehyde may be reduced, and when the composition ratio (z/y) is more than 100, the relative content of vanadium (V) is Since it is small, the reactivity of the catalyst material and formaldehyde may be reduced. Accordingly, the supported amount of the catalyst material within the above-described range may be further increased, and the conversion rate of formaldehyde to trioxane may be improved.

Based on the total volume of the catalyst, the element phosphorus (P) may be supported by about 0.9 to 1.1 mol, and within this range, the catalytic performance of the catalyst material may be well implemented.

The method for synthesizing trioxane using such a catalyst includes a catalyst material preparation step, a catalyst preparation step, and a conversion reaction step for converting formaldehyde into trioxane.

First, in the catalyst material preparation step, Phosphoric acid (H ₃ PO ₄ ), Vanadium pentoxide (V ₂ O ₅ ) and Molybdenum trioxide (MoO ₃ ) are mixed in water to form a mixture, the mixture is stirred, and then filtered after reduced pressure It is a step of preparing a catalyst material by extracting the liquid and drying it.

Here, agitation may be performed at a temperature of 70 to 90° C. at a speed of 400 to 600 rpm for 2 to 4 hours, and under these conditions, the catalyst material can be prepared in high yield and exhibit uniform performance.

Then, a step of preparing a catalyst for trioxane synthesis by supporting the catalyst material on an inert support is performed. Here, the inert support may include activated carbon having a large specific surface area, so that when the catalyst material is supported on the support, the contact area between the catalyst material and formaldehyde may increase.

Next, a conversion reaction step of converting formaldehyde into trioxane by contacting the catalyst for trioxane synthesis with formaldehyde is performed.

Here, the formaldehyde may be treated as much as a predetermined processing amount (flow rate, flow rate). The predetermined throughput may be 0.001 to 0.3 kg/h, where a throughput of 0.25 kg/h or more may correspond to a demonstration scale rather than a laboratory scale.

The trioxane synthesis method according to the embodiments has a reaction pressure of about 1 to 5 bar, by optimizing the operating conditions such as the flow rate (throughput) of formaldehyde, catalyst loading, reaction pressure, etc., 0.3 kg/hr treatment, which is an empirical scale At scale, yields of about 41% can be realized.

At this time, as the reaction pressure increases, the conversion rate of formaldehyde to trioxane may increase. The reaction in which trioxane is produced from formaldehyde is a reaction in which 3 moles of reactant are converted into 1 mole of product and follows Le Chatelier's principle.

On the other hand, in order to increase the yield of trioxane, there may be a ratio between an appropriate amount of formaldehyde treatment (flow rate) and a catalyst material loading amount. For example, the natural log (ln) value of the amount of formaldehyde treated per mass of the catalyst material supported on the inert support may be 3.4 to 3.6, and within this range, the yield of trioxane may be higher.

If the preparation method of the catalyst containing the catalyst material is described as an example, Phosphoric acid (H ₃ PO ₄ ) 0.98 g, Vanadium pentoxide (V ₂ O ₅ ) 0.18 g, Molybdenum trioxide (MoO ₃ ) 14.39 g and water 225 ml are mixed, stirred at about 80 ° C. at a speed of about 500 rpm for about 3 hours, then, after reduced pressure, the filtrate is extracted and dried at a temperature of about 85 ° C. to prepare a catalyst material. Next, the prepared catalyst material may be supported on an activated carbon support to prepare a catalyst.

Hereinafter, the present invention will be described with reference to Examples and Experimental Examples, but the present invention is not limited by the following contents.

Experimental Example 1 - Experiment with the influence of the carrier

P _0.01 V _0.001 Mo _0.1 catalyst material was used, and the effect of the support was evaluated. Specifically, when there is no support, when the support is silica (SiO ₂ ), when the support is activated carbon, when the support is alumina (γ-Al ₂ O ₃ ) Conversion according to the temperature of formaldehyde, foam The reaction rate of the aldehyde and the BET surface area were evaluated. The conversion rate according to temperature is shown in FIG. 1A, the reaction rate is shown in FIG. 1B, and the BET surface area is shown in FIG. 1C. Here, the filling amount of the catalyst material is about 1 g, the reaction gas is about 95 ppm formaldehyde/N ₂ balance, the gas flow rate at the inlet of the experimental equipment is about 100 ml/min, and the reaction temperature is set to about 110 ℃ to 150 ℃ became For concentration analysis, gas chromatography HP6890 equipment was used, which included a Porapak-T packed column (2M, 80/100 ss, Agilent Tech.) and a TCD detector.

1a to 1c, when the support is activated carbon and when the support is alumina, a relatively high conversion of formaldehyde was shown.

Comparing the reaction rate of formaldehyde according to the supported amount of the active ingredient, the catalyst material PVMo, the BET surface area of the activated carbon support was found to be the largest, and the highest reaction rate was exhibited when the activated carbon support was applied. From this, it can be seen that the BET surface area (specific surface area) of activated carbon is relatively high, and the dispersion degree of the catalyst material is relatively high, and thus the conversion rate and reaction rate of formaldehyde are high.

Table 1 below is a table summarizing the catalysts prepared according to Examples and Comparative Examples, and the following experiments were carried out with the catalysts described in Table 1 below.

[Table 1]

Experimental Example 2 - Trioxane production catalyst reaction experiment according to the amount of formaldehyde treatment

The pyrolysis formaldehyde treatment amount was set to 0.001 to 0.3 kg/h, the catalyst loading was set to about 100 to 170 g, the reaction temperature was set to about 110 ° C. to 150 ° C., and the reaction pressure was set to atmospheric pressure (1 bar) to 5 bar. . For concentration analysis, gas chromatography HP6890 equipment was used, which included a Porapak-T packed column (2M, 80/100 ss, Agilent Tech.) and a TCD detector. To recover the generated trioxane, about 350 g of _{ethylbenzene (ethylbenzene, C 8} H _{10 ) was used.}

Experimental Example 2-1 - In the case of trioxane production of 0.001 kg / h treatment scale

Using the catalysts P-DE (Comparative Example) and P-KA (Comparative Example) of Table 1, the conversion rate of formaldehyde to trioxane according to the reaction temperature was evaluated. At this time, 100 g of the catalyst material was used, and the flow rate of formaldehyde was 0.001 kg/h, N ₂ 40 ml/min. The results are shown in Figure 2a.

Referring to FIG. 2A , the conversion rate of both catalyst materials decreased as the temperature increased, and the P-DE decreased relatively steeply, so that it did not function as a catalyst at 130° C. or higher.

In addition, using the catalysts P-DE (comparative example), P-KA (comparative example), P _0.01 V _0.005 Mo _0.10 /SI (comparative example) and P _0.01 V _0.005 Mo _0.10 /AC (example) of Table 1 , the conversion rate of formaldehyde to trioxane was evaluated. At this time, 100 g of the catalyst material was used, the flow rate of formaldehyde was 0.001 kg/h, N ₂ 40 ml/min, and the reaction temperature was 110 °C. The results are shown in Figure 2b. In Figure 2b, (a) is when the catalyst is P-DE, (b) is when the catalyst is P-KA, (c) is when the catalyst is P _0.01 V _0.005 Mo _0.10 /SI, (d) is the catalyst is The case of P _0.01 V _0.005 Mo _0.10 /AC is shown, respectively.

Referring to FIG. 2b, the yield of trioxane of the P-DE and P-KA catalyst materials showed the maximum values of 19.2% and 14.2%, respectively, at the reaction temperature of 110° C. under atmospheric pressure (1 bar), PVMo-SI and PVMo-AC catalyst, the yield of trioxane was 24.7% and 28.2%, respectively (atmospheric pressure condition).

On the other hand, when the reaction pressure was increased to 2 bar, the yield of trioxane was improved except in the case of P-DE, and a yield of 31.7% was secured in the PVMo-AC catalyst. This can be interpreted as the reaction in which trioxane is produced from formaldehyde is a reaction in which 3 moles of reactant is converted into 1 mole of product, and it can be interpreted as being due to the fact that the forward reaction is promoted by the increase of the reaction pressure according to Le Chatelier's principle. there is.

Experimental Example 2-2 - In the case of trioxane production of 0.06 kg / h treatment scale

The conversion rate of formaldehyde to trioxane according to the flow rate of formaldehyde was evaluated by using 0.1 wt.% (based on the total catalyst) of P _0.01 V _0.005 Mo _{0.20 /AC (Example) catalyst of Table 1.} At this time, 100 g of the catalyst material was used, N ₂ 40 ml/min, and the reaction pressure was maintained at 5 bar. The results are shown in Figure 3a.

Referring to FIG. 3a , the trioxane yield decreased as the amount of formaldehyde (flow rate) increased.

On the other hand, _{0.1 wt.% (based on the total catalyst) of the P 0.01} V _0.005 Mo _0.20 /AC catalyst in Table 1 was used to evaluate the conversion rate of formaldehyde to trioxane according to the reaction pressure. At this time, 170 g of the catalyst material was used, the flow rate of formaldehyde was 0.06 kg/h, N ₂ 40 ml/min, and the reaction temperature was 110 °C. The results are shown in Figure 3b.

Referring to Figure 3b, the yield of trioxane was increased as the reaction pressure increased.

On the other hand, using the P _0.01 V _0.005 Mo _0.10 /AC (Example) catalyst in Table 1, the conversion rate of formaldehyde to trioxane according to the catalyst material loading was evaluated. At this time, 100 g of the catalyst material was used, the flow rate of formaldehyde was 0.06 kg/h, N ₂ 40 ml/min, and the reaction temperature was 110° C., and the reaction pressure was maintained at 2 bar. The results are shown in Figure 3c.

Referring to FIG. 3c , the yield of trioxane increased with an increase in the amount of catalyst material supported at the same pressure.

On the other hand, the conversion rate of formaldehyde to trioxane according to the reaction pressure was evaluated using the _{P 0.01} V _0.005 Mo _{0.10 /AC (Example) catalyst in Table 1 at 2.0 wt.% (based on the total catalyst).} At this time, 100 g of the catalyst material was used, the flow rate of formaldehyde was 0.06 kg/h, N ₂ 40 ml/min, and the reaction temperature was 110 °C. The results are shown in Figure 3d.

Referring to Figure 3d, the yield of trioxane was increased as the reaction pressure increased, and when the reaction pressure was 2 bar or more, the yield exceeded 30%.

Experimental Example 2-3 - In the case of trioxane production of 0.3 kg / h treatment scale

_{P 0.01} V _0.005 Mo _0.20 /AC (Example) catalyst in Table 1 was used in 2.0 wt.% (based on the total catalyst) to evaluate the conversion rate of formaldehyde to trioxane according to the amount of catalyst material loaded. At this time, 170 g of the catalyst material was used, the flow rate of formaldehyde was 0.3 kg/h, N ₂ 40 ml/min, the reaction temperature was 110° C., and the reaction pressure was maintained at 5 bar. The results are shown in Figure 4a. In addition, using an infrared spectrometer (Bruker, ALPHA FT-IR Spectrometer), the FTIR analysis result according to the concentration of the trioxane solution is shown in FIG. 4b, and the calculation of the yield of trioxane by the FTIR calibration curve is shown in FIG. 4c . Here, the trioxane solution (recovery solution) refers to a standard solution in which the generated trioxane is dissolved in ethylbenzene.

Referring to FIG. 4A , the yield of trioxane increased as the amount of supported catalyst material increased, and a yield of 37% was finally secured (when the amount of supported catalyst was about 2.0 wt.%).

4b and 4c, ^{trioxane was detected at a wavelength of 932.47 cm -1} , and the trioxane concentration of the recovery solution was found to be 10.99 wt.%, and the yield at this time was calculated to be 41.2%.

As a result of analyzing the results of the above experimental examples, it was found that there was an appropriate ratio of formaldehyde treatment amount and catalyst material loading amount for increasing the yield of trioxane, and the analysis results are shown in FIG. 5 .

1A to 5 , when the PVMo catalyst material was supported on activated carbon (AC) and an alumina support, the conversion rate of formaldehyde was improved. In particular, the reaction rate of the catalyst supporting the catalyst material on the activated carbon support was high, and from this, the use of the activated carbon support was found to be advantageous in converting formaldehyde compared to the use of other supports.

Specifically, it was found to be advantageous to maintain the natural logarithm of the amount of formaldehyde treated per weight of supported PVMo at 3.5 in order to obtain a high yield of trioxane.

Although the preferred embodiment of the present invention has been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements by those skilled in the art using the basic concept of the present invention as defined in the following claims are also provided. is within the scope of the

Claims (10)

A catalyst material comprising phosphorus (P), vanadium (V) and molybdenum (Mo) as constituent elements, and an inert support on which the catalyst material is supported
including,
The catalyst material has the following chemical formula, and promotes the conversion reaction of formaldehyde to trioxane.
Catalyst for trioxane synthesis.
[Formula 1]
P _x V _y Mo _z H _m O _n
(In Formula 1, 0<x≤1.2, 0<y≤2, 0<y≤20, 10≤z/y≤100, 0<m<4, 0<n<70)
In claim 1,
The inert support is a catalyst for trioxane synthesis comprising activated carbon (activated carbon).
In claim 1,
A catalyst for trioxane synthesis in which 0.9 to 1.1 mol of the phosphorus (P) is supported based on the total volume of the catalyst for trioxane synthesis.
Phosphoric acid (H ₃ PO ₄ ), Vanadium pentoxide (V ₂ O ₅ ) and Molybdenum trioxide (MoO ₃ ) were mixed in water to form a mixture, the mixture was stirred, and then the filtrate was extracted and dried under reduced pressure. preparing a catalyst material;
preparing a catalyst for trioxane synthesis by supporting the catalyst material on an inert support, and
A conversion reaction step of converting formaldehyde into trioxane by treating formaldehyde using the catalyst for trioxane synthesis
including,
The catalyst material comprises phosphorus (P), vanadium (V) and molybdenum (Mo) as constituent elements, and promotes the conversion reaction of the formaldehyde to the trioxane,
The catalyst material has the formula
A trioxane synthesis method using a catalyst for trioxane synthesis.
[Formula 1]
P _x V _y Mo _z H _m O _n
(In Formula 1, 0<x≤1.2, 0<y≤2, 0<y≤20, 10≤z/y≤100, 0<m<4, 0<n<70)
In claim 4,
In the conversion reaction step,
A trioxane synthesis method using a catalyst for trioxane synthesis in which the formaldehyde is treated by a predetermined amount.
In claim 5,
A trioxane synthesis method using a catalyst for trioxane synthesis having a natural log (ln) value of 3.4 to 3.6 of the amount of formaldehyde treated per mass of the catalyst material supported on the inert support.
In claim 5,
The predetermined throughput is 0.001 ~ 0.3 kg / h of trioxane synthesis method using a catalyst for trioxane synthesis.
In claim 4,
In the step of preparing the catalyst material,
The stirring is a trioxane synthesis method using a catalyst for trioxane synthesis performed at a speed of 400 to 600 rpm for 2 to 4 hours at a temperature of 70 to 90 ℃.
In claim 4,
In the conversion reaction step,
A trioxane synthesis method using a catalyst for trioxane synthesis in which the conversion rate of the formaldehyde to the trioxane increases as the reaction pressure of the conversion reaction increases.
In claim 4,
The inert support is a trioxane synthesis method comprising activated carbon (activated carbon).

Images