WO2018123363A1

WO2018123363A1 - Production method for paraffin

Info

Publication number: WO2018123363A1
Application number: PCT/JP2017/041978
Authority: WO
Inventors: 修司津野; 晃裕桑名; 良一郎酒井
Original assignee: 住友精化株式会社
Priority date: 2016-12-28
Filing date: 2017-11-22
Publication date: 2018-07-05
Also published as: KR20190100905A; KR102468527B1; TWI741077B; CN109843835B; JP2018104380A; TW201835013A; CN109843835A; JP6251377B1

Abstract

[Problem] To provide a method capable of stably and efficiently producing a high-purity paraffin from a high-purity olefin which is easily available, while inhibiting side reactions and eliminating variation in the amount of produced impurities. [Solution] This method comprises loading a plurality of granular materials not having catalyst activity into a reaction tower 10, at least a portion of the granular materials being used as carriers supporting a catalyst, and reacting hydrogen and an olefin in a gas phase state in the presence of the catalyst in the reactor tower 10, to produce a paraffin. The proportion of the weight of the catalyst supported by the carriers with respect to the sum of the weight of the carriers and the weight of the catalyst supported by the carriers is not less than 0.001% but less than 0.01%.

Description

Paraffin production method

The present invention relates to a method for producing high purity paraffin by a hydrogenation reaction to an olefin in the presence of a catalyst.

In recent years, the need for high purity paraffin such as high purity ethane and high purity propane is increasing. For example, high-purity propane as a raw material for a high-pressure silicon carbide (SiC) semiconductor is required to make the concentration of each impurity contained less than 1.0 vol ppm in order to realize the high pressure resistance of silicon carbide. .

As a method for producing high purity paraffin, a method of distilling and purifying low purity paraffin is known. However, this method requires a large-scale distillation facility for separating impurities, resulting in a large investment. Moreover, since the facilities are large-scale, a large amount of energy is required for operation. In particular, when distilling low-purity propane containing propylene as an impurity, it is difficult to purify by distillation because the difference in boiling points between propane and propylene is small.

Further, a method for producing propane by hydrogenation reaction to liquid phase propylene in the presence of a catalyst is known (Patent Document 1). However, when the raw material propylene is in a liquid phase, if the raw material concentration increases, the heat of reaction increases and heat removal becomes difficult. Propylene is decomposed into impurities due to excessive temperature rise, and the impurity concentration increases. Therefore, in order to produce high purity paraffin by hydrogenation reaction to the liquid phase raw material, it is necessary to make the raw material concentration about 25% or less, so it is difficult to produce high purity paraffin efficiently. .

Therefore, it has been proposed to produce paraffin by a hydrogenation reaction to a gas phase olefin (Patent Document 2). At this time, the catalyst supported by the carrier and alumina balls having no catalytic activity are packed in the reaction tower, and the heat of reaction due to the hydrogenation reaction in the presence of the catalyst is removed by diffusion to the alumina balls or heat transfer. ing. As a result, the decomposition of the olefin due to an excessive temperature rise is prevented, and the impurity concentration is reduced. Further, the alumina balls and the like are decreased as the gas flow in the reaction tower goes downstream, and the ratio of the catalyst is increased. As a result, the olefin and hydrogen are reliably reacted to prevent the unreacted olefin from being mixed into the paraffin, thereby reducing the impurity concentration.

US Pat. No. 3,509,226 JP 2014-84285 A

According to the method described in Patent Document 2, since the gas phase olefin is used as the raw material, the reaction heat can be easily removed even if the raw material concentration is increased as compared with the case where the liquid phase raw material is used. However, there are variations in the amount of impurities produced, and there is a problem that high-purity paraffin cannot be produced stably and efficiently.

An object of the present invention is to solve the above-mentioned problems in the prior art in a method for producing paraffin by a reaction between a gas phase olefin and hydrogen.

According to the present invention, a plurality of granular members having no catalytic activity are packed in a reaction tower, and at least a part of the granular members is used as a carrier supporting a catalyst, and gas in the presence of the catalyst in the reaction tower is used. In the method for producing paraffin by the reaction of olefin and hydrogen in a phase state, all of the above-mentioned total weight of the total weight of all the granular members including the support and the total weight of the catalyst supported by all the supports The ratio of the total weight of the catalyst supported by the support is 0.001% or more and less than 0.01%, and each of the supports with respect to the sum of the weight of each of the supports and the weight of the catalyst supported by each of the supports The ratio of the weight of the catalyst supported by is 0.001% or more and less than 0.01%.

The present invention is based on the following findings.
In the prior art described in Patent Document 2, alumina balls and the carrier carrying the catalyst are mixed in the upstream region of the gas flow where the reaction is active, and the volume of the alumina balls and the like and the volume of the entire carrier carrying the catalyst are mixed. The volume ratio of alumina balls or the like with respect to the sum is 90 to 99%. When the proportion of alumina balls or the like having no catalytic activity is high, the catalyst is unevenly distributed in the reaction tower and there is no reproducibility of the mixed state. Further, in Patent Document 2, the ratio of the weight of the catalyst supported by each carrier to the sum of the weight of each carrier and the weight of the catalyst supported by each carrier is 0.1 to 1.0%. Therefore, the heat of reaction increases at a position where the catalyst is unevenly distributed, and the olefin is decomposed and becomes impurities due to an excessive temperature rise due to local heat generation. Thereby, in the prior art, the amount of impurities produced varies, and high-purity paraffin cannot be produced stably and efficiently.
On the other hand, according to the present invention, the ratio of the weight of the catalyst supported by each support to the sum of the weight of each support and the weight of the catalyst supported by each support is set to 0.01%, which is smaller than that in the above prior art. By making it less than this, reaction heat can be reduced to prevent an excessive temperature rise due to local heat generation, impurity generation due to decomposition of olefins can be suppressed, and variations in the amount of impurity generation can be prevented. In addition, since a granular member that is not used as a carrier is not required or the mixing ratio can be reduced, it is possible to prevent variations in the amount of impurity generation. By setting the ratio of the weight of the catalyst supported by each support to the sum of the weight of each support and the weight of the catalyst supported by each support to be 0.001% or more, the hydrogenation reaction to the olefin is surely caused. Thus, it is possible to reliably prevent the unreacted olefin from being mixed as impurities into the produced paraffin.

By making all of the granular member the carrier carrying the catalyst, it is possible to more reliably cause a hydrogenation reaction to the olefin and prevent the unreacted olefin from being mixed as an impurity in the produced paraffin, In addition, the catalyst distribution in the reaction tower can be made uniform, and variations in the amount of impurities produced can be reliably prevented.

In the present invention, not all of the granular members having catalytic activity packed in the reaction tower are the carriers supporting the catalyst, and a part of the granular members are the carriers supporting the catalyst, It is preferable to mix with the remainder of the granular member not carrying the catalyst.
As a result, the ratio of the weight of the catalyst carried by each carrier to the sum of the weight of each carrier and the weight of the catalyst carried by each carrier is 0.001% or more and less than 0.01%. In the present invention, not only a carrier carrying a catalyst but also a granular member that is not made a carrier and does not carry a catalyst is charged in the reaction tower, the amount of the catalyst is ensured and the hydrogenation reaction to the olefin is reliably generated. It is possible to prevent the unreacted olefin from being mixed as impurities into the produced paraffin.

The olefin and paraffin preferably each have 2 to 4 carbon atoms. That is, propane (C ₃ H ₈ ) by hydrogenation reaction to propylene (C ₃ H ₆ ), ethane (C ₂ H ₆ ) by hydrogenation reaction to ethylene (C ₂ H ₄ ), n-butene or It is preferable to produce butane (C ₄ H ₁₀ ) by hydrogenation reaction to isobutene (C ₄ H ₈ ), respectively.

It is preferable that the catalyst contains palladium and the support is alumina.

The purity of the paraffin is preferably 99.99 vol% or more, more preferably 99.999 vol% or more.

According to the present invention, it is possible to provide a method capable of stably and efficiently producing a high-purity paraffin from easily available high-purity olefins while suppressing side reactions and without causing variations in the amount of impurities produced.

BRIEF DESCRIPTION OF THE DRAWINGS Structure explanatory drawing of the paraffin manufacturing apparatus in embodiment of this invention.

The paraffin production apparatus 1 shown in FIG. 1 supplies ethylene, propylene, n-butene, isobutene, or the like as an olefin in a gas phase state from an olefin gas cylinder 2. The supplied olefin is decompressed by the first pressure reducing valve 3, is set to a set flow rate by the first flow rate control valve 4 with a flow meter, and is introduced into the gas mixer 5. Further, the paraffin production apparatus 1 supplies hydrogen in a gas phase state from a hydrogen gas cylinder 6. The supplied hydrogen is depressurized by the second pressure reducing valve 7, is set to a set flow rate by the second flow rate control valve 8 with a flow meter, and is introduced into the gas mixer 5. The olefin and hydrogen mixed in the gas mixer 5 are introduced as raw materials into the cylindrical reaction tower 10 from the upper inlet 10a.

In order to prevent a decrease in the purity of the paraffin produced, the purity of the olefin as the raw material is preferably 99.99 vol% or more.

Since the hydrogenation reaction to the olefin is a reduction reaction in which the reaction proceeds in the direction of decreasing the number of moles, the reaction rate can be increased by supplying more hydrogen than the theoretical equivalent to the reaction tower 10. Further, when the supply amount of hydrogen to the reaction tower 10 is less than 1.00 times mol with respect to the supply amount of olefin, the raw material olefin remains, and when the supply amount exceeds 2.00 times mol, removal of hydrogen in the subsequent step Becomes troublesome. Therefore, the supply amount of hydrogen is preferably 1.00 to 2.00 times mol, more preferably 1.00 to 1.20 times mol, relative to the supply amount of olefin. Moreover, in order to prevent the purity reduction of the paraffin manufactured, the purity of hydrogen as a raw material is preferably 99 vol% or more, more preferably 99.9 vol% or more.

The reaction tower 10 is filled with a plurality of granular members. In the present embodiment, all the granular members packed in the reaction tower 10 are used as a carrier carrying a catalyst.

As the catalyst, a known reduction catalyst can be used. For example, a metal catalyst such as palladium, platinum, rhodium, ruthenium, or nickel can be used. In the present embodiment, palladium is used. The material of the carrier is not limited as long as it does not have a catalytic activity capable of supporting the catalyst, and in this embodiment, the carrier is alumina. The shape of the carrier is spherical in the present embodiment, but is not particularly limited. For example, the shape may be a columnar shape, a pellet, or the like. The carrier may carry two or more kinds of catalysts.

The ratio of the weight of the catalyst supported by each support to the sum of the weight of each support in the reaction tower 10 and the weight of the catalyst supported by each support is 0.001% or more and less than 0.01%. That is, the weight of the carrier, each w _s, the weight of the catalyst support, each carrying as w _c, are _{0.001 ≦ w c × 100 / (} w s + w c) <0.01.
In addition, since all the granular members packed in the reaction tower 10 are used as the support carrying the catalyst, the total weight of all the granular members including the support in the reaction tower 10 and the total weight of the catalyst supported by all the supports. The ratio of the total weight of the catalyst supported by all the carriers to the sum of is 0.001% or more and less than 0.01%.

The reaction between the olefin in the gas phase and hydrogen in the presence of the catalyst in the reaction tower 10 generates ethane, propane, butane or the like in the gas phase as paraffin. In order to control the internal temperature of the reaction tower 10, the reaction tower 10 is covered with a cooling jacket 11, and a cooling device 12 for sucking, cooling, and refluxing the refrigerant in the cooling jacket 11 is provided. It is measured by the thermometer 13. The internal temperature of the reaction tower 10 is set to a temperature at which the paraffin is not liquefied so as not to make it difficult to control the reaction rate, and the temperature at which impurities are not increased by the decomposition of the paraffin. For example, when propane is produced as paraffin, the internal temperature of the reaction tower 10 is preferably −42 to 250 ° C., more preferably 0 to 250 ° C.

The paraffin produced by the hydrogenation reaction to the olefin in the reaction tower 10 is discharged from the lower outlet 10b of the reaction tower 10 and introduced into the product tank 15 through the back pressure valve 14 for adjusting the internal pressure of the reaction tower 10. The internal pressure of the reaction tower 10 is measured by the pressure gauge 16. If the internal pressure of the reaction tower 10 becomes too high, the hydrogenation reaction is promoted, but the heat of reaction cannot be controlled and impurities may increase, and the reaction gas may be liquefied to form a liquid phase reaction. Therefore, it is preferable to control appropriately. For example, when producing propane as paraffin, the internal pressure of the reaction column 10 is preferably 0.0 to 0.5 MPaG, more preferably 0.1 to 0.5 MPaG.

Favorable results are obtained as the gas flow rate and space velocity during the reduction reaction become smaller. For example, when propane is produced as paraffin, the space velocity SV in the standard state gas amount is preferably 1000 / h or less, and more preferably 500 / h or less. When the space velocity is 1000 / h or less, the hydrogenation reaction does not become insufficient, and it is possible to prevent unreacted raw materials from remaining.

In order to analyze impurities contained in the paraffin generated by the hydrogenation reaction, a part of the gas discharged from the outlet 10 b of the reaction tower 10 is introduced into the gas chromatograph 17.

In this embodiment, in order to separate hydrogen from paraffin produced by the reaction of olefin and hydrogen, a cooling device 18 for cooling and liquefying the gas phase paraffin introduced into the product tank 15 is provided. The cooling temperature by the cooling device 18 is lower than the boiling point of paraffin and higher than the boiling point of hydrogen. Hydrogen contained as an impurity in the paraffin is discharged from the product tank 15 via the third flow control valve 19 with a flow meter without being liquefied and separated from the paraffin, thereby increasing the purity of the paraffin. In this embodiment, the concentration of hydrogen contained in the paraffin is less than 1.0 vol. Hydrogen separated from paraffin may be recovered and returned to the reaction tower 10 to be reused as a raw material.

[Example 1]
Propane was manufactured by the hydrogenation reaction to propylene using the paraffin manufacturing apparatus 1 of the said embodiment.
The reaction tower 10 was made of stainless steel and had an inner diameter of 31 mm. The filling height of the granular member in the reaction tower 10 was 50 cm. All the granular members packed in the reaction tower 10 were used as carriers for supporting the catalyst. That is, the ratio of the sum of the volume of the entire carrier carrying the catalyst and the volume of the whole granular member not carrying the catalyst to the volume of the whole carrier carrying the catalyst was set to 1 time. As the carrier supporting the catalyst, one manufactured by N.E. Chemcat Co., Ltd. having an average particle diameter of 3 mm was used. Each support in this example was made of α-alumina, and supported by palladium (Pd) as a catalyst. The ratio of the weight of the catalyst supported by each support to the sum of the weight of each support and the weight of the catalyst supported by each support (hereinafter, this ratio is referred to as the “support ratio” of the catalyst by the support) is 0.001% It was.
Propylene with a purity exceeding 99.99 vol% is supplied from the olefin gas cylinder 2, introduced into the gas mixer 5 at a flow rate of 1.0 L / min, and hydrogen with a purity exceeding 99.999 vol% is supplied from the hydrogen gas cylinder 6. It was introduced into the gas mixer 5 at a flow rate of 1.1 L / min. Propylene and hydrogen were mixed in the mixer 5 at room temperature and then introduced into the reaction tower 10. At this time, the internal pressure of the reaction tower 10 was set to 0.3 MPaG, and water having a temperature of 40 ° C. was circulated in the cooling jacket 11 as a refrigerant.
Due to the hydrogenation reaction to propylene in the reaction tower 10 under the above conditions, a maximum exothermic temperature of 230 ° C. was exhibited at a position 7 cm from the inlet 10a in the reaction tower 10.
When impurities contained in the propane gas discharged from the outlet 10b of the reaction tower 10 are analyzed by a gas chromatograph 17 manufactured by Shimadzu Corporation, impurities other than hydrogen are residual propylene <0.1 vol ppm, methane 0.3 vol ppm, Ethane 0.5 vol ppm and butane 0.6 vol ppm.

[Comparative Example 1]
Propane was produced by a hydrogenation reaction to propylene under the same conditions as in Example 1 except that the catalyst was supported on the support at 0.0005%.
Due to the hydrogenation reaction to propylene in the reaction tower 10 under the above conditions, a maximum exothermic temperature of 220 ° C. was shown at a position 10 cm from the inlet 10 a in the reaction tower 10.
When impurities contained in the propane gas discharged from the outlet 10b of the reaction tower 10 are analyzed by a gas chromatograph 17 manufactured by Shimadzu Corporation, impurities other than hydrogen are 1.3 vol ppm of residual propylene, 0.2 vol ppm of methane, ethane. 0.3 vol ppm, butane <0.1 vol ppm.

[Comparative Example 2]
The catalyst loading rate on the carrier was 0.0005%, the height of the reaction tower 10 was doubled in Example 1, and the packing height of the carrier carrying the catalyst in the reaction tower 10 was doubled in Example 1. . Other than that, propane was produced by a hydrogenation reaction to propylene under the same conditions as in Example 1.
The maximum exothermic temperature of 220 ° C. was exhibited at a position 9 cm from the inlet 10a in the reaction tower 10 by the hydrogenation reaction to propylene in the reaction tower 10 under the above conditions.
When impurities contained in the propane gas discharged from the outlet 10b of the reaction tower 10 are analyzed using a gas chromatograph 17 manufactured by Shimadzu Corporation, impurities other than hydrogen are 1.2 vol ppm of residual propylene, 0.1 vol ppm of methane, ethane. 0.3 vol ppm, butane <0.1 vol ppm.

[Comparative Example 3]
The catalyst loading rate by the carrier was 0.01%, and each carrier was made of γ-alumina. Other than that, propane was produced by a hydrogenation reaction to propylene under the same conditions as in Example 1.
Due to the hydrogenation reaction to propylene in the reaction tower 10 under the above conditions, a maximum exothermic temperature of 240 ° C. was exhibited at a position 7 cm from the inlet 10 a in the reaction tower 10.
When impurities contained in the propane gas discharged from the outlet 10b of the reaction tower 10 are analyzed by a gas chromatograph 17 manufactured by Shimadzu Corporation, impurities other than hydrogen are residual propylene <0.1 vol ppm, methane 1.0 vol ppm, Ethane was 0.9 vol ppm and butane was 1.0 vol ppm.

[Comparative Example 4]
The catalyst loading rate by the carrier was 0.5%, and each carrier was made of γ-alumina. Other than that, propane was produced by a hydrogenation reaction to propylene under the same conditions as in Example 1.
The maximum exothermic temperature of 400 ° C. was exhibited at a position 4 cm from the inlet 10a in the reaction tower 10 by the hydrogenation reaction to propylene in the reaction tower 10 under the above conditions.
When impurities contained in the propane gas discharged from the outlet 10b of the reaction tower 10 are analyzed by a gas chromatograph 17 manufactured by Shimadzu Corporation, impurities other than hydrogen are residual propylene <0.1 vol ppm and methane <0.1 vol ppm. Ethane 1.6 vol% and butane 1900 vol ppm.

[Comparative Example 5]
A part of the granular member packed in the reaction tower 10 was used as a carrier carrying a catalyst. As the carrier, a material manufactured by N.E. Chemcat Co., Ltd. having a material of γ-alumina and an average particle diameter of 3 mm was used. The remainder of the granular member that does not carry the catalyst was alumina balls manufactured by ASONE Co., Ltd. having an average particle diameter of 3 mm. The catalyst loading rate by the carrier was 0.5%. The ratio of the sum of the volume of the total carrier carrying the catalyst and the volume of the whole granular member not carrying the catalyst to the volume of the whole carrier carrying the catalyst was 500 times. The carrier carrying the catalyst and the granular member not carrying the catalyst were mixed and packed into the reaction tower 10 so that the height dimension was 50 cm. Other than that, propane was produced by a hydrogenation reaction to propylene under the same conditions as in Example 1.
Due to the hydrogenation reaction to propylene in the reaction tower 10 under the above conditions, a maximum exothermic temperature of 50 ° C. was exhibited at a position 5 cm from the inlet 10 a in the reaction tower 10.
When impurities contained in the propane gas discharged from the outlet 10b of the reaction tower 10 are analyzed by a gas chromatograph 17 manufactured by Shimadzu Corporation, impurities other than hydrogen are 30% by volume of residual propylene, 1.3% by volume of methane, 0. They were 4 vol ppm and butane 0.5 vol ppm.

Table 1 below shows the analysis results in Example 1 and Comparative Examples 1 to 5.

[Example 2]
Ethylene with a purity of more than 99.99 vol% was supplied from the olefin gas cylinder 2, and ethane was produced by hydrogenation reaction to ethylene under the same conditions as in Example 1.
Due to the hydrogenation reaction to ethylene in the reaction tower 10 under the above conditions, a maximum exothermic temperature of 250 ° C. was shown at a position 6 cm from the inlet 10 a in the reaction tower 10.
When impurities contained in the ethane gas discharged from the outlet 10b of the reaction tower 10 are analyzed by a gas chromatograph 17 manufactured by Shimadzu Corporation, impurities other than hydrogen are residual ethylene <0.1 vol ppm, methane 0.3 vol ppm, propane <0.1 vol ppm.

[Comparative Example 6]
Ethane was produced by hydrogenation reaction to ethylene under the same conditions as in Example 2 except that the catalyst was supported on the support at 0.0005%.
Due to the hydrogenation reaction to ethylene in the reaction tower 10 under the above conditions, a maximum exothermic temperature of 240 ° C. was exhibited at a position 8 cm from the inlet 10a in the reaction tower 10.
When impurities contained in ethane gas discharged from the outlet 10b of the reaction tower 10 are analyzed by a gas chromatograph 17 manufactured by Shimadzu Corporation, impurities other than hydrogen are 1.0 vol ppm of residual ethylene, 0.2 vol ppm of methane, propane < It was 0.1 vol ppm.

[Comparative Example 7]
The catalyst loading rate by the carrier was 0.01%, and each carrier was made of γ-alumina. Other than that, ethane was produced by hydrogenation reaction to ethylene under the same conditions as in Example 2.
The maximum exothermic temperature of 260 ° C. was exhibited at a position 5 cm from the inlet 10a in the reaction tower 10 by the hydrogenation reaction to ethylene in the reaction tower 10 under the above conditions.
When impurities contained in ethane gas discharged from the outlet 10b of the reaction tower 10 are analyzed by a gas chromatograph 17 manufactured by Shimadzu Corporation, impurities other than hydrogen are residual ethylene <0.1 vol ppm, methane 1.0 vol ppm, propane <0.1 vol ppm.

Table 2 below shows the analysis results in Example 2 and Comparative Examples 6 and 7.

From Examples 1 and 2 and Comparative Examples 1 to 7, when the supporting rate of the metal catalyst used for the olefin hydrogenation reaction is less than 0.01%, local heat generation in the reaction tower 10 is reduced, and it is generated by a side reaction. It can be confirmed that the concentration of each impurity produced can be less than 1.0 vol. In addition, when the loading rate is 0.0005%, the unreacted olefin cannot be sufficiently reduced even if the height of the reaction column 10 and the packing height of the carrier supporting the catalyst are increased, whereas 0.001% By doing this, it can be confirmed that the unreacted olefin can be sufficiently reduced.

According to the above embodiment, the catalyst activity is achieved by making the ratio of the weight of the catalyst supported by each carrier to the sum of the weight of each carrier and the weight of the catalyst supported by each carrier less than 0.01%. Even if no granular member is mixed, the reaction heat can be reduced to prevent an excessive temperature rise due to local heat generation, the generation of impurities due to the decomposition of olefins can be suppressed, and variations in the amount of generated impurities can be prevented. In addition, by eliminating the need for a granular member that is not used as a carrier, local heat generation can be prevented, and variations in the amount of impurities generated can be prevented. By setting the ratio of the weight of the catalyst supported by each support to the sum of the weight of each support and the weight of the catalyst supported by each support to be 0.001% or more, the hydrogenation reaction to the olefin is surely caused. It is possible to prevent the unreacted olefin from being mixed as impurities in the produced paraffin. In addition, by making the granular member a carrier carrying a catalyst, a hydrogenation reaction to the olefin can be caused more reliably, and unreacted olefin can be prevented from being mixed as an impurity in the produced paraffin. In addition, the uneven distribution of the catalyst in the reaction tower 10 can be reliably reduced, and variations in the amount of impurities produced can be reliably prevented.

The purity of the paraffin produced according to the above embodiment is preferably 99.99 vol% or more, and more preferably 99.999 vol% or more.

The present invention is not limited to the above embodiments and examples.
For example, not all of the granular members packed in the reaction tower 10 are used as a carrier carrying a catalyst, but a part of the granular members packed in the reaction tower 10 is a carrier carrying a catalyst, and the granular member does not carry a catalyst. May be mixed with the rest of. In this case, the ratio of the weight of the catalyst supported by each support to the sum of the weight of each support in the reaction tower 10 and the weight of the catalyst supported by each support is 0.001% or more and less than 0.01%. In addition, the ratio of the total weight of the catalyst supported by all the supports to the sum of the total weight of all the granular members including the support in the reaction tower 10 and the total weight of the catalyst supported by all the supports is 0. 001% or more and less than 0.01%. That is, not only is 0.001 ≦ w _c × 100 / (w _s + w _c ) <0.01, but the total weight of the granular members that are used as carriers in the reaction tower 10 is Σw _s , and the granular members that are not used as carriers. Where Σw _g is the total weight of the catalyst and Σw _c is the total weight of the catalyst supported by all the carriers, 0.001 ≦ Σw _c × 100 / (Σw _s + Σw _g + Σw _c ). As a result, in the present invention where 0.001 ≦ w _c × 100 / (w _s + w _c ) <0.01, not only the carrier carrying the catalyst but also the granular member not carrying the catalyst and not carrying the catalyst reacts. Even when the column 10 is packed, it is possible to ensure the amount of catalyst to cause a hydrogenation reaction to the olefin, and to prevent the unreacted olefin from being mixed as impurities into the produced paraffin. Since w _c × 100 / (w _s + w _c ) <0.01, Σw _c × 100 / (Σw _s + Σw _g + Σw _c ) <0.01.

Also, the method for separating hydrogen from paraffin produced by the reaction of olefin and hydrogen is not particularly limited. For example, gas phase paraffin introduced into the product tank 15 is adsorbed by an adsorbent in an adsorption tower by a pressure swing adsorption method, and hydrogen is discharged from the adsorption tower as a non-adsorbed gas so that the paraffin is not liquefied. May be separated from the paraffin to increase the purity of the paraffin.

DESCRIPTION OF SYMBOLS 1 ... Paraffin manufacturing apparatus, 2 ... Olefin gas cylinder, 6 ... Hydrogen gas cylinder, 10 ... Reaction tower, 15 ... Product tank.

Claims

Packing a plurality of granular members having no catalytic activity into a reaction tower;
At least a part of the granular member is a carrier carrying a catalyst,
In the method for producing paraffin by the reaction of olefin in a gas phase with hydrogen in the presence of the catalyst in the reaction tower,
The ratio of the total weight of the catalyst supported by all the carriers to the sum of the total weight of all the granular members including the carrier and the total weight of the catalysts supported by all the carriers is 0.001% And less than 0.01%,
The ratio of the weight of the catalyst carried by each carrier to the sum of the weight of each carrier and the weight of the catalyst carried by each carrier is 0.001% or more and less than 0.01%. A method for producing paraffin.
The method for producing paraffin according to claim 1, wherein all the granular members are used as the carrier carrying the catalyst.
The method for producing paraffin according to claim 1, wherein a part of the granular member is used as the carrier carrying the catalyst and mixed with the rest of the granular member not carrying the catalyst.
The method for producing paraffin according to any one of claims 1 to 3, wherein the olefin is ethylene, propylene, n-butene or isobutene.
The method for producing paraffin according to any one of claims 1 to 4, wherein the catalyst contains palladium, and the carrier is alumina.
The method for producing paraffin according to any one of claims 1 to 5, wherein the purity of the paraffin is 99.99 vol% or more.