TWI741077B - Method for producing paraffin - Google Patents

Method for producing paraffin Download PDF

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TWI741077B
TWI741077B TW106140683A TW106140683A TWI741077B TW I741077 B TWI741077 B TW I741077B TW 106140683 A TW106140683 A TW 106140683A TW 106140683 A TW106140683 A TW 106140683A TW I741077 B TWI741077 B TW I741077B
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catalyst
paraffin wax
carrier
reaction tower
reaction
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TW106140683A
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TW201835013A (en
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津野修司
桑名晃裕
酒井良一郎
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日商住友精化股份有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C9/00—Aliphatic saturated hydrocarbons
    • C07C9/02—Aliphatic saturated hydrocarbons with one to four carbon atoms
    • C07C9/06—Ethane
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C9/00—Aliphatic saturated hydrocarbons
    • C07C9/02—Aliphatic saturated hydrocarbons with one to four carbon atoms
    • C07C9/08—Propane
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

本發明提供一種能夠由可容易獲取之高純度烯烴，於抑制副反應並且雜質生成量不產生偏差之狀況下，穩定地高效地製造高純度之石蠟的方法。 本發明係將不具有觸媒活性之複數個粒狀構件填充至反應塔10，將上述粒狀構件之中之至少一部分設為擔載有觸媒之載體，於上述反應塔10中於上述觸媒之存在下藉由氣相狀態之烯烴與氫氣之反應而製造石蠟。將上述載體各者所擔載之上述觸媒之重量相對於上述載體各者之重量與上述載體各者所擔載之上述觸媒之重量之和的比率設為0.001%以上且未達0.01%。The present invention provides a method that can produce high-purity paraffin wax stably and efficiently from easily obtainable high-purity olefins under the condition that side reactions are suppressed and the amount of impurity produced does not vary. In the present invention, a plurality of granular members without catalyst activity are filled in the reaction tower 10, at least a part of the granular members is set as a carrier carrying a catalyst, and the catalyst is placed in the reaction tower 10 In the presence of medium, paraffin wax is produced by the reaction of olefin and hydrogen in the gas phase. The ratio of the weight of the catalyst carried by each of the above-mentioned carriers relative to the weight of each of the above-mentioned carriers and the weight of the above-mentioned catalyst carried by each of the above-mentioned carriers is set to 0.001% or more and less than 0.01% .

Description

石蠟之製造方法Manufacturing method of paraffin wax

本發明係關於一種於觸媒之存在下藉由對烯烴之氫化反應而製造高純度之石蠟的方法。The present invention relates to a method for producing high-purity paraffin wax by hydrogenation of olefins in the presence of a catalyst.

近年來，越來越需要高純度乙烷、高純度丙烷等高純度石蠟。例如，關於作為高耐壓碳化矽(SiC)半導體之原料之高純度丙烷，為了實現碳化矽之高耐壓性，要求將含有之雜質各者之濃度設為未達1.0 vol ppm。 作為高純度石蠟之製造方法，已知有對低純度石蠟進行蒸餾精製之方法。然而，於該方法中，用以將雜質分離之蒸餾設備規模大而投資額變大。又，因設備規模大，故運轉需要巨大之能量。尤其，於對以雜質之形式包含丙烯之低純度丙烷進行蒸餾之情形時，因丙烷與丙烯之沸點差較小，故利用蒸餾進行精製較為困難。 又，已知有於觸媒之存在下藉由對液相丙烯之氫化反應而製造丙烷之方法(專利文獻1)。然而，於原料之丙烯為液相之情形時，若原料濃度變高，則反應熱變大，而除熱變得困難，因過度之溫度上升，導致丙烯被分解而成為雜質，從而使雜質濃度變高。因此，為了藉由對液相原料之氫化反應而製造高純度之石蠟，必須使原料濃度為25%左右以下，因此，高效地製造高純度之石蠟較為困難。 因此，提出了藉由對氣相狀態之烯烴之氫化反應而製造石蠟之方法(專利文獻2)。此時，將載體所擔載之觸媒及不具有觸媒活性之氧化鋁球等填充至反應塔，將由觸媒之存在下之氫化反應產生之反應熱藉由向氧化鋁球等之解吸或傳熱等去除。藉此，防止因過度之溫度上升引起之烯烴之分解，而使雜質濃度降低。進而，隨著朝向反應塔中之氣流之下游，使氧化鋁球等減少，而使觸媒之比率增加。藉此，使烯烴與氫氣確實地反應，而防止未反應之烯烴混入至石蠟，從而使雜質濃度降低。 [先前技術文獻] [專利文獻] [專利文獻1]美國專利第3509226號說明書 [專利文獻2]日本專利特開2014-84285號公報In recent years, there has been an increasing need for high-purity paraffin waxes such as high-purity ethane and high-purity propane. For example, with regard to high-purity propane as a raw material for high-voltage silicon carbide (SiC) semiconductors, in order to achieve the high-voltage resistance of silicon carbide, the concentration of each of the impurities contained in it is required to be less than 1.0 vol ppm. As a method for producing high-purity paraffin wax, a method of distilling and refining low-purity paraffin wax is known. However, in this method, the scale of the distillation equipment for separating impurities is large and the investment amount becomes large. In addition, due to the large scale of the equipment, a huge amount of energy is required for operation. In particular, when distilling low-purity propane containing propylene as an impurity, since the boiling point difference between propane and propylene is small, purification by distillation is difficult. In addition, a method for producing propane by hydrogenation of liquid-phase propylene in the presence of a catalyst is known (Patent Document 1). However, when the raw material propylene is in the liquid phase, if the raw material concentration becomes higher, the heat of reaction becomes larger and heat removal becomes difficult. Due to the excessive temperature rise, the propylene is decomposed and becomes an impurity, thereby increasing the impurity concentration. Becomes high. Therefore, in order to produce high-purity paraffin wax by hydrogenation of liquid-phase raw materials, the raw material concentration must be about 25% or less. Therefore, it is difficult to efficiently produce high-purity paraffin wax. Therefore, a method for producing paraffin wax by hydrogenation of olefins in a gaseous state has been proposed (Patent Document 2). At this time, the catalyst supported by the carrier and alumina balls without catalyst activity are filled into the reaction tower, and the reaction heat generated by the hydrogenation reaction in the presence of the catalyst is desorbed or desorbed to the alumina balls, etc. Heat transfer and other removal. This prevents the decomposition of olefins caused by excessive temperature rise and reduces the concentration of impurities. Furthermore, as it goes to the downstream of the gas flow in the reaction tower, the alumina balls etc. decrease, and the ratio of the catalyst increases. Thereby, the olefin and the hydrogen are surely reacted, and the unreacted olefin is prevented from being mixed into the paraffin, thereby reducing the impurity concentration. [Prior Art Document] [Patent Document] [Patent Document 1] Specification of U.S. Patent No. 3509226 [Patent Document 2] Japanese Patent Laid-Open No. 2014-84285

[發明所欲解決之問題] 根據專利文獻2中記載之方法，將氣相之烯烴作為原料，因此，與使用液相之原料之情形相比，即便提高原料濃度，反應熱之去除亦較為容易。然而，雜質生成量存在偏差，而存在無法穩定地高效地製造高純度之石蠟之問題。 本發明之目的在於解決藉由氣相狀態之烯烴與氫氣之反應而製造石蠟之方法中之上述先前技術之問題。 [解決問題之技術手段] 本發明係將不具有觸媒活性之複數個粒狀構件填充至反應塔，將上述粒狀構件之中之至少一部分設為擔載有觸媒之載體，於上述反應塔中於上述觸媒之存在下藉由氣相狀態之烯烴與氫氣之反應而製造石蠟之方法，其特徵在於：將全部上述載體所擔載之上述觸媒之總重量相對於包含上述載體之全部上述粒狀構件之總重量與全部上述載體所擔載之上述觸媒之總重量之和的比率設為0.001%以上且未達0.01%，且將上述載體各者所擔載之上述觸媒之重量相對於上述載體各者之重量與上述載體各者所擔載之上述觸媒之重量之和的比率設為0.001%以上且未達0.01%。 本發明基於以下之見解。 於專利文獻2中記載之先前技術中，於反應活躍之氣流之上游區域，將氧化鋁球等與擔載有觸媒之載體進行混合，將氧化鋁球等之體積相對於氧化鋁球等之體積與擔載有觸媒之全部載體之體積之和的比率設為90～99%。如此於不具有觸媒活性之氧化鋁球等之比率較高之情形時，於反應塔中，觸媒偏集存在，又，亦無混合狀態之再現性。進而，於專利文獻2中，載體各者所擔載之觸媒之重量相對於載體各者之重量與載體各者所擔載之觸媒之重量之和的比率係設為0.1～1.0%。因此，於觸媒偏集存在之位置，反應熱增多，因由局部發熱引起之過度之溫度上升，導致烯烴被分解而成為雜質。藉此，於先前技術中，雜質生成量產生偏差，而無法穩定地高效地製造高純度之石蠟。 相對於此，根據本發明，將載體各者所擔載之觸媒之重量相對於載體各者之重量與載體各者所擔載之觸媒之重量之和的比率設為小於上述先前技術中之該比率之未達0.01%，藉此，能夠減少反應熱而能夠防止因局部發熱引起之過度之溫度上升，而能夠抑制因烯烴之分解引起之雜質生成，從而能夠防止雜質生成量產生偏差。又，無需未設為載體之粒狀構件或者能夠縮小混合比率，因此，能夠防止雜質生成量產生偏差。藉由將載體各者所擔載之觸媒之重量相對於載體各者之重量與載體各者所擔載之觸媒之重量之和的比率設為0.001%以上，而能夠使對烯烴之氫化反應確實地發生，從而能夠確實地防止未反應之烯烴以雜質之形式混入至所製造之石蠟。 藉由將全部上述粒狀構件設為擔載有上述觸媒之上述載體，而能夠使對烯烴之氫化反應更確實地發生，從而能夠防止未反應之烯烴以雜質之形式混入至所製造之石蠟，又，能夠使反應塔中之觸媒之分佈均勻化，而能夠確實地防止雜質生成量產生偏差。 於本發明中，較佳為不將全部填充至上述反應塔之不具有觸媒活性之上述粒狀構件設為擔載有上述觸媒之上述載體，而將上述粒狀構件之中之一部分設為擔載有上述觸媒之上述載體，並與剩餘之未擔載上述觸媒之上述粒狀構件進行混合。 藉此，於上述載體各者所擔載之上述觸媒之重量相對於上述載體各者之重量與上述載體各者所擔載之上述觸媒之重量之和的比率成為0.001%以上且未達0.01%之本發明中，於不僅擔載有觸媒之載體被填充至反應塔，且未被設為載體而未擔載觸媒之粒狀構件亦被填充至反應塔之情形時，亦能夠確保觸媒量而使對烯烴之氫化反應確實地發生，從而能夠防止未反應之烯烴以雜質之形式混入至所製造之石蠟。 上述烯烴及石蠟較佳為各者碳數為2～4。即，較佳為分別藉由對丙烯(C3 H6 )之氫化反應而製造丙烷(C3 H8 )，藉由對乙烯(C2 H4 )之氫化反應而製造乙烷(C2 H6 )，藉由對正丁烯或異丁烯(C4 H8 )之氫化反應而製造丁烷(C4 H10 )。 較佳為，上述觸媒包含鈀，上述載體為氧化鋁。 上述石蠟之純度較佳為99.99 vol%以上，更佳為99.999 vol%以上。 [發明之效果] 根據本發明，可提供一種能夠由可容易獲取之高純度烯烴，於抑制副反應並且雜質生成量不產生偏差之狀況下，穩定地高效地製造高純度之石蠟的方法。[Problem to be solved by the invention] According to the method described in Patent Document 2, gas phase olefins are used as raw materials. Therefore, compared with the case of using liquid phase raw materials, it is easier to remove the heat of reaction even if the raw material concentration is increased. . However, the amount of impurities produced varies, and there is a problem that high-purity paraffin wax cannot be produced stably and efficiently. The purpose of the present invention is to solve the above-mentioned problems of the prior art in the method of producing paraffin wax by the reaction of olefins in the gas phase state with hydrogen. [Technical Means for Solving the Problem] The present invention fills a reaction tower with a plurality of granular members that do not have catalytic activity, and sets at least a part of the granular members as a carrier carrying a catalyst to perform the reaction The method for producing paraffin wax by reacting olefins in the gas phase with hydrogen in the presence of the catalyst in the tower is characterized in that: the total weight of the catalyst supported by all the carriers is relative to the total weight of the carrier containing the carrier The ratio of the total weight of all the above-mentioned granular members to the total weight of the above-mentioned catalyst carried by all the above-mentioned carriers is set to 0.001% or more and less than 0.01%, and the above-mentioned catalyst carried by each of the above-mentioned carriers The ratio of the weight to the sum of the weight of each of the above-mentioned carriers and the weight of the above-mentioned catalyst carried by each of the above-mentioned carriers is set to 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 like are mixed with a catalyst-carrying carrier in the upstream region of the airflow where the reaction is active, and the volume of the alumina balls and the like is relative to the volume of the alumina balls and the like. The ratio of the volume to the sum of the volume of all the carriers carrying the catalyst is set to 90-99%. In this way, when the ratio of alumina balls that do not have catalyst activity is high, in the reaction tower, the catalyst is segregated and there is no reproducibility of the mixed state. Furthermore, in Patent Document 2, 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 set to 0.1 to 1.0%. Therefore, at the location where the catalyst is concentrated, the heat of reaction increases, and the excessive temperature rise caused by the local heating causes the olefin to be decomposed and becomes an impurity. As a result, in the prior art, the amount of impurities produced varies, and high-purity paraffin wax cannot be produced stably and efficiently. In contrast, according to the present invention, 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 set to be smaller than in the above-mentioned prior art The ratio is less than 0.01%, thereby reducing the heat of reaction, preventing excessive temperature rise due to local heating, suppressing the generation of impurities due to the decomposition of olefins, and preventing deviations in the amount of impurities generated. In addition, there is no need for a granular member that is not used as a carrier or the mixing ratio can be reduced. Therefore, it is possible to prevent variation in the amount of impurity generation. By setting 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 at 0.001% or more, hydrogenation of olefins can be achieved The reaction occurs reliably, so that unreacted olefins can be reliably prevented from being mixed into the manufactured paraffin in the form of impurities. By using all the above-mentioned granular members as the above-mentioned carrier supporting the above-mentioned catalyst, the hydrogenation reaction of the olefin can be more reliably performed, and the unreacted olefin can be prevented from being mixed into the manufactured paraffin as an impurity. In addition, it is possible to make the distribution of the catalyst in the reaction tower uniform, and it is possible to reliably prevent variation in the amount of impurity produced. In the present invention, it is preferable not to set all the granular members without catalyst activity that are filled into the reaction tower as the carrier carrying the catalyst, and to set a part of the granular members. It is the above-mentioned carrier which carries the above-mentioned catalyst, and is mixed with the remaining granular member which does not carry the above-mentioned catalyst. As a result, the ratio of the weight of the catalyst carried on each of the carriers to the sum of the weight of each of the carriers and the weight of the catalyst carried on each of the carriers becomes 0.001% or more and less than In the present invention of 0.01%, not only the carrier carrying the catalyst is filled into the reaction tower, but also the granular member that is not set as a carrier and not carrying the catalyst is also filled into the reaction tower. Ensuring the amount of catalyst to ensure that the hydrogenation reaction of olefins occurs reliably, so as to prevent unreacted olefins from being mixed into the manufactured paraffin as impurities. The above-mentioned olefins and paraffins preferably each have 2 to 4 carbon atoms. That is, it is preferable to produce propane (C 3 H 8 ) by hydrogenation reaction of propylene (C 3 H 6 ), and produce ethane (C 2 H 4 ) by hydrogenation reaction of ethylene (C 2 H 4 ). 6 ), through the hydrogenation of n-butene or isobutene (C 4 H 8 ) to produce butane (C 4 H 10 ). Preferably, the catalyst includes palladium, and the carrier is alumina. The purity of the paraffin wax is preferably 99.99 vol% or more, more preferably 99.999 vol% or more. [Effects of the Invention] According to the present invention, it is possible to provide a method for stably and efficiently producing high-purity paraffin wax from easily obtainable high-purity olefins, while suppressing side reactions and without variation in the amount of impurity generation.

圖1所示之石蠟製造裝置1自烯烴氣體料缸2以氣相狀態之烯烴之形式供給乙烯、丙烯、正丁烯或異丁烯等。該供給之烯烴藉由第1減壓閥3被減壓，藉由附流量計之第1流量控制閥4被設為設定流量，並被導入至氣體混合器5。又，石蠟製造裝置1自氫氣料缸6供給氣相狀態之氫氣。該供給之氫氣藉由第2減壓閥7被減壓，藉由附流量計之第2流量控制閥8被設為設定流量，並被導入至氣體混合器5。於氣體混合器5中經混合之烯烴與氫氣被作為原料自上部入口10a導入至筒狀之反應塔10。 為了防止所製造之石蠟之純度下降，作為原料之烯烴之純度較佳為99.99 vol%以上。 對烯烴之氫化反應係反應向莫耳數減少之方向進展之還原反應，因此，藉由向反應塔10供給多於理論當量之氫氣，能夠使反應速度上升。又，若向反應塔10供給之氫氣之量相對於烯烴之供給量低於1.00倍莫耳，則作為原料之烯烴會殘留，若超過2.00倍莫耳，則後續步驟中之氫氣之去除變得麻煩。由此，氫氣之供給量較佳為相對於烯烴之供給量為1.00～2.00倍莫耳，更佳為1.05～1.20倍莫耳。又，為了防止所製造之石蠟之純度下降，作為原料之氫氣之純度較佳為99 vol%以上，更佳為99.9 vol%以上。 於反應塔10填充有複數個粒狀構件。於本實施形態中，將填充至反應塔10之全部粒狀構件設為擔載有觸媒之載體。 作為觸媒，可使用公知之還原觸媒，例如可使用鈀、鉑、銠、釕、鎳等金屬觸媒，於本實施形態中係設為鈀。載體只要為能夠擔載觸媒之不具有觸媒活性者，則材質並無限定，於本實施形態中係設為氧化鋁。載體之形狀於本實施形態中係設為球形，但並無特別限定，例如亦可為圓柱狀、顆粒狀等，尺寸於本實施形態中係設為平均粒徑3 mm，但亦並無特別限定。再者，載體亦可擔載2種以上之觸媒。 反應塔10中之載體各者所擔載之觸媒之重量相對於載體各者之重量與載體各者所擔載之觸媒之重量之和的比率係設為0.001%以上且未達0.01%。即，將載體各者之重量設為ws，將載體各者所擔載之觸媒之重量設為wc，並設為0.001≦wc×100/(ws＋wc)＜0.01。 又，填充至反應塔10之全部粒狀構件係設為擔載有觸媒之載體，因此，全部載體所擔載之觸媒之總重量相對於包含反應塔10中之載體之全部粒狀構件之總重量與全部載體所擔載之觸媒之總重量之和的比率係設為0.001%以上且未達0.01%。 於反應塔10中於觸媒之存在下藉由氣相狀態之烯烴與氫氣之反應，生成氣相狀態之乙烷、丙烷、或丁烷等作為石蠟。為了控制反應塔10之內部溫度，反應塔10被冷卻套11覆蓋，並設置對冷卻套11內之冷媒進行抽吸、冷卻使其回流之冷卻裝置12，反應塔10之內部溫度係由溫度計13測定。反應塔10之內部溫度係為了反應速度控制不會變得困難而設為石蠟不會液化之溫度，又，係設為不會因石蠟之分解引起雜質增加之溫度。例如於製造丙烷作為石蠟之情形時，反應塔10之內部溫度較佳為設為-42～250℃，更佳為設為0～250℃。 藉由反應塔10中之對烯烴之氫化反應而生成之石蠟係自反應塔10之下部出口10b被排出，並經由用以調節反應塔10之內部壓力之背壓閥14而被導入至製品槽15，反應塔10之內部壓力係由壓力計16測定。反應塔10之內部壓力若變得過高，則會促進氫化反應，但有無法控制反應熱而導致雜質增加之虞，又，有反應氣體液化而成為液相反應之虞，因此，較佳為適當進行控制。例如於製造丙烷作為石蠟之情形時，反應塔10之內部壓力通常較佳為設為0.0～0.5 MPaG，更佳為設為0.1～0.5 MPaG。 還原反應時之氣體流速或空間速度越小，則越可獲得較佳之結果。例如於製造丙烷作為石蠟之情形時，標準狀態氣體量下之空間速度SV較佳為設為1000/h以下，更佳為設為500/h以下。藉由空間速度成為1000/h以下，而能夠於氫化反應不會變得不充分之狀況下防止未反應之原料殘留。 為了對藉由氫化反應而生成之石蠟中包含之雜質進行分析，自反應塔10之出口10b排出之氣體之一部分被導入至氣體層析儀17。 於本實施形態中，為了自藉由烯烴與氫氣之反應而生成之石蠟將氫氣分離，設置用以將被導入至製品槽15之氣相之石蠟冷卻而使之液化之冷卻裝置18。冷卻裝置18之冷卻溫度係設為低於石蠟之沸點且高於氫氣之沸點。以雜質之形式包含於石蠟中之氫氣不液化，而自製品槽15經由附流量計之第3流量控制閥19排出，從而自石蠟分離，藉此，能夠提高石蠟之純度。於本實施形態中，石蠟中包含之氫氣之濃度係設為未達1.0 vol ppm。亦可對自石蠟分離之氫氣進行回收，使其返回至反應塔10，藉此，作為原料進行再利用。 [實施例] [實施例1] 使用上述實施形態之石蠟製造裝置1，藉由對丙烯之氫化反應而製造丙烷。 反應塔10係設為不鏽鋼製且內徑31 mm。將反應塔10中之粒狀構件之填充高度設為50 cm。將填充至反應塔10之全部粒狀構件設為擔載觸媒之載體。即，將擔載有觸媒之全部載體之體積與不擔載觸媒之全部粒狀構件之體積之和相對於擔載有觸媒之全部載體之體積之比率設為1倍。作為擔載有觸媒之載體，使用平均粒徑3 mm之N.E.CHEMCAT(股)製造者。本實施例之各載體係α氧化鋁製，且擔載有鈀(Pd)作為觸媒。將載體各者所擔載之觸媒之重量相對於載體各者之重量與載體各者所擔載之觸媒之重量之和的比率(以下，將該比率稱為載體擔載觸媒之「擔載率」)設為0.001%。 自烯烴氣體料缸2供給純度超過99.99 vol%之丙烯，以1.0 L/min之流量導入至氣體混合器5，自氫氣料缸6供給純度超過99.999 vol%之氫氣，以1.1 L/min之流量導入至氣體混合器5。將丙烯及氫氣於混合器5中於室溫下進行混合之後，導入至反應塔10。此時，反應塔10之內部壓力係設為0.3 MPaG，使作為冷媒之溫度40℃之水於冷卻套11中循環。 於上述條件下於反應塔10中藉由對丙烯之氫化反應，於反應塔10內之距入口10a為7 cm之位置顯示出最大發熱溫度230℃。 利用島津製作所(股)製造之氣體層析儀17對自反應塔10之出口10b排出之丙烷氣體中包含之雜質進行分析後，氫氣以外之雜質為殘留丙烯＜0.1 vol ppm、甲烷0.3 vol ppm、乙烷0.5 vol ppm、丁烷0.6 vol ppm。 [比較例1] 將載體擔載觸媒之擔載率設為0.0005%，除此以外，於與實施例1相同之條件下，藉由對丙烯之氫化反應而製造丙烷。 藉由上述條件下之反應塔10中之對丙烯之氫化反應，於反應塔10內之距入口10a為10 cm之位置顯示出最大發熱溫度220℃。 利用島津製作所(股)製造之氣體層析儀17對自反應塔10之出口10b排出之丙烷氣體中包含之雜質進行分析後，氫氣以外之雜質為殘留丙烯1.3 vol ppm、甲烷0.2 vol ppm、乙烷0.3 vol ppm、丁烷＜0.1 vol ppm。 [比較例2] 將載體擔載觸媒之擔載率設為0.0005%，將反應塔10之高度設為實施例1之2倍，將擔載有觸媒之載體之反應塔10中之填充高度設為實施例1之2倍。除此以外，於與實施例1相同之條件下，藉由對丙烯之氫化反應而製造丙烷。 藉由上述條件下之反應塔10中之對丙烯之氫化反應，於反應塔10內之距入口10a為9 cm之位置顯示出最大發熱溫度220℃。 利用島津製作所(股)製造之氣體層析儀17對自反應塔10之出口10b排出之丙烷氣體中包含之雜質進行分析後，氫氣以外之雜質為殘留丙烯1.2 vol ppm、甲烷0.1 vol ppm、乙烷0.3 vol ppm、丁烷＜0.1 vol ppm。 [比較例3] 將載體擔載觸媒之擔載率設為0.01%，將各載體設為γ氧化鋁製。除此以外，於與實施例1相同之條件下，藉由對丙烯之氫化反應而製造丙烷。 藉由上述條件下之反應塔10中之對丙烯之氫化反應，於反應塔10內之距入口10a為7 cm之位置顯示出最大發熱溫度240℃。 利用島津製作所(股)製造之氣體層析儀17對自反應塔10之出口10b排出之丙烷氣體中包含之雜質進行分析後，氫氣以外之雜質為殘留丙烯＜0.1 vol ppm、甲烷1.0 vol ppm、乙烷0.9 vol ppm、丁烷1.0 vol ppm。 [比較例4] 將載體擔載觸媒之擔載率設為0.5%，將各載體設為γ氧化鋁製。除此以外，於與實施例1相同之條件下，藉由對丙烯之氫化反應而製造丙烷。 藉由上述條件下之反應塔10中之對丙烯之氫化反應，於反應塔10內之距入口10a為4 cm之位置顯示出最大發熱溫度400℃。 利用島津製作所(股)製造之氣體層析儀17對自反應塔10之出口10b排出之丙烷氣體中包含之雜質進行分析後，氫氣以外之雜質為殘留丙烯＜0.1 vol ppm、甲烷＜0.1 vol ppm、乙烷1.6 vol%、丁烷1900 vol ppm。 [比較例5] 將填充至反應塔10之粒狀構件之中之一部分設為擔載有觸媒之載體。作為載體，使用材質為γ氧化鋁、平均粒徑3 mm之N.E.CHEMCAT(股)製造者。剩餘之不擔載觸媒之粒狀構件係設為平均粒徑3 mm之AS ONE(股)製造之氧化鋁球。將載體擔載觸媒之擔載率設為0.5%。將擔載有觸媒之全部載體之體積與不擔載觸媒之全部粒狀構件之體積之和相對於擔載有觸媒之全部載體之體積之比率設為500倍。將擔載有觸媒之載體與不擔載觸媒之粒狀構件進行混合，以高度方向尺寸成為50 cm之方式填充至反應塔10。除此以外，於與實施例1相同之條件下，藉由對丙烯之氫化反應而製造丙烷。 藉由上述條件下之反應塔10中之對丙烯之氫化反應，於反應塔10內之距入口10a為5 cm之位置顯示出最大發熱溫度50℃。 利用島津製作所(股)製造之氣體層析儀17對自反應塔10之出口10b排出之丙烷氣體中包含之雜質進行分析後，氫氣以外之雜質為殘留丙烯30 vol%、甲烷1.3 vol ppm、乙烷0.4 vol ppm、丁烷0.5 vol ppm。 以下之表1表示實施例1及比較例1～5中之分析結果。 [表1]

Figure 106140683-A0304-0001
[實施例2] 自烯烴氣體料缸2供給純度超過99.99 vol%之乙烯，除此以外，於與實施例1相同之條件下，藉由對乙烯之氫化反應而製造乙烷。 藉由上述條件下之反應塔10中之對乙烯之氫化反應，於反應塔10內之距入口10a為6 cm之位置顯示出最大發熱溫度250℃。 利用島津製作所(股)製造之氣體層析儀17對自反應塔10之出口10b排出之乙烷氣體中包含之雜質進行分析後，氫氣以外之雜質為殘留乙烯＜0.1 vol ppm、甲烷0.3 vol ppm、丙烷＜0.1 vol ppm。 [比較例6] 將載體擔載觸媒之擔載率設為0.0005%，除此以外，於與實施例2相同之條件下，藉由對乙烯之氫化反應而製造乙烷。 藉由上述條件下之反應塔10中之對乙烯之氫化反應，於反應塔10內之距入口10a為8 cm之位置顯示出最大發熱溫度240℃。 利用島津製作所(股)製造之氣體層析儀17對自反應塔10之出口10b排出之乙烷氣體中包含之雜質進行分析後，氫氣以外之雜質為殘留乙烯1.0 vol ppm、甲烷0.2 vol ppm、丙烷＜0.1 vol ppm。 [比較例7] 將載體擔載觸媒之擔載率設為0.01%，將各載體設為γ氧化鋁製。除此以外，於與實施例2相同之條件下，藉由對乙烯之氫化反應而製造乙烷。 藉由上述條件下之反應塔10中之對乙烯之氫化反應，於反應塔10內之距入口10a為5 cm之位置顯示出最大發熱溫度260℃。 利用島津製作所(股)製造之氣體層析儀17對自反應塔10之出口10b排出之乙烷氣體中包含之雜質進行分析後，氫氣以外之雜質為殘留乙烯＜0.1 vol ppm、甲烷1.0 vol ppm、丙烷＜0.1 vol ppm。 以下之表2表示實施例2及比較例6、7中之分析結果。 [表2]
Figure 106140683-A0304-0002
 根據實施例1、2及比較例1～7，可確認：藉由將烯烴之氫化反應所使用之金屬觸媒之擔載率設為未達0.01%，而能夠使反應塔10中之局部發熱降低，能夠使副反應中生成之雜質各者之濃度未達1.0 vol ppm，從而能夠抑制雜質生成量。又，可確認：於將擔載率設為0.0005%之情形時，即便增加反應塔10之高度及擔載有觸媒之載體之填充高度，亦無法充分地減少未反應烯烴，相對於此，藉由設為0.001%，而能夠充分地減少未反應烯烴。 根據上述實施形態，藉由將載體各者所擔載之觸媒之重量相對於載體各者之重量與載體各者所擔載之觸媒之重量之和的比率設為未達0.01%，即便不混合不具有觸媒活性之粒狀構件，亦能夠減少反應熱而防止因局部發熱引起之過度之溫度上升，而能夠抑制因烯烴之分解引起之雜質生成，從而能夠防止雜質生成量產生偏差。又，由於可無需未設為載體之粒狀構件，亦能夠防止局部發熱，從而能夠防止雜質生成量產生偏差。藉由將載體各者所擔載之觸媒之重量相對於載體各者之重量與載體各者所擔載之觸媒之重量之和的比率設為0.001%以上，而能夠使對烯烴之氫化反應確實地發生，從而能夠防止未反應之烯烴以雜質之形式混入至所製造之石蠟。又，藉由將全部粒狀構件設為擔載有觸媒之載體，而能夠使對烯烴之氫化反應更確實地發生，從而能夠防止未反應之烯烴以雜質之形式混入至所製造之石蠟，進而，能夠使反應塔10中之觸媒之偏集存在確實地降低，從而能夠確實地防止雜質生成量產生偏差。 藉由上述實施形態而製造之石蠟之純度較佳為99.99 vol%以上，更佳為99.999 vol%以上。 本發明並不限定於上述實施形態或實施例。 例如，亦可不將填充至反應塔10之全部粒狀構件設為擔載有觸媒之載體，而將填充至反應塔10之粒狀構件之中之一部分設為擔載有觸媒之載體，並與剩餘之不擔載觸媒之粒狀構件進行混合。於該情形時，不僅將反應塔10中之載體各者所擔載之觸媒之重量相對於載體各者之重量與載體各者所擔載之觸媒之重量之和的比率設為0.001%以上且未達0.01%，亦將全部載體所擔載之觸媒之總重量相對於包含反應塔10中之載體之全部粒狀構件之總重量與全部載體所擔載之觸媒之總重量之和的比率設為0.001%以上且未達0.01%。即，不僅設為0.001≦wc×100/(ws＋wc)＜0.01，亦將反應塔10中之設為載體之粒狀構件之總重量設為Σws，將未設為載體之粒狀構件之總重量設為Σwg，將由全部載體擔載之觸媒之總重量設為Σwc，並設為0.001≦Σwc×100/(Σws＋Σwg＋Σwc)。藉此，於成為0.001≦wc×100/(ws＋wc)＜0.01之本發明中，於不僅擔載有觸媒之載體被填充至反應塔10，未被設為載體而未擔載觸媒之粒狀構件亦被填充至反應塔10之情形時，亦能夠確保觸媒量而使對烯烴之氫化反應確實地發生，從而能夠防止未反應之烯烴以雜質之形式混入至所製造之石蠟。再者，因為wc×100/(ws＋wc)＜0.01，故成為Σwc×100/(Σws＋Σwg＋Σwc)＜0.01。 又，自藉由烯烴與氫氣之反應產生之石蠟將氫氣分離之方法並無特別限定。例如，亦可藉由壓力振盪吸附法使被導入至製品槽15之氣相之石蠟於吸附塔內吸附至吸附劑，並將氫氣作為非吸附氣體自吸附塔排出，藉此，於不使石蠟液化之狀況下將氫氣自石蠟分離，從而提高石蠟之純度。The paraffin production device 1 shown in FIG. 1 supplies ethylene, propylene, n-butene, or isobutylene from the olefin gas cylinder 2 in the form of olefin in the gas phase. The supplied olefin is decompressed by the first pressure reducing valve 3, is set to a set flow rate by the first flow control valve 4 with a flow meter, and is introduced into the gas mixer 5. In addition, the paraffin production device 1 supplies hydrogen gas in the gas phase from the hydrogen gas cylinder 6. The supplied hydrogen gas is decompressed by the second pressure reducing valve 7, is set to the set flow rate by the second flow 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 the purity of the paraffin wax produced from decreasing, the purity of the olefin used as the raw material is preferably 99.99 vol% or more. The hydrogenation reaction of olefins is a reduction reaction in which the reaction progresses toward the reduction of the molar number. Therefore, by supplying more than the theoretical equivalent of hydrogen to the reaction tower 10, the reaction rate can be increased. In addition, if the amount of hydrogen supplied to the reaction tower 10 is less than 1.00 times mol relative to the amount of olefin supplied, the olefin used as the raw material will remain, and if it exceeds 2.00 times mol, the removal of hydrogen in the subsequent step will become trouble. Therefore, the supply amount of hydrogen is preferably 1.00 to 2.00 times mol relative to the supply amount of olefin, and more preferably 1.05 to 1.20 times mol. In addition, in order to prevent the purity of the paraffin wax produced from decreasing, the purity of the hydrogen used as the raw material is preferably 99 vol% or more, and more preferably 99.9 vol% or more. The reaction tower 10 is filled with a plurality of granular members. In this embodiment, all the granular members filled 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, and nickel can be used. In this embodiment, palladium is used. The material of the carrier is not limited as long as it is capable of supporting the catalyst and does not have catalytic activity. In this embodiment, it is made of alumina. The shape of the carrier is spherical in this embodiment, but it is not particularly limited. For example, it may be cylindrical, granular, etc., and the size is set to an average particle diameter of 3 mm in this embodiment, but there is no particular limitation. limited. Furthermore, the carrier can also carry more than two types of catalysts. The ratio of the weight of the catalyst carried by each carrier in the reaction tower 10 to the sum of the weight of each carrier and the weight of the catalyst carried by each carrier is set to 0.001% or more and less than 0.01% . That is, let the weight of each carrier be ws, and the weight of the catalyst carried by each carrier be wc, and set 0.001≦wc×100/(ws+wc)<0.01. In addition, all the granular components filled in the reaction tower 10 are set as carriers carrying the catalyst. Therefore, the total weight of the catalyst carried by all the carriers is relative to all the granular components including the carriers in the reaction tower 10 The ratio of the total weight of the total weight to the total weight of the catalyst carried by all carriers is set to 0.001% or more and less than 0.01%. In the reaction tower 10, in the presence of a catalyst, ethane, propane, or butane in the gas phase is generated as paraffin by the reaction of olefin in the gas phase with hydrogen. In order to control the internal temperature of the reaction tower 10, the reaction tower 10 is covered by a cooling jacket 11, and a cooling device 12 for sucking and cooling the refrigerant in the cooling jacket 11 is provided. The internal temperature of the reaction tower 10 is measured by a thermometer 13 Determination. The internal temperature of the reaction tower 10 is set to a temperature at which paraffin wax does not liquefy in order to prevent the control of the reaction rate from becoming difficult, and is set to a temperature at which impurities do not increase due to the decomposition of paraffin wax. For example, in the case of producing propane as paraffin, the internal temperature of the reaction tower 10 is preferably -42 to 250°C, more preferably 0 to 250°C. The paraffin wax produced by the hydrogenation reaction of the olefin in the reaction tower 10 is discharged from the lower outlet 10b of the reaction tower 10, and is introduced into the product tank through the back pressure valve 14 used to adjust the internal pressure of the reaction tower 10 15. The internal pressure of the reaction tower 10 is measured by a pressure gauge 16. If the internal pressure of the reaction tower 10 becomes too high, the hydrogenation reaction will be promoted, but there is a possibility that the heat of reaction cannot be controlled and impurities increase, and the reaction gas may liquefy and become a liquid phase reaction. Therefore, it is preferably Control appropriately. For example, in the case of producing propane as paraffin, the internal pressure of the reaction tower 10 is usually preferably set to 0.0-0.5 MPaG, more preferably set to 0.1-0.5 MPaG. The smaller the gas flow rate or space velocity during the reduction reaction, the better the result can be obtained. For example, in the case of producing propane as paraffin, the space velocity SV under the standard gas volume is preferably set to 1000/h or less, and more preferably set to 500/h or less. By making the space velocity 1000/h or less, it is possible to prevent unreacted raw materials from remaining under the condition that the hydrogenation reaction does not become insufficient. In order to analyze the impurities contained in the paraffin wax produced 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 the present embodiment, in order to separate hydrogen from the paraffin produced by the reaction of olefin and hydrogen, a cooling device 18 for cooling and liquefying the paraffin in the gas phase introduced into the product tank 15 is provided. The cooling temperature of the cooling device 18 is set to be lower than the boiling point of paraffin wax and higher than the boiling point of hydrogen. The hydrogen contained in the paraffin in the form of impurities does not liquefy, and the self-made tank 15 is discharged through the third flow control valve 19 with a flow meter to separate from the paraffin, thereby improving the purity of the paraffin. In this embodiment, the concentration of hydrogen contained in paraffin wax is set to less than 1.0 vol ppm. It is also possible to recover the hydrogen separated from the paraffin and return it to the reaction tower 10 to be reused as a raw material. [Examples] [Example 1] Using the paraffin production apparatus 1 of the above-mentioned embodiment, propane was produced by hydrogenation of propylene. The reaction tower 10 is made of stainless steel and has an inner diameter of 31 mm. The filling height of the granular components in the reaction tower 10 is set to 50 cm. All the granular members filled in the reaction tower 10 are used as a carrier supporting the catalyst. That is, the ratio of the sum of the volume of all the carriers carrying the catalyst and the volume of all the granular members not carrying the catalyst to the volume of all the carriers carrying the catalyst is set to 1 time. As the carrier carrying the catalyst, NECHEMCAT (stock) manufacturer with an average particle diameter of 3 mm is used. Each carrier system of this embodiment is made of α alumina, and carries palladium (Pd) as a catalyst. 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 (hereinafter, this ratio is referred to as the "carrier-supported catalyst" Load rate") is set to 0.001%. Supply propylene with a purity of more than 99.99 vol% from the olefin gas cylinder 2 and introduce it to the gas mixer 5 at a flow rate of 1.0 L/min, and supply hydrogen with a purity of more than 99.999 vol% from the hydrogen cylinder 6 at a flow rate of 1.1 L/min Into the gas mixer 5. After mixing propylene and hydrogen in the mixer 5 at room temperature, they are introduced into the reaction tower 10. At this time, the internal pressure of the reaction tower 10 is set to 0.3 MPaG, and water at a temperature of 40° C. as a refrigerant is circulated in the cooling jacket 11. Under the above conditions, by the hydrogenation reaction of propylene in the reaction tower 10, a position 7 cm from the inlet 10a in the reaction tower 10 showed a maximum exothermic temperature of 230°C. After analyzing the impurities contained in the propane gas discharged from the outlet 10b of the reaction tower 10 using a gas chromatograph 17 manufactured by Shimadzu Corporation, the impurities other than hydrogen are residual propylene <0.1 vol ppm, methane 0.3 vol ppm, Ethane is 0.5 vol ppm, butane is 0.6 vol ppm. [Comparative Example 1] Except that the loading rate of the carrier-supported catalyst was set to 0.0005%, under the same conditions as in Example 1, propane was produced by hydrogenation of propylene. According to the hydrogenation reaction of propylene in the reaction tower 10 under the above-mentioned conditions, the maximum exothermic temperature of 220° C. is shown at a position 10 cm away from the inlet 10a in the reaction tower 10. After analyzing the impurities contained in the propane gas discharged from the outlet 10b of the reaction tower 10 using the gas chromatograph 17 manufactured by Shimadzu Corporation, the impurities other than hydrogen are residual propylene 1.3 vol ppm, methane 0.2 vol ppm, and ethyl Alkane 0.3 vol ppm, butane <0.1 vol ppm. [Comparative Example 2] The loading rate of the carrier-supported catalyst was set to 0.0005%, the height of the reaction tower 10 was set to twice that of Example 1, and the reaction tower 10 with the catalyst-supported carrier was filled The height is set to twice that of Example 1. Except for this, under the same conditions as in Example 1, propane was produced by the hydrogenation reaction of propylene. According to the hydrogenation reaction of propylene in the reaction tower 10 under the above conditions, the position within the reaction tower 10 at a distance of 9 cm from the inlet 10a shows a maximum exothermic temperature of 220°C. After analyzing the impurities contained in the propane gas discharged from the outlet 10b of the reaction tower 10 using the gas chromatograph 17 manufactured by Shimadzu Corporation, the impurities other than hydrogen are residual propylene 1.2 vol ppm, methane 0.1 vol ppm, and ethyl Alkane 0.3 vol ppm, butane <0.1 vol ppm. [Comparative Example 3] The supporting rate of the carrier-supported catalyst was 0.01%, and each carrier was made of γ alumina. Except for this, under the same conditions as in Example 1, propane was produced by the hydrogenation reaction of propylene. According to the hydrogenation reaction of propylene in the reaction tower 10 under the above conditions, the maximum exothermic temperature of 240° C. is shown at a position 7 cm away from the inlet 10a in the reaction tower 10. After analyzing the impurities contained in the propane gas discharged from the outlet 10b of the reaction tower 10 using a gas chromatograph 17 manufactured by Shimadzu Corporation, the impurities other than hydrogen are residual propylene <0.1 vol ppm, methane 1.0 vol ppm, Ethane is 0.9 vol ppm, butane is 1.0 vol ppm. [Comparative Example 4] The loading rate of the carrier-supported catalyst was 0.5%, and each carrier was made of γ alumina. Except for this, under the same conditions as in Example 1, propane was produced by the hydrogenation reaction of propylene. According to the hydrogenation reaction of propylene in the reaction tower 10 under the above-mentioned conditions, the position of the reaction tower 10 at a position 4 cm away from the inlet 10a shows a maximum exothermic temperature of 400°C. After analyzing the impurities contained in the propane gas discharged from the outlet 10b of the reaction tower 10 using a gas chromatograph 17 manufactured by Shimadzu Corporation, the impurities other than hydrogen are residual propylene <0.1 vol ppm and methane <0.1 vol ppm , Ethane 1.6 vol%, butane 1900 vol ppm. [Comparative Example 5] A part of the granular members filled in the reaction tower 10 was used as a carrier carrying a catalyst. As the carrier, a manufacturer of NECHEMCAT (stock) with a material of γ alumina and an average particle size of 3 mm was used. The remaining granular components that do not support the catalyst are alumina balls made by AS ONE (strand) with an average particle diameter of 3 mm. The loading rate of the carrier-supported catalyst is set to 0.5%. The ratio of the sum of the volume of all the carriers carrying the catalyst and the volume of all the granular members not carrying the catalyst to the volume of all the carriers carrying the catalyst was set to 500 times. The carrier supporting the catalyst and the granular member not supporting the catalyst are mixed, and the reaction tower 10 is filled so that the dimension in the height direction becomes 50 cm. Except for this, under the same conditions as in Example 1, propane was produced by the hydrogenation reaction of propylene. According to the hydrogenation reaction of propylene in the reaction tower 10 under the above-mentioned conditions, the maximum exothermic temperature of 50°C is shown at a position 5 cm from the inlet 10a in the reaction tower 10. After analyzing the impurities contained in the propane gas discharged from the outlet 10b of the reaction tower 10 using a gas chromatograph 17 manufactured by Shimadzu Corporation, the impurities other than hydrogen are residual propylene 30 vol%, methane 1.3 vol ppm, and ethyl 0.4 vol ppm for butane and 0.5 vol ppm for butane. Table 1 below shows the analysis results in Example 1 and Comparative Examples 1 to 5. [Table 1]
Figure 106140683-A0304-0001
 [Example 2] Except that ethylene having a purity of more than 99.99 vol% was supplied from the olefin gas cylinder 2, under the same conditions as in Example 1, ethane was produced by hydrogenation of ethylene. According to the hydrogenation reaction of ethylene in the reaction tower 10 under the above conditions, the position within the reaction tower 10 at a distance of 6 cm from the inlet 10a shows a maximum exothermic temperature of 250°C. After analyzing the impurities contained in the ethane gas discharged from the outlet 10b of the reaction tower 10 using a gas chromatograph 17 manufactured by Shimadzu Corporation, the impurities other than hydrogen are residual ethylene <0.1 vol ppm and methane 0.3 vol ppm , Propane <0.1 vol ppm. [Comparative Example 6] Except that the loading rate of the carrier-supported catalyst was set to 0.0005%, under the same conditions as in Example 2, ethane was produced by the hydrogenation reaction of ethylene. According to the hydrogenation reaction of ethylene in the reaction tower 10 under the above conditions, the maximum exothermic temperature of 240° C. is shown in the reaction tower 10 at a position 8 cm from the inlet 10a. After analyzing the impurities contained in the ethane gas discharged from the outlet 10b of the reaction tower 10 using a gas chromatograph 17 manufactured by Shimadzu Corporation, the impurities other than hydrogen are residual ethylene 1.0 vol ppm, methane 0.2 vol ppm, Propane <0.1 vol ppm. [Comparative Example 7] The supporting rate of the carrier-supported catalyst was 0.01%, and each carrier was made of γ alumina. Except for this, under the same conditions as in Example 2, ethane was produced by the hydrogenation reaction of ethylene. According to the hydrogenation reaction of ethylene in the reaction tower 10 under the above conditions, the position within the reaction tower 10 at a distance of 5 cm from the inlet 10a shows a maximum exothermic temperature of 260°C. After analyzing the impurities contained in the ethane gas discharged from the outlet 10b of the reaction tower 10 using the gas chromatograph 17 manufactured by Shimadzu Corporation, the impurities other than hydrogen are residual ethylene <0.1 vol ppm and 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. [Table 2]
Figure 106140683-A0304-0002
 According to Examples 1 and 2 and Comparative Examples 1 to 7, it can be confirmed that by setting the loading rate of the metal catalyst used in the hydrogenation reaction of olefins to less than 0.01%, local heat generation in the reaction tower 10 can be achieved By reducing, the concentration of each of the impurities generated in the side reaction can be less than 1.0 vol ppm, so that the amount of impurities generated can be suppressed. In addition, it can be confirmed that when the loading rate is set to 0.0005%, even if the height of the reaction tower 10 and the filling height of the catalyst-supported carrier are increased, the unreacted olefin cannot be sufficiently reduced. In contrast, By setting it to 0.001%, unreacted olefins can be sufficiently reduced. According to the above embodiment, by setting 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 to less than 0.01%, even Without mixing granular members with no catalytic activity, the heat of reaction can be reduced to prevent excessive temperature rise due to local heat generation, and the generation of impurities due to the decomposition of olefins can be suppressed, thereby preventing deviations in the amount of impurities generated. In addition, since the granular member that is not used as a carrier is not required, localized heat generation can be prevented, and thus variation in the amount of impurity generation can be prevented. By setting 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 at 0.001% or more, hydrogenation of olefins can be achieved The reaction takes place reliably, so that unreacted olefins can be prevented from being mixed into the manufactured paraffin in the form of impurities. In addition, by setting all the granular components as a carrier supporting the catalyst, the hydrogenation reaction of the olefin can be more reliably generated, and the unreacted olefin can be prevented from being mixed into the manufactured paraffin as an impurity. Furthermore, the segregation of the catalyst in the reaction tower 10 can be reliably reduced, and it is possible to reliably prevent variation in the amount of impurity produced. The purity of the paraffin produced by the above embodiment is preferably 99.99 vol% or more, more preferably 99.999 vol% or more. The present invention is not limited to the above-mentioned embodiment or examples. For example, instead of setting all the granular members filled in the reaction tower 10 as a carrier carrying the catalyst, a part of the granular members filled in the reaction tower 10 may be set as a carrier carrying the catalyst. And mixed with the remaining granular components that do not support the catalyst. In this case, not only the ratio of the weight of the catalyst carried by each carrier in the reaction tower 10 to the sum of the weight of each carrier and the weight of the catalyst carried by each carrier in the reaction tower 10 is set to 0.001% Above and less than 0.01%, the total weight of the catalysts carried by all the carriers is relative to the total weight of all the granular components including the carriers in the reaction tower 10 and the total weight of the catalysts carried by all the carriers The sum ratio is set to 0.001% or more and less than 0.01%. That is, not only set 0.001≦wc×100/(ws+wc)<0.01, but also set the total weight of the granular members as carriers in the reaction tower 10 as Σws, and set the total weight of the granular members not as carriers Set as Σwg, set the total weight of the catalyst carried by all carriers as Σwc, and set 0.001≦Σwc×100/(Σws＋Σwg＋Σwc). Thereby, in the present invention that becomes 0.001≦wc×100/(ws+wc)<0.01, not only the carrier carrying the catalyst is filled into the reaction tower 10, but the particles that are not set as a carrier and not carrying the catalyst are filled in the reaction tower 10 In the case where the shape member is also filled in the reaction tower 10, the amount of catalyst can be ensured so that the hydrogenation reaction of the olefin can occur reliably, and the unreacted olefin can be prevented from being mixed into the manufactured paraffin as an impurity. Furthermore, since wc×100/(ws+wc)<0.01, Σwc×100/(Σws+Σwg+Σwc)<0.01. In addition, the method of separating hydrogen from the paraffin produced by the reaction of olefin and hydrogen is not particularly limited. For example, the gas phase paraffin introduced into the product tank 15 can be adsorbed to the adsorbent in the adsorption tower by the pressure oscillation adsorption method, and hydrogen gas can be discharged from the adsorption tower as a non-adsorbed gas, thereby preventing the paraffin from being used. Under the condition of liquefaction, the hydrogen is separated from the paraffin to improve the purity of the paraffin.

1‧‧‧石蠟製造裝置2‧‧‧烯烴氣體料缸3‧‧‧第1減壓閥4‧‧‧第1流量控制閥5‧‧‧氣體混合器6‧‧‧氫氣料缸7‧‧‧第2減壓閥8‧‧‧第2流量控制閥10‧‧‧反應塔10a‧‧‧上部入口10b‧‧‧下部出口11‧‧‧冷卻套12‧‧‧冷卻裝置13‧‧‧溫度計14‧‧‧背壓閥15‧‧‧製品槽16‧‧‧壓力計17‧‧‧氣體層析儀18‧‧‧冷卻裝置19‧‧‧第3流量控制閥1‧‧‧Paraffin manufacturing equipment2‧‧‧Olefin gas cylinder 3‧‧‧The first pressure reducing valve 4‧‧‧The first flow control valve ‧Second pressure reducing valve 8‧‧‧Second flow control valve 10‧‧‧Reaction tower 10a‧‧‧Upper inlet 10b‧‧‧Lower outlet 11‧‧‧Cooling jacket 12‧‧‧Cooling device 13‧‧‧Temperature meter 14‧‧‧Back pressure valve 15‧‧‧Product tank 16‧‧‧Pressure gauge 17‧‧‧Gas chromatograph 18‧‧‧Cooling device 19‧‧‧The third flow control valve

圖1係本發明之實施形態中之石蠟製造裝置之構成說明圖。Fig. 1 is an explanatory diagram of the structure of the paraffin wax manufacturing apparatus in the embodiment of the present invention.

1‧‧‧石蠟製造裝置 1‧‧‧Paraffin wax manufacturing device

2‧‧‧烯烴氣體料缸 2‧‧‧Olefin gas cylinder

3‧‧‧第1減壓閥 3‧‧‧The first pressure reducing valve

4‧‧‧第1流量控制閥 4‧‧‧The first flow control valve

5‧‧‧氣體混合器 5‧‧‧Gas mixer

6‧‧‧氫氣料缸 6‧‧‧Hydrogen tank

7‧‧‧第2減壓閥 7‧‧‧The second pressure reducing valve

8‧‧‧第2流量控制閥 8‧‧‧Second flow control valve

10‧‧‧反應塔 10‧‧‧Reaction Tower

10a‧‧‧上部入口 10a‧‧‧Upper entrance

10b‧‧‧下部出口 10b‧‧‧Lower exit

11‧‧‧冷卻套 11‧‧‧Cooling Jacket

12‧‧‧冷卻裝置 12‧‧‧Cooling device

13‧‧‧溫度計 13‧‧‧Thermometer

14‧‧‧背壓閥 14‧‧‧Back pressure valve

15‧‧‧製品槽 15‧‧‧Product Slot

16‧‧‧壓力計 16‧‧‧Pressure gauge

17‧‧‧氣體層析儀 17‧‧‧Gas Chromatograph

18‧‧‧冷卻裝置 18‧‧‧Cooling device

19‧‧‧第3流量控制閥 19‧‧‧The third flow control valve

Claims (10)

一種石蠟之製造方法，其係將不具有觸媒活性之複數個粒狀構件填充至反應塔，將上述粒狀構件之中之至少一部分設為擔載有觸媒之載體，於上述反應塔中於上述觸媒之存在下藉由氣相狀態之烯烴與氫氣之反應而製造石蠟的方法，其特徵在於：將全部上述載體所擔載之上述觸媒之總重量相對於包含上述載體之全部上述粒狀構件之總重量與全部上述載體所擔載之上述觸媒之總重量之和的比率設為0.001%以上且未達0.01%，且將上述載體各者所擔載之上述觸媒之重量相對於上述載體各者之重量與上述載體各者所擔載之上述觸媒之重量之和的比率設為0.001%以上且未達0.01%。 A method for manufacturing paraffin wax, which is to fill a reaction tower with a plurality of granular members that do not have catalyst activity, and set at least a part of the granular members as a catalyst-carrying carrier in the reaction tower The method for producing paraffin wax by the reaction of olefin and hydrogen in the gas phase in the presence of the above catalyst is characterized in that: the total weight of the above catalyst carried by all the above-mentioned carriers is relative to all the above-mentioned carriers containing the above-mentioned carrier The ratio of the total weight of the granular member to the total weight of the above-mentioned catalyst carried by all the above-mentioned carriers is set to 0.001% or more and less than 0.01%, and the weight of the above-mentioned catalyst carried by each of the above-mentioned carriers The ratio with respect to the weight of each of the above-mentioned carriers and the weight of the above-mentioned catalyst carried by each of the above-mentioned carriers is set to be 0.001% or more and less than 0.01%. 如請求項1之石蠟之製造方法，其中將全部上述粒狀構件設為擔載有上述觸媒之上述載體。 The method for manufacturing paraffin wax according to claim 1, wherein all the granular members are set as the carrier carrying the catalyst. 如請求項1之石蠟之製造方法，其中將上述粒狀構件之中之一部分設為擔載有上述觸媒之上述載體，並與剩餘之未擔載上述觸媒之上述粒狀構件進行混合。 The method for manufacturing paraffin wax according to claim 1, wherein a part of the granular member is set as the carrier carrying the catalyst, and is mixed with the remaining granular member not supporting the catalyst. 如請求項1至3中任一項之石蠟之製造方法，其中上述烯烴為乙烯、丙烯、正丁烯或異丁烯。 The method for producing paraffin wax according to any one of claims 1 to 3, wherein the above-mentioned olefin is ethylene, propylene, n-butene or isobutene. 如請求項1至3中任一項之石蠟之製造方法，其中上述觸媒包含鈀，上述載體為氧化鋁。 The method for producing paraffin wax according to any one of claims 1 to 3, wherein the catalyst includes palladium, and the carrier is alumina. 如請求項4之石蠟之製造方法，其中上述觸媒包含鈀，上述載體為氧化鋁。 According to claim 4, the method for manufacturing paraffin wax, wherein the catalyst includes palladium, and the carrier is alumina. 如請求項1至3中任一項之石蠟之製造方法，其中上述石蠟之純度為99.99vol%以上。 According to the method for manufacturing paraffin wax according to any one of claims 1 to 3, wherein the purity of the paraffin wax is 99.99 vol% or more. 如請求項4之石蠟之製造方法，其中上述石蠟之純度為99.99vol%以上。 Such as the method for manufacturing paraffin wax of claim 4, wherein the purity of the paraffin wax is 99.99 vol% or more. 如請求項5之石蠟之製造方法，其中上述石蠟之純度為99.99vol%以上。 Such as the method for manufacturing paraffin wax of claim 5, wherein the purity of the paraffin wax is 99.99 vol% or more. 如請求項6之石蠟之製造方法，其中上述石蠟之純度為99.99vol%以上。 Such as the method for manufacturing paraffin wax of claim 6, wherein the purity of the paraffin wax is 99.99 vol% or more.
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