JPH10101601A - Production of ethanol - Google Patents
Production of ethanolInfo
- Publication number
- JPH10101601A JPH10101601A JP8262091A JP26209196A JPH10101601A JP H10101601 A JPH10101601 A JP H10101601A JP 8262091 A JP8262091 A JP 8262091A JP 26209196 A JP26209196 A JP 26209196A JP H10101601 A JPH10101601 A JP H10101601A
- Authority
- JP
- Japan
- Prior art keywords
- silica
- catalyst
- carrier
- silica gel
- average pore
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 111
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000003054 catalyst Substances 0.000 claims abstract description 46
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 37
- 239000011148 porous material Substances 0.000 claims abstract description 31
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000005977 Ethylene Substances 0.000 claims abstract description 25
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 25
- 239000002245 particle Substances 0.000 claims description 22
- 238000006703 hydration reaction Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 18
- 230000000694 effects Effects 0.000 abstract description 14
- 230000000887 hydrating effect Effects 0.000 abstract 1
- 239000000741 silica gel Substances 0.000 description 33
- 229910002027 silica gel Inorganic materials 0.000 description 33
- 235000019441 ethanol Nutrition 0.000 description 17
- 238000010998 test method Methods 0.000 description 8
- 238000012937 correction Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 210000003278 egg shell Anatomy 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 235000010724 Wisteria floribunda Nutrition 0.000 description 3
- 238000002144 chemical decomposition reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 102000002322 Egg Proteins Human genes 0.000 description 2
- 108010000912 Egg Proteins Proteins 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910002026 crystalline silica Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 1
- XVNRSQASUCMHGX-UHFFFAOYSA-N O[Si](O)(O)O.OP(O)(O)=O Chemical compound O[Si](O)(O)O.OP(O)(O)=O XVNRSQASUCMHGX-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 102220058912 rs786203228 Human genes 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、エチレン水和反応
によるエタノールの製造方法に関する。更に詳しくは、
エチレンの水和反応に使用される燐酸触媒の担持体であ
るシリカに関するものである。TECHNICAL FIELD The present invention relates to a method for producing ethanol by an ethylene hydration reaction. More specifically,
The present invention relates to silica, which is a support for a phosphoric acid catalyst used in the hydration reaction of ethylene.
【０００２】[0002]
【従来の技術】エチレンを気相中で高温、高圧において
水蒸気と反応させてエタノールを製造することは公知で
ある。これらエタノールの合成は触媒の存在下で実施さ
れ、しかも担体上に担持されている燐酸が触媒として通
常使用される。また、その担持体としては、珪質支持
体、例えば珪藻土あるいはシリカゲルが用いられる
（「アルコールハンドブック」発酵工業協会発行、昭和
６１年３月八版 70頁参照）。2. Description of the Prior Art It is known to produce ethanol by reacting ethylene with water vapor at high temperature and high pressure in the gas phase. The synthesis of these ethanols is carried out in the presence of a catalyst, and phosphoric acid supported on a carrier is usually used as a catalyst. As the carrier, a siliceous support, for example, diatomaceous earth or silica gel is used (see “Alcohol Handbook”, published by the Fermentation Industry Association, March 8, 1986, p. 70).
【０００３】特開昭５２−１３３０９５号公報、特公昭
５３−３７３１５号公報、特開平６−１８４０２２号公
報等には、一般的記載として平均細孔容積０．６ｍｌ／
ｇ以上のシリカ担体を用いることが述べられているが、
具体例でに使用されているのはシリカ担体の平均細孔容
積は高々１．２０ｍｌ／ｇであり、且つ燐酸担持量の少
ない触媒によりエチレンの水和反応を行っているため
に、エチレンの転化率及びエチレン選択率は満足できる
ものではない。また、これら先行技術には、シリカゲル
の細孔容積のエチレン転化率およびエタノール収率等へ
の影響についての認識は全くない。さらに、このような
触媒では、水蒸気と接触したときに物理的ならびに化学
的な劣化が起き、その為、長期間使用することにより活
性の低下をきたし、且つ甚だしいときには担体粒子が互
いに凝集してブロック状となり、触媒取替え、抜き出し
時に極めて困難性を有する場合がある。また、これら触
媒のエタノールの活性は一般に選択率は高いものの収率
が低く、工業的に更なる高収率の得られる触媒技術の開
発が望まれている。[0003] JP-A-52-133095, JP-B-53-37315, JP-A-6-184022 and the like generally describe an average pore volume of 0.6 ml / liter.
Although it is stated that a silica carrier of g or more is used,
In the specific example, the average pore volume of the silica carrier is at most 1.20 ml / g, and the hydration reaction of ethylene is carried out with a catalyst having a small amount of phosphoric acid. Rate and ethylene selectivity are not satisfactory. Further, these prior arts have no recognition of the effect of the pore volume of silica gel on the ethylene conversion, ethanol yield, and the like. In addition, such catalysts undergo physical and chemical degradation upon contact with water vapor, which leads to reduced activity over long periods of use, and in extreme cases, the carrier particles aggregate and block. And it may be extremely difficult to replace or withdraw the catalyst. In addition, the activity of ethanol in these catalysts is generally high in selectivity but low in yield, and there is an industrial demand for the development of a catalyst technology capable of obtaining a higher yield.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、エチレン水
和反応によりエタノールを製造する際に、従来のシリカ
担持燐酸触媒よりも収率および選択性に優れ、エタノー
ル生産収率をより高くすることができるばかりでなく、
触媒系の経時的活性低下が少なく、担体の粒子強度の物
理的及び化学的な低下を防止して触媒の寿命を延ばすこ
とができる、より高性能な新規の触媒系を提供するもの
である。SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing ethanol by an ethylene hydration reaction which has a higher yield and selectivity than conventional silica-supported phosphoric acid catalysts and a higher ethanol production yield. Not only can be
An object of the present invention is to provide a novel high-performance catalyst system which has a small decrease in activity of the catalyst system over time and can prevent a physical and chemical decrease in the particle strength of the carrier and extend the life of the catalyst.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、鋭意研究
の結果、エチレン水和反応によるエタノールの製造を行
うに際し、上記の課題を解決するためには、特定の細孔
容積を有するシリカ担体を使用し、さらに好ましくは、
特定のエチレン水和反応条件下において、特に高い特定
の比表面積、細孔直径、純度、および粒子強度を持つ球
状シリカを使用することによって、触媒系の性能を改善
することができることを見出だし、本発明を完成するに
至った。すなわち、本発明は、シリカ担体上に担持され
た燐酸触媒からなる触媒系の存在下に、エチレンの水和
反応によりエタノールを製造する方法において、該シリ
カ担体が少なくとも１．２３ｍｌ/ｇの平均細孔容積を
有することを特徴とするエタノールの製造方法である。Means for Solving the Problems As a result of intensive studies, the present inventors have found that when producing ethanol by the ethylene hydration reaction, in order to solve the above-mentioned problems, silica having a specific pore volume is required. Using a carrier, more preferably,
Under certain ethylene hydration reaction conditions, it has been found that the use of spherical silica with a particularly high specific surface area, pore diameter, purity, and particle strength can improve the performance of the catalyst system, The present invention has been completed. That is, the present invention provides a method for producing ethanol by a hydration reaction of ethylene in the presence of a catalyst system comprising a phosphoric acid catalyst supported on a silica carrier, wherein the silica carrier has an average fineness of at least 1.23 ml / g. A method for producing ethanol, characterized by having a pore volume.
【０００６】[0006]
１．シリカ担体 本発明で使用されるシリカ担体は、少なくとも１．２３
ｍｌ／ｇ以上、好ましくは１．３１ｍｌ／ｇ以上で、通
常は２．０ｍｌ／ｇ以下の平均細孔容積を有するもので
ある。平均細孔容積が１．２３ｍｌ／ｇ未満であると、
燐酸の担持量が少なくなり、エチレン転化率の低下が著
しくその改良効果が期待できない。また、細孔容積が大
きすぎると、エチレンの水和反応中に高圧、高温下での
シリカゲルの化学劣化が起き易く、触媒寿命を低下さ
せ、粒子強度も低くなる傾向があるので、実用的にはシ
リカ担体の平均細孔容積の上限は２．０ｍｌ／ｇ程度で
ある。1. Silica carrier The silica carrier used in the present invention has at least 1.23
It has an average pore volume of not less than ml / g, preferably not less than 1.31 ml / g, and usually not more than 2.0 ml / g. When the average pore volume is less than 1.23 ml / g,
The supported amount of phosphoric acid is reduced, and the conversion of ethylene is significantly reduced, so that its improvement effect cannot be expected. Also, if the pore volume is too large, chemical degradation of silica gel under high pressure and high temperature is likely to occur during the hydration reaction of ethylene, reducing the catalyst life and reducing the particle strength. The upper limit of the average pore volume of the silica carrier is about 2.0 ml / g.
【０００７】シリカ担体は、さらに少なくとも平均９ｎ
ｍ、好ましくは少なくとも２０ｎｍ、より好ましくは２
５ｎｍ以上の平均細孔直径を有し、比表面積が５０〜４
００m2/gの範囲であり、少なくとも９９重量％のシリカ
の純度を有するものであり、平均粒子径２〜６ｍｍの範
囲の球形状であり、嵩密度が０．３〜０．６Kg／ｌの範
囲にあるものが好ましい。 平均細孔直径が小さすぎる
と、シリカゲルの一次粒子が小さくなり、反応初期にポ
ーラスなシリカゲルが燐酸に溶解され、非ポーラスなシ
リカ結晶が担体シリカゲル表面に再沈、堆積してその表
面を覆ってしまい、結果として触媒活性を低下させてし
まう。シリカ担体の粒子径および嵩密度が小さすぎると
反応器での圧力損失が大きくなり、また大きすぎると反
応器に充填できる触媒量が少なくなってしまう。また粒
子の強度は、１．５ｋｇ以上で高いほど好ましいが、高
すぎると大きな細孔容積を維持するのが難しく、実質
上、１．５〜５．０ｋｇの範囲にあることが好ましい。
上述したシリカゲルは、基本的には、例えば、特公平７
−６４５４３号及び特開昭５８−１３５１１９号公報に
記載されている方法によって製造することができる。ま
た、このようなシリカ担体は、富士シリシア化学（株）
から入手することができ、例えば商品名：「キャリアク
ト」Ｑ１０ＨＰ、Ｑ３０ＨＰ、Ｑ５０ＨＰ等がその一例
である。The silica carrier further comprises at least 9n on average
m, preferably at least 20 nm, more preferably 2
It has an average pore diameter of 5 nm or more and a specific surface area of 50 to 4
In the range of 00m 2 / g, at least 99% by weight are those having a purity of silica, a spherical shape in a range of the average particle diameter of 2 to 6 mm, a bulk density of 0.3~0.6Kg / l Those in the range are preferred. If the average pore diameter is too small, the primary particles of the silica gel will become small, the porous silica gel will be dissolved in phosphoric acid at the beginning of the reaction, and the non-porous silica crystals will reprecipitate and deposit on the surface of the carrier silica gel, covering the surface. As a result, the catalyst activity is reduced. If the particle size and bulk density of the silica carrier are too small, the pressure loss in the reactor will increase, and if it is too large, the amount of catalyst that can be charged into the reactor will decrease. Further, the strength of the particles is preferably as high as 1.5 kg or more, but if it is too high, it is difficult to maintain a large pore volume, and it is preferable that the strength is substantially in the range of 1.5 to 5.0 kg.
The above-mentioned silica gel is basically, for example,
-64543 and JP-A-58-135119. Such a silica carrier is available from Fuji Silysia Chemical Ltd.
For example, the product name: "Carrierct" Q10HP, Q30HP, Q50HP, etc. is an example.
【０００８】２. エチレン水和反応 （ 触媒の調製）シリカゲルを触媒の支持体として用
い、予め１５〜８０重量％の燐酸水溶液に所定のシリカ
ゲルを浸漬した後、乾燥処理を行うなどによって、シリ
カゲルに燐酸を担持させることができる。この場合の含
浸支持体は使用前に乾燥して触媒系粒子とされるが、そ
の燐酸濃度は該粒子全重量に対して５〜７０重量％、好
ましくは、１０〜７０重量％、更に好ましくは、２０〜
６０重量％、最も好ましくは、４０〜６０重量％程度で
ある。2. Ethylene hydration reaction (Preparation of catalyst) Using silica gel as a catalyst support, a predetermined silica gel is immersed in a 15 to 80% by weight phosphoric acid aqueous solution in advance, and then dried to carry out a drying treatment. Phosphoric acid can be supported. In this case, the impregnated support is dried before use to obtain catalyst-based particles, and its phosphoric acid concentration is 5 to 70% by weight, preferably 10 to 70% by weight, more preferably 10 to 70% by weight based on the total weight of the particles. 20, 20
It is about 60% by weight, most preferably about 40 to 60% by weight.
【０００９】（エチレン水和反応）エチレンと水とを原
料として気相反応によりエタノールを製造する場合、本
発明の特徴を最も良く享受するには、上記のようにして
得られた触媒粒子を１００〜４００℃、好ましくは２０
０〜３５０℃の範囲の温度で使用することである。反応
圧力は通常１０，０００ＫＰａ以下、好ましくは３，０
００〜１０，０００ＫＰａの範囲の圧力下に実施され
る。反応温度および反応圧力は一般に高くするほど高い
エチレン転化率が得られて好ましいが、温度、圧力の過
度の増大は副生成物が増大する恐れがあり、逆に低すぎ
ると反応が進まない。エチレンと水のモル比は、反応条
件下で水の凝縮が起こらないように、水／エチレン＝
０．１〜０．８の範囲内で実施することが好ましい。(Ethylene Hydration Reaction) In the case where ethanol is produced by a gas phase reaction using ethylene and water as raw materials, the catalyst particles obtained as described above must be mixed with 100 parts in order to obtain the best characteristics of the present invention. ~ 400 ° C, preferably 20
To be used at a temperature in the range of 0 to 350 ° C. The reaction pressure is usually 10,000 KPa or less, preferably 3.0 KPa.
It is carried out under a pressure in the range from 00 to 10,000 KPa. In general, the higher the reaction temperature and the reaction pressure, the higher the ethylene conversion can be obtained, which is preferable. However, if the temperature and pressure are excessively increased, the by-products may increase. The molar ratio of ethylene to water is such that water / ethylene =
It is preferable to carry out in the range of 0.1 to 0.8.
【００１０】[0010]
【実施例】以下、実施例及び比較例を挙げて本発明をさ
らに詳細に説明する。なお、ここで使用した実施例のシ
リカゲルは、富士シリシア化学（株）に於いて（ゾル、
ゲル法により）製造されたものである。また、比較例と
しては、従来型のシリカゲルである W.R.Grace & Co 社
製の＃５７を用いた。これらのシリカゲルの物性値を表
−１に示す。The present invention will be described below in more detail with reference to Examples and Comparative Examples. The silica gel of the example used here was manufactured by Fuji Silysia Chemical Ltd. (Sol,
(By a gel method). As a comparative example, a conventional silica gel # 57 manufactured by WRGrace & Co was used. Table 1 shows the physical property values of these silica gels.
【００１１】［シリカゲルの試験方法］ （純度：SiO2として) ＪＩＳＫ1150−1994 シリカゲル
試験方法（５.６.５によった。 （比表面積）ＪＩＳＫ1150−1994 シリカゲル試験方法
(５.１)によった。 （平均細孔容積）ＪＩＳＫ1150−1994 シリカゲル試験
方法(５.２)によった。 （平均細孔直径）ＪＩＳＫ1150−1994 シリカゲル試験
方法(５.３)によった。 （粒子強度）ＪＩＳＫ1150−1994 シリカゲル試験方法
(５.９.２)によった。 （平均粒子径）ＪＩＳＫ1150−1994 シリカゲル試験方
法(５.７.１)によった。 （かさ密度）ＪＩＳＫ1150−1994 シリカゲル試験方法
(５.１０)によった。[Test Method for Silica Gel] (Purity: as SiO 2 ) JIS K1150-1994 Silica gel test method (according to 5.6.5. (Specific surface area) JIS K1150-1994 silica gel test method
According to (5.1). (Average pore volume) According to JIS K1150-1994 silica gel test method (5.2). (Average pore diameter) According to JIS K1150-1994 silica gel test method (5.3). (Particle strength) JIS K1150-1994 Silica gel test method
According to (5.9.2). (Average particle size) According to JIS K1150-1994 silica gel test method (5.7.1). (Bulk density) JIS K1150-1994 Silica gel test method
According to (5.10).
【００１２】実施例および比較例 （触媒の調製）実施例として、富士シリシア（株）から
入手しシリカ担体（商品名「キャリアクト」Ｑ１０Ｈ
Ｐ、Ｑ３０ＨＰ及びＱ５０ＨＰ）、および比較例とし
て、従来型のW.R.Grace & Co 社製の＃５７を触媒の支
持体として用い、予め６５重量％の燐酸水溶液に所定の
シリカゲルを１時間浸漬した後、ロート上に移し燐酸水
溶液を完全に液切りした。乾燥処理は窒素気流中、１５
０℃で、２０時間を掛けて行い、シリカゲルに燐酸を担
持させた触媒粒子を調製した。触媒粒子の燐酸濃度は、
浸漬前の乾燥シリカの重量および燐酸を担持し、乾燥処
理した触媒粒子の全重量をそれぞれ測定し求めた。その
結果を表−１に示す。W.R.Grace & Co 社製の＃５７
は、上記処方によって燐酸を担持した場合、その粒子の
粒子強度は、約半分程度まで低下するが、実施例である
本発明品に於いては、いづれも強度低下は見られなかっ
た。Examples and Comparative Examples (Preparation of Catalyst) As an example, a silica carrier (trade name “Caractact” Q10H) obtained from Fuji Silysia Ltd. was used.
P, Q30HP and Q50HP), and as a comparative example, using a conventional type # 57 manufactured by WRGrace & Co as a catalyst support, previously immersing predetermined silica gel in a 65% by weight aqueous phosphoric acid solution for 1 hour, It was transferred to the top and the phosphoric acid aqueous solution was completely drained. Drying is performed in a nitrogen stream at 15
The reaction was performed at 0 ° C. for 20 hours to prepare catalyst particles having phosphoric acid supported on silica gel. The phosphoric acid concentration of the catalyst particles is
The weight of the dried silica before immersion and the total weight of the catalyst particles carrying phosphoric acid and dried were measured and determined. Table 1 shows the results. # 57 made by WRGrace & Co
When phosphoric acid was supported by the above formulation, the particle strength of the particles was reduced to about half, but in the present invention product as an example, no reduction in strength was observed in any case.
【００１３】（エチレン水和反応）上記で得られた各触
媒粒子４０ｍｌを充填した内径約２ｃｍの銅内張りＳＵ
Ｓ製の縦型固定層流通管状小型反応器を用いて、表−２
に示す合成条件にてエタノールの合成を行った。反応を
経過し、安定な定常活性が得られたことを確認してから
（約６時間後）、反応出口のガスを全量気相でガスクロ
マトグラフに導入し分析した。これら合成実験にて得ら
れた結果を表−１に示す。(Ethylene hydration reaction) A copper-lined SU having an inner diameter of about 2 cm filled with 40 ml of each of the catalyst particles obtained above.
Using a vertical fixed-bed flow tubular small reactor made of S, Table-2
The synthesis of ethanol was carried out under the following synthesis conditions. After the reaction was completed and it was confirmed that stable steady-state activity was obtained (after about 6 hours), all of the gas at the reaction outlet was introduced into a gas chromatograph in gas phase and analyzed. Table 1 shows the results obtained in these synthesis experiments.
【００１４】（実験結果の考察）触媒の寿命には２種類
の要因が存在する。すなわち、その１つは、初期の粒子
強度が弱い為に反応器に投入した際、自重の為、あるい
は反応の立ち上げあるいは停止中断による熱刺激の為に
シリカゲルが破砕、凝集しブロック化してしまう、いわ
ゆる物理的劣化現象である。この場合は、初期のシリカ
粒子の強度を大きくすること、及び製造時の構造的な歪
みの少ないものにすることによって触媒調整工程での燐
酸担持による強度低下を防ぐことが効果的である。実施
例である本発明で限定される特定のシリカゲルに於いて
は、比較例である従来型のW.R.Grace & Co 社製の＃５
７と比較してすべて良好な結果が得られていることが表
−１に示したデータから明らかである。(Consideration of Experimental Results) There are two factors in the life of the catalyst. That is, one of them is that silica gel is crushed, agglomerated and blocked due to its own weight or thermal stimulation due to the start or stop of the reaction when it is put into the reactor because the initial particle strength is weak. This is a so-called physical deterioration phenomenon. In this case, it is effective to increase the strength of the silica particles at the initial stage and to reduce the structural distortion at the time of production so as to prevent the strength from being reduced by phosphoric acid loading in the catalyst preparation step. In the specific silica gel limited by the present invention, which is an example, the conventional WRGrace & Co # 5, which is a comparative example, is used.
It is clear from the data shown in Table 1 that good results were all obtained as compared with No. 7.
【００１５】触媒の寿命のもう一つの要因に、化学的劣
化によるシリカゲルの粒子強度の経時劣化及びエタノー
ルの合成活性の低下現象がある。この現象は、シリカの
水熱反応条件下でシリカゲル（非晶性）が燐酸と反応し
ケイ燐酸塩となり一旦燐酸中に溶解する。この時シリカ
ゲルの細孔構造が徐々に崩壊する。更にこのケイ燐酸塩
のシリカ成分が反応経過と共にシリカゲル表面にシリカ
結晶として卵の殻状に析出する。このシリカの結晶は、
シリカゲルのように細孔構造がほとんどなく燐酸の保持
能力に劣る為、殻の成長と共に徐々に触媒活性も低下し
ていくと考えられる。従って、この触媒の化学的寿命の
判定方法としては、反応中生成した結晶性シリカによる
シリカゲルの表面への卵の殻状物の堆積の状況を走査型
電子顕微鏡などによって観察すればよい。Another factor in the life of the catalyst is a phenomenon in which the particle strength of silica gel deteriorates with time due to chemical deterioration and a phenomenon in which the activity of synthesizing ethanol decreases. This phenomenon occurs because silica gel (amorphous) reacts with phosphoric acid to form silicic acid phosphate under hydrothermal reaction conditions of silica, and is once dissolved in phosphoric acid. At this time, the pore structure of the silica gel gradually collapses. Further, the silica component of the silicate is precipitated on the surface of the silica gel as silica crystals in the form of an egg shell as the reaction progresses. This silica crystal is
It is thought that the catalytic activity gradually decreases with the growth of the shell, because it has little pore structure and is inferior in the ability to retain phosphoric acid as in silica gel. Therefore, as a method of determining the chemical life of the catalyst, the state of the deposition of egg shells on the surface of the silica gel by the crystalline silica generated during the reaction may be observed by a scanning electron microscope or the like.
【００１６】小型反応器で１２時間反応後、使用した触
媒を取り出して、反応活性の劣化の兆候と判断される、
反応中生成した結晶性シリカによるシリカゲルの表面へ
の卵の殻状物の堆積の状況を走査型電子顕微鏡にて観察
した。その結果、平均細孔直径が比較的小さい本発明の
Ｑ１０ＨＰについては、シリカゲルの表面への卵の殻状
物の堆積が観察された。一方、平均細孔直径を大きくし
た実施例中の本発明品のシリカゲルであるＱ３０ＨＰ及
びＱ５０ＨＰについてはシリカゲルの表面への卵の殻状
物の堆積が観察されなかった。After reacting in a small reactor for 12 hours, the used catalyst is taken out and judged to be a sign of deterioration of the reaction activity.
The state of the deposition of egg shells on the silica gel surface by the crystalline silica produced during the reaction was observed with a scanning electron microscope. As a result, for the Q10HP of the present invention having a relatively small average pore diameter, deposition of egg shells on the surface of silica gel was observed. On the other hand, for the silica gels Q30HP and Q50HP of the product of the present invention in the examples in which the average pore diameter was increased, no egg shell was deposited on the surface of the silica gel.
【００１７】[0017]
【発明の効果】本発明は、細孔容積が比較的大きなシリ
カ担体を使用することにより、さらに平均細孔直径およ
び比表面積の最適な多孔性シリカを担持体として用いて
シリカ担持燐酸触媒を使うことによって高活性で且つ高
選択性で、エタノールを製造することが可能であり、従
来のシリカ担持燐酸触媒より長期間使用できる、触媒寿
命の長い工業的に優れた方法である。According to the present invention, a silica carrier having a relatively large pore volume is used, and a silica-supported phosphoric acid catalyst is further used by using a porous silica having an optimum average pore diameter and a specific surface area as a carrier. As a result, it is possible to produce ethanol with high activity and high selectivity, and this is an industrially superior method that can be used for a longer time than a conventional phosphoric acid catalyst supported on silica and has a long catalyst life.
【００１８】[0018]
【表１】 [Table 1]
【００１９】[0019]
【表２】 [Table 2]
【手続補正書】[Procedure amendment]
【提出日】平成８年１０月２９日[Submission date] October 29, 1996
【手続補正１】[Procedure amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】請求項３[Correction target item name] Claim 3
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【手続補正２】[Procedure amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００３[Correction target item name] 0003
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【０００３】特開昭５２−１３３０９５号公報、特公昭
５３−３７３１５号公報、特開平６−１８４０２２号公
報等には、一般的記載として平均細孔容積０．６ｍｌ／
ｇ以上のシリカ担体を用いることが述べられているが、
具体例で使用されているのはシリカ担体の平均細孔容積
は高々１．２０ｍｌ／ｇであり、且つ燐酸担持量の少な
い触媒によりエチレンの水和反応を行っているために、
エチレンの転化率及びエチレン選択率は満足できるもの
ではない。また、これら先行技術には、シリカゲルの細
孔容積のエチレン転化率およびエタノール収率等への影
響についての認識は全くない。さらに、このような触媒
では、水蒸気と接触したときに物理的ならびに化学的な
劣化が起き、その為、長期間使用することにより活性の
低下をきたし、且つ甚だしいときには担体粒子が互いに
凝集してブロック状となり、触媒取替え、抜き出し時に
極めて困難性を有する場合がある。また、これら触媒の
エタノールの活性は一般に選択率は高いものの収率が低
く、工業的に更なる高収率の得られる触媒技術の開発が
望まれている。[0003] JP-A-52-133095, JP-B-53-37315, JP-A-6-184022 and the like generally describe an average pore volume of 0.6 ml / liter.
Although it is stated that a silica carrier of g or more is used,
In the specific examples, the average pore volume of the silica carrier is at most 1.20 ml / g, and the hydration reaction of ethylene is carried out with a catalyst having a small amount of phosphoric acid,
Ethylene conversion and ethylene selectivity are not satisfactory. Further, these prior arts have no recognition of the effect of the pore volume of silica gel on the ethylene conversion, ethanol yield, and the like. In addition, such catalysts undergo physical and chemical degradation upon contact with water vapor, which leads to reduced activity over long periods of use, and in extreme cases, the carrier particles aggregate and block. And it may be extremely difficult to replace or withdraw the catalyst. In addition, the activity of ethanol in these catalysts is generally high in selectivity but low in yield, and there is an industrial demand for the development of a catalyst technology capable of obtaining a higher yield.
Claims (4)
なる触媒系の存在下に、エチレンの水和反応によりエタ
ノールを製造する方法において、該シリカ担体が少なく
とも１．２３ｍｌ/ｇの平均細孔容積を有することを特
徴とするエタノールの製造方法。1. A method for producing ethanol by a hydration reaction of ethylene in the presence of a catalyst system comprising a phosphoric acid catalyst supported on a silica support, wherein the silica support has an average pore size of at least 1.23 ml / g. A method for producing ethanol, having a volume.
ｌ/ｇの平均細孔容積を有し且つ少なくとも９ｎｍの平
均細孔直径を有する請求項１記載の方法。2. The method according to claim 1, wherein the silica carrier is at least 1.31 m.
The method of claim 1 having an average pore volume of 1 / g and having an average pore diameter of at least 9 nm.
２．０ｍｌ/ｇの平均細孔容積を有し且つ少なくとも２
０ｎｍの平均細孔直径を有する請求項１又は１記載の方
法。3. The method according to claim 1, wherein the silica carrier is at least 1.23 to
Having an average pore volume of 2.0 ml / g and at least 2
A method according to claim 1 or 1 having an average pore diameter of 0 nm.
範囲の平均粒子強度を有する請求項１〜３のいずれかに
記載の方法。4. The method according to claim 1, wherein the silica carrier has an average particle strength in the range from 1.5 to 5.0 kg.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8262091A JPH10101601A (en) | 1996-10-02 | 1996-10-02 | Production of ethanol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8262091A JPH10101601A (en) | 1996-10-02 | 1996-10-02 | Production of ethanol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10101601A true JPH10101601A (en) | 1998-04-21 |
Family
ID=17370917
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8262091A Pending JPH10101601A (en) | 1996-10-02 | 1996-10-02 | Production of ethanol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10101601A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110086928A1 (en) * | 2005-04-15 | 2011-04-14 | Olah George A | Mitigating or eliminating the carbon footprint of human activities |
| WO2020090756A1 (en) | 2018-11-02 | 2020-05-07 | 昭和電工株式会社 | Method for producing alcohol and catalyst for producing alcohol |
| WO2021205900A1 (en) * | 2020-04-10 | 2021-10-14 | 昭和電工株式会社 | Method for producing alcohol |
-
1996
- 1996-10-02 JP JP8262091A patent/JPH10101601A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110086928A1 (en) * | 2005-04-15 | 2011-04-14 | Olah George A | Mitigating or eliminating the carbon footprint of human activities |
| WO2020090756A1 (en) | 2018-11-02 | 2020-05-07 | 昭和電工株式会社 | Method for producing alcohol and catalyst for producing alcohol |
| KR20210035232A (en) | 2018-11-02 | 2021-03-31 | 쇼와 덴코 가부시키가이샤 | Alcohol production method and alcohol production catalyst |
| CN112930333A (en) * | 2018-11-02 | 2021-06-08 | 昭和电工株式会社 | Method for producing alcohol and catalyst for alcohol production |
| JPWO2020090756A1 (en) * | 2018-11-02 | 2021-09-30 | 昭和電工株式会社 | Alcohol production method and catalyst for alcohol production |
| CN112930333B (en) * | 2018-11-02 | 2023-10-03 | 株式会社力森诺科 | Alcohol production method and catalyst for alcohol production |
| US11981622B2 (en) | 2018-11-02 | 2024-05-14 | Resonac Corporation | Method for producing alcohol and catalyst for producing alcohol |
| WO2021205900A1 (en) * | 2020-04-10 | 2021-10-14 | 昭和電工株式会社 | Method for producing alcohol |
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