JPH03236338A - Production of phenol - Google Patents
Production of phenolInfo
- Publication number
- JPH03236338A JPH03236338A JP2031373A JP3137390A JPH03236338A JP H03236338 A JPH03236338 A JP H03236338A JP 2031373 A JP2031373 A JP 2031373A JP 3137390 A JP3137390 A JP 3137390A JP H03236338 A JPH03236338 A JP H03236338A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- phenol
- yield
- benzene
- mol
- 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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000003054 catalyst Substances 0.000 claims abstract description 45
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- ZJRXSAYFZMGQFP-UHFFFAOYSA-N barium peroxide Chemical compound [Ba+2].[O-][O-] ZJRXSAYFZMGQFP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001506 calcium phosphate Substances 0.000 claims abstract description 7
- 229910000389 calcium phosphate Inorganic materials 0.000 claims abstract description 7
- 235000011010 calcium phosphates Nutrition 0.000 claims abstract description 7
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims abstract description 7
- RAOSIAYCXKBGFE-UHFFFAOYSA-K [Cu+3].[O-]P([O-])([O-])=O Chemical compound [Cu+3].[O-]P([O-])([O-])=O RAOSIAYCXKBGFE-UHFFFAOYSA-K 0.000 claims abstract 3
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 11
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 3
- 239000001913 cellulose Substances 0.000 abstract description 3
- 229920002678 cellulose Polymers 0.000 abstract description 3
- 239000000377 silicon dioxide Substances 0.000 abstract description 3
- 239000011230 binding agent Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 229910052814 silicon oxide Inorganic materials 0.000 abstract description 2
- 239000012808 vapor phase Substances 0.000 abstract 2
- 229910000365 copper sulfate Inorganic materials 0.000 abstract 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 abstract 1
- 238000005469 granulation Methods 0.000 abstract 1
- 230000003179 granulation Effects 0.000 abstract 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 18
- 229910019142 PO4 Inorganic materials 0.000 description 11
- 239000001569 carbon dioxide Substances 0.000 description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000001272 nitrous oxide Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000010457 zeolite Substances 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
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はフェノールの製法に関する。さらに詳しくは本
発明はベンゼンと水とを気相接触反応させて、１工程で
フェノールを製造する方法に用いる触媒に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a process for producing phenol. More specifically, the present invention relates to a catalyst used in a method for producing phenol in one step by subjecting benzene and water to a gas phase catalytic reaction.
従来、ベンゼンからフェノールを１工程で製造する方法
としては、触媒の存在下にベンゼンと酸素とを反応させ
る直接酸化法が知られている。しかし、この場合、ベン
ゼンの完全酸化が起こり、フェノールの選択率が大変低
い（特開昭５６−８７５２７号）。Conventionally, as a method for producing phenol from benzene in one step, a direct oxidation method in which benzene and oxygen are reacted in the presence of a catalyst is known. However, in this case, complete oxidation of benzene occurs and the selectivity for phenol is very low (Japanese Patent Application Laid-open No. 87527/1983).
また、ベンゼンと亜酸化窒素とを触媒の存在下に反応さ
せて、フェノールを製造する方法も知られている。しか
し、この場合、原料の亜酸化窒素は高価である上に、フ
ェノールの収率は低い（特開昭５８−１４６５２２ ）
。Furthermore, a method for producing phenol by reacting benzene and nitrous oxide in the presence of a catalyst is also known. However, in this case, the raw material nitrous oxide is expensive and the yield of phenol is low (Japanese Patent Application Laid-Open No. 146522/1983).
.
本発明者らはベンゼンと水とを気相接触反応させて、１
工程でフェノールを製造する新規なフェノール製法を検
討してきた。また、その際に使用する触媒として、リン
酸および／またはリン酸塩を含有する触媒を開示した。The present inventors carried out a gas phase contact reaction between benzene and water, and
We have been investigating a new phenol production method that produces phenol in a process. Moreover, as a catalyst used at that time, a catalyst containing phosphoric acid and/or a phosphate salt was disclosed.
しかしながら、この方法ではまだフェノールの収率が十
分ではなく、フェノールの収率を向上させるために触媒
の改良が望まれていた。However, this method still does not provide a sufficient yield of phenol, and it has been desired to improve the catalyst in order to improve the yield of phenol.
〔発明が解決しようとする課題］
本発明の課題は、高収率でヘンゼンからフエノルを１工
程で製造する工業的方法を提供することである。すなわ
ち、本発明の課題は、ベンゼンと水との気相接触反応に
おいて、高収率でフェノルを製造する触媒を提供するこ
とである。[Problem to be Solved by the Invention] An object of the present invention is to provide an industrial method for producing phenol from Hensen in one step with high yield. That is, an object of the present invention is to provide a catalyst that produces phenol in high yield in a gas phase catalytic reaction between benzene and water.
（課題を解決するための手段〕
本発明者らは、上記課題に関して種々検討した結果、ヘ
ンゼンと水との気相接触反応において、触媒がリン政調
である場合にはリン政調触媒の活性は十分ではなく、−
回通過によるフェノールの収率は６％に過ぎない。本発
明者らはリン政調を第一成分とし、これに第二成分を添
加することによりフェノール収率を向上させる触媒を見
出す目的のもとに添加物質について研究した結果、過酸
化バリウムおよび酸化バリウムが添加物質として極めて
有効であることを見出した。(Means for Solving the Problems) As a result of various studies regarding the above problems, the present inventors found that in the gas phase contact reaction between Hensen and water, when the catalyst is a phosphorus catalyst, the activity of the phosphorus catalyst is sufficient. rather than −
The yield of phenol from the double pass is only 6%. The present inventors conducted research on additive substances with the aim of finding a catalyst that improves the phenol yield by using phosphorus as the first component and adding a second component to it. As a result, barium peroxide and barium oxide was found to be extremely effective as an additive substance.
すなわち、ｌ化バリウムおよび／または酸化バＩＪウム
をリン政調に添加することによって得た触媒Ｍｉ威酸物
用いてヘンゼンと水を気相接触反応した場合には、８％
のフェノールの一回通過収率が得られることを見出した
。That is, when Hensen and water are subjected to a gas phase contact reaction using a catalyst Mi oxide obtained by adding barium chloride and/or barium oxide to phosphorus, 8%
It was found that a single pass yield of phenol of
すなわち、本発明の要旨とするところは、上記した新規
な触媒Ｍｉ戒物の存在下に、ヘンゼンと水を気相接触反
応させることにある。That is, the gist of the present invention is to cause a gas phase contact reaction between Hensen and water in the presence of the above-mentioned novel catalyst Mi compound.
さらに詳しくは、本発明に用いられる触媒は、過酸化バ
リウムおよび酸化バリウムからなる群から選ばれた一種
または二種の物質とリン政調を含有する触媒である。More specifically, the catalyst used in the present invention is a catalyst containing one or two substances selected from the group consisting of barium peroxide and barium oxide and phosphate.
さらに上記した本発明による触媒にリン酸カルシウムを
添加することがフェノールの収率向上に良い効果がある
ことを見出した。すなわち、本発明に用いられる触媒は
、過酸化バリウムおよび酸化バリウムからなる群から選
ばれた一種または二種の物質とリン政調およびリン酸カ
ルシウムを含有する触媒をも含む。Furthermore, it has been found that adding calcium phosphate to the above-mentioned catalyst according to the present invention has a positive effect on improving the yield of phenol. That is, the catalyst used in the present invention also includes a catalyst containing one or two substances selected from the group consisting of barium peroxide and barium oxide, phosphate, and calcium phosphate.
よた、本発明者らは本発明による触媒として、リン政調
、リン酸カルシウム、過酸化バリウムおよび酸化バリウ
ムを含有する触媒がフェノールの収率に最も良い効果が
あることを見出した。Furthermore, the present inventors have found that the catalyst according to the present invention containing phosphate, calcium phosphate, barium peroxide and barium oxide has the best effect on the yield of phenol.
本発明による触媒中におけるリン政調の含量は特に制限
するものではないが、モル％で表わすと１〜８０％、好
ましくは１０〜７０％である。また、過酸化バリウムの
含量は特に制限するものではないが、モル％で表られす
と１０〜６０％、好ましくは２０〜５０％である。また
、酸化バリウムの含量は特に制限するものではないが、
１０〜６０％、好ましくは２０〜５０％の範囲である。The content of phosphorus in the catalyst of the present invention is not particularly limited, but expressed in mol% is 1 to 80%, preferably 10 to 70%. Further, the content of barium peroxide is not particularly limited, but expressed in mol% is 10 to 60%, preferably 20 to 50%. In addition, the content of barium oxide is not particularly limited, but
It ranges from 10 to 60%, preferably from 20 to 50%.
また、リン酸カルシウムの含量は特に制限するものでは
ないが、１０〜６０％、好ましくは２０〜５０％の範囲
である。Further, the content of calcium phosphate is not particularly limited, but is in the range of 10 to 60%, preferably 20 to 50%.
また、本発明による触媒をシリカ、アルミナ、シリカ−
アルミナ、ゼオライト、ケイソウ土、活性白土、酸化チ
タン、酸化マグネシウム、活性炭などの担体に担持して
使用してもよい。Moreover, the catalyst according to the present invention can be used as a catalyst of silica, alumina, silica
It may be used by being supported on a carrier such as alumina, zeolite, diatomaceous earth, activated clay, titanium oxide, magnesium oxide, or activated carbon.
また、触媒物質を造粒するためにバインダーとしてケイ
ソウ土、コロイダルシリカ等の酸化珪素を触媒物質の中
に混合して使用してもよい。Further, in order to granulate the catalyst material, silicon oxide such as diatomaceous earth or colloidal silica may be mixed into the catalyst material and used as a binder.
また、セルローズ、澱粉、その他の有機化合物や炭等の
粉末、粒、繊維等を触媒の中に混合し、触媒の前処理の
時に焼却し、空洞を残し、多孔質の触媒を製造すれば、
触媒の性能、特にフェノール収率向上に良い効果がある
。In addition, if powders, grains, fibers, etc. of cellulose, starch, other organic compounds, charcoal, etc. are mixed into the catalyst and incinerated during pretreatment of the catalyst, leaving cavities and producing a porous catalyst.
It has a positive effect on catalyst performance, especially on improving phenol yield.
ヘンゼンおよび水の使用量は特に限定されるものではな
いが、すべてのヘンゼンが対応するフェノールに変化す
るためには、ベンゼンに対して等モル以上の水が必要で
ある。Although the amounts of henzene and water to be used are not particularly limited, in order for all of the henzene to be converted into the corresponding phenol, an equimolar or more amount of water is required relative to benzene.
本発明の方法においては、反応は、通常、不活性ガス雰
囲気中、常圧または加圧下において実施される。不活性
ガスとしては窒素、ヘリウム、アルゴン、二酸化炭素等
があげられる。In the method of the present invention, the reaction is usually carried out in an inert gas atmosphere under normal pressure or increased pressure. Examples of the inert gas include nitrogen, helium, argon, and carbon dioxide.
本発明の方法において、反応温度は２００〜６００°Ｃ
１好ましくは３００〜５５０’Ｃの範囲である。２００
°Ｃ未満では本発明による反応が起こらず、６００°Ｃ
を越えると副生物が多く生成する。In the method of the present invention, the reaction temperature is 200-600°C
1 preferably in the range of 300 to 550'C. 200
The reaction according to the present invention does not occur below 600°C.
Exceeding this will produce many by-products.
本発明の方法は気相で実施することができる。The method of the invention can be carried out in the gas phase.
すなわち、固定層、流動層または移動層反応器のいずれ
でも実施できる。また、反応器または反応管中で、前記
触媒の存在下に、ベンゼンおよび水を加熱することによ
り、本発明の方法は実施される。That is, it can be carried out in a fixed bed, fluidized bed or moving bed reactor. The process of the invention is also carried out by heating benzene and water in the presence of the catalyst in a reactor or reaction tube.
本発明の方法において、フェノールは反応生成物から適
当な方法、たとえば、蒸留のような常法によって容易に
分離精製できる。In the method of the present invention, phenol can be easily separated and purified from the reaction product by an appropriate method, for example, a conventional method such as distillation.
以下、実施例により本発明の詳細な説明する。 Hereinafter, the present invention will be explained in detail with reference to Examples.
実施例１
試薬Ｃｕ：＋（ＰＯ４）ｚ ’ ３ＨｚＯ１３，６ｇ
（０，０３１モル）、Ｃａ：＋（ＰＯ４）ｚ ７．８
ｇ（０，０２５モル） 、Ｂａ０ｚ ８．６ｇ（０，０
５モル）およびＢａＯ７，８ｇ （０，０５モル）を粉
砕機でよく混合した。これを２０ｍ／ｍφＸ １０ｍ／
ｍの錠剤にした後、乳鉢で１０〜３２メツシユに破砕し
た。Example 1 Reagent Cu: +(PO4)z' 3HzO13.6g
(0,031 mol), Ca:+(PO4)z 7.8
g (0,025 mol), Ba0z 8.6 g (0,0
5 mol) and 7.8 g (0.05 mol) of BaO were thoroughly mixed in a grinder. This is 20m/mφX 10m/
The tablets were made into 10 to 32 mesh tablets in a mortar.
この触媒５ ｍｌを内径１５ｎｕｎのパイレックスガラ
ス製流通型反応管に充填した。その反応管を窒素中４０
０’Ｃで１時間焼成した。5 ml of this catalyst was filled into a Pyrex glass flow-through reaction tube having an inner diameter of 15 nm. The reaction tube was placed in nitrogen for 40 minutes.
It was baked at 0'C for 1 hour.
この反応管の前部は、１京料挿入管およびガス導入管に
連結され、原料気化部を構威し、後部は空冷部を経て受
器と連結されていた。この反応管の内温を５００°Ｃに
保ち、液空間速度１．０ｍ／ｈｒでヘンゼン、１．２ｍ
Ｎ／ｈｒで水を別々に原料挿入管より反応部に挿入し１
．これと同時に窒素３５＋１／ｍｉｎを常圧下で通した
。The front part of this reaction tube was connected to the 1,000 yen feed insertion pipe and the gas introduction pipe, forming a raw material vaporization section, and the rear part was connected to the receiver via an air cooling section. The internal temperature of this reaction tube was maintained at 500°C, and the liquid space velocity was 1.0 m/hr.
Water was separately introduced into the reaction section from the raw material insertion tube at a rate of N/hr.
．． At the same time, nitrogen was passed through at 35+1/min under normal pressure.
反応管を出て凝縮した反応生成物をガスクロマトグラフ
にて分析すると、ベンゼン転化率８．２％、フェノール
選択率９８．１％、フェノール収率８．０％でフェノー
ルが得られた。副生物はほとんど得られなかった。また
、ガス分析の結果、二酸化炭素および一酸化炭素の生成
はほとんど観察されなかった。When the reaction product condensed after exiting the reaction tube was analyzed by gas chromatography, phenol was obtained with a benzene conversion rate of 8.2%, a phenol selectivity of 98.1%, and a phenol yield of 8.0%. Almost no by-products were obtained. Furthermore, as a result of gas analysis, almost no production of carbon dioxide or carbon monoxide was observed.
実施例２
実施例１の触媒の代わりに試薬
ＣＬＩ３（ＰＯ４）Ｚ ・３Ｈ２０１３，６ｇ （０，
０３１モル）、Ｃａ５（ＰＯ４）ｚ ７．８ｇ （０
，０２５モル）およびＢａ０ｚ ８．６ｇ（０，０５モ
ル）の混合物を触媒とし、以下、実施例１と同様に実施
した結果、ベンゼン転化率８．１％、フェノール選択率
９２．６％、フェノール収率７．５％でフェノールを得
た。また、二酸化炭素および一酸化炭素の生成が少量観
察された。Example 2 Reagent CLI3(PO4)Z ・3H2013,6g (0,
031 mol), Ca5(PO4)z 7.8g (0
, 025 mol) and 8.6 g (0.05 mol) of Ba0z as a catalyst, the following procedure was carried out in the same manner as in Example 1. As a result, the benzene conversion rate was 8.1%, the phenol selectivity was 92.6%, and the phenol selectivity was 92.6%. Phenol was obtained with a yield of 7.5%. Also, small amounts of carbon dioxide and carbon monoxide production were observed.
実施例３
実施例１の触媒の代わりに試薬
Ｃｕｚ（Ｐｏ４）ｚ ・３Ｈ２０１３，６ｇ （０，０
３１モル）、Ｃａｚ（ＰＯ４）ｚ ７．８ｇ （０，
０２５モル）およびＢａＯ７，８ｇ（０，０５モル）の
混合物を触媒とし、以下、実施例１と同様に実施した結
果、ベンゼン転化率７．４％、フェノール選択率９７．
８％、フェノール収率７，２％でフェノールを得た。ま
た、二酸化炭素および一酸化炭素の生成が微量観察され
た。Example 3 Reagent Cuz(Po4)z ・3H2013,6g (0,0
31 mol), Caz(PO4)z 7.8g (0,
Using a mixture of 0.25 mol) and 7.8 g (0.05 mol) of BaO as a catalyst, the same procedure as in Example 1 was carried out, resulting in a benzene conversion of 7.4% and a phenol selectivity of 97.
Phenol was obtained with a phenol yield of 8% and a phenol yield of 7.2%. In addition, trace amounts of carbon dioxide and carbon monoxide were observed.
実施例４
実施例１の触媒の代わりに試薬
Ｃｕｚ（ＰＯ４）ｚ ＋ ３Ｈ２０１３，６ｇ （０，
０３１モル）、Ｂａ０ｚ ８．６ ｇ （０，０５モル
）およびＢａＯ７，８ｇ （０，０５モル）の混合物を
触媒とし、以下、実施例１と同様に実施した結果、ベン
ゼン転化率８．０％、フェノール選択率９１．３％、フ
ェノール収率７．３％でフェノールを得た。また、二酸
化炭素および一酸化炭素の生成が少量観察された。Example 4 Reagent Cuz(PO4)z + 3H2013,6g (0,
031 mol), Ba0z 8.6 g (0.05 mol) and BaO 7.8 g (0.05 mol) as a catalyst, the same procedure as in Example 1 was carried out, and as a result, the benzene conversion rate was 8.0%. , phenol was obtained with a phenol selectivity of 91.3% and a phenol yield of 7.3%. Also, small amounts of carbon dioxide and carbon monoxide production were observed.
実施例５
実施例１の触媒の代わりに試薬
Ｃｕ、（ＰＯ４）ｚ ・３Ｈｚ０ １３．６ｇ （０，
０３１モル）およびＢａ０ｚ ８．６ｇ （０，０５モ
ル）の混合物を触媒とし、以下、実施例１と同様に実施
した結果、ベンゼン転化率７．８％、フェノール選択率
９２．３％、フェノール収率７．２％でフェノールを得
た。また、二酸化炭素および一酸化炭素の生成が少量観
察された。Example 5 Reagent Cu, (PO4)z ・3Hz0 13.6g (0,
Using a mixture of 0.31 mol) and 8.6 g (0.05 mol) of BaOz as a catalyst, the following procedure was carried out in the same manner as in Example 1. As a result, the benzene conversion rate was 7.8%, the phenol selectivity was 92.3%, and the phenol yield was 7.8%. Phenol was obtained with a yield of 7.2%. Also, small amounts of carbon dioxide and carbon monoxide production were observed.
実施例６
実施例１の触媒の代わりに試薬
Ｃｕ１（ＰＯａ）ｚ Ｈ３ＨＪ １３．６ｇ （０，
０３１モル）およびＢａＯ７，８ｇ’（０，０５モル）
の混合物を触媒とし、以下、実施例１と同様に実施した
結果、ベンゼン転化率７．５％、フェノール選択率９３
．３％、フェノール収率７．０％でフェノールを得た。Example 6 Reagent Cu1(POa)z H3HJ 13.6g (0,
031 mol) and BaO7.8 g' (0.05 mol)
Using a mixture of as a catalyst, the following procedure was carried out in the same manner as in Example 1. As a result, the benzene conversion rate was 7.5% and the phenol selectivity was 93.
．． Phenol was obtained with a phenol yield of 7.0%.
また、二酸化炭素および一酸化炭素の生成が少量観察さ
れた。Also, small amounts of carbon dioxide and carbon monoxide production were observed.
比較例１
実施例１の触媒の代わりに試薬
Ｃｕ：＋（ＰＯＪｚ ・３ＨｚＯを触媒として、以下、
実施例１と同様に実施した結果、ベンゼン転化率６．２
％、フェノールＭ 択率９１，９％、フェノール収率５
．７％でフェノールを得た。また、二酸化炭素および一
酸化炭素の生成が少量観察された。Comparative Example 1 Using the reagent Cu:+(POJz ・3HzO as a catalyst instead of the catalyst in Example 1, the following
As a result of carrying out the same procedure as in Example 1, the benzene conversion rate was 6.2.
%, phenol M selectivity 91.9%, phenol yield 5
．． Phenol was obtained at 7%. Also, small amounts of carbon dioxide and carbon monoxide production were observed.
比較例２
実施例１の触媒の代かりに試薬
ＣＬＩ３（ＰＯ４）２ ・３ＨＪ １３．６ｇ （０
，０３１モル）およびｃａｓ（ＰＯ，）、 ７．８ｇ
（０，０２５モル） ｃ７）混合物を触媒とし、以下、
実施例１と同様に実施した結果、ベンゼン転化＄６．５
％、フェノール選択率９３．８％、フェノール収率６．
１％でフェノールを得た。また、二酸化炭素および一酸
化炭素の生成が少量観察された。Comparative Example 2 Reagent CLI3(PO4)2 ・3HJ 13.6g (0
,031 mol) and cas(PO,), 7.8 g
(0,025 mol) c7) Using the mixture as a catalyst, the following:
As a result of carrying out the same procedure as in Example 1, the benzene conversion was $6.5.
%, phenol selectivity 93.8%, phenol yield 6.
Phenol was obtained at 1%. Also, small amounts of carbon dioxide and carbon monoxide production were observed.
（発明の効果〕
本発明によれば、ヘンゼンからフェノールを１工程で従
来になく高収率で製造することができる。(Effects of the Invention) According to the present invention, phenol can be produced from Hensen in one step at a higher yield than ever before.
Claims (1)
製造するに際し、過酸化バリウムおよび酸化バリウムか
らなる群から選ばれた一種または二種の物質とリン酸銅
を含有する触媒を用いることを特徴とするフェノールの
製法。 ２）過酸化バリウムおよび酸化バリウムからなる群から
選ばれた一種または二種の物質とリン酸銅およびリン酸
カルシウムを含有する触媒を用いて行う請求項１に記載
の製法。[Claims] 1) When producing phenol by subjecting benzene and water to a gas phase contact reaction, the product contains one or two substances selected from the group consisting of barium peroxide and barium oxide and copper phosphate. A method for producing phenol characterized by using a catalyst. 2) The method according to claim 1, which is carried out using a catalyst containing one or two substances selected from the group consisting of barium peroxide and barium oxide, and copper phosphate and calcium phosphate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2031373A JPH03236338A (en) | 1990-02-14 | 1990-02-14 | Production of phenol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2031373A JPH03236338A (en) | 1990-02-14 | 1990-02-14 | Production of phenol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03236338A true JPH03236338A (en) | 1991-10-22 |
Family
ID=12329453
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2031373A Pending JPH03236338A (en) | 1990-02-14 | 1990-02-14 | Production of phenol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03236338A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5952532A (en) * | 1997-07-31 | 1999-09-14 | Sunoco, Inc. | Hydroxylation of aromatics using molecular oxygen as the terminal oxidant without coreductant |
| US5962752A (en) * | 1997-07-31 | 1999-10-05 | Sun Company, Inc. | Leached alumina vanadyl catalysts for hydroxylation of aromatics using molecular oxygen as the terminal oxidant without coreductant |
| US5981424A (en) * | 1997-07-31 | 1999-11-09 | Sunoco, Inc. (R&M) | Catalysts for hydroxylation and ammination of aromatics using molecular oxygen as the terminal oxidant without coreductant |
-
1990
- 1990-02-14 JP JP2031373A patent/JPH03236338A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5952532A (en) * | 1997-07-31 | 1999-09-14 | Sunoco, Inc. | Hydroxylation of aromatics using molecular oxygen as the terminal oxidant without coreductant |
| US5962752A (en) * | 1997-07-31 | 1999-10-05 | Sun Company, Inc. | Leached alumina vanadyl catalysts for hydroxylation of aromatics using molecular oxygen as the terminal oxidant without coreductant |
| US5981424A (en) * | 1997-07-31 | 1999-11-09 | Sunoco, Inc. (R&M) | Catalysts for hydroxylation and ammination of aromatics using molecular oxygen as the terminal oxidant without coreductant |
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