JPH03115244A - Production of dihydric phenol monoalkyl ether - Google Patents
Production of dihydric phenol monoalkyl etherInfo
- Publication number
- JPH03115244A JPH03115244A JP1251977A JP25197789A JPH03115244A JP H03115244 A JPH03115244 A JP H03115244A JP 1251977 A JP1251977 A JP 1251977A JP 25197789 A JP25197789 A JP 25197789A JP H03115244 A JPH03115244 A JP H03115244A
- Authority
- JP
- Japan
- Prior art keywords
- dihydric phenol
- catalyst
- reaction
- granular
- hours
- 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.)
- Granted
Links
- -1 phenol monoalkyl ether Chemical class 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 90
- 238000006243 chemical reaction Methods 0.000 claims abstract description 59
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 24
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 19
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004327 boric acid Substances 0.000 claims abstract description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 11
- 239000012495 reaction gas Substances 0.000 claims abstract description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- 239000004480 active ingredient Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 4
- 239000003814 drug Substances 0.000 abstract description 2
- 239000002304 perfume Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 230000006866 deterioration Effects 0.000 abstract 1
- 229940079593 drug Drugs 0.000 abstract 1
- 239000012808 vapor phase Substances 0.000 abstract 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 52
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 43
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 42
- 238000006266 etherification reaction Methods 0.000 description 22
- 229960001867 guaiacol Drugs 0.000 description 22
- 239000000243 solution Substances 0.000 description 21
- 239000007864 aqueous solution Substances 0.000 description 12
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 10
- 229960002645 boric acid Drugs 0.000 description 10
- 235000010338 boric acid Nutrition 0.000 description 10
- 238000004817 gas chromatography Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- 235000011007 phosphoric acid Nutrition 0.000 description 9
- 230000007423 decrease Effects 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 description 8
- 239000011148 porous material Substances 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 6
- 229910052796 boron Inorganic materials 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000002168 alkylating agent Substances 0.000 description 2
- 229940100198 alkylating agent Drugs 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- XNMWMBDFIURVIN-UHFFFAOYSA-N 1-chlorocyclohexa-3,5-diene-1,2-diol Chemical compound OC1C=CC=CC1(O)Cl XNMWMBDFIURVIN-UHFFFAOYSA-N 0.000 description 1
- LNTVWURFZCEJDN-UHFFFAOYSA-N 1-methylcyclohexa-3,5-diene-1,2-diol Chemical compound CC1(O)C=CC=CC1O LNTVWURFZCEJDN-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- XDVOLDOITVSJGL-UHFFFAOYSA-N 3,7-dihydroxy-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound O1B(O)OB2OB(O)OB1O2 XDVOLDOITVSJGL-UHFFFAOYSA-N 0.000 description 1
- WWOBYPKUYODHDG-UHFFFAOYSA-N 4-chlorocatechol Chemical compound OC1=CC=C(Cl)C=C1O WWOBYPKUYODHDG-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- YDHWWBZFRZWVHO-UHFFFAOYSA-N [hydroxy(phosphonooxy)phosphoryl] phosphono hydrogen phosphate Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(=O)OP(O)(O)=O YDHWWBZFRZWVHO-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001348 alkyl chlorides Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000001555 benzenes Chemical group 0.000 description 1
- ZSJHIZJESFFXAU-UHFFFAOYSA-N boric acid;phosphoric acid Chemical compound OB(O)O.OP(O)(O)=O ZSJHIZJESFFXAU-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- AJPXTSMULZANCB-UHFFFAOYSA-N chlorohydroquinone Chemical compound OC1=CC=C(O)C(Cl)=C1 AJPXTSMULZANCB-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- VGTPKLINSHNZRD-UHFFFAOYSA-N oxoborinic acid Chemical compound OB=O VGTPKLINSHNZRD-UHFFFAOYSA-N 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
この発明は、気体状態の二価フェノールおよび低級モノ
アルコールを特定の固定触媒上に供給して、両者を反応
させて、二価フェノールモノアルキルエーテルを高い転
化率および収率で生成させることができる二価フェノー
ルモノアルキルエーテルの工業的な製法に係わる。[Detailed Description of the Invention] [Industrial Application Field] This invention supplies a gaseous dihydric phenol and a lower monoalcohol onto a specific fixed catalyst and reacts them to produce a dihydric phenol monoalkyl. The present invention relates to an industrial method for producing dihydric phenol monoalkyl ethers that can produce ethers at high conversion rates and yields.
グアヤコールなどの二価フェノールモノアルキルエーテ
ルは、香料や医薬品の中間原料として有用な物質である
。Dihydric phenol monoalkyl ethers such as guaiacol are useful substances as intermediate raw materials for perfumes and pharmaceuticals.
二価フェノールを低級モノアルコールでエーテル化して
、二価フェノールモノアルキルエーテルを製造する方法
は、従来、種々の製法が知られている。Various methods are conventionally known for producing dihydric phenol monoalkyl ether by etherifying dihydric phenol with a lower monoalcohol.
まず、公知の二価フェノールモノアルキルエーテルの製
造法としては、二価フェノールを、ジメチル硫酸、塩化
アルキルとアルカリとの組み合わせ、炭酸ジメチルなど
のアルキル化剤によってエーテル化する液相法が知られ
ている。First, as a known method for producing dihydric phenol monoalkyl ether, a liquid phase method is known in which dihydric phenol is etherified using an alkylating agent such as dimethyl sulfate, a combination of alkyl chloride and an alkali, or dimethyl carbonate. There is.
しかし、一般に前述の液相法において使用するアルキル
化剤は極めて高価であり、また、煩雑な廃水処理を行う
必要があるという問題点を有している。However, the alkylating agents used in the above-mentioned liquid phase method are generally extremely expensive, and they also have the problem of requiring complicated wastewater treatment.
また、公知の二価フェノールモノアルキルエーチルの製
造法として、下記に例示する公知文献によって、気相法
が知られており、
■ Chem、 Abs、 55−7336(1960
) Masloboino−Zhirovaya Pr
om、 26 (10) 24〜27(1,960)■
西ドイツ特許第827803号明細書■ 特公昭53
−35062号公報
■ 特公昭55−33658号公報
■ 特公昭55−6618号公報
■ 日本化学会誌(12) 233H1985)および
特公昭56−6618号公報
例えば、カテコールなどの二価フェノールとメタノール
などの低級モノアルコールとを、気相で、(a)リン酸
とホウ酸とからなる触媒〔文献■〜■〕(ロ)アルミニ
ウム、リン、ホウ素および酸素からなる触媒〔文献■〜
■〕
(C)カオリン触媒〔文献■〕など
の特定の触媒とそれぞれ接触させて、エーテル化反応さ
せて、グアヤコールなとの二価フェノールモノアルキル
エーテルを生成させる方法が、挙げられる。In addition, as a known method for producing dihydric phenol monoalkyl ethyl, a gas phase method is known according to the known literature exemplified below.
) Masloboino-Zhirovaya Pr
om, 26 (10) 24-27 (1,960) ■
West German Patent No. 827803 Specification■ Special Publication No. 1973
-35062 Publication ■ Japanese Patent Publication No. 55-33658 ■ Special Publication No. 55-6618 ■ Journal of the Chemical Society of Japan (12) 233H1985) and Special Publication No. 56-6618 For example, dihydric phenols such as catechol and lower grades such as methanol. monoalcohol in a gas phase, (a) a catalyst consisting of phosphoric acid and boric acid [References ■~■] (b) a catalyst consisting of aluminum, phosphorus, boron, and oxygen [References ■~
(2) (C) A method in which a dihydric phenol monoalkyl ether such as guaiacol is produced by contacting with a specific catalyst such as a kaolin catalyst [Reference (2)] and causing an etherification reaction.
しかし、前記の公知のリン酸とホウ酸とからなる触媒を
使用する製法(a)では、グアヤコールなどの選択率が
80〜90%程度であり必ずしも充分ではなく、また、
前記のリン酸−ホウ酸系触媒では、BPO,成分が反応
時にしだいに減少してしまうので、触媒寿命が著しく短
く、工業的に適当ではないという問題点を有しているの
である。However, in the production method (a) using the above-mentioned known catalyst consisting of phosphoric acid and boric acid, the selectivity for guaiacol etc. is about 80 to 90%, which is not necessarily sufficient, and
The above-mentioned phosphoric acid-boric acid catalyst has a problem in that the BPO component gradually decreases during the reaction, so the catalyst life is extremely short and it is not suitable for industrial use.
また、前記の公知のアルミニウム、ホウ素、リンおよび
酸素からなる触媒を使用する製法(ハ)では、二価フェ
ノールモノアルキルエーテルが高い選択率で得られ、し
かもBPO,成分の減少もかなり改善されているけれど
も、極めて長時間の反応ではやはり触媒の活性がしだい
に低下し、しかも、触媒の機械的強度も徐々に低下する
ことがあるという問題点を有していた。In addition, in the above-mentioned production method (c) using the known catalyst consisting of aluminum, boron, phosphorus, and oxygen, dihydric phenol monoalkyl ether can be obtained with high selectivity, and the reduction of BPO and other components has also been considerably improved. However, in extremely long-term reactions, the activity of the catalyst gradually decreases, and furthermore, the mechanical strength of the catalyst may also gradually decrease.
さらに、前記の公知のカオリン触媒を使用する製法(C
)では、二価フェノールモノアルキルエーテルの選択率
が約80%程度に過ぎず、副生成物の生成が10%もあ
るので、工業的に実施することが困難であるという問題
点があった。Furthermore, the production method using the above-mentioned known kaolin catalyst (C
), the selectivity of dihydric phenol monoalkyl ether is only about 80%, and the production of by-products is as much as 10%, making it difficult to implement industrially.
この発明の目的は、二価フェノールと低級モノ7)li
ミコールの長時間のエーテル化反応において活性や機械
的強度の低下が少ない固定触媒を使用して、気相で、二
価フェノールと低級モノアルコールとから高い転化率お
よび選択率で二価フェノールモノアルキルエーテルを工
業的に製造することができる方法を提供することである
。The purpose of this invention is to combine dihydric phenol and lower monomer 7) li
In the long-term etherification reaction of mycol, dihydric phenol monoalkyl can be converted from dihydric phenol and lower monoalcohol with high conversion rate and selectivity in the gas phase using a fixed catalyst with little loss of activity and mechanical strength. The object of the present invention is to provide a method by which ether can be produced industrially.
この発明は、気体状態の二価フェノールおよび低級モノ
アルコールを、粒状の不活性アルミナにホウ酸と燐酸と
から得られた活性成分を担持してなる粒状触媒上に供給
して、反応温度200〜400“C1および、常圧下に
、二価フェノールと低級モノアルコールとを気相で、前
記触媒と接触させ、反応させて、二価フェノールモノア
ルキルエーテルを生成させ、その後、反応ガスを冷却し
て、反応液を得ることを特徴とする二価フェノールモノ
アルキルエーテルの製法に関する。In this invention, a gaseous dihydric phenol and a lower monoalcohol are supplied onto a granular catalyst formed by supporting an active ingredient obtained from boric acid and phosphoric acid on granular inert alumina, and the reaction temperature is 200 to 200. 400"C1 and a dihydric phenol and a lower monoalcohol are brought into contact with the catalyst in the gas phase under normal pressure to react to produce a dihydric phenol monoalkyl ether, and then the reaction gas is cooled. , relates to a method for producing dihydric phenol monoalkyl ether, which is characterized by obtaining a reaction solution.
以下に、この発明の方法を詳しく説明する。 The method of this invention will be explained in detail below.
この発明においては、二価フェノールおよび低級モノア
ルコールを気体状態で、特定の粒状触媒上に供給するの
であるが、例えば、前記粒状触媒の充填された反応管又
は反応槽とは別に設置された蒸発器において二価フェノ
ールの低級モノアルコール溶液を加熱・気化して両者共
に気体状態で前記反応管又は反応槽内の粒状触媒の充填
層上へ供給する方法が好ましく、また、前記二価フェノ
ールと低級モノアルコールとを別々に加熱・気化してそ
れぞれ気体状態として、それぞれを反応管又は反応槽へ
供給する方法であってもよい。In this invention, dihydric phenol and lower monoalcohol are supplied in a gaseous state onto a specific granular catalyst. It is preferable to heat and vaporize a lower monoalcohol solution of dihydric phenol in a vessel and supply both in a gaseous state onto a packed bed of granular catalyst in the reaction tube or reaction tank. A method may also be used in which the monoalcohol and the monoalcohol are heated and vaporized separately to make each into a gaseous state, and each is supplied to a reaction tube or a reaction tank.
この発明において使用される前記二価フェノールは、置
換基を有していない二価フェノール、および、ベンゼン
核の水素原子が炭素数1〜4の低級アルキル基又はハロ
ゲン原子で置換されている二価フェノールなどであれば
よく、例えば、カテコール、ハイドロキノン、レゾルシ
ンなどの置換基を有していない二価フェノール類、4−
メチルカテコール、2−メチルカテコール、2−メチル
ハイドロキノンなどの低級アルキル基を有する二価フェ
ノール類、そして、4−クロルカテコール、2−クロル
カテコール、2−クロルハイドロキノンなどのハロゲン
置換二価フェノールを挙げることができる。The dihydric phenol used in this invention includes a dihydric phenol without a substituent, and a dihydric phenol in which the hydrogen atom of the benzene nucleus is substituted with a lower alkyl group having 1 to 4 carbon atoms or a halogen atom. For example, dihydric phenols without substituents such as catechol, hydroquinone, resorcinol, 4-
Dihydric phenols having a lower alkyl group, such as methylcatechol, 2-methylcatechol, and 2-methylhydroquinone, and halogen-substituted dihydric phenols, such as 4-chlorocatechol, 2-chlorocatechol, and 2-chlorohydroquinone. I can do it.
この発明で使用される低級モノアルコールは、炭素数1
〜6、特に炭素数1〜4の直鎖状又は分岐状脂肪族モノ
アルコールであればよく、例えば、メタノール、エタノ
ール、n−プロパツール、インプロパツール、n−ブタ
ノール、イソブタノール、第2級ブタノール、第3級ブ
タノールなどを挙げることができる。The lower monoalcohol used in this invention has 1 carbon number.
- 6, especially linear or branched aliphatic monoalcohols having 1 to 4 carbon atoms, such as methanol, ethanol, n-propanol, impropanol, n-butanol, isobutanol, secondary Examples include butanol, tertiary butanol, and the like.
この発明において使用される粒状触媒は、粒状の不活性
アルミナにホウ酸と燐酸とからなる活性成分を担持して
なる粒状触媒であり、反応管または反応槽に充填されて
固定触媒床(触媒充填層)、または、移動触媒床を好適
に形成しうるものが特に好ましい。The granular catalyst used in this invention is a granular catalyst made by supporting active components consisting of boric acid and phosphoric acid on granular inert alumina, and is packed into a reaction tube or reaction tank to form a fixed catalyst bed (catalyst packed bed). Particularly preferred are those which can suitably form a layer) or a moving catalyst bed.
前記の触媒充填層は、各粒状触媒の平均粒径が1〜10
I!IIII、特に好ましくは2〜8rm程度であり、
そして、充填層の嵩密度が0.8〜1.2g/mj!程
度であり、さらに、充填層の空隙率が30〜35%程度
であることが好ましく、また、移動触媒床に使用される
各粒状触媒の平均粒径は、0.1〜5肛、特に好ましく
は0.5〜3IlII11程度であることが好ましい。In the catalyst packed bed, each granular catalyst has an average particle size of 1 to 10
I! III, particularly preferably about 2 to 8 rm,
And the bulk density of the packed bed is 0.8 to 1.2 g/mj! Further, it is preferable that the porosity of the packed bed is about 30 to 35%, and the average particle size of each granular catalyst used in the mobile catalyst bed is particularly preferably 0.1 to 5 mm. is preferably about 0.5 to 3IlII11.
前記の粒状触媒において担体として使用される不活性ア
ルミナは、その結晶構造がα型である粒状の酸化アルミ
ニウム(α−アルミナとも言う)であればよく、α−ア
ルミナ中に一部θ型の酸化アルミニウムが含有されてい
るものであってもよい。その不活性アルミナは、平均粒
径が1〜10皿、特に好ましくは2〜8W程度である球
状または最大径1−10mmを有するタブレット状のも
のが好ましい。The inert alumina used as a support in the above-mentioned granular catalyst may be granular aluminum oxide (also referred to as α-alumina) whose crystal structure is α-type. It may also contain aluminum. The inert alumina is preferably spherical with an average particle diameter of 1 to 10 mm, particularly preferably about 2 to 8 W, or tablet-shaped with a maximum diameter of 1 to 10 mm.
なお、前記のα−アルミナは、種々のアルミナ中で最も
高温で熱処理されて得られるものであるので、化学的に
最も不活性であり、また、化学的及び熱的に安定してい
るものであり、そのアルミナの結晶構造のli1!認は
、r触媒工学講座(10) 27(1977) 元素
別触媒便覧(地人書館発行)」に記載されているX線回
折法で行うことができる。The α-alumina mentioned above is the one obtained by heat treatment at the highest temperature among the various aluminas, so it is the most chemically inert and chemically and thermally stable. Yes, the crystal structure of alumina is li1! The identification can be carried out by the X-ray diffraction method described in "Catalyst Engineering Course (10) 27 (1977) Catalyst Handbook by Element (Published by Chijinshokan)".
また、前記粒状触媒の調製に使用されるホウ酸としては
、−船釣には、オルトホウ酸を好適に使用することがで
きるが、メタホウ酸、四ホウ酸、ホウ酸のアルキルエス
テルなども使用することができる。Further, as the boric acid used for preparing the granular catalyst, - for boat fishing, orthoboric acid can be suitably used, but metaboric acid, tetraboric acid, alkyl esters of boric acid, etc. can also be used. be able to.
また、前記粒状触媒の調製に使用される燐酸としては、
オルトリン酸を好適に使用することができるが、ビロリ
ン酸、四リン酸、ポリメタリン酸なども使用することが
できる。In addition, the phosphoric acid used for preparing the granular catalyst is as follows:
Orthophosphoric acid can be preferably used, but birophosphoric acid, tetraphosphoric acid, polymetaphosphoric acid, etc. can also be used.
前記の粒状触媒において、粒状の不活性な酸化アルミニ
ウムに担持されたホウ酸と燐酸とから得られた活性成分
は、ホウ素(B)とリン(P)とで示されるホウ素成分
とリン成分との組成比(B:Pの原子比)が、1 :
0.1〜1:1.5、特に好ましくはl:o、2〜1:
1.2程度であることが好ましく、又、前記活性成分の
合計量が、B t O3とP z Osの合計量で示し
て、粒状触媒の全重量に対して約2〜50重量%、特に
5〜40重量%程度の割合となるように、粒状の不活性
な酸化アルミニウムに担持されていることが好ましい。In the above granular catalyst, the active component obtained from boric acid and phosphoric acid supported on granular inert aluminum oxide is a combination of boron component and phosphorus component represented by boron (B) and phosphorus (P). The composition ratio (atomic ratio of B:P) is 1:
0.1-1:1.5, particularly preferably l:o, 2-1:
1.2, and the total amount of the active components is about 2 to 50% by weight, especially about 2 to 50% by weight based on the total weight of the particulate catalyst, expressed as the total amount of B t O3 and P z Os. It is preferable that it is supported on granular inert aluminum oxide at a ratio of about 5 to 40% by weight.
前記の粒状触媒の調製は、ホウ酸と燐酸とを前述の活性
成分の組成比の割合で混合し、この混合物に約0.2〜
5重量倍、特に好ましくは0.2〜4重量倍の水を加え
て活性成分水溶液を調製し、そして、「この水溶液に前
記の粒状の不活性アルミナ担体を浸漬した後、50〜1
50°C1特に70〜120°Cの温度で、2〜30時
間加熱攪拌し、次いで、適当な方法で乾燥すること」を
数回繰り返す方法を好適に挙げることができる。The above granular catalyst is prepared by mixing boric acid and phosphoric acid at the composition ratio of the active ingredients described above, and adding about 0.2 to
An aqueous solution of the active ingredient is prepared by adding 5 times by weight, particularly preferably 0.2 to 4 times by weight, water, and "after immersing the granular inert alumina carrier in this aqueous solution, 50 to 1
Preferred methods include heating and stirring at a temperature of 50°C, particularly 70 to 120°C, for 2 to 30 hours, and then drying by an appropriate method several times.
前述のようにして得られた粒状触媒は、必要であれば、
空気中、200〜600°Cの温度で、1〜10時間焼
成してもよい。The granular catalyst obtained as described above can be treated with, if necessary,
It may be baked in air at a temperature of 200 to 600°C for 1 to 10 hours.
この発明の製法においては、気体状態の二価フェノール
および低級モノアルコールを、前記の粒状触媒上に供給
して、反応温度200〜400℃、好ましくは230〜
350℃、特に好ましくは240〜330℃、および、
常圧(好ましくは0.8〜1.4気圧、特に好ましくは
0.9〜1.2気圧)下に、二価フェノールと低級モノ
アルコールとを気相で、前記粒状触媒と接触させ、反応
させて、二価フェノールモノアルキルエーテルを生成さ
せ、その後、反応ガスを冷却して、二価フェノールモノ
アルキルエーテルを主として含有する反応液を得るので
ある。In the production method of this invention, gaseous dihydric phenol and lower monoalcohol are supplied onto the granular catalyst, and the reaction temperature is 200-400°C, preferably 230-400°C.
350°C, particularly preferably 240-330°C, and
Under normal pressure (preferably 0.8 to 1.4 atm, particularly preferably 0.9 to 1.2 atm), dihydric phenol and lower monoalcohol are brought into contact with the granular catalyst in the gas phase to react. Then, the reaction gas is cooled to obtain a reaction liquid mainly containing dihydric phenol monoalkyl ether.
この発明において、二価フェノールの供給量は、触媒1
dあたり、0.05〜10 g/h r、特に好ましく
は0.1〜5g/hr、さらに好ましくは、0.2〜3
g/hr程度の割合となる量であることが好ましい。In this invention, the amount of dihydric phenol supplied is 1
per d, 0.05 to 10 g/hr, particularly preferably 0.1 to 5 g/hr, even more preferably 0.2 to 3
It is preferable that the amount is at a rate of approximately g/hr.
そして、この発明では、低級モノアルコールの供給量は
、二価フェノール1モルに対して、1〜50モル倍、特
に好ましくは2〜10モル倍程度の割合となる量である
ことが好ましい。In the present invention, the amount of lower monoalcohol supplied is preferably in a ratio of about 1 to 50 moles, particularly preferably about 2 to 10 moles, per mole of dihydric phenol.
また、この発明において、反応ガスの冷却は、反応生成
物が常圧で液状となるような温度以下であればよく、特
に、反応液の取扱いの上からは、反応液を40°C以下
の温度に冷却することが好ましい。In addition, in this invention, the reaction gas may be cooled as long as it is at a temperature below which the reaction product becomes liquid at normal pressure. Preferably, it is cooled to temperature.
以下、実施例および比較例を示し、この発明をさらに詳
しく説明する。EXAMPLES Hereinafter, the present invention will be explained in more detail by showing Examples and Comparative Examples.
なお、この発明は、その趣旨を越えない限り以下の実施
例に限定されるものではない。Note that this invention is not limited to the following examples unless it exceeds the spirit thereof.
また、各実施例におけるエーテル化反応前および反応後
の粒状触媒の機械的強度(圧壊強度)は、本屋式圧壊試
験機を使用して測定した。In addition, the mechanical strength (crushing strength) of the granular catalyst before and after the etherification reaction in each Example was measured using a Honya type crushing tester.
実施例1
〔触媒の調製〕
攪拌機、温度計、滴下ロートおよび冷却管を付設された
4つロセバラブルフラスコに、Hs B 0315.5
g(0,25モル)および水90gを入れ、油浴で水溶
液の温度を100°Cにまで加熱し、その温度で攪拌し
ながら、滴下ロートから85重量%HsP0428.8
g (0,25モル)を約1時間でゆっ(りと滴下して
、その後、その水溶液を前記温度に維持して20時間攪
拌し、最後に、冷却した後、水を加えて水溶液全体を2
00gに希釈して、BPO,水溶液を調製した。Example 1 [Catalyst Preparation] Hs B 0315.5 was added to four rosetteable flasks equipped with a stirrer, a thermometer, a dropping funnel and a cooling tube.
(0.25 mol) and 90 g of water, heated the aqueous solution to 100 °C in an oil bath, and while stirring at that temperature, added 85% by weight HsP0428.8 from the dropping funnel.
g (0.25 mol) was slowly added dropwise in about 1 hour, then the aqueous solution was maintained at the above temperature and stirred for 20 hours, and finally, after cooling, water was added to dissolve the entire aqueous solution. 2
00g to prepare a BPO aqueous solution.
次に、α−アルミナ(不二見研磨材工業■製、商品名;
AM−334、粒子径;1mm、比表面積;7.2rr
r/g、細孔容積0.36ad/g) 50mI!、(
47g)に、BPO,水溶液25gを添加してホットプ
レート上で乾燥し、更に、その乾燥物にBPO,水溶液
25gを添加してホットプレート上で乾燥し、さらに、
その乾燥物を400°Cで、4時間焼成して、粒状触媒
を調製した。Next, α-alumina (manufactured by Fujimi Abrasive Industry ■, product name;
AM-334, particle size: 1 mm, specific surface area: 7.2rr
r/g, pore volume 0.36ad/g) 50mI! ,(
47 g), 25 g of BPO, aqueous solution was added and dried on a hot plate, further, 25 g of BPO, aqueous solution was added to the dried product and dried on a hot plate, and further,
The dried product was calcined at 400°C for 4 hours to prepare a granular catalyst.
前記の粒状触媒は、活性成分がBPO,で示して14重
量%担持されていた。In the granular catalyst, 14% by weight of the active component, expressed as BPO, was supported.
耐熱性ガラス製反応管(内径;30mm、長さ;500
m+n)に、前述のようにして調製した粒状触媒25m
f(26,9g、嵩比重;1.0B)を充填すると共に
、その充填層の上部に予熱用ガラスピーズ(径;2ff
i、嵩比重;1.52)を充填し、窒素ガスを流通させ
ながら、約270°Cまで昇温し、次いで、カテコール
のメタノール溶液(カテコール濃度50重量%)を、気
体状態で、供給速度15mj!/hrで、粒状触媒の充
填層上へ、44時間連続的に供給して、カテコールとメ
タノールとを反応させて、グアヤコールを生成させ、そ
の反応ガスを20°Cに冷却して、グアヤコールを主と
して含有する反応液を捕集した。Heat-resistant glass reaction tube (inner diameter: 30 mm, length: 500 mm
m+n), 25 m of the granular catalyst prepared as described above.
f (26.9g, bulk specific gravity: 1.0B), and preheating glass beads (diameter: 2ff) were placed on the top of the packed bed.
i, bulk specific gravity; 1.52), heated to approximately 270°C while flowing nitrogen gas, and then a methanol solution of catechol (catechol concentration: 50% by weight) in a gaseous state at a feeding rate. 15mj! /hr continuously for 44 hours onto a packed bed of granular catalyst to react catechol and methanol to produce guaiacol, and cool the reaction gas to 20°C to mainly produce guaiacol. The reaction solution containing was collected.
前記の反応開始から4時間後および44時間後の各反応
液をガスクロマトグラフィー分析することにより、反応
液中の各成分の定量分析をそれぞれ行った。その結果か
ら算出されたカテコール転化率、グアヤコール選択率、
ベラトロールM択率、および、その他側生成物(核メチ
ル化物など)の選択率は、第1表のようであった。Quantitative analysis of each component in the reaction solution was performed by gas chromatography analysis of each reaction solution 4 hours and 44 hours after the start of the reaction. Catechol conversion rate, guaiacol selectivity calculated from the results,
The selectivity of veratrol M and the selectivity of other side products (nuclear methylated products, etc.) were as shown in Table 1.
カテコール転化率
グアヤコール選択率
ベラトロール選択率
その他側生成物選択率
4時間後 44時間後
31.2% 2
99.5% 9
0.2%
0.3%
9.3%
9.3%
0.2%
0.5%
なお、前記の粒状触媒の圧壊強度は、前記のエーテル化
反応前および反応開始から44時間後において、いずれ
も1.7kg/粒であり、エーテル化反応による前記粒
状触媒の機械的強度の低下は認められなかった。Catechol conversion Guaiacol selectivity Veratrol selectivity Other product selectivity After 4 hours After 44 hours 31.2% 2 99.5% 9 0.2% 0.3% 9.3% 9.3% 0.2 % 0.5% The crushing strength of the granular catalyst was 1.7 kg/granule both before the etherification reaction and 44 hours after the start of the reaction, and the crushing strength of the granular catalyst during the etherification reaction was 1.7 kg/granule. No decrease in target strength was observed.
実施例2
〔触媒の調製〕
α−アルミナ担体へのBPO,水溶液の添加を4回行っ
たほかは、実施例1と同様にして粒状触媒を調製した。Example 2 [Catalyst Preparation] A granular catalyst was prepared in the same manner as in Example 1, except that BPO and aqueous solution were added to the α-alumina carrier four times.
その粒状触媒は、活性成分がBPO,で示して28重重
量担持されていた。The granular catalyst had a weight loading of 28 by weight of the active component, expressed as BPO.
前述のようにして調製した粒状触媒25m2(30,9
g)を使用し、反応時間を56時間としたほかは、実施
例1と同様にして、カテコールとメタノールとを反応さ
せて、グアヤコールを主として含有する反応液を捕集し
た。25 m2 (30,9 m2) of granular catalyst prepared as described above
Catechol and methanol were reacted in the same manner as in Example 1, except that g) was used and the reaction time was 56 hours, and a reaction liquid mainly containing guaiacol was collected.
前記の反応開始から2時間後および56時間後の各反応
液をガスクロマトグラフィー分析した。Each reaction solution was analyzed by gas chromatography 2 hours and 56 hours after the start of the reaction.
その結果を第2表に示す。The results are shown in Table 2.
2時間後
56時間後
カテコール転化率 29.7% 29.9%グア
ヤコール選択率 98.6% 99.3%ベラトロ
ール選択率 0.4% 0.3%その他側生成
物選択率 1.0% 0.4%なお、前記の粒状
触媒の圧壊強度は、前記のエーテル化反応前および反応
開始から56時間後において、いずれも1.7kg/粒
であり、実施例1と同様に、エーテル化反応による前記
粒状触媒の機械的強度の低下は認められなかった。Catechol conversion after 2 hours and 56 hours 29.7% 29.9% Guaiacol selectivity 98.6% 99.3% Veratrol selectivity 0.4% 0.3% Other product selectivity 1.0% 0 .4% The crushing strength of the granular catalyst was 1.7 kg/granule both before the etherification reaction and 56 hours after the start of the reaction, and as in Example 1, No decrease in mechanical strength of the granular catalyst was observed.
比較例1
〔触媒の調製〕
担体としてr−アルミナ(住友化学工業■製、商品名、
NKHl−24、粒子径;2+11111、比表面積;
110rrf/g、細孔容積0.90crl/ g )
を使用したほかは、実施例1と同様にして、粒状触媒を
調製した。Comparative Example 1 [Preparation of catalyst] r-alumina (manufactured by Sumitomo Chemical Co., Ltd., trade name,
NKHl-24, particle size; 2+11111, specific surface area;
110rrf/g, pore volume 0.90crl/g)
A granular catalyst was prepared in the same manner as in Example 1 except that .
その粒状触媒は、活性成分がBPO,で示して14重重
量担持されていた。The granular catalyst had a 14 weight loading of the active component, expressed as BPO.
前述のようにして調製した粒状触媒25m2(14,8
g)を使用し、反応時間を6時間としたほかは、実施例
1と同様にして、カテコールとメタノールとを反応させ
て、グアヤコールを主として含有する反応液を捕集した
。25 m2 (14,8 m2 of granular catalyst prepared as described above)
Catechol and methanol were reacted in the same manner as in Example 1, except that g) was used and the reaction time was changed to 6 hours, and a reaction liquid mainly containing guaiacol was collected.
前記の反応開始がら1時間後および6時間後の各反応液
をガスクロマトグラフィー分析した。その結果を第3表
に示す。Each reaction solution was analyzed by gas chromatography 1 hour and 6 hours after the start of the reaction. The results are shown in Table 3.
カテコール転化率
グアヤコール選択率
ベラトロール選択率
その他側生成物選択率
1時間後 6時間後
32.8% 15.2%
92.1% 95.4%
4、0% 2.6%
3.9% 2.1%
比較例2
〔触媒の調製〕
担体としてγ−アルミナ(住友化学工業■製、商品名、
KHT−46、粒子径;2mm、比表面積H1,0rr
f/g、細孔容積0.43cIl/g)を使用したほか
は、実施例1と同様にして、粒状触媒を調製した。Catechol conversion Guaiacol selectivity Veratrol selectivity Other product selectivity After 1 hour After 6 hours 32.8% 15.2% 92.1% 95.4% 4, 0% 2.6% 3.9% 2 .1% Comparative Example 2 [Catalyst Preparation] γ-Alumina (manufactured by Sumitomo Chemical Co., Ltd., trade name,
KHT-46, particle size: 2 mm, specific surface area H1,0rr
A granular catalyst was prepared in the same manner as in Example 1, except that pore volume (pore volume: 0.43 cIl/g) was used.
その粒状触媒は、活性成分がBPO,で示して14重量
%担持されていた。The granular catalyst contained 14% by weight of the active component, expressed as BPO.
前述のようにして調製した粒状触媒25m2(20,9
g)を使用し、反応時間を12時間としたほかは、実施
例1と同様にして、カテコールとメタノールとを反応さ
せて、グアヤコールを主として含有する反応液を補集し
た。25 m2 (20,9 m2) of granular catalyst prepared as described above
Catechol and methanol were reacted in the same manner as in Example 1, except that g) was used and the reaction time was changed to 12 hours, and the reaction liquid mainly containing guaiacol was collected.
前記の反応開始から2時間後および12時間後の各反応
液をガスクロマトグラフィー分析した。Each reaction solution was analyzed by gas chromatography 2 hours and 12 hours after the start of the reaction.
その結果を第4表に示す。The results are shown in Table 4.
第
4
表
2時間後
12時間後
カテコール転化率 20.7% 21.9%グア
ヤコール選択率 97.6% 97.4%ベラトロ
ール選択率 1.9% 1.9%その他側生成
物選択率 0.6% 0.7%比較例3
〔触媒の調製〕
担体として、活性炭(呉羽化学工業■製、商品名;クレ
ハビーズ、粒子径;1晒、比表面積;1000r+(/
g、細孔容積0.67cffl/g)を使用したほかは
、実施例1と同様にして、粒状触媒を調製した。Table 4 Catechol conversion after 2 hours and 12 hours 20.7% 21.9% Guaiacol selectivity 97.6% 97.4% Veratrol selectivity 1.9% 1.9% Other product selectivity 0. 6% 0.7% Comparative Example 3 [Preparation of catalyst] Activated carbon (manufactured by Kureha Chemical Industry ■, trade name: Kureha Beads, particle size: 1 bleached, specific surface area: 1000r+(/
A granular catalyst was prepared in the same manner as in Example 1, except that the pore volume was 0.67 cffl/g).
前述のようにして調製した粒状触媒25mff1(13
,8g)を使用し、反応時間を22時間としたほかは、
実施例1と同様にして、カテコールとメタノールとを反
応させて、グアヤコールを主として含有する反応液を捕
集した。25 mff1 (13
, 8g) and the reaction time was 22 hours.
In the same manner as in Example 1, catechol and methanol were reacted, and a reaction liquid mainly containing guaiacol was collected.
前記の反応開始から2時間後および22時間後の各反応
液をガスクロマトグラフィー分析した結果を第5表に示
す。Table 5 shows the results of gas chromatography analysis of each reaction solution 2 hours and 22 hours after the start of the reaction.
2時間後 22時間後
カテコール転化率 77.2% 21.0%グア
ヤコール選択率 94.6% 98.7%ベラトロ
ール選択率 4.5% 0.8%その他側生成
物選択率 1.0% 0.5%実施例3
カテコールのエタノール溶液(カテコール濃度:50重
重量)を供給速度15 m l /hrで粒状触媒上へ
供給し、反応温度を280°Cおよび反応時間を30時
間としたほかは、実施例1と同様にして、カテコールと
エタノールとを反応させて、グエトールを主として含有
する反応液を捕集した。After 2 hours After 22 hours Catechol conversion rate 77.2% 21.0% Guaiacol selectivity 94.6% 98.7% Veratrol selectivity 4.5% 0.8% Other product selectivity 1.0% 0 .5% Example 3 An ethanol solution of catechol (catechol concentration: 50 wt) was fed onto the granular catalyst at a feed rate of 15 ml/hr, the reaction temperature was 280°C, and the reaction time was 30 hours. In the same manner as in Example 1, catechol and ethanol were reacted, and a reaction solution containing mainly guetol was collected.
前記の反応開始から2時間後および30時間後の各反応
液をガスクロマトグラフィー分析した。Each reaction solution was analyzed by gas chromatography 2 hours and 30 hours after the start of the reaction.
その結果を第6表に示す。The results are shown in Table 6.
2時間後
30時間後
カテコール転化率 26,3% 29.8%グエ
トール選択率 98.7% 98゜6%その他側
生成物選択率 1.2% 1.3%なお、前記の
粒状触媒の圧壊強度は、前記のエーテル化反応前および
反応開始から30時間後において、いずれも1.7 )
cg/粒であり、実施例1と同様に、エーテル化反応に
よる前記粒状触媒の機械的強度の低下は認められなかっ
た。After 2 hours and after 30 hours, catechol conversion rate 26.3% 29.8% Guetol selectivity 98.7% 98°6% Other side product selectivity 1.2% 1.3% Note that the crushing of the granular catalyst mentioned above The strength was 1.7 both before the etherification reaction and 30 hours after the start of the reaction.
cg/grain, and similarly to Example 1, no decrease in the mechanical strength of the granular catalyst due to the etherification reaction was observed.
実施例4
ハイドロキノンのメタノール溶液(ハイドロキノン濃度
:25重量%)を供給速度30mf/hrで粒状触媒上
へ供給し、反応時間を30時間としたほかば、実施例1
と同様にして、ハイドロキノンとメタノールとを反応さ
せて、ハイドロキノンモノメチルエーテルを主として含
有する反応液を捕集した。Example 4 Example 1 except that a methanol solution of hydroquinone (hydroquinone concentration: 25% by weight) was supplied onto the granular catalyst at a supply rate of 30 mf/hr, and the reaction time was 30 hours.
In the same manner as above, hydroquinone and methanol were reacted, and a reaction liquid mainly containing hydroquinone monomethyl ether was collected.
前記の反応開始から2時間後および30時間後の各反応
液をガスクロマトグラフィー分析した。Each reaction solution was analyzed by gas chromatography 2 hours and 30 hours after the start of the reaction.
その結果を第7表に示す。The results are shown in Table 7.
2時間後 30時間後
ハイ
ドロキノン転化率
1.5%
1.0%
その他側生成物選択率 3.0% 2.8%なお
、前記の粒状触媒の圧壊強度は、前記のエーテル化反応
前および反応開始から30時間後において、いずれも1
.1’Kg/粒であり、実施例1と同様に、エーテル化
反応による前記粒状触媒の機械的強度の低下は認められ
なかった。After 2 hours After 30 hours Hydroquinone conversion rate 1.5% 1.0% Other side product selectivity 3.0% 2.8% The crushing strength of the granular catalyst is the same as that before the etherification reaction and after the reaction. 1 after 30 hours from the start
.. 1'Kg/grain, and similarly to Example 1, no decrease in the mechanical strength of the granular catalyst due to the etherification reaction was observed.
実施例5
〔触媒の調製〕
担体としてα−アルミナ(不二見研磨材工業■製、商品
名iAM−334、粒子径; 3. O+nm、比表面
積;7.On(/g、細孔容積0.38cn/g)を使
用し、このα−アルミナ担体へのBPO,水溶液の添加
を8回行ったほかは、実施例1と同様にして粒状触媒を
調製した。Example 5 [Preparation of catalyst] α-alumina (manufactured by Fujimi Abrasive Industry ■, trade name: iAM-334, particle size: 3.0+nm, specific surface area: 7.On(/g, pore volume: 0.000 nm) was used as a carrier. A granular catalyst was prepared in the same manner as in Example 1, except that BPO and an aqueous solution were added to the α-alumina carrier eight times.
その粒状触媒は、活性成分がBPO,で示して20.6
重量%担持されていた。The granular catalyst has an active component of BPO, 20.6
% by weight was supported.
前述のようにして調製した粒状触媒25mj2(25,
0g、嵩比重;1.00)を使用し、カテコールのメタ
ノール溶液(カテコール濃度;50重置火)を供給速度
5m1/hrで粒状触媒上へ供給しながら、反応温度を
以下に示すように変えて、30時間反応させたほかは、
実施例1と同様にして、カテコールとメタノールとを反
応させて、グアヤコールを主として含有する反応液を捕
集した反丑赫[変
反応開始から10時間目まで ;250’C10時間を
越え20時間目まで; 27o″020時間を越え30
時間目まで; 3oo″C前記の反応開始から10時間
後、20時間後および30時間後の各反応液をガスクロ
マトグラフィー分析した。その結果を第8表に示す。Particulate catalyst 25mj2 (25,
0 g, bulk specific gravity: 1.00), and while supplying a methanol solution of catechol (catechol concentration: 50 ply) onto the granular catalyst at a supply rate of 5 ml/hr, the reaction temperature was changed as shown below. In addition to reacting for 30 hours,
In the same manner as in Example 1, catechol and methanol were reacted, and a reaction liquid mainly containing guaiacol was collected. Until; 27 o'clock over 20 hours 30
3oo''C Each reaction solution was analyzed by gas chromatography 10 hours, 20 hours and 30 hours after the start of the reaction. The results are shown in Table 8.
10時間後 20時間後 30時間後
カテコール
転化率
30.1%
43.4%
72.9%
グアヤコール
選択率
98.9%
99.0%
97.7%
ベラトロール
選択率 0.37% 0.66%その他側生成
物選択率 0.75% 0.32% 0.28%
2.00%
なお、前記の粒状触媒の圧壊強度は、前記のエーテル化
反応前および反応開始から30時間後において、いずれ
も3.9kg/粒であり、実施例1と同様に、エーテル
化反応による前記粒状触媒の機械的強度の低下は認めら
れなかった。After 10 hours After 20 hours After 30 hours Catechol conversion rate 30.1% 43.4% 72.9% Guaiacol selectivity 98.9% 99.0% 97.7% Veratrol selectivity 0.37% 0.66% Other side product selectivity 0.75% 0.32% 0.28%
2.00% The crushing strength of the granular catalyst was 3.9 kg/granule both before the etherification reaction and 30 hours after the start of the reaction, and as in Example 1, the etherification reaction No decrease in the mechanical strength of the granular catalyst was observed.
実施例6
〔触媒の調製〕
H3B Ozの水溶液への85重量%H,PO4の滴下
量を、以下に示すように、リン(P)/ホウ素(B)の
原子比が0.2〜1.2となるように変えたこと、及び
、担体としてα−アルミナ(不二見研磨材工業■製、商
品名;AM−334、粒子径;3、 Orfm、比表面
積H5,6nf/g、細孔容積o、34al/ g )
を使用したことのほがは、実施例1と同様にして、次に
示すa −eの5種類の粒状触媒を調製した。Example 6 [Catalyst Preparation] As shown below, the amount of 85% by weight H, PO4 added to an aqueous solution of H3BOz was adjusted so that the atomic ratio of phosphorus (P)/boron (B) was 0.2 to 1. 2, and α-alumina (manufactured by Fujimi Abrasive Industry ■, product name: AM-334, particle size: 3, Orfm, specific surface area H5.6nf/g, pore volume o, 34al/g)
In the same manner as in Example 1, five types of granular catalysts a to e shown below were prepared.
10.7g/4.4g
8、9 g / 4.4 g
7、1 g/4.4 g
3、6 g/4.4 g
1、’8 g / 4.4 g
上記活性成分担持量は、
1.2
1.0
0.8
0、4
0.2
a −eの5種類
の粒状触媒のいずれにおいても、触媒100mJ!中の
、P t OsおよびBzOsとして計算しての含浸1
(g)として示されている。10.7g/4.4g 8,9g/4.4g 7,1g/4.4g 3,6g/4.4g 1,'8g/4.4g The above active ingredient loading is , 1.2 1.0 0.8 0, 4 0.2 a - e, the catalyst was 100 mJ! Impregnation calculated as P t Os and BzOs in 1
(g).
前述のようにして鋼製したa −eの5種類の粒状触媒
をいずれも25ml使用し、反応時間を8時間としたほ
かは、実施例1と同様にして、カテコールとメタノール
とを反応させて、グアヤコールを主として含有する反応
液を捕集した。Catechol and methanol were reacted in the same manner as in Example 1, except that 25 ml of each of the five types of granular catalysts a to e made of steel as described above was used, and the reaction time was 8 hours. , the reaction solution containing mainly guaiacol was collected.
前記の反応開始から8時間後の各反応液をガスクロマト
グラフィー分析した。その結果を第9表に示す。Eight hours after the start of the reaction, each reaction solution was analyzed by gas chromatography. The results are shown in Table 9.
第
9
表
触媒の種類
8時間後
比較例4
〔触媒の調製〕
H,BO,の水溶液へ85重量%HsPOaを滴下しな
かったこと、
すなわち、
P/B
(原子比)
0.0としたことのほかは、実施例6と同様にして、粒
状触媒を調製した。Table 9 Catalyst type Comparative example 4 after 8 hours [Preparation of catalyst] 85% by weight HsPOa was not dropped into the aqueous solution of H, BO, that is, P/B (atomic ratio) was set to 0.0. A granular catalyst was prepared in the same manner as in Example 6 except for the following.
その粒状触媒は、活性成分としてのホウ素成分が、触媒
100mf中の820.含浸量で示して、4.4g担持
されていた。The granular catalyst has a boron component as an active component of 820 mf per 100 mf of catalyst. In terms of impregnated amount, 4.4 g was supported.
前述のようにして調製した粒状触媒25mj!を使用し
たほかは、実施例6と同様にして、カテコールとメタノ
ールとを反応させて、グアヤコールを主として含有する
反応液を捕集した。25mj of granular catalyst prepared as described above! Catechol and methanol were reacted in the same manner as in Example 6, except that guaiacol was used, and a reaction solution mainly containing guaiacol was collected.
前記の反応開始から8時間後の反応液をガスクロマトグ
ラフィー分析した結果を第10表に示す。Table 10 shows the results of gas chromatography analysis of the reaction solution 8 hours after the start of the reaction.
第
表
8時間後
カテコール転化率 1.1%グアヤコール選
択率 98.9%ベラトロール選択率
0.0%その他側生成物選択率 1.1%〔本発
明の作用効果〕
この発明の製法によれば、粒状の不活性アルミナにホウ
酸と燐酸とから得られた活性成分が担持されている粒状
触媒を使用して気相で二価フェノールと低級モノアルコ
ールとのエーテル化反応を行っているので、二価フェノ
ールと低級モノアルコールとのエーテル化反応が、二価
フェノールの高い転化率で行われ、そして、二価フェノ
ールモノアルキルエーテルを高い選択率(収率)で工業
的に長期間得ることができるのである。Table: Catechol conversion rate after 8 hours 1.1% Guaiacol selectivity 98.9% Veratrol selectivity
0.0% Other side product selectivity 1.1% [Effects of the present invention] According to the production method of the present invention, an active ingredient obtained from boric acid and phosphoric acid is supported on granular inert alumina. Since the etherification reaction between dihydric phenol and lower monoalcohol is carried out in the gas phase using a granular catalyst, the etherification reaction between dihydric phenol and lower monoalcohol can be performed with a high conversion rate of dihydric phenol. It is possible to obtain dihydric phenol monoalkyl ether industrially with high selectivity (yield) over a long period of time.
Claims (1)
、粒状の不活性アルミナにホウ酸と燐酸とから得られた
活性成分を担持してなる粒状触媒上に供給して、反応温
度200〜400℃、および、常圧下に、二価フェノー
ルと低級モノアルコールとを気相で、前記触媒と接触さ
せ、反応させて、二価フェノールモノアルキルエーテル
を生成させ、その後、反応ガスを冷却して、反応液を得
ることを特徴とする二価フェノールモノアルキルエーテ
ルの製法。Gaseous dihydric phenol and lower monoalcohol are fed onto a granular catalyst made of granular inert alumina supporting an active ingredient obtained from boric acid and phosphoric acid, and the reaction temperature is 200 to 400°C, and , under normal pressure, dihydric phenol and lower monoalcohol are brought into contact with the catalyst in the gas phase and reacted to produce dihydric phenol monoalkyl ether, and then the reaction gas is cooled to form a reaction liquid. A method for producing dihydric phenol monoalkyl ether, characterized in that it obtains.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1251977A JP2526135B2 (en) | 1989-09-29 | 1989-09-29 | Manufacturing method of divalent phenol monoalkyl ether |
EP90402669A EP0420756B1 (en) | 1989-09-29 | 1990-09-27 | Process for catalytically producing monoalkylether of dihydric phenol compound |
US07/589,612 US5189225A (en) | 1989-09-29 | 1990-09-28 | Process for catalytically producing monoalkylether of dihydric phenol compound |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1251977A JP2526135B2 (en) | 1989-09-29 | 1989-09-29 | Manufacturing method of divalent phenol monoalkyl ether |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH03115244A true JPH03115244A (en) | 1991-05-16 |
JP2526135B2 JP2526135B2 (en) | 1996-08-21 |
Family
ID=17230818
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP1251977A Expired - Lifetime JP2526135B2 (en) | 1989-09-29 | 1989-09-29 | Manufacturing method of divalent phenol monoalkyl ether |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2526135B2 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6013002A (en) * | 1997-10-14 | 2000-01-11 | Toyota Jidosha Kabushiki Kaisha | Rotary power transmission apparatus |
EP0914854A3 (en) * | 1997-10-28 | 2002-01-02 | Ube Industries Limited | Apparatus and process for generating mixed multi-component vapor |
-
1989
- 1989-09-29 JP JP1251977A patent/JP2526135B2/en not_active Expired - Lifetime
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6013002A (en) * | 1997-10-14 | 2000-01-11 | Toyota Jidosha Kabushiki Kaisha | Rotary power transmission apparatus |
EP0914854A3 (en) * | 1997-10-28 | 2002-01-02 | Ube Industries Limited | Apparatus and process for generating mixed multi-component vapor |
US6512147B2 (en) | 1997-10-28 | 2003-01-28 | Ube Industries, Ltd. | Apparatus and process for generating mixed multi-component vapor |
Also Published As
Publication number | Publication date |
---|---|
JP2526135B2 (en) | 1996-08-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4201880A (en) | Preparation of ortho-alkylated phenols | |
EP1880761A1 (en) | Method for preparing catalyst for production of methacrylic acid | |
EP2436443A1 (en) | Method for producing a catalyst for producing methacrylic acid, and method for producing methacrylic acid | |
WO1984000749A1 (en) | Catalytic process for the production of methanol | |
EP0509927B1 (en) | Method of producing a monoalkylether of a dihydric phenol compound | |
JPH0412182B2 (en) | ||
JPH03115244A (en) | Production of dihydric phenol monoalkyl ether | |
US4517389A (en) | Process for methylating the ortho position of a phenol | |
CN101239889B (en) | Method for preparing reaction liquid containing alkylphenol product | |
EP0420756B1 (en) | Process for catalytically producing monoalkylether of dihydric phenol compound | |
US4097411A (en) | Catalyst for preparation of ortho-alkylated phenols | |
CA2171263C (en) | Thoria catalyst | |
JPS59228940A (en) | Catalyst and method for ortho-alkylating hydroxylic aromaticcompound | |
JPH07265710A (en) | Orthoalkylation catalyst of phenols, precursor thereof and production of orthoalkylated phenols using catalyst | |
JP2578028B2 (en) | Preparation of dihydric phenol alkyl ether | |
US4618733A (en) | Vapor phase nitration of aromatic compounds | |
JPH0525550B2 (en) | ||
US5977416A (en) | Dehydration catalyst and process for producing a monoalkylether of a dihydric phenolic compound using same | |
JP2865165B2 (en) | Process for producing alkyl ethers of phenols and catalyst used in the process | |
WO2007119607A1 (en) | Process for producing methacrolein and/or methacrylic acid | |
US4013705A (en) | Ammoxidation process for making dicyanonaphthalene | |
JP2544238B2 (en) | Method for producing divalent phenol monoalkyl ether | |
EP0184569B1 (en) | Vapor phase nitration catalysts and processes for the preparation and use thereof | |
EP0182771B1 (en) | Vapor phase nitration catalysts and processes for the preparation and use thereof | |
JP2608820B2 (en) | Preparation of dihydric phenol alkyl ether |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090531 Year of fee payment: 13 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090531 Year of fee payment: 13 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100531 Year of fee payment: 14 |
|
EXPY | Cancellation because of completion of term | ||
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100531 Year of fee payment: 14 |