JPH0418042A - Method for increasing carbon atoms of alcohols with methanol - Google Patents
Method for increasing carbon atoms of alcohols with methanolInfo
- Publication number
- JPH0418042A JPH0418042A JP2120525A JP12052590A JPH0418042A JP H0418042 A JPH0418042 A JP H0418042A JP 2120525 A JP2120525 A JP 2120525A JP 12052590 A JP12052590 A JP 12052590A JP H0418042 A JPH0418042 A JP H0418042A
- Authority
- JP
- Japan
- Prior art keywords
- periodic table
- metals
- group
- alcohol
- methanol
- 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
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 150000001298 alcohols Chemical class 0.000 title claims description 13
- 238000000034 method Methods 0.000 title claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 title abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 42
- 239000002184 metal Substances 0.000 claims abstract description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- 230000000737 periodic effect Effects 0.000 claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims abstract 3
- 150000001875 compounds Chemical class 0.000 claims abstract 2
- 150000002739 metals Chemical class 0.000 claims description 29
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- 238000003763 carbonization Methods 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 31
- 239000002994 raw material Substances 0.000 abstract description 7
- -1 aromatic alcohols Chemical class 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 8
- 238000004817 gas chromatography Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- 238000005255 carburizing Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 238000010574 gas phase reaction Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- PFNHSEQQEPMLNI-UHFFFAOYSA-N 2-methyl-1-pentanol Chemical compound CCCC(C)CO PFNHSEQQEPMLNI-UHFFFAOYSA-N 0.000 description 1
- 241000264877 Hippospongia communis Species 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- ZONYXWQDUYMKFB-UHFFFAOYSA-N flavanone Chemical compound O1C2=CC=CC=C2C(=O)CC1C1=CC=CC=C1 ZONYXWQDUYMKFB-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000007163 homologation reaction Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- XYWJNTOURDMTPI-UHFFFAOYSA-N procodazole Chemical compound C1=CC=C2NC(CCC(=O)O)=NC2=C1 XYWJNTOURDMTPI-UHFFFAOYSA-N 0.000 description 1
- 229950000989 procodazole Drugs 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 229910001952 rubidium oxide Inorganic materials 0.000 description 1
- CWBWCLMMHLCMAM-UHFFFAOYSA-M rubidium(1+);hydroxide Chemical compound [OH-].[Rb+].[Rb+] CWBWCLMMHLCMAM-UHFFFAOYSA-M 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 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〕
本願発明はアルコール類の増炭反応に関し、詳しくはメ
タノールを増炭剤として使用して、例えばメタノールと
エタノールからプロパツール及びブタノールを、メタノ
ールとプロパツールからブタノール及びアミルアルコー
ルを得る如く、原料として使用する脂肪族又は芳香族ア
ルコール類とメタノールから原料アルコール類より炭素
数が１以上多いアルコールを製造する方法に関するもの
である。Detailed Description of the Invention [Industrial Field of Application] The present invention relates to the carburization reaction of alcohols, and more specifically, the present invention relates to the carburization reaction of alcohols, and more specifically, the process of converting propatool and butanol from methanol and ethanol by using methanol as a carburization agent. The present invention relates to a method for producing an alcohol having one or more more carbon atoms than the raw material alcohols from aliphatic or aromatic alcohols and methanol used as raw materials, such as obtaining butanol and amyl alcohol from propatool.
［従来の技術］
従来からメタノールを原料として合成ガスを使用し、エ
タノールを得る反応は所謂ホモロゲーション反応として
良く知られており、多くの特許が出願されている。[Prior Art] Conventionally, the reaction of using methanol as a raw material and synthesis gas to obtain ethanol has been well known as a so-called homologation reaction, and many patents have been filed.
例えばＣｏ、Ｒｈ等の金属錯体を使用し高圧下でメタノ
ールと合成ガスからエタノールを主として得るものであ
る。For example, ethanol is mainly obtained from methanol and synthesis gas under high pressure using metal complexes such as Co and Rh.
一方、合成ガス及びメタノールを増炭剤として使用し、
メタノールとエタノールからプロパツールを得る方法き
しては次の特許が知られている。On the other hand, using synthesis gas and methanol as a carburizing agent,
The following patents are known regarding methods for obtaining propatool from methanol and ethanol.
即ち、ＵＳＰ第３９７２９５２号公報（１９７６）では
メタノールとエタノールを使用して、触媒としてＰｔ、
Ｒｈ等の貴金属を担持した触媒の存在下、高圧の合成ガ
スを使用してプロパツールを主として得ている。That is, in USP No. 3,972,952 (1976), methanol and ethanol are used as catalysts, and Pt,
Proper tools are mainly obtained using high-pressure synthesis gas in the presence of a catalyst supporting a noble metal such as Rh.
しかしながら、上記ＵＳＰの方法は触媒の担体としての
酸化アルミナの存在が必要であり又、高価な金属である
ＰＬ、Ｒｈ等をかなりの量必要とする。However, the above USP method requires the presence of alumina oxide as a catalyst carrier and also requires considerable amounts of expensive metals such as PL and Rh.
その上、高圧の合成ガス存在下で反応する必要があるた
め高圧反応装置が必要であり、装置等の設備費は大きく
なる。Furthermore, since it is necessary to carry out the reaction in the presence of high-pressure synthesis gas, a high-pressure reactor is required, which increases equipment costs.
本願発明は、上記の高価な触媒を使用することなく、更
に低圧下で反応が行われことから経済的なアルコール類
の増炭反応方法を提供せんとするものである。The present invention aims to provide an economical method for the carbonization reaction of alcohols since the reaction is carried out under low pressure without using the above-mentioned expensive catalyst.
本願発明者は従来の技術に比べて特別な装置を必要とせ
ず、安価な触媒でメタノールによる増炭反応を種々検討
した結果本願発明に至った。The inventors of the present application have conducted various studies on the carburizing reaction using methanol, which does not require any special equipment compared to the conventional technology and uses an inexpensive catalyst, and has thus arrived at the present invention.
即ち、本願発明は下記反応式（ＩＩ）に示した反応によ
りメタノールを使用してアルコール類の増炭反応を行う
に当り触媒として、下記触媒（Ａ）又は（Ａ）と（Ｂ）
とを併用して該アルコール類より炭素数が１以上多いア
ルコール類の製造方法を従来するものである。That is, the present invention uses the following catalyst (A) or (A) and (B) as a catalyst when carrying out a carburization reaction of alcohols using methanol according to the reaction shown in the following reaction formula (II).
This is a conventional method for producing alcohols having one or more more carbon atoms than the alcohols.
（Ａ）ＭｇＯ１ＣａＯ等の周期律表第ＩＩＡ族の金属及
び／又はそれらの金属酸化物から選ばれた１種以上。(A) One or more selected from metals of Group IIA of the periodic table such as MgO1CaO and/or metal oxides thereof.
（Ｂ）Ｆｅ、Ｎｉ、Ｃｏ等の周期律表第■族の金属、Ｍ
ｎ等の周期律表ＶＩＩＡ族の金属、Ｃｒ、Ｍ。(B) Metals of group Ⅰ of the periodic table such as Fe, Ni, Co, etc., M
Metals of group VIIA of the periodic table such as n, Cr, M.
等の周期律表第ＶＩＡ族の金属、Ｚｎ、Ｃｄ等の周期律
表第１［Ｂ族の金属、Ｃｕ、Ａｇ等の周期律表第ＩＢ族
の金属、Ｌｉ、Ｎａ、に等の周律率表第ＶＩＡ族の金属
及び／又はそれらの金属酸化物から選ばれた１種以上。metals of group VIA of the periodic table, such as Zn, Cd, etc., metals of group B of the periodic table, such as Cu, Ag, metals of group IB of the periodic table, such as Li, Na, etc. One or more selected from Group VIA metals and/or metal oxides thereof.
〕
（ここで、Ｒ＋、Ｒｚは水素又は炭素数１〜５のアルキ
ル基を、Ｒ：ｌ、Ｒ４はメチル基又は水素であるが、Ｒ
３、Ｒ−が同時にメチル基である場合を除く。更に、Ｒ
３、Ｒ４が同時に水素の場合はＲ２は炭素数１〜Ｉ２の
アルキル基を表す）
本願発明で使用する触媒は特別な処理は特に必要でない
。] (Here, R+, Rz are hydrogen or an alkyl group having 1 to 5 carbon atoms, R:l, R4 are a methyl group or hydrogen, but R
3. Except when R- is also a methyl group. Furthermore, R
(3. When R4 is hydrogen, R2 represents an alkyl group having 1 to 12 carbon atoms) The catalyst used in the present invention does not require any special treatment.
（Ａ）の周期律表第ｎＡ族の金属酸化物としては酸化マ
グネシュウム、酸化力ルシュウム、酸化ストロンチウム
、酸化ルビジュムが挙げられるが通常の方法で合成して
も市販品を使用してもよい。Examples of the metal oxide of group nA of the periodic table (A) include magnesium oxide, rusium oxide, strontium oxide, and rubidium oxide, but they may be synthesized by conventional methods or commercially available products may be used.
（Ｂ）の金属及び金属酸化物としては周期律表第■族の
金属としてＦｅ、Ｃｏ、Ｎｉ、Ｐｄ、ＰＬ、Ｒｕ、Ｒｈ
等を、第■族の金属としてＭｎ、Ｒｅ等を、第ＶＩＡ族
の金属としてＣｒ、Ｍｏ等を、第１ＩＢ族の金属として
Ｚｎ、Ｃｄ等を、第ＩＢ族の金属としてＣｕ、Ａｇ等を
、第ＩＡ族の金属としてＬｉ、Ｎａ、に、Ｒｂ等を使用
することができる。The metals and metal oxides of (B) include Fe, Co, Ni, Pd, PL, Ru, Rh as metals of group Ⅰ of the periodic table.
etc., Mn, Re, etc. as Group Ⅰ metals, Cr, Mo, etc. as Group VIA metals, Zn, Cd, etc. as Group IB metals, Cu, Ag, etc. as Group IB metals. , Li, Na, Rb, etc. can be used as the Group IA metal.
金属はいかなる型でも使用できるが、好ましくは水溶性
を有する方が好ましい。Although any type of metal can be used, it is preferable that the metal is water-soluble.
例えば、硝酸塩、硫酸塩、塩化物等が特に好ましい。For example, nitrates, sulfates, chlorides, etc. are particularly preferred.
触媒は（Ａ）、（Ｂ）単独で顆粒、錠剤、球状、円柱状
、ハニカム状に成型して使用可能であるが、通常の触媒
に用いられる担体、例えばＴ−アルミナ、シリカゲル、
シリカ−アルミナ、珪藻土、活性炭などの担体に担持し
てもよい。The catalysts (A) and (B) can be used alone in the form of granules, tablets, spheres, cylinders, or honeycombs, but they can be used on carriers commonly used for catalysts, such as T-alumina, silica gel,
It may be supported on a carrier such as silica-alumina, diatomaceous earth, or activated carbon.
又、（Ａ）に（Ｂ）を担持させた触媒も使用できる。
この場合（Ｂ）の担持量としては（Ａ）１００部に対し
て１〜３０部、好ましくは１〜１０部が良い。 反応は
メタノールと原料アルコールを気化させて触媒と接触さ
せる気相反応で行なう方が好ましい。Further, a catalyst in which (B) is supported on (A) can also be used.
In this case, the amount of (B) supported is 1 to 30 parts, preferably 1 to 10 parts, per 100 parts of (A). The reaction is preferably carried out in a gas phase reaction in which methanol and raw alcohol are vaporized and brought into contact with a catalyst.
気相反応としては固定床方式、流動床方式等の各方式を
採用出来る。As the gas phase reaction, various methods such as a fixed bed method and a fluidized bed method can be adopted.
固定床でこの反応を行なう場合のガス空間速度はｌ Ｏ
Ｏ〜１００００ ／ Ｈｒが好ましい。When this reaction is carried out in a fixed bed, the gas hourly space velocity is l O
O~10000/Hr is preferable.
反応圧は常圧で充分であるが、加圧で行なっても良い。Normal pressure is sufficient for the reaction pressure, but the reaction may be carried out under increased pressure.
使用するアルコール化合物としては、エタノール、プロ
パツール、ブタノール、アミルアルコール、ヘキサノー
ル、ヘプタツール等の炭素数２〜５の脂肪族アルコール
が使用できる。As the alcohol compound used, aliphatic alcohols having 2 to 5 carbon atoms such as ethanol, propatool, butanol, amyl alcohol, hexanol, and heptatool can be used.
例えば、エタノールを使用すれば生成物としては主とし
てｎ−プロパツール、５ｅｃ−ブタノール１、ｎ−ブタ
ノールが得られる。For example, if ethanol is used, the products will mainly be n-propanol, 5ec-butanol 1, and n-butanol.
又、アミルアルコールを使用すれば主としてｎ−ヘキシ
ルアルコール、２−メチルアミルアルコール、２−メチ
ルヘキシルアルコール、ｎ−ドデシルアルコールが性成
する。If amyl alcohol is used, n-hexyl alcohol, 2-methylamyl alcohol, 2-methylhexyl alcohol, and n-dodecyl alcohol are mainly formed.
更に、２−フェニル−エタノール、２−フェニル−ｌプ
ロパツール等の芳香族アルコールを使用しても同様な増
炭反応を行なうことができる。Furthermore, a similar carburization reaction can be carried out using aromatic alcohols such as 2-phenyl-ethanol and 2-phenyl-l propazol.
メタノールと原料アルコール化合物の比は広く変えるこ
とが可能であるが、メタノール１部に対して原料アルコ
ール１０〜０．０１部、好ましくは１〜０．０５部が良
い。Although the ratio of methanol to raw alcohol compound can vary widely, it is preferably 10 to 0.01 part, preferably 1 to 0.05 part, of raw alcohol to 1 part of methanol.
反応温度も広く変えることができるが、２００〜４５０
°Ｃ１好ましくは２５０〜４００°Ｃが良い。The reaction temperature can also be varied widely, but from 200 to 450
°C1 is preferably 250 to 400 °C.
この際必要に応じて原料アルコール、メタノールと共に
反応系にガスを流すことも可能であり、使用するガスと
しては窒素ガス、水素ガス、合成ガスいずれでも良い。At this time, it is possible to flow a gas into the reaction system together with the raw material alcohol and methanol if necessary, and the gas used may be any of nitrogen gas, hydrogen gas, and synthetic gas.
本願発明によればメタノールと脂肪族、芳香族アルコー
ルを比較的良好な反応率で反応させることが可能であり
、又高い選択率で前記一般式〔■〕で表される原料アル
コールより炭素数が１以上多いアルコールを収率よく得
ることができる。According to the present invention, it is possible to react methanol with an aliphatic or aromatic alcohol at a relatively good reaction rate, and it is also possible to react with a relatively good reaction rate between methanol and an aliphatic or aromatic alcohol. One or more alcohols can be obtained in good yield.
次に本願発明を触媒の調製例と実施例に別けて詳細に説
明する。Next, the present invention will be explained in detail using catalyst preparation examples and examples.
触媒（１）の調製
イオン交換水５００ｍ１に酸化マグネシウム２０ ｇｒ
をゆっくり加え、分散させた後に一昼夜攪拌後、蒸発乾
固し１２０°Ｃで乾燥した。Preparation of catalyst (1) 20 gr of magnesium oxide in 500 ml of ion-exchanged water
was slowly added, dispersed, stirred for a day and night, and then evaporated to dryness and dried at 120°C.
触媒（２）〜（５）の調製
上記触媒〔Ｉ〕で調整した触媒２０ｇｒをイオン交換水
５００ｍｆに分散させた後に下記の金属塩を所定量加え
て一昼夜攪拌後、１２０ ’Ｃで乾燥後、窒素気流下６
００°Ｃまで５″Ｃ／ｍｉｎで昇温後２時間処理し、触
媒（２）〜（４）を得た。Preparation of catalysts (2) to (5) After dispersing 20g of the catalyst prepared in the above catalyst [I] in 500mf of ion-exchanged water, a predetermined amount of the following metal salt was added, stirred all day and night, and dried at 120'C. Under nitrogen flow 6
After raising the temperature to 00°C at a rate of 5″C/min, the mixture was treated for 2 hours to obtain catalysts (2) to (4).
触媒（２） Ｍｎ（ＮＯ８）ｚ・９）ｔｗｏ ３．
２３ｇｒ触媒（３） Ｎｉ （ＮＯ３） ２ ・６）
＋２０ ３．（１６ｇｒ触媒（４） Ｚｎ（ＮＯｆｆ
）ｚ ・６１１ｚＯ２，８２ｇｒ実施例 １
上記で調製した触媒（１）の１ ｇｒを内径１５ｍｍ
の反応管に充填した。Catalyst (2) Mn(NO8)z・9) two 3.
23gr catalyst (3) Ni (NO3) 2 ・6)
+20 3. (16gr catalyst (4) Zn(NOff
)z ・611zO2, 82grExample 1 1g of the catalyst (1) prepared above was heated to an inner diameter of 15mm.
was filled into a reaction tube.
エタノール／メタノール／Ｎ２のモル比を１７１０／４
０ になるように調整した。The molar ratio of ethanol/methanol/N2 is 1710/4.
Adjusted to be 0.
反応温度を３６０°Ｃにして、常圧下 ５Ｖ＝１５００
／ Ｈｒで反応させた。The reaction temperature was 360°C, under normal pressure 5V = 1500
/Hr.
生成物をトラップし、ガスクロマトグラフにより分析し
た。The product was trapped and analyzed by gas chromatography.
実施例 ２
実施例１において、エタノール／メタノール／Ｎ２のモ
ル比を１／２０／４０にした以外は実施例１と同様に反
応させ、得られた生成物をガスクロにより分析した。Example 2 The reaction was carried out in the same manner as in Example 1 except that the molar ratio of ethanol/methanol/N2 was changed to 1/20/40, and the obtained product was analyzed by gas chromatography.
実施例 ３
実施例Ｉにおいて反応温度を３４０″Ｃに変えた以外は
同様に反応させ、得られた生成物をガスクロにより分析
した。Example 3 A reaction was carried out in the same manner as in Example I except that the reaction temperature was changed to 340''C, and the obtained product was analyzed by gas chromatography.
実施例 ４
調製した触媒（２）を１．０ ｇｒ使用した以外は実施
例１と同様に反応させ、得られた生成物をガスクロによ
り分析した。Example 4 The reaction was carried out in the same manner as in Example 1 except that 1.0 gr of the prepared catalyst (2) was used, and the obtained product was analyzed by gas chromatography.
実施例 ５
調製した触媒（３）を使用した以外は実施例１と同様に
反応させ、得られた生成物をガスクロにより分析した。Example 5 The reaction was carried out in the same manner as in Example 1 except that the prepared catalyst (3) was used, and the obtained product was analyzed by gas chromatography.
実施例 ６
調製した触媒（４）を１．Ｏｇｒ使用する以外は実施例
１と同様に反応させ、得られた生成物をガスクロにより
分析した。Example 6 The prepared catalyst (4) was subjected to 1. The reaction was carried out in the same manner as in Example 1 except that Ogr was used, and the obtained product was analyzed by gas chromatography.
上記実施例で得られた分析結果をまとめて表−１に示す
。The analysis results obtained in the above examples are summarized in Table 1.
表−１転化エタノール基準選択率（ｍｏｌｅχ）実施例
１２３４５６
アセトアルテヒト １６．８ １２．４ ２
３．７ ３１．９ ３９．４ ４７．４ｎ
−ブ■パへル ５１．６ ５０．７ ６４．
２ ２４．３ １９．７ １１．９ｎ−ブ
タへル ３．４ ｔｒ Ｏｔ
ｒ １．Ｏｔｒｉｓｏ−ブタへル １５．
３ ２７．６ ７．７ ９．９
５．３ ３．９その他 ｔｒ １．９
０ ３．７ ２．１ ２．９エタ八ル転化率
１６．８ ２９．５ ７．９ ３２．９ ２６．２
３２．１特許出願人 日産化学工業株式会社Table-1 Converted ethanol standard selectivity (moleχ) Example 123456 Acetaltecht 16.8 12.4 2
3.7 31.9 39.4 47.4n
-B■Pahel 51.6 50.7 64.
2 24.3 19.7 11.9n-butahel 3.4 tr Ot
r1. Otriso-butahel 15.
3 27.6 7.7 9.9
5.3 3.9 Others tr 1.9
0 3.7 2.1 2.9 Ethanol conversion rate 16.8 29.5 7.9 32.9 26.2
32.1 Patent applicant Nissan Chemical Industries, Ltd.
Claims (4)
は触媒（Ａ）と（Ｂ）とを併用して反応させることを特
徴とする該アルコール類の増炭方法。 （Ａ）周期律表第IIＡ族の金属及び／又はそれらの金属
の酸化物から選ばれる１種以上。 （Ｂ）周期律表第VIII族の金属、周期律表第VIIＡ族の
金属、周律率表第VIＡ族の金属、周期律表第IIＢ族の金
属、周期律表第 I Ｂ族の金属、周期律表第 I Ａ族の金
属及び／又はそれらの金属酸化物の中から選ばれる１種
以上。(1) A method for increasing carbonization of alcohols, which comprises reacting alcohols and methanol using the following catalyst (A) or a combination of catalysts (A) and (B). (A) One or more selected from metals of Group IIA of the periodic table and/or oxides of those metals. (B) Metals from Group VIII of the Periodic Table, metals from Group VIIA of the Periodic Table, metals from Group VIA of the Periodic Table, metals from Group IIB of the Periodic Table, metals from Group IB of the Periodic Table, One or more metals selected from Group IA metals of the periodic table and/or their metal oxides.
の酸化物として、ＭｇＯ及び／又はＣａＯを触媒として
使用することを特徴とする請求項第１項記載のアルコー
ル類の増炭方法。(2) The method for increasing carbonization of alcohols according to claim 1, characterized in that MgO and/or CaO is used as a catalyst as a metal of Group IIA of the periodic table and/or an oxide of those metals. .
の酸化物として、ＭｇＯ及び／又はＣａＯと、周期律表
第VIII族の金属としてＮｉ、周期律表第VIIＡ族の金属
としてＭｎ、周期律表第IIＢ族の金属としてＺｎ及び／
又はそれらの金属酸化物の中から選ばれた１種以上とを
使用することを特徴とする請求項第１項記載のアルコー
ル類の増炭方法。(3) MgO and/or CaO as metals in Group IIA of the periodic table and/or oxides of those metals, Ni as metals in group VIII of the periodic table, and Mn as metals in group VIIA of the periodic table. , Zn and/or as metals of group IIB of the periodic table.
2. The method for increasing carbonization of alcohols according to claim 1, characterized in that one or more selected from among these metal oxides are used.
３項記載の増炭方法により下記一般式〔 I 〕で示され
る化合物を製造する方法。 ▲数式、化学式、表等があります▼〔 I 〕 （但し、Ｒ＿１、Ｒ＿２はメチル基又は水素原子を表が
、同時にメチル基である場合を除く）。(4) A method for producing a compound represented by the following general formula [I] by the carbon enrichment method according to claim 3, using ethanol as the alcohol. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] (However, R_1 and R_2 are methyl groups or hydrogen atoms, except when they are both methyl groups).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2120525A JPH0418042A (en) | 1990-05-10 | 1990-05-10 | Method for increasing carbon atoms of alcohols with methanol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2120525A JPH0418042A (en) | 1990-05-10 | 1990-05-10 | Method for increasing carbon atoms of alcohols with methanol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0418042A true JPH0418042A (en) | 1992-01-22 |
Family
ID=14788420
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2120525A Pending JPH0418042A (en) | 1990-05-10 | 1990-05-10 | Method for increasing carbon atoms of alcohols with methanol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0418042A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5700754A (en) * | 1994-10-18 | 1997-12-23 | Chisso Corporation | Barium/calcium catalyst and a process for producing the same |
| CN100389101C (en) * | 2005-09-28 | 2008-05-21 | 中国石油化工股份有限公司 | Production of Guerbet alcohol |
| JP2008303160A (en) * | 2007-06-06 | 2008-12-18 | Mitsubishi Chemicals Corp | Method for producing alcohol |
| WO2009028166A1 (en) * | 2007-08-24 | 2009-03-05 | Kabushiki Kaisha Sangi | Method for synthesis of chemical industrial raw material or fuel composition |
| US7807857B2 (en) | 2008-12-22 | 2010-10-05 | E. I. Dupont De Nemours And Company | Lanthanum-promoted supported metal catalysts and process for producing guerbet alcohols using same |
| US8603201B2 (en) | 2007-08-24 | 2013-12-10 | Kabushiki Kaisha Sangi | Method of synthesizing chemical industry raw materials and fuel compositions |
| JP2016079143A (en) * | 2014-10-20 | 2016-05-16 | 三菱瓦斯化学株式会社 | Producing method of isobutyraldehyde |
| JP2016079145A (en) * | 2014-10-20 | 2016-05-16 | 三菱瓦斯化学株式会社 | Producing method of isobutanol |
| CN108117480A (en) * | 2016-11-26 | 2018-06-05 | 中国科学院大连化学物理研究所 | A kind of catalyzed conversion methanol and alcohol mixeding liquid prepare the new method of isobutanol |
-
1990
- 1990-05-10 JP JP2120525A patent/JPH0418042A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5700754A (en) * | 1994-10-18 | 1997-12-23 | Chisso Corporation | Barium/calcium catalyst and a process for producing the same |
| CN100389101C (en) * | 2005-09-28 | 2008-05-21 | 中国石油化工股份有限公司 | Production of Guerbet alcohol |
| JP2008303160A (en) * | 2007-06-06 | 2008-12-18 | Mitsubishi Chemicals Corp | Method for producing alcohol |
| WO2009028166A1 (en) * | 2007-08-24 | 2009-03-05 | Kabushiki Kaisha Sangi | Method for synthesis of chemical industrial raw material or fuel composition |
| RU2485087C2 (en) * | 2007-08-24 | 2013-06-20 | Кабусики Кайся Санги | Method for synthesis of chemical industry raw material and fuel compositions |
| US8603201B2 (en) | 2007-08-24 | 2013-12-10 | Kabushiki Kaisha Sangi | Method of synthesizing chemical industry raw materials and fuel compositions |
| US7807857B2 (en) | 2008-12-22 | 2010-10-05 | E. I. Dupont De Nemours And Company | Lanthanum-promoted supported metal catalysts and process for producing guerbet alcohols using same |
| JP2016079143A (en) * | 2014-10-20 | 2016-05-16 | 三菱瓦斯化学株式会社 | Producing method of isobutyraldehyde |
| JP2016079145A (en) * | 2014-10-20 | 2016-05-16 | 三菱瓦斯化学株式会社 | Producing method of isobutanol |
| CN108117480A (en) * | 2016-11-26 | 2018-06-05 | 中国科学院大连化学物理研究所 | A kind of catalyzed conversion methanol and alcohol mixeding liquid prepare the new method of isobutanol |
| CN108117480B (en) * | 2016-11-26 | 2021-09-03 | 中国科学院大连化学物理研究所 | Method for preparing isobutanol by catalytic conversion of mixed solution of methanol and ethanol |
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