JP2013056847A - Method of producing lower saturated aldehyde from 1,2-diol - Google Patents
Method of producing lower saturated aldehyde from 1,2-diol Download PDFInfo
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- JP2013056847A JP2013056847A JP2011196125A JP2011196125A JP2013056847A JP 2013056847 A JP2013056847 A JP 2013056847A JP 2011196125 A JP2011196125 A JP 2011196125A JP 2011196125 A JP2011196125 A JP 2011196125A JP 2013056847 A JP2013056847 A JP 2013056847A
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- 229920006395 saturated elastomer Polymers 0.000 title claims abstract description 33
- 150000000180 1,2-diols Chemical class 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 20
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title abstract 3
- 239000003054 catalyst Substances 0.000 claims abstract description 137
- 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 43
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000001257 hydrogen Substances 0.000 claims abstract description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000010949 copper Substances 0.000 claims abstract description 26
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052802 copper Inorganic materials 0.000 claims abstract description 24
- 229910052709 silver Inorganic materials 0.000 claims abstract description 20
- 239000004332 silver Substances 0.000 claims abstract description 20
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 19
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 6
- 239000010457 zeolite Substances 0.000 claims abstract description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims abstract description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 3
- 229910002651 NO3 Inorganic materials 0.000 claims abstract 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical group CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims description 98
- 238000004519 manufacturing process Methods 0.000 claims description 50
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 42
- 150000001299 aldehydes Chemical class 0.000 claims description 40
- 235000013772 propylene glycol Nutrition 0.000 claims description 38
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 36
- 238000006297 dehydration reaction Methods 0.000 claims description 8
- -1 ammine complex Chemical compound 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 50
- 239000002994 raw material Substances 0.000 abstract description 31
- 239000002131 composite material Substances 0.000 abstract description 23
- 150000001875 compounds Chemical class 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract description 7
- 229960004063 propylene glycol Drugs 0.000 description 37
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 23
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 17
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- 239000012159 carrier gas Substances 0.000 description 8
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 7
- CSZCLQLJVFLXLI-UHFFFAOYSA-N 2-ethyl-4-methyl-1,3-dioxolane Chemical compound CCC1OCC(C)O1 CSZCLQLJVFLXLI-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 6
- 235000011187 glycerol Nutrition 0.000 description 6
- 239000011964 heteropoly acid Substances 0.000 description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 5
- 239000003377 acid catalyst Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000013065 commercial product Substances 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 230000036962 time dependent Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- 239000003225 biodiesel Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000007037 hydroformylation reaction Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 239000012494 Quartz wool Substances 0.000 description 2
- 238000006137 acetoxylation reaction Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- RBHJBMIOOPYDBQ-UHFFFAOYSA-N carbon dioxide;propan-2-one Chemical compound O=C=O.CC(C)=O RBHJBMIOOPYDBQ-UHFFFAOYSA-N 0.000 description 2
- 150000001728 carbonyl compounds Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- JARKCYVAAOWBJS-UHFFFAOYSA-N hexanal Chemical compound CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 229940015975 1,2-hexanediol Drugs 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- JGLMVXWAHNTPRF-CMDGGOBGSA-N CCN1N=C(C)C=C1C(=O)NC1=NC2=CC(=CC(OC)=C2N1C\C=C\CN1C(NC(=O)C2=CC(C)=NN2CC)=NC2=CC(=CC(OCCCN3CCOCC3)=C12)C(N)=O)C(N)=O Chemical compound CCN1N=C(C)C=C1C(=O)NC1=NC2=CC(=CC(OC)=C2N1C\C=C\CN1C(NC(=O)C2=CC(C)=NN2CC)=NC2=CC(=CC(OCCCN3CCOCC3)=C12)C(N)=O)C(N)=O JGLMVXWAHNTPRF-CMDGGOBGSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229920004482 WACKER® Polymers 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- FHKSXSQHXQEMOK-UHFFFAOYSA-N hexane-1,2-diol Chemical compound CCCCC(O)CO FHKSXSQHXQEMOK-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 1
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- PXXVOLRLZXINTK-UHFFFAOYSA-N propanal Chemical compound CCC=O.CCC=O PXXVOLRLZXINTK-UHFFFAOYSA-N 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000003419 tautomerization reaction Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil 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
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
本発明は、低級飽和アルデヒドを製造する方法に関し、特に１，２−ジオールを原料とし、低級飽和アルデヒドを製造する方法に関する。 The present invention relates to a method for producing a lower saturated aldehyde, and more particularly to a method for producing a lower saturated aldehyde using 1,2-diol as a raw material.
プロパナール（プロピオンアルデヒド）に代表される低級飽和アルデヒド類は溶剤原料、化成品中間体、医薬品中間体製造用溶媒などとして用いられ化学工業上重要な物質である。低級飽和アルデヒドは、そのアルデヒドの有する炭素数により製造方法は大きく異なる。例えばＣ２アルデヒドであるアセトアルデヒドはエチレンのワッカー酸化により工業的に製造され（非特許文献１）、Ｃ４アルデヒドであるブチルアルデヒドはプロピレンのヒドロホルミル化反応で製造されるのが一般的である（非特許文献２）。 Lower saturated aldehydes typified by propanal (propionaldehyde) are important substances in the chemical industry, used as solvent raw materials, chemical intermediates, pharmaceutical intermediate production solvents and the like. The production method of the lower saturated aldehyde varies greatly depending on the carbon number of the aldehyde. For example, acetaldehyde, which is a C2 aldehyde, is industrially produced by Wacker oxidation of ethylene (Non-Patent Document 1), and butyraldehyde, which is a C4 aldehyde, is generally produced by a hydroformylation reaction of propylene (Non-Patent Document 1). 2).
一方、Ｃ３のアルデヒドであるプロピオンアルデヒドはエチレンのヒドロホルミル化反応により得られるか（非特許文献２）、プロピレンのアセトキシル化により得られた酢酸アリルを加水分解して得られるアリルアルコール（特許文献１）、あるいはプロピレンオキサイドを原料としてその異性化により得られるアリルアルコールを原料として（特許文献２）、その部分水素化により得ることが出来る。また、ヘテロポリ酸をシリカ等の担体に担持した触媒が、気相における１，２−プロパンジオールの脱水反応によるプロピオンアルデヒド製造において、高い活性を持つことが知られている（特許文献４）。 On the other hand, propionaldehyde, which is an aldehyde of C3, can be obtained by a hydroformylation reaction of ethylene (Non-patent Document 2) or allyl alcohol obtained by hydrolysis of allyl acetate obtained by acetoxylation of propylene (Patent Document 1) Alternatively, it can be obtained by partial hydrogenation using allyl alcohol obtained by isomerization using propylene oxide as a raw material (Patent Document 2). In addition, it is known that a catalyst in which a heteropolyacid is supported on a carrier such as silica has high activity in the production of propionaldehyde by dehydration reaction of 1,2-propanediol in the gas phase (Patent Document 4).
しかしながら、ヒドロホルミル化反応装置の建設には膨大な設備投資が必要であり、プロピレンのアセトキシル化においては反応に酢酸を用いることから耐食性の設備が必要となりこちらも設備投資が膨大になる。一方、プロピレンオキサイドを原料とした場合、反応性の高いプロピレンオキサイドは取扱いが難しく爆発の危険がある。更に、アリルアルコールを原料として部分水素化で飽和アルデヒドを得る場合、一部カルボニル部分も水素化され目的生成物の選択率が低下する場合がある。また、１−プロパノールを脱水素してプロピオンアルデヒドを得る方法もあるが、原料である１−プロパノールの供給に問題がある。更には、これらの低級飽和アルデヒドを製造する際の原料は全て化石燃料である石油由来の化合物であり、近年懸念されている地球環境保全のためにもこれらの使用は好ましくない。 However, the construction of the hydroformylation reaction apparatus requires a huge investment in equipment, and in the acetoxylation of propylene, acetic acid is used for the reaction, which requires a corrosion-resistant equipment, and the equipment investment is enormous. On the other hand, when propylene oxide is used as a raw material, highly reactive propylene oxide is difficult to handle and there is a risk of explosion. Furthermore, when a saturated aldehyde is obtained by partial hydrogenation using allyl alcohol as a raw material, a part of the carbonyl moiety may be hydrogenated to lower the selectivity of the desired product. There is also a method for obtaining propionaldehyde by dehydrogenating 1-propanol, but there is a problem in supplying 1-propanol as a raw material. Furthermore, the raw materials for producing these lower-saturated aldehydes are all petroleum-derived compounds that are fossil fuels, and their use is not preferable for the preservation of the global environment, which has recently been a concern.
一方、再生可能エネルギーとして近年注目を浴びているＢＤＦ（Ｂｉｏ Ｄｉｅｓｅｌ Ｆｕｅｌ）は油脂である動植物油をメタノールと触媒によりメチルエステル（ＦＡＭＥ）にエステル交換して製造されるが、その際多量にグリセリンが副生する。しかし、現在この副生グリセリンを有効利用する決定的な手段は見つかっておらず、資源の有効利用という観点から非常に大きな問題である。 On the other hand, BDF (Bio Diesel Fuel), which has been attracting attention as a renewable energy in recent years, is produced by transesterifying animal and vegetable oils, which are fats and oils, to methyl ester (FAME) using methanol and a catalyst. By-product. However, a decisive means for effectively using this by-product glycerin has not been found at present, which is a very big problem from the viewpoint of effective use of resources.
本発明者はこれまで、多価アルコールからのヒドロキシケトン製造用触媒および製造方法（特許文献３）、あるいは、グリセリンからのグリコール製造方法（国際公開２０１０−０１６４６２号パンフレット）といったグリセリンの有効利用について種々の有用化合物合成を成功させてきた。また、更にグリセリンから製造したグリコールからの低級飽和アルデヒド製造方法を開発した（特許文献４）。しかしながら、このような気相における１，２−プロパンジオールの脱水反応によるプロピオンアルデヒド製造では、触媒が短時間で失活してしまうことがある。したがって、更に効率よくグリコールから低級飽和アルデヒドを製造する方法を開発することが更なる課題とされた。即ち本発明の目的は、上記従来の技術課題を解決することであり、１，２−ジオールを原料とし、低級飽和アルデヒドを効率よく製造する方法を提供することである。 Until now, the present inventor has variously used for effective utilization of glycerin such as a catalyst for hydroxyketone production from polyhydric alcohol and a production method (Patent Document 3), or a glycol production method from glycerin (International Publication 2010-016462). Has been successfully synthesized. Furthermore, a method for producing a lower saturated aldehyde from glycol produced from glycerin was developed (Patent Document 4). However, in the production of propionaldehyde by such dehydration reaction of 1,2-propanediol in the gas phase, the catalyst may be deactivated in a short time. Therefore, it has been a further problem to develop a method for producing a lower saturated aldehyde from glycol more efficiently. That is, an object of the present invention is to solve the above-described conventional technical problems, and to provide a method for efficiently producing a lower saturated aldehyde using 1,2-diol as a raw material.
本発明者は、グリセリンから製造した１，２−プロパンジオールの用途として、１，２−プロパンジオールの脱水反応によりプロパナールを製造する方法及び同方法に適した触媒系を鋭意検討した。その結果、酸触媒により１，２−ジオールを脱水させ低級飽和アルデヒドを得る系において、酸触媒に銅或いは銀の金属成分を担持させ、反応系に水素を共存させることで、触媒活性の経時劣化を抑えることができることを見出した。さらに、このような触媒系を用いることにより、上記の課題に合致した、１，２−ジオール等の隣接する水酸基を持つ多価アルコールを原料とし、低級飽和アルデヒド等のカルボニル化合物を効率よく製造する方法が達成されることを知見し、本発明を完成するに至った。 The present inventors diligently studied a method for producing propanal by a dehydration reaction of 1,2-propanediol and a catalyst system suitable for the method as a use of 1,2-propanediol produced from glycerin. As a result, in a system in which 1,2-diol is dehydrated with an acid catalyst to obtain a lower saturated aldehyde, the catalytic activity is deteriorated over time by supporting a copper or silver metal component in the acid catalyst and coexisting hydrogen in the reaction system. It was found that it can be suppressed. Furthermore, by using such a catalyst system, a carbonyl compound such as a lower saturated aldehyde can be efficiently produced from a polyhydric alcohol having an adjacent hydroxyl group such as 1,2-diol, which meets the above-mentioned problems. It has been found that the method is achieved, and the present invention has been completed.
本発明の低級飽和アルデヒド製造方法は、以下の項（１）〜（６）で定義される。
（１）銅−触媒担体複合体からなる触媒又は銀−触媒担体複合体からなる触媒により、水素共存下で、脱水反応により１，２−ジオールから低級飽和アルデヒドを製造する方法。（２）銅又は銀が、硝酸塩、硫酸塩、酢酸塩、塩基性炭酸塩、アンミン錯体及び塩化物から選ばれるいずれか一種類以上を触媒担体に接触させ、焼成することにより担持されたものである（１）に記載の製造方法。
（３）銅又は銀を担持する触媒担体が、アルミナ、シリカアルミナ及びゼオライトから選ばれるいずれか一種類以上である（１）又は（２）に記載の製造方法。
（４）銅又は銀を担持する触媒担体が、アルミナである（１）〜（３）のいずれかに記載の製造方法。
（５）１，２−ジオールが、１，２−プロパンジオールである（１）〜（４）のいずれかに記載の製造方法。
（６）低級飽和アルデヒドが、プロパナールである（１）〜（５）のいずれかに記載の製造方法。
The lower saturated aldehyde production method of the present invention is defined by the following items (1) to (6).
(1) A method for producing a lower saturated aldehyde from 1,2-diol by a dehydration reaction in the presence of hydrogen with a catalyst comprising a copper-catalyst carrier complex or a catalyst comprising a silver-catalyst carrier complex. (2) Copper or silver is supported by bringing one or more selected from nitrates, sulfates, acetates, basic carbonates, ammine complexes and chlorides into contact with the catalyst support and firing. The manufacturing method as described in (1).
(3) The production method according to (1) or (2), wherein the catalyst carrier supporting copper or silver is at least one selected from alumina, silica alumina, and zeolite.
(4) The production method according to any one of (1) to (3), wherein the catalyst carrier supporting copper or silver is alumina.
(5) The production method according to any one of (1) to (4), wherein the 1,2-diol is 1,2-propanediol.
(6) The production method according to any one of (1) to (5), wherein the lower saturated aldehyde is propanal.
本発明により、１，２−ジオールを原料とし、低級飽和アルデヒドを効率よく製造する方法が提供される。 The present invention provides a method for efficiently producing a lower saturated aldehyde using 1,2-diol as a raw material.
本発明は、銅−触媒担体複合体からなる触媒又は銀−触媒担体複合体からなる触媒により、水素共存下で、脱水反応により１，２−ジオールから低級飽和アルデヒドを製造する方法に関する。
本発明の低級飽和アルデヒドの製造方法に用いる触媒は、銅−触媒担体複合体からなる触媒又は銀−触媒担体複合体からなる触媒である。ここで、「触媒担体」とは、触媒を担持する機能を有する組成物又は化合物を意味し、触媒担体自身が、触媒としての機能を有するものであってよい。
銅−触媒担体複合体又は銀−触媒担体複合体を触媒として用いることで、触媒の活性の劣化を抑制することができ、１，２−ジオールの転化率、アルデヒド選択率ともに経時低下を抑制することができ、結果としてアルデヒドを良好な収率で製造することができる。これは触媒に銅又は銀を担持させ、水素共存下で反応させることで、反応が進行するとともに触媒に析出する炭素の生成が抑えられたためと考えられる。特にアルミナを触媒に用いた場合には、１，２−ジオールの転化率の低下が更に抑制され、高いアルデヒド選択率を示し、加えて、生成したアルデヒドが原料のジオールと反応することで生成してしまう副生物であるジオキソラン（ＤＸＬ）等の選択率が低い。また、銀を担持した場合には、１，２−ジオールの転化率の低下が抑制され、更に高いアルデヒド選択率を示し、副生物であるジオキソラン（ＤＸＬ）等の選択率が低い。
本発明の低級飽和アルデヒドの製造方法に用いる触媒とは、隣接する水酸基を有する多価アルコール等における脱水反応活性を有する触媒を示す。このような触媒に使用される触媒担体としては、酸触媒として機能する触媒担体が好ましく、具体的にはアルミナ、シリカアルミナ、ゼオライトなどが好ましく例示でき、アルミナがより好ましい。これらのうち１種を使用してよく、又は２種以上を組み合わせて使用してもよい。
本発明は、上記のとおり、脱水反応により１，２−ジオールから低級飽和アルデヒドを製造する方法に関するが、本発明はさらに、酸触媒における、触媒の活性の劣化抑制方法を提供するものである。
The present invention relates to a method for producing a lower saturated aldehyde from 1,2-diol by a dehydration reaction in the presence of hydrogen with a catalyst comprising a copper-catalyst carrier composite or a catalyst comprising a silver-catalyst carrier composite.
The catalyst used in the method for producing a lower saturated aldehyde of the present invention is a catalyst comprising a copper-catalyst carrier complex or a catalyst comprising a silver-catalyst carrier complex. Here, the “catalyst carrier” means a composition or compound having a function of supporting a catalyst, and the catalyst carrier itself may have a function as a catalyst.
By using a copper-catalyst carrier complex or a silver-catalyst carrier complex as a catalyst, it is possible to suppress the deterioration of the activity of the catalyst, and to suppress the deterioration with time in both 1,2-diol conversion rate and aldehyde selectivity. As a result, the aldehyde can be produced in good yield. This is presumably because copper or silver was supported on the catalyst and reacted in the presence of hydrogen to suppress the generation of carbon deposited on the catalyst while the reaction proceeded. In particular, when alumina is used as a catalyst, the decrease in the conversion rate of 1,2-diol is further suppressed, showing high aldehyde selectivity, and in addition, the produced aldehyde is produced by reacting with the raw material diol. The selectivity of dioxolane (DXL), which is a by-product, is low. Moreover, when carrying | supporting silver, the fall of the conversion rate of 1, 2- diol is suppressed, a still higher aldehyde selectivity is shown, and the selectivity of dioxolane (DXL) etc. which are a by-product is low.
The catalyst used in the method for producing a lower saturated aldehyde of the present invention refers to a catalyst having a dehydration reaction activity in a polyhydric alcohol having an adjacent hydroxyl group. As the catalyst carrier used for such a catalyst, a catalyst carrier that functions as an acid catalyst is preferable. Specifically, alumina, silica alumina, zeolite, and the like can be preferably exemplified, and alumina is more preferable. One of these may be used, or two or more may be used in combination.
As described above, the present invention relates to a method for producing a lower saturated aldehyde from 1,2-diol by a dehydration reaction. The present invention further provides a method for suppressing deterioration of the activity of a catalyst in an acid catalyst.
本発明の低級飽和アルデヒドの製造方法に用いる触媒は、銅又は銀が触媒担体に担持した、銅又は銀と触媒担体との複合体からなる。銅−触媒担体複合体又は銀−触媒担体複合体における触媒担体への銅又は銀成分の担持方法は含浸法、共沈法等公知の方法を用いることが可能である。例えば、硝酸銅水溶液又は硝酸銀水溶液を銅又は銀成分として、触媒担体成分であるアルミナに含浸することによって得られる固体を乾燥、焼成して得られる複合体が触媒として使用可能である。銅又は銀成分としては、溶媒への溶解性を有するものであれば限定されず、適宜選択することができるが、具体的には銅又は銀の硝酸塩、硫酸塩、酢酸塩、塩基性炭酸塩、アンミン錯体、塩化物などが好ましく例示できる。これらのうち１種を使用してよく、又は２種以上を組み合わせて使用してもよい。 The catalyst used in the method for producing a lower saturated aldehyde of the present invention comprises a composite of copper or silver and a catalyst support, in which copper or silver is supported on the catalyst support. As a method for supporting the copper or silver component on the catalyst carrier in the copper-catalyst carrier composite or the silver-catalyst carrier composite, known methods such as an impregnation method and a coprecipitation method can be used. For example, a composite obtained by drying and calcining a solid obtained by impregnating alumina as a catalyst carrier component with a copper nitrate aqueous solution or a silver nitrate aqueous solution as a copper or silver component can be used as a catalyst. The copper or silver component is not limited as long as it has solubility in a solvent, and can be appropriately selected. Specifically, copper or silver nitrate, sulfate, acetate, basic carbonate , Ammine complex, chloride and the like can be preferably exemplified. One of these may be used, or two or more may be used in combination.
また、銅−触媒担体複合体又は銀−触媒担体複合体における、銅又は銀（酸化銅又は酸
化銀換算）：触媒担体の含有比は、重量比で１：９〜１：１９５とすることが好ましい。銅−触媒担体複合体又は銀−触媒担体複合体中の、触媒担体に対する銅又は銀の含有比が０．００５〜０．１である場合、十分な触媒活性を得ることができ、触媒活性が短時間で低下することを防げる。
Further, the content ratio of copper or silver (in terms of copper oxide or silver oxide): catalyst support in the copper-catalyst support composite or the silver-catalyst support composite may be 1: 9 to 1: 195 by weight. preferable. When the content ratio of copper or silver to the catalyst support in the copper-catalyst support composite or silver-catalyst support composite is 0.005 to 0.1, sufficient catalytic activity can be obtained, and the catalytic activity is Prevents a drop in a short time.
上記銅−触媒担体複合体又は銀−触媒担体複合体の具体例は、銅−アルミナ複合体、銅−シリカアルミナ複合体、銅−ゼオライト複合体、銀−アルミナ複合体、銀−シリカアルミナ複合体、銀−ゼオライト複合体などが挙げられる。好ましくは、銅−アルミナ複合体、銀−アルミナ複合体である。 Specific examples of the copper-catalyst support composite or the silver-catalyst support composite include a copper-alumina composite, a copper-silica alumina composite, a copper-zeolite composite, a silver-alumina composite, and a silver-silica alumina composite. And silver-zeolite composites. Preferred are a copper-alumina composite and a silver-alumina composite.
上記アルミナ、シリカアルミナ、ゼオライトなどの酸触媒は市販品あるいは公知の方法にて調合したもの等、いずれの形態のものでも触媒担体として使用することが可能である。同様に上記銅−触媒担体複合体又は銀−触媒担体複合体についても市販品、市販品を還元したもの、当該銅又は銀成分の市販品あるいは公知の方法にて調合したものなどを触媒担体に担持させたもの等、いずれの形態のものでも触媒として使用することが可能である。 The acid catalyst such as alumina, silica alumina, and zeolite can be used as a catalyst carrier in any form such as a commercial product or a compound prepared by a known method. Similarly, for the above-mentioned copper-catalyst carrier composite or silver-catalyst carrier composite, a commercial product, a product obtained by reducing a commercial product, a commercial product of the copper or silver component, or a compound prepared by a known method is used as a catalyst carrier. Any form such as a supported one can be used as a catalyst.
本発明の低級飽和アルデヒド製造方法は、隣接する水酸基を持つ１，２−ジオールを上記銅−触媒担体複合体又は銀−触媒担体複合体を触媒として用いることで、１，２−ジオールの二級水酸基のみを選択的に脱離させ、生成したエノール中間体が互変異性によりカルボニル体に異性化することによって低級飽和アルデヒドが生成することが特徴である。 The lower saturated aldehyde production method of the present invention uses 1,2-diol having an adjacent hydroxyl group as a catalyst by using the above-mentioned copper-catalyst carrier complex or silver-catalyst carrier complex as a catalyst. It is characterized in that a lower saturated aldehyde is produced by selectively removing only a hydroxyl group and isomerizing the produced enol intermediate to a carbonyl compound by tautomerism.
本発明の製造方法の原料となる１，２−ジオールの具体例は、１，２−プロパンジオール、１，２−ブタンジオール、１，２−ペンタンジオール、１，２−ヘキサンジオールなどが挙げられるが、既に発明者らが見出した技術により、バイオディーゼル燃料を製造する際の副生物であるグリセリンから１，２−プロパンジオールを製造することができることから、１，２−プロパンジオールを原料とすることが好ましい。 Specific examples of 1,2-diol used as a raw material for the production method of the present invention include 1,2-propanediol, 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, and the like. However, 1,2-propanediol can be produced from glycerin, which is a by-product in producing biodiesel fuel, by the technology already found by the inventors. It is preferable.
本発明の製造方法の原料の１，２−ジオールは、原料中に水分を含んでいてもよい。１，２−ジオール中の水分含有量は、０〜９５重量％の範囲が好ましい。従来の製造方法では、目的物である低級飽和アルデヒド（プロパナール等）からの副生成物（アセタール、ジオキソラン等）の生成を抑制するため、多量の水を原料に含有させて反応させることが必要となる場合があった。本発明の製造方法によれば、原料中に水分を含まなくても高いアルデヒド選択率を示すため、工業的に高効率な反応を実施することが可能となる。 The raw material 1,2-diol of the production method of the present invention may contain moisture in the raw material. The water content in 1,2-diol is preferably in the range of 0 to 95% by weight. In the conventional production method, in order to suppress the formation of by-products (such as acetal and dioxolane) from the target lower saturated aldehyde (such as propanal), it is necessary to contain a large amount of water in the raw material for reaction. There was a case. According to the production method of the present invention, a high aldehyde selectivity is exhibited even if the raw material does not contain moisture, and therefore, an industrially highly efficient reaction can be carried out.
本発明の低級飽和アルデヒドの製造で使用される反応装置は特に限定されないが、工業的には、原料をガス化して適当な触媒層を通過させておこなう形式の気相流通反応が可能な装置が好ましい。気相流通反応装置を用いる場合、たとえば、気相流通反応装置に所定量の触媒を入れ、これを公知の方法で前処理することにより活性な触媒層を気相流通反応装置内に形成させる。ここに、原料の１，２−ジオールをガス化し、供給することにより低級飽和アルデヒドを製造することが可能である。 The reaction apparatus used in the production of the lower saturated aldehyde of the present invention is not particularly limited, but industrially, there is an apparatus capable of performing a gas-phase flow reaction of a type in which a raw material is gasified and passed through an appropriate catalyst layer. preferable. When using a gas-phase flow reaction apparatus, for example, a predetermined amount of catalyst is put into the gas-phase flow reaction apparatus and pretreated by a known method to form an active catalyst layer in the gas-phase flow reaction apparatus. It is possible to produce a lower saturated aldehyde by gasifying and supplying the raw material 1,2-diol.
また、上記触媒の前処理は、触媒層を活性化させることができる公知の方法を用いることができ、例えば、反応条件と同条件（例えば、水素気流中、３００℃〜４００℃程度）で１時間程度熱処理を行う等により、触媒層を活性化させることが挙げられる。 The catalyst pretreatment may be performed by a known method that can activate the catalyst layer. For example, the pretreatment of the catalyst may be performed under the same conditions as the reaction conditions (for example, about 300 ° C. to 400 ° C. in a hydrogen stream). For example, the catalyst layer may be activated by performing a heat treatment for about an hour.
また、本発明の製造方法で得られる低級飽和アルデヒドとしては、プロパナール、ブタナール、ペンタナール、ヘキサナールなどが挙げられ、特にプロパナールが好ましい。 Further, examples of the lower saturated aldehyde obtained by the production method of the present invention include propanal, butanal, pentanal, hexanal and the like, and propanal is particularly preferable.
本発明の低級飽和アルデヒド製造方法の反応温度は、２５０℃〜４００℃の温度範囲、
すなわち、１，２−ジオールが気相状態として存在する温度が好適である。反応を十分に進行させるためには２５０℃以上が好ましく、生成物選択率を良好に保つためには２７５℃以上が好ましい。より好ましい温度範囲としては３００℃〜４００℃の範囲であり、より収率が高くなることから、３００℃〜３７５℃の範囲が更に好ましく、３００℃〜３５０℃の範囲が最も好ましい。
The reaction temperature of the lower saturated aldehyde production method of the present invention is a temperature range of 250 ° C to 400 ° C,
That is, a temperature at which 1,2-diol exists as a gas phase is preferable. In order to sufficiently advance the reaction, 250 ° C. or higher is preferable, and in order to keep the product selectivity favorable, 275 ° C. or higher is preferable. A more preferable temperature range is 300 ° C. to 400 ° C., and since the yield is higher, a range of 300 ° C. to 375 ° C. is more preferable, and a range of 300 ° C. to 350 ° C. is most preferable.
本発明に用いる触媒の量及び低級飽和アルデヒド製造方法の反応時間は、触媒重量に対する単位時間当たりの原料フィード重量（ＷＨＳＶ：Ｗｅｉｇｈｔ Ｈｏｕｒｌｙ Ｓｐａｃｅ Ｖｅｌｏｃｉｔｙ；単位、ｈ-1）で代表され、ＷＨＳＶ値で、０．１から２０ｈ-1の範囲で利用可能であり、触媒の寿命及び収率の観点から好ましくはＷＨＳＶ値で、０．５から７ｈ-1の範囲であり、更に好ましくはＷＨＳＶ値で、１から６ｈ-1の範囲である。 The amount of the catalyst used in the present invention and the reaction time of the method for producing a lower saturated aldehyde are represented by a raw material feed weight per unit time (WHSV: Weight Hourly Space Velocity; unit, h −1 ) relative to the catalyst weight, and is a WHSV value. available from 0.1 in the range of 20h -1, preferably WHSV value in terms of life and yield of the catalyst is in the range of 7h -1 from 0.5, more preferably at WHSV values, 1 To 6h −1 .
以下、実施例により本発明の効果を具体的に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the effects of the present invention will be specifically described by way of examples, but the present invention is not limited thereto.
参考例、実施例、比較例において、反応は常圧固定床流通式反応装置を用いた。反応管には内径１７ｍｍのガラス管を用い、加熱は長さ約３００ｍｍの電気管状炉を用いて加熱した。反応器内部には触媒を保持する石英ウールを設置し石英ウール上に触媒を所定量設置した（触媒層）。原料の１，２−プロパンジオール（プロピレングリコール）は市販の試薬（和光純薬製特級グレード）をそのまま希釈せずに用いた。原料の供給はマイクロフィーダーを用いて所定の供給速度で反応装置上部の壁面に供給した。キャリアガスも反応器の上部より供給され、反応器上部から下部へのダウンフローとなる。原料は反応管内壁を伝って管の下部へと落ちていく間に電気炉によって加熱蒸発され、触媒層へと導かれる。気化した原料もキャリアガスと同様にダウンフローで反応管上部から下部へと流れる。
触媒層を通過した反応ガスは反応管下部から反応装置をでて、アセトンドライアイスにて冷却されたトラップへと導かれる。反応生成物はここで冷却、凝縮され一部オフガスはトラップで凝縮せずに系外へと導かれる。
アセトンドライアイストラップにて凝縮した反応生成物はガスクロマトグラフィー（島津製作所製ＧＣ−８Ａ ＦＩＤ検出器、カラム：ＤＢ−ＷＡＸワイドボア０．５３ｍｍ膜厚１μｍ ３０ｍ、キャリアガス：ヘリウム）にて分析、定量された。
検量線補正後、原料のプロピレングリコールの残量、生成物のプロパナールの収量を決定し、この値から転化率（モル％）及び選択率（モル％）を求めた。転化率（モル％）及び選択率（モル％）は、以下の式に基づき、求められる。
In the reference examples, examples and comparative examples, the reaction was carried out using an atmospheric pressure fixed bed flow type reactor. A glass tube having an inner diameter of 17 mm was used as the reaction tube, and heating was performed using an electric tubular furnace having a length of about 300 mm. Quartz wool holding the catalyst was placed inside the reactor, and a predetermined amount of catalyst was placed on the quartz wool (catalyst layer). As the raw material 1,2-propanediol (propylene glycol), a commercially available reagent (special grade manufactured by Wako Pure Chemical Industries) was used as it was without being diluted. The raw material was supplied to the wall surface of the upper part of the reactor using a microfeeder at a predetermined supply rate. The carrier gas is also supplied from the upper part of the reactor, resulting in a downward flow from the upper part of the reactor to the lower part. The raw material is heated and evaporated by an electric furnace while flowing through the inner wall of the reaction tube to the lower part of the tube, and is led to the catalyst layer. The vaporized raw material also flows from the upper part to the lower part of the reaction tube in a down flow like the carrier gas.
The reaction gas that has passed through the catalyst layer exits the reaction apparatus from the bottom of the reaction tube and is led to a trap cooled with acetone dry ice. The reaction product is cooled and condensed here, and part of the off-gas is led out of the system without being condensed in the trap.
The reaction product condensed in the acetone dry ice strap is analyzed and quantified by gas chromatography (GC-8A FID detector, manufactured by Shimadzu Corporation, column: DB-WAX wide bore 0.53 mm, film thickness 1 μm 30 m, carrier gas: helium). It was done.
After calibration curve correction, the remaining amount of raw material propylene glycol and the yield of product propanal were determined, and the conversion (mol%) and selectivity (mol%) were determined from these values. The conversion rate (mol%) and the selectivity (mol%) are obtained based on the following formula.
転化率（モル％）＝［（原料の量（モル）−原料の残量（モル））／原料の量（モル）］×１００
選択率（モル％）＝［目的物の収量（モル）／（原料の量（モル）−原料の残量（モル））］×１００
Conversion (mol%) = [(Amount of raw material (mol) −Remaining amount of raw material (mol)) / Amount of raw material (mol)] × 100
Selectivity (mol%) = [Yield of target product (mol) / (Amount of raw material (mol) −Remaining amount of raw material (mol))] × 100
＜参考例１＞
（触媒の調製）
シリカ（富士シリシア化学製、キャリアクトＱ１０）に公知の含浸法にて、３０重量％のヘテロポリ酸（ケイタングステン酸、和光純薬製 特級試薬）を担持し、シリカ担持ケイタングステン酸を調製した。これらの触媒におけるケイタングステン酸の担持量は３０重量％であった。
<Reference Example 1>
(Preparation of catalyst)
Silica (manufactured by Fuji Silysia Chemical Co., Caractect Q10) was loaded with 30% by weight of heteropolyacid (silicotungstic acid, Wako Pure Chemicals special grade reagent) by a known impregnation method to prepare silica-supported silicotungstic acid. The supported amount of silicotungstic acid in these catalysts was 30% by weight.
（ヘテロポリ酸触媒を用いたプロパナールの製造）
上記調製した触媒０．５ｇを固定床常圧気相流通反応装置内に設置した。その後、水素気流中２５０℃に触媒層を加熱し、１時間前処理を施した。前処理後、固定床常圧気相流
通反応装置の上部からキャリアガスとして水素を９０ｍｌ／ｍｉｎの流速で流し、水を含まない１，２−プロパンジオールを１．９２ｍｌ／ｈにて水素と共に供給して気化させて触媒層へ供給し反応を行った。なお、トラップの冷却は、氷水とした。１，２−プロパンジオール転化率、プロパナール選択率及びＤＸＬ選択率を表１に示す。
(Production of propanal using heteropolyacid catalyst)
0.5 g of the prepared catalyst was placed in a fixed bed atmospheric pressure gas flow reactor. Thereafter, the catalyst layer was heated to 250 ° C. in a hydrogen stream and pretreated for 1 hour. After the pretreatment, hydrogen is supplied as a carrier gas from the upper part of the fixed bed atmospheric pressure gas flow reactor at a flow rate of 90 ml / min, and water-free 1,2-propanediol is supplied together with hydrogen at 1.92 ml / h. Vaporized and supplied to the catalyst layer for reaction. The trap was cooled with ice water. Table 1 shows the 1,2-propanediol conversion, propanal selectivity, and DXL selectivity.
ヘテロポリ酸を触媒とすると、１，２−プロパンジオール転化率、プロパナール選択率が、時間の経過に従い、大きく減少した。結果を図５に示す。 When the heteropolyacid was used as a catalyst, the 1,2-propanediol conversion rate and propanal selectivity were greatly reduced with the passage of time. The results are shown in FIG.
＜比較例１＞
（触媒の調製）
シリカアルミナ（Ｎ６３２ＨＮ、日揮化学製）を触媒として用いた。
<Comparative Example 1>
(Preparation of catalyst)
Silica alumina (N632HN, manufactured by JGC Chemical) was used as a catalyst.
（シリカアルミナ触媒を用いたプロパナールの製造）
上記調製した触媒０．３ｇを固定床常圧気相流通反応装置内に設置した。その後、水素気流中３００℃に触媒層を加熱し、１時間前処理を施した。前処理後、固定床常圧気相流通反応装置の上部からキャリアガスとして水素を９０ｍｌ／ｍｉｎの流速で流し、水を含まない１，２−プロパンジオールを３．６５ｍｌ／ｈにて水素と共に供給して気化させて触媒層へ供給し反応を行った。１，２−プロパンジオール転化率、プロパナール選択率及びＤＸＬ選択率を表２に示す。
(Production of propanal using silica alumina catalyst)
0.3 g of the catalyst prepared above was placed in a fixed bed atmospheric pressure gas flow reactor. Thereafter, the catalyst layer was heated to 300 ° C. in a hydrogen stream and pretreated for 1 hour. After the pretreatment, hydrogen is supplied as a carrier gas from the upper part of the fixed bed atmospheric pressure gas flow reactor at a flow rate of 90 ml / min, and water-free 1,2-propanediol is supplied together with hydrogen at 3.65 ml / h. Vaporized and supplied to the catalyst layer for reaction. Table 2 shows the 1,2-propanediol conversion, propanal selectivity and DXL selectivity.
＜実施例１＞
（触媒の調製）
シリカアルミナ（Ｎ６３２ＨＮ、日揮化学製）を担体として用いて、含浸法により銅を担持し、銅担持シリカアルミナを調製した。
すなわち、Ｎ６３２ＨＮに分解後のＣｕＯが２ｗｔ．％となるようにＣｕ（ＮＯ3）2を含浸した後、１００℃で一晩乾燥させ、５００℃で２時間焼成し、２ｗｔ．％でＣｕＯを担持したＮ６３２ＨＮを得た。以下、表記は「Ｎ６３２ＨＮ−ＣｕＯ−２」（担体名−金属−担持量（ｗｔ．％））とする。
<Example 1>
(Preparation of catalyst)
Using silica alumina (N632HN, JGC Chemical Co., Ltd.) as a carrier, copper was supported by an impregnation method to prepare copper-supported silica alumina.
That is, CuO after decomposition into N632HN is 2 wt. % Impregnated with Cu (NO 3 ) 2 , dried at 100 ° C. overnight, calcined at 500 ° C. for 2 hours, and 2 wt. % N632HN carrying CuO was obtained. Hereinafter, the notation is “N632HN—CuO-2” (support name—metal—supported amount (wt.%)).
（銅担持シリカアルミナ触媒を用いたプロパナールの製造）
上記調製した触媒０．３ｇを固定床常圧気相流通反応装置内に設置した。その後、水素気流中３００℃に触媒層を加熱し、１時間前処理を施した。前処理後、固定床常圧気相流通反応装置の上部からキャリアガスとして水素を９０ｍｌ／ｍｉｎの流速で流し、水を含まない１，２−プロパンジオールを３．６５ｍｌ／ｈにて水素と共に供給して気化させて触媒層へ供給し反応を行った。１，２−プロパンジオール転化率、プロパナール選択率及
びＤＸＬ選択率を表２に示す。
(Production of propanal using a copper-supported silica-alumina catalyst)
0.3 g of the catalyst prepared above was placed in a fixed bed atmospheric pressure gas flow reactor. Thereafter, the catalyst layer was heated to 300 ° C. in a hydrogen stream and pretreated for 1 hour. After the pretreatment, hydrogen is supplied as a carrier gas from the upper part of the fixed bed atmospheric pressure gas flow reactor at a flow rate of 90 ml / min, and water-free 1,2-propanediol is supplied together with hydrogen at 3.65 ml / h. Vaporized and supplied to the catalyst layer for reaction. Table 2 shows the 1,2-propanediol conversion, propanal selectivity and DXL selectivity.
比較例１の水素共存下シリカアルミナ触媒では、１，２−プロパンジオール転化率、プロパナール選択率が、時間の経過に従い、減少した。
これに対し、実施例１の水素共存下銅担持シリカアルミナ触媒では、１，２−プロパンジオール転化率の低下が抑制された。すなわち、活性の低下が抑制されていることがわかる。また、プロパナール選択率の低下も抑制された。結果を図１に示す。なお、工業的には、数％程度の触媒活性の低下でも、効率（触媒の寿命及び収率等）への影響が非常に大きいため、活性の劣化を抑制することは大変有用である。
In the silica alumina catalyst in the presence of hydrogen of Comparative Example 1, the 1,2-propanediol conversion rate and propanal selectivity decreased with the passage of time.
On the other hand, in the copper-supported silica-alumina catalyst in the presence of hydrogen in Example 1, a decrease in the 1,2-propanediol conversion rate was suppressed. That is, it turns out that the fall of activity is suppressed. Moreover, the fall of the propanal selectivity was also suppressed. The results are shown in FIG. Industrially, even if the catalyst activity is reduced by about several percent, the effect on the efficiency (lifetime and yield of the catalyst, etc.) is very large. Therefore, it is very useful to suppress the deterioration of the activity.
＜実施例２＞
（銀担持シリカアルミナ触媒を用いたプロパナールの製造）
シリカアルミナ（Ｎ６３２ＨＮ、日揮化学製）に担持させる金属を銀とした以外は実施例１に準じて反応を行った。すなわち、Ｎ６３２ＨＮに分解後のＡｇ2Ｏが２ｗｔ．％となるようにＡｇＮＯ3を含浸し、Ｎ６３２ＨＮ−Ａｇ2Ｏ−２」を調製し、触媒として用いた。１，２−プロパンジオール転化率、プロパナール選択率及びＤＸＬ選択率を表３に示す。
<Example 2>
(Production of propanal using silver supported silica alumina catalyst)
Reaction was performed according to Example 1 except that the metal supported on silica alumina (N632HN, JGC Chemical Co., Ltd.) was silver. That is, Ag 2 O after decomposition into N632HN is 2 wt. N632HN—Ag 2 O-2 ”was prepared by impregnating with AgNO 3 so as to be a catalyst, and used as a catalyst. Table 3 shows 1,2-propanediol conversion, propanal selectivity, and DXL selectivity.
水素共存下銀担持シリカアルミナ触媒では、１，２−プロパンジオール転化率の低下が抑制された。すなわち、銅担持触媒と同様に、活性の低下が抑制されていることがわかる。また、副生成物の生成が抑制され、プロパナール選択率が向上した。結果を図２に示す。 In the silver-supported silica-alumina catalyst in the presence of hydrogen, the decrease in 1,2-propanediol conversion was suppressed. That is, it can be seen that the decrease in activity is suppressed as in the copper-supported catalyst. Moreover, the production | generation of the by-product was suppressed and the propanal selectivity improved. The results are shown in FIG.
＜実施例３＞
（触媒の調製）
アルミナ（ＤＣ２２８２、ダイヤキャタリスト製）を担体として用いて、含浸法により銅を担持し、銅担持アルミナを調製した。
すなわち、ＤＣ２２８２に分解後のＣｕＯが２ｗｔ．％となるようにＣｕ（ＮＯ3）2を含浸した後、１００℃で一晩乾燥させ、５００℃で２時間焼成し、２ｗｔ．％でＣｕＯを担持したＤＣ２２８２を得た。以下、表記は「ＤＣ２２８２−ＣｕＯ−２」（担体名−金属−担持量（ｗｔ．％））とする。
<Example 3>
(Preparation of catalyst)
Copper was supported by an impregnation method using alumina (DC2282, manufactured by Dia Catalyst) as a carrier to prepare copper-supported alumina.
That is, CuO after decomposition into DC2282 is 2 wt. % Impregnated with Cu (NO 3 ) 2 , dried at 100 ° C. overnight, calcined at 500 ° C. for 2 hours, and 2 wt. DC 2282 carrying CuO at% was obtained. Hereinafter, the notation is “DC2282-CuO-2” (support name−metal−supported amount (wt.%)).
（銅担持アルミナ触媒を用いたプロパナールの製造）
上記調製した触媒０．５ｇを固定床常圧気相流通反応装置内に設置した。その後、水素気流中３５０℃に触媒層を加熱し、１時間前処理を施した。前処理後、固定床常圧気相流通反応装置の上部からキャリアガスとして水素を９０ｍｌ／ｍｉｎの流速で流し、水を含まない１，２−プロパンジオールを１．９２ｍｌ／ｈにて水素と共に供給して気化させて触媒層へ供給し反応を行った。プロパナール選択率、ＤＸＬ選択率及びその他の化合物の選択率を表４に示す。
(Production of propanal using copper supported alumina catalyst)
0.5 g of the prepared catalyst was placed in a fixed bed atmospheric pressure gas flow reactor. Thereafter, the catalyst layer was heated to 350 ° C. in a hydrogen stream and pretreated for 1 hour. After the pretreatment, hydrogen is supplied as a carrier gas from the upper part of the fixed bed atmospheric pressure gas flow reactor at a flow rate of 90 ml / min, and water-free 1,2-propanediol is supplied together with hydrogen at 1.92 ml / h. Vaporized and supplied to the catalyst layer for reaction. Table 4 shows propanal selectivity, DXL selectivity, and selectivity of other compounds.
＜比較例２＞
（アルミナ触媒を用いたプロパナールの製造）
アルミナ（ＤＣ２２８２、ダイヤキャタリスト製）を触媒とした以外は実施例３に準じて反応を行った。プロパナール選択率、ＤＸＬ選択率及びその他の化合物の選択率を表４に示す。
<Comparative example 2>
(Production of propanal using alumina catalyst)
The reaction was performed according to Example 3 except that alumina (DC2282, manufactured by Dia Catalyst) was used as a catalyst. Table 4 shows propanal selectivity, DXL selectivity, and selectivity of other compounds.
水素共存下アルミナ触媒では、初期活性は大きいものの反応時間の経過と共に触媒の失活が顕著であった。
水素共存下銅担持アルミナ触媒では、１，２−プロパンジオール転化率は、いずれの反応時間においても９９．５％以上であった。すなわち、触媒活性が低下しないことがわかる。また、プロパナール選択率も低下するのではなく、経時的に向上した。結果を図３に示す。
また、従来技術のヘテロポリ酸触媒では、プロパナール選択率を向上させるために、原料を水で希釈する必要があったが、本発明の触媒では、原料を水で希釈しなくても、高い選択性が得られることがわかる。
In the alumina catalyst in the presence of hydrogen, although the initial activity was large, the deactivation of the catalyst was remarkable as the reaction time passed.
In the copper-supported alumina catalyst in the presence of hydrogen, the 1,2-propanediol conversion rate was 99.5% or more at any reaction time. That is, it turns out that catalyst activity does not fall. In addition, the propanal selectivity was not decreased but improved with time. The results are shown in FIG.
In addition, in the prior art heteropolyacid catalyst, it was necessary to dilute the raw material with water in order to improve the propanal selectivity, but with the catalyst of the present invention, high selection is possible without diluting the raw material with water. It can be seen that sex is obtained.
＜実施例４＞
（温度の影響）
反応温度を４００℃とした以外は実施例３に準じて反応を行った。３５０℃と４００℃
におけるプロパナール選択率、ＤＸＬ選択率及びその他の化合物の選択率を表５に示す。
<Example 4>
(Effect of temperature)
The reaction was performed according to Example 3 except that the reaction temperature was 400 ° C. 350 ° C and 400 ° C
Table 5 shows the propanal selectivity, DXL selectivity and selectivity of other compounds.
反応温度が４００℃でも、１，２−プロパンジオール転化率は、いずれの反応時間においても９９．５％以上であった。すなわち、触媒活性が低下せず、プロパナール選択率も、経時的に向上した。結果を図３に示す。 Even when the reaction temperature was 400 ° C., the 1,2-propanediol conversion rate was 99.5% or more in any reaction time. That is, the catalytic activity did not decrease, and the propanal selectivity also improved over time. The results are shown in FIG.
＜比較例３＞
（水素共存の影響）
キャリアガスとして、窒素を３０ｍｌ／ｍｉｎとした以外は実施例３に準じて反応を行った。プロパナール選択率、ＤＸＬ選択率及びその他の化合物の選択率を表６に示す。
<Comparative Example 3>
(Influence of hydrogen coexistence)
The reaction was performed according to Example 3 except that nitrogen was changed to 30 ml / min as the carrier gas. Table 6 shows propanal selectivity, DXL selectivity, and selectivity of other compounds.
１，２−プロパンジオール転化率は、いずれの反応時間においても９９．５％以上であった。水素共存下に比べ、プロパナール選択率が低いことがわかる。結果を図４に示す。 The 1,2-propanediol conversion rate was 99.5% or more at any reaction time. It can be seen that the propanal selectivity is lower than in the presence of hydrogen. The results are shown in FIG.
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| WO2016185392A1 (en) | 2015-05-19 | 2016-11-24 | Eni S.P.A. | Process and apparatus for the production of aldehydes starting from 1,2-diols |
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| JP2019523254A (en) * | 2016-08-24 | 2019-08-22 | サザン・リサーチ・インスティテュート | Compositions and methods for the production of acrylonitrile |
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| JP6393591B2 (en) * | 2014-11-12 | 2018-09-19 | 日立造船株式会社 | Aldehyde decomposition catalyst, exhaust gas treatment facility, and exhaust gas treatment method |
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| JP2016513009A (en) * | 2013-11-18 | 2016-05-12 | エルジー・ケム・リミテッド | Catalyst for glycerol dehydration reaction, method for producing the same, and method for producing acrolein |
| WO2016185392A1 (en) | 2015-05-19 | 2016-11-24 | Eni S.P.A. | Process and apparatus for the production of aldehydes starting from 1,2-diols |
| JP2019523254A (en) * | 2016-08-24 | 2019-08-22 | サザン・リサーチ・インスティテュート | Compositions and methods for the production of acrylonitrile |
| JP2019025389A (en) * | 2017-07-26 | 2019-02-21 | 国立大学法人 熊本大学 | Manufacturing method of ammonia combustion catalyst, and method of using heat generated by ammonia catalyst combustion |
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