JP2014534253A - 不均一反応系にて環状アセタールを製造する方法 - Google Patents
不均一反応系にて環状アセタールを製造する方法 Download PDFInfo
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- JP2014534253A JP2014534253A JP2014542869A JP2014542869A JP2014534253A JP 2014534253 A JP2014534253 A JP 2014534253A JP 2014542869 A JP2014542869 A JP 2014542869A JP 2014542869 A JP2014542869 A JP 2014542869A JP 2014534253 A JP2014534253 A JP 2014534253A
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- JP
- Japan
- Prior art keywords
- production method
- formaldehyde
- aprotic compound
- formaldehyde source
- cyclic acetal
- 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
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- -1 cyclic acetal Chemical class 0.000 title claims abstract description 93
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 title claims description 52
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 346
- 150000001875 compounds Chemical class 0.000 claims abstract description 142
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000002638 heterogeneous catalyst Substances 0.000 claims abstract description 16
- 239000011949 solid catalyst Substances 0.000 claims abstract description 13
- 239000008098 formaldehyde solution Substances 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims description 54
- 238000000034 method Methods 0.000 claims description 54
- 230000008569 process Effects 0.000 claims description 39
- 229920000642 polymer Polymers 0.000 claims description 23
- 239000007787 solid Substances 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 20
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 19
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 16
- 230000002378 acidificating effect Effects 0.000 claims description 13
- 238000009835 boiling Methods 0.000 claims description 12
- 229920002866 paraformaldehyde Polymers 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 239000007848 Bronsted acid Substances 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002841 Lewis acid Substances 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 7
- 150000007517 lewis acids Chemical class 0.000 claims description 7
- 229920006324 polyoxymethylene Polymers 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 238000010924 continuous production Methods 0.000 claims description 4
- 238000005342 ion exchange Methods 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 claims description 4
- 229920012196 Polyoxymethylene Copolymer Polymers 0.000 claims description 3
- 229920009382 Polyoxymethylene Homopolymer Polymers 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 150000002894 organic compounds Chemical class 0.000 claims description 3
- 230000003068 static effect Effects 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims 2
- 239000003054 catalyst Substances 0.000 abstract description 48
- 239000003456 ion exchange resin Substances 0.000 abstract description 4
- 229920003303 ion-exchange polymer Polymers 0.000 abstract description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 abstract description 3
- 238000000895 extractive distillation Methods 0.000 abstract 1
- 239000011541 reaction mixture Substances 0.000 description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 26
- 239000007789 gas Substances 0.000 description 14
- 125000005704 oxymethylene group Chemical group [H]C([H])([*:2])O[*:1] 0.000 description 12
- 238000002844 melting Methods 0.000 description 11
- 230000008018 melting Effects 0.000 description 11
- 239000000377 silicon dioxide Substances 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- UYVWNPAMKCDKRB-UHFFFAOYSA-N 1,2,4,5-tetraoxane Chemical compound C1OOCOO1 UYVWNPAMKCDKRB-UHFFFAOYSA-N 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000012263 liquid product Substances 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 125000004122 cyclic group Chemical group 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 5
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000006085 branching agent Substances 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- 150000001491 aromatic compounds Chemical class 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
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- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
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- 239000004927 clay Substances 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 150000003462 sulfoxides Chemical class 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- AUAGGMPIKOZAJZ-UHFFFAOYSA-N 1,3,6-trioxocane Chemical compound C1COCOCCO1 AUAGGMPIKOZAJZ-UHFFFAOYSA-N 0.000 description 2
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 239000011951 cationic catalyst Substances 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 230000009918 complex formation Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000011964 heteropoly acid Substances 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 239000011968 lewis acid catalyst Substances 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
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- 150000003457 sulfones Chemical class 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- FQERLIOIVXPZKH-UHFFFAOYSA-N 1,2,4-trioxane Chemical compound C1COOCO1 FQERLIOIVXPZKH-UHFFFAOYSA-N 0.000 description 1
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical compound C1COCOC1 VDFVNEFVBPFDSB-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- YLAGPJFRSLGWBF-UHFFFAOYSA-N 2,2-dibutylthiolane 1,1-dioxide Chemical compound CCCCC1(CCCC)CCCS1(=O)=O YLAGPJFRSLGWBF-UHFFFAOYSA-N 0.000 description 1
- RHWGYBXYCHBKKN-UHFFFAOYSA-N 2,2-diethylthiolane 1,1-dioxide Chemical compound CCC1(CC)CCCS1(=O)=O RHWGYBXYCHBKKN-UHFFFAOYSA-N 0.000 description 1
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- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
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- 238000001577 simple distillation Methods 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 description 1
- 150000003460 sulfonic acids Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
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Abstract
Description
(1)通常の担体物質(例えば、シリカ、カーボン、シリカ-アルミナ組合せ物、またはアルミナ)上に担持させることができる、酸性金属酸化物組合せ物で代表される固体触媒。これらの金属酸化物組合せ物は、それ自体で使用することもできるし、あるいは無機酸もしくは有機酸をドーピングして使用することもできる。この種の触媒の好適な例は、非晶質シリカ-アルミナや酸性クレー(例えば、スメクタイト、無機もしくは有機の酸処理クレー、柱状クレー、または通常はプロトン型のゼオライト)、金属酸化物(例えば、約1:1のモル組合せのZrO2-TiO2)、および硫酸化金属酸化物(例えば硫酸化ZrO2)である;
(2)幾つかのタイプのカチオン交換樹脂を酸触媒として使用して反応を行うことができる。最も一般的には、このような樹脂は、SO3H基を芳香族基上にグラフトするように官能化された、スチレン、エチルビニルベンゼン、およびジビニルベンゼンのコポリマーを含む。これらの酸性樹脂は、種々の物理的構造形態にて(例えば、ゲル形態にて、マクロ網状構造形態にて、あるいはシリカ、カーボン、もしくはカーボンナノチューブ等の担体物質上に担持された形態にて)使用することができる。他のタイプの樹脂としては、カルボン酸基もしくはスルホン酸基を、またはカルボン酸基とスルホン酸基の両方を有するペルフッ化樹脂がある。このような樹脂の公知の例は、NAFION(商標)とAMBERLYST樹脂である。フッ化樹脂は、それ自体で使用することもできるし、あるいはシリカ、カーボン、または金属酸化物及び/又はシリカの高度分散網目中に捕捉されたカーボンナノチューブ等の不活性物質上に担持させることもできる;
(3)シリカ、シリカ−アルミナ組合せ物、アルミナ、ゼオライト、シリカ、活性炭、砂、及び/又はシリカゲル等の、通常は孤立電子対を有する不均一固体を、メタスルホン酸やp-トルエンスルホン酸等のブレンステッド酸触媒のための担体として、あるいはルイス酸部位を有する化合物(例えばSbF5)のための担体として使用して、相互作用を起こさせ、強いブレンステッド酸性をもたらすことができる。ゼオライト、シリカ、メソポーラスシリカ、またはポリマー(例えばポリシロキサン)等の不均一固体を、ブレンステッド酸基もしくはその前駆体による化学グラフトによって官能化して、スルホン酸及び/又はカルボン酸等の酸性基もしくはその前駆体を組み込むことができる。官能化は、例えばシリカのSiOH基とクロロスルホン酸との反応による固体上への直接グラフト;あるいは、例えばパーフルオロアルキルシラン誘導体であってよい有機スペーサーによって固体に結びつけることができる;等の、当業界に公知の種々の方法にて導入することができる。ブレンステッド酸官能化シリカはさらに、中性またはイオン性のテンプレーティング法(その後に、チオールから対応するスルホン酸への酸化を行う)を使用して、Si(OR)4と例えば3-メルカプトプロピル-トリ-メトキシシランとの共縮合によるゾル-ゲルプロセス(例えばチオール官能化シリカをもたらす)によって作製することもできる。官能化固体は、そのままの形態(すなわち粉末形態)でも、ゼオライト膜の形態(または、膜中の他のポリマーとの混合物等の他の多くの形態)でも、固体押出物の形態でも、あるいは例えば構造的無機担体(コージェライトのモノリス)のコーティングの形態でも使用することができる;および
(4)最も一般的には、式HxPMyOzを有する不均一ヘテロポリ酸。式中、Pは中心原子(一般にはケイ素またリン)を表わす。周辺原子が中心原子を、一般には対称様式にて取り囲んでいる。最も一般的な周辺元素Mは、通常はMoまたはWであるが、V、Nb、およびTaも、当該目的に対して好適である。指数xyzは、公知の様式にて分子中の原子比を定めており、型通りの仕方で決定することができる。これらのポリ酸は、よく知られているように、多くの結晶形にて見出されるが、不均一化学種に対する最も一般的な結晶形はケギン構造と呼ばれている。このようなヘテロポリ酸は、熱安定性が高く、非腐食性である。不均一ヘテロポリ酸は、シリカゲル、珪藻土、カーボン、カーボンナノチューブ、およびイオン交換樹脂から選ばれる担体上に使用するのが好ましい。好ましい不均一ヘテロポリ酸は、ここでは式H3PM12O40(式中、Mは、W及び/又はMoを表わす)で示すことができる。好ましいPM部分の例は、PW12、PMo12、PW12/SiO2、PW12/炭素、およびSiW12で示すことができる。
[0063]このときR3とR4は独立して、分岐鎖または非分岐鎖であってよいC1-C8アルキルから選ばれ、好ましくはR3とR4は独立して、メチルまたはエチルである。
[0092]最終転化率=(反応の終了時における、重量%で表示される反応混合物中のトリオキサンの量)/(t=0における、重量%で表示される反応混合物中のホルムアルデヒド源の量[反応混合物中のホルムアルデヒド源の初期量])
[0093]本発明の方法のさらなる好ましい実施態様によれば、ホルムアルデヒド源の環状アセタール(好ましくはトリオキサン及び/又はテトラオキサン)への最終転化率は、12%超、好ましくは14%超、さらに好ましくは16%超、さらに好ましくは20%超、特に30%超、とりわけ50%超(例えば80%超または90%超)である。
R1-(O-CH2)q-O-R2 (I)
(式中、R1とR2は、互いに独立して一価の有機基であって、好ましくはブチル、プロピル、エチル、そして特にメチル等のアルキル基であり;qは1〜50の整数である)の化合物である。
[00119]本実施例では、強酸性のイオン交換樹脂〔Amberlyst15(登録商標)、湿潤形、DOW CHEMICAL社から市販〕を触媒として使用した。使用前に、樹脂をスルホランに対して状態調節した(樹脂の細孔中の水をスルホランで交換)。
12 第1の固定床反応器
14 非プロトン性化合物ストリーム
15 気体/液体ストリーム
16 液体ストリーム
18 気体/液体フラッシュドラム
20 熱交換器
22 液体出口ストリーム
24 第2の固定床反応器
26 蒸気/未転化ホルムアルデヒドストリーム
28 液体ストリーム
30 気体/液体出口ストリーム
32 第2のフラッシュドラム
34 生成物ストリーム
36 オフガスストリーム
50 撹拌タンク反応器
52 インプット
54 非プロトン性化合物供給ライン
56 アウトガスストリーム
58 液体生成物ストリーム
60 熱交換器
62 液体生成物ストリーム
64 再循環ストリーム
Claims (25)
- 液体非プロトン性化合物を含む液体媒体とホルムアルデヒド源とを、固体触媒を含む不均一触媒の存在下で接触させる工程;および
ホルムアルデヒド源を少なくともある程度は環状アセタールに転化させる工程;
を含む環状アセタールの製造方法。 - 不均一触媒が酸性イオン交換物質を含む、請求項1に記載の製造方法。
- 不均一触媒が、固体担体上に固定されたルイス酸またはブレンステッド酸を含む、請求項1に記載の製造方法。
- 固体担体が無機物質である、請求項3に記載の製造方法。
- 固体担体が、ポリマーを含む有機物質である、請求項3に記載の製造方法。
- ホルムアルデヒド源がガス状ホルムアルデヒドを含む、請求項1に記載の製造方法。
- ホルムアルデヒド源が、パラホルムアルデヒド、ポリオキシメチレンホモポリマー、ポリオキシメチレンコポリマー、ホルムアルデヒド水溶液、またはこれらの混合物を含む、請求項1に記載の製造方法。
- ホルムアルデヒド源が、ホルムアルデヒドとトリオキサンとの混合物を含む、請求項1に記載の製造方法。
- 不均一触媒が、固体担体上に固定化された、有機溶融塩中に溶解したルイス酸またはブレンステッド酸を含む、請求項1に記載の製造方法。
- 製造方法が連続的な製造方法である、請求項1に記載の製造方法。
- ホルムアルデヒド源が、約30℃〜約200℃の、例えば約80℃〜約120℃の温度、および約0.15バール〜約5バールの、例えば約1バール〜約2バールの圧力にて環状アセタールに転化される、請求項1に記載の製造方法。
- 不均一触媒が固定床に収容され、ホルムアルデヒド源と液体媒体が固定床を、約5m/時〜約200m/時の、例えば約15m/時〜約100m/時の空塔液体速度で流れる、請求項1に記載の製造方法。
- ホルムアルデヒド源が、ホルムアルデヒド源と液体媒体とが供給される入口を有する反応器中にて環状アセタールに転化され、反応器が、反応器入口にて、約2kg/kg〜約30kg/kgの、例えば約5kg/kg〜約10kg/kgの液体-気体質量比を有する、請求項12に記載の製造方法。
- ホルムアルデヒド源が、撹拌タンク反応器中にて環状アセタールに転化され、このとき不均一触媒が該タンク反応器内で懸濁されている、請求項1に記載の製造方法。
- 非プロトン性化合物が極性非プロトン性化合物である、請求項1に記載の製造方法。
- 非プロトン性化合物が、1バールでの測定にて140℃以上の、さらに好ましくは160℃以上の、特に180℃以上の沸点を有する、請求項1〜15の一項以上に記載の製造方法。
- 非プロトン性化合物が、25℃での測定にて15超の、好ましくは20超の、さらに好ましくは25超の、そして特に30超の相対静的誘電率を有する、請求項1〜16の一項以上に記載の製造方法。
- ホルムアルデヒド源の30%超、好ましくは50%超、そして特に80%超が、反応進行時に1種以上の環状アセタールに転化される、請求項1〜17の一項以上に記載の製造方法。
- 非プロトン性化合物がイオウ含有有機化合物を含む、請求項1〜18の一項以上に記載の製造方法。
- 非プロトン性化合物がスルホランである、請求項1〜20の一項以上に記載の製造方法。
- 蒸留によって環状アセタールを液体媒体から分離する工程をさらに含む、請求項1〜23の一項以上に記載の製造方法。
- 環状アセタールからポリオキシメチレンを製造する工程をさらに含む、請求項1〜24の一項以上に記載の製造方法。
Applications Claiming Priority (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP11190567.5 | 2011-11-24 | ||
EP11190586 | 2011-11-24 | ||
EP11190574.1 | 2011-11-24 | ||
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WO2013076291A1 (en) * | 2011-11-24 | 2013-05-30 | Ticona Gmbh | Process for recycling polyacetals |
CN105218513B (zh) * | 2014-05-29 | 2017-12-12 | 中国石油大学(北京) | 一种合成三聚甲醛的方法 |
FR3024729B1 (fr) * | 2014-08-07 | 2018-09-07 | Arkema France | Procede de preparation du trioxane |
CN104478848B (zh) * | 2015-01-09 | 2016-06-29 | 开封龙宇化工有限公司 | 一种三聚甲醛脱轻塔分离器加碱水洗装置及使用方法 |
CN105175389B (zh) * | 2015-09-10 | 2018-09-07 | 中国石油大学(北京) | 一种利用酸和盐催化甲醛合成三聚甲醛的方法 |
CN107474037A (zh) * | 2017-07-03 | 2017-12-15 | 湖北三里枫香科技有限公司 | 一种多级固定床型三聚甲醛生产工艺方法及制备装置 |
FR3108909A1 (fr) * | 2020-04-07 | 2021-10-08 | Arkema Fance | Recyclage de polyacétal pour la production de polyoxyméthylènedialkyléthers |
WO2021213663A1 (de) * | 2020-04-23 | 2021-10-28 | Wacker Chemie Ag | Verfahren zur herstellung von aldehyden aus 1,3,5-trioxanen |
WO2022036163A1 (en) * | 2020-08-14 | 2022-02-17 | Celanese International Corporation | Use of biomass to produce polyoxymethylene copolymers |
CN112724118B (zh) * | 2020-12-08 | 2023-02-28 | 中国石油大学(华东) | 一种石油基塑料pom的生物质醇解方法 |
US20220380557A1 (en) * | 2021-05-20 | 2022-12-01 | Xerox Corporation | Polyoxymethylene microparticles and methods of production and use thereof |
US11643486B1 (en) | 2022-06-08 | 2023-05-09 | Arkema Inc. | Non-linear vinylidene fluoride copolymers |
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