JP6570320B2 - ジエンの製造方法 - Google Patents
ジエンの製造方法 Download PDFInfo
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- JP6570320B2 JP6570320B2 JP2015110059A JP2015110059A JP6570320B2 JP 6570320 B2 JP6570320 B2 JP 6570320B2 JP 2015110059 A JP2015110059 A JP 2015110059A JP 2015110059 A JP2015110059 A JP 2015110059A JP 6570320 B2 JP6570320 B2 JP 6570320B2
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- Prior art keywords
- catalyst
- olefin
- diene
- group
- raw material
- Prior art date
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- 238000000066 reactive distillation Methods 0.000 claims description 33
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- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- NLDGJRWPPOSWLC-UHFFFAOYSA-N deca-1,9-diene Chemical compound C=CCCCCCCC=C NLDGJRWPPOSWLC-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- DKUYEPUUXLQPPX-UHFFFAOYSA-N dibismuth;molybdenum;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mo].[Mo].[Bi+3].[Bi+3] DKUYEPUUXLQPPX-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 230000000447 dimerizing effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910021432 inorganic complex Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
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- C07C5/23—Rearrangement of carbon-to-carbon unsaturated bonds
- C07C5/25—Migration of carbon-to-carbon double bonds
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- B01J23/681—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with arsenic, antimony or bismuth
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- B01J23/686—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten with molybdenum
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Description
rY(%)=mP/m01×100 (1)
mPは、工程2において得られる生成物におけるジエンの濃度である。m01は、工程2へ供される反応物(後述する仕掛油A)における内部オレフィンの濃度の合計である。
工程1で用いる原料は、分枝オレフィン及び直鎖オレフィンを含む。分枝オレフィンの炭素数は、例えば、4〜10であってよく、4〜6であってもよい。直鎖オレフィンの炭素数は、例えば、4〜10であってよく、4〜6であってもよい。分枝オレフィンの炭素数は、直鎖オレフィンの炭素数と同一であってもよい。分枝オレフィンの炭素数は、直鎖オレフィンの炭素数と異なっていてもよい。直鎖オレフィンの炭素数は、目的とするジエンの炭素数と同じであってよい。すなわち、直鎖オレフィンは、工程2の生成物として想定されるジエン中に存在する二重結合の一つを水素化した場合に得られるモノオレフィンであってよい。
工程2では、工程1で得られた内部オレフィンを第2の触媒(第2異性化触媒)によって異性化して末端オレフィンを生成すると共に、異性化によって生成した末端オレフィンを第1の触媒(脱水素触媒)によって酸化的に脱水素して、ジエンを生成する。工程2で用いる第2異性化触媒は、工程1で用いる上記第1異性化触媒とは異なる。工程2では、元々仕掛油Aに含まれていた末端オレフィンを酸化的に脱水素して、ジエンを生成してよい。
以下の手順で、第1の触媒(脱水素触媒)を調製した。
<原子比>
Mo:Bi:Co:Ni:Fe:Na:B:K:Si
=12:5:2.5:2.5:0.4:0.35:0.2:0.08:24
<合成例B1>
硝酸ニッケル6水和物10gに対し蒸留水600mlを添加し、硝酸ニッケル水溶液を調製した。次に、硝酸ニッケル水溶液を撹拌しながら、硝酸ニッケル水溶液にNaX型ゼオライト成型体50gを徐々に加えることにより、ゼオライトのイオン交換を行った。イオン交換後のゼオライトを、硝酸ニッケルが残らないように蒸留水で洗浄した後、180℃の乾燥機中で一晩乾燥させた。以上の工程により、第2の触媒(第2異性化触媒)である触媒B1を得た。触媒B1は、Niを含むNaX型ゼオライト(NiX)である。
硝酸銀30gに対して蒸留水600mlを添加し、硝酸銀水溶液を調製した。次に、硝酸銀水溶液を撹拌しながら、硝酸銀水溶液にNaX型ゼオライト成型体(東ソー社製、シリカアルミナ比=2.5)50gを徐々に加えることにより、ゼオライトのイオン交換を行った。イオン交換後のゼオライトを、硝酸銀が残らないように蒸留水で洗浄した後、180℃の乾燥機中で一晩乾燥させた。乾燥後、上記のイオン交換を繰り返した後、硝酸銀が残らないように蒸留水で洗浄した。洗浄後のゼオライトを180℃の乾燥機中で一晩乾燥させた。以上の工程により、第2の触媒である触媒B2を得た。触媒B2は、Agを含むNaX型ゼオライト(AgX)である。
<原料の調製>
以下の成分を含む実施例1の原料を調製した。原料中の分枝オレフィン(イソブテン)の質量含有率がC1であり、原料中の直鎖オレフィン(1−ブテン、シス−2−ブテン、及びトランス−2−ブテン)の質量含有率がC2であるとき、C2/C1は2.6であった。
イソブタン: 41.0質量%
イソブテン: 13.0質量%
1−ブテン: 12.0質量%
ノルマルブタン: 12.0質量%
シス−2−ブテン: 9.0質量%
トランス−2−ブテン: 13.0質量%
以下の通り、工程1の反応蒸留を行った。
実施例1の工程2では、触媒Aと触媒B1とを混合して、管型の反応器に充填した。反応器は、内径が14mmであり全長が60cmであるSUS製チューブであった。反応器へ充填した全触媒(触媒A及び触媒B1)の体積は17ccであった。全触媒における触媒Aの含有量は、90体積%に調整した。全触媒における触媒B1の含有量は、10体積%に調整した。全触媒におけるNiの含有量を、誘導結合プラズマ発光分光分析法(ICP発光分光分析法)により分析した。全触媒におけるNiの含有量を、下記表1に示す。
留分Aの流入速度: 2.16g/h
空気の流入速度: 60cc/min
水蒸気の流入速度: 1.5g/h
RY=(MP/M01)×100 (1a)
式1aに記載のMPは、生成ガス中のブタジエンの濃度(質量%)である。Mbとは、留分A中のシス−2−ブテンの濃度及びトランス−2−ブテンの濃度の合計である。
実施例1と同様に、実施例2の工程1を実施した。実施例1と同様の分析の結果、実施例2で得られた留分Aは実施例1の留分Aと同じであることが確認された。また、実施例2で得られた留分Bは実施例1の留分Bと同じであることが確認された。
実施例1と同様に、実施例3の工程1を実施した。実施例1と同様の分析の結果、実施例3で得られた留分Aは実施例1の留分Aと同じであることが確認された。また、実施例3で得られた留分Bは実施例1の留分Bと同じであることが確認された。
実施例1と同様に、比較例1の工程1を実施した。実施例1と同様の分析の結果、比較例1で得られた留分Aは実施例1の留分Aと同じであることが確認された。また、比較例1で得られた留分Bは実施例1の留分Bと同じであることが確認された。
Claims (12)
- 少なくとも分枝オレフィン及び直鎖オレフィンを含む原料から、前記分枝オレフィンを除去し、内部オレフィンを得る工程1と、
第1の触媒及び第2の触媒を用いた酸化的脱水素により、前記内部オレフィンからジエンを生成する工程2と、を備え、
前記第1の触媒が、ビスマス、モリブテン及び酸素を含む複合酸化物のみからなり、
前記第2の触媒が、シリカ及びアルミナからなる群より選択される少なくとも一種を含む、
ジエンの製造方法。 - 前記直鎖オレフィンの少なくとも一部が末端オレフィンであり、
前記工程1では、反応蒸留により、前記原料から前記分枝オレフィンを除去し、且つ、前記末端オレフィンを前記内部オレフィンに異性化する、
請求項1に記載のジエンの製造方法。 - 前記第2の触媒が、担体と、前記担体に担持された元素と、を有し、
前記担体が、シリカ及びアルミナからなる群より選択される少なくとも一種を含み、
前記担体に担持された元素が、周期表第10族元素、周期表第11族元素及びランタノイドからなる群より選択される少なくとも一種である、
請求項1又は2に記載のジエンの製造方法。 - 前記周期表第10族元素がNiであり、前記周期表第11族元素がCu、Ag又はAuであり、前記ランタノイドがLaである、
請求項3に記載のジエンの製造方法。 - 前記周期表第11族元素として、Agが前記担体に担持されている、
請求項3又は4に記載のジエンの製造方法。 - 前記第2の触媒が、シリカ及びアルミナを含み、
前記第2の触媒のアンモニア−昇温脱離法で測定される全酸量が、0.11mmol/g以下である、請求項1又は2に記載のジエンの製造方法。 - 前記第2の触媒が、シリカ及びアルミナを含み、
前記第2の触媒の、アンモニア−昇温脱離法で測定される全酸点の量A1に対する、600℃以上の温度範囲で測定される酸点の量A2の比A2/A1が、0.03以上である、請求項1、2及び6のいずれか一項に記載のジエンの製造方法。 - 前記第2の触媒が、シリカ及びアルミナを含み、
前記第2の触媒におけるAlに対するSiのモル比(Si/Al)が100以上である、請求項1、2、6及び7のいずれか一項に記載のジエンの製造方法。 - 前記原料中の前記分枝オレフィンの質量含有率がC1であり、前記原料中の前記直鎖オレフィンの質量含有率がC2であるとき、C2/C1が0.1〜5.0である、
請求項1〜8のいずれか一項に記載のジエンの製造方法。 - 前記直鎖オレフィンがブテンを含む、
請求項1〜9のいずれか一項に記載のジエンの製造方法。 - 前記原料が、重油留分の流動接触分解により得られ、
前記分枝オレフィン又は前記直鎖オレフィンの炭素数が4である、
請求項1〜10のいずれか一項に記載のジエンの製造方法。 - 前記原料が、ナフサの熱分解により得られ、
前記分枝オレフィン又は前記直鎖オレフィンの炭素数が4である、
請求項1〜10のいずれか一項に記載のジエンの製造方法。
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