JP2017523125A - トルエンジアミンの製造方法 - Google Patents
トルエンジアミンの製造方法 Download PDFInfo
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- JP2017523125A JP2017523125A JP2016567521A JP2016567521A JP2017523125A JP 2017523125 A JP2017523125 A JP 2017523125A JP 2016567521 A JP2016567521 A JP 2016567521A JP 2016567521 A JP2016567521 A JP 2016567521A JP 2017523125 A JP2017523125 A JP 2017523125A
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- dinitrotoluene
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- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- DYSXLQBUUOPLBB-UHFFFAOYSA-N 2,3-dinitrotoluene Chemical compound CC1=CC=CC([N+]([O-])=O)=C1[N+]([O-])=O DYSXLQBUUOPLBB-UHFFFAOYSA-N 0.000 claims abstract description 97
- 239000003054 catalyst Substances 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 47
- 230000008569 process Effects 0.000 claims abstract description 25
- 239000007858 starting material Substances 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims description 65
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 239000008346 aqueous phase Substances 0.000 claims description 29
- 238000002156 mixing Methods 0.000 claims description 29
- 239000012071 phase Substances 0.000 claims description 26
- 238000005191 phase separation Methods 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 17
- 238000005984 hydrogenation reaction Methods 0.000 claims description 16
- 238000009297 electrocoagulation Methods 0.000 claims description 14
- 239000011541 reaction mixture Substances 0.000 claims description 14
- 238000004140 cleaning Methods 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000012043 crude product Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 238000005054 agglomeration Methods 0.000 claims 1
- 230000002776 aggregation Effects 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 67
- 238000006243 chemical reaction Methods 0.000 description 47
- 239000002253 acid Substances 0.000 description 28
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 26
- 229910017604 nitric acid Inorganic materials 0.000 description 26
- 239000012074 organic phase Substances 0.000 description 17
- ZPTVNYMJQHSSEA-UHFFFAOYSA-N 4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1 ZPTVNYMJQHSSEA-UHFFFAOYSA-N 0.000 description 14
- 238000006396 nitration reaction Methods 0.000 description 12
- 239000002699 waste material Substances 0.000 description 12
- 238000000605 extraction Methods 0.000 description 10
- 230000003068 static effect Effects 0.000 description 9
- 230000007935 neutral effect Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000002351 wastewater Substances 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910000564 Raney nickel Inorganic materials 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 4
- 238000010626 work up procedure Methods 0.000 description 4
- GAKLFAZBKQGUBO-UHFFFAOYSA-N 2-methyl-3-nitrophenol Chemical compound CC1=C(O)C=CC=C1[N+]([O-])=O GAKLFAZBKQGUBO-UHFFFAOYSA-N 0.000 description 3
- SLAMLWHELXOEJZ-UHFFFAOYSA-N 2-nitrobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1[N+]([O-])=O SLAMLWHELXOEJZ-UHFFFAOYSA-N 0.000 description 3
- 239000007868 Raney catalyst Substances 0.000 description 3
- -1 amine compound Chemical class 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000002828 nitro derivatives Chemical class 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000009295 crossflow filtration Methods 0.000 description 2
- VMMLSJNPNVTYMN-UHFFFAOYSA-N dinitromethylbenzene Chemical class [O-][N+](=O)C([N+]([O-])=O)C1=CC=CC=C1 VMMLSJNPNVTYMN-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 201000006747 infectious mononucleosis Diseases 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 102100034095 5'(3')-deoxyribonucleotidase, cytosolic type Human genes 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 101000591192 Homo sapiens 5'(3')-deoxyribonucleotidase, cytosolic type Proteins 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000010936 aqueous wash Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- VLZLOWPYUQHHCG-UHFFFAOYSA-N nitromethylbenzene Chemical compound [O-][N+](=O)CC1=CC=CC=C1 VLZLOWPYUQHHCG-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000004998 toluenediamines Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/08—Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/04—Breaking emulsions
- B01D17/045—Breaking emulsions with coalescers
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Abstract
Description
・反応区画が、反応中に常に水素で飽和されており、
・芳香族ポリニトロ化合物が、反応系に存在する触媒(「触媒充填」)に対して特定の重量比を維持して系に充填され、かつ、
・充填された芳香族ポリニトロ化合物の濃度が、反応区画において所定の限界値を超えない
場合に、選択性、触媒の効果寿命および生産性の点で特に有効である。
(i)トルエンをジニトロ化してジニトロトルエンを形成する工程;
(ii)(ii.1)水相を除去する工程、および、それに続く(ii.2)少なくとも一つの水性洗浄媒体により、工程(ii.1)で得られたジニトロトルエン相を少なくとも一段階洗浄する工程であって、各洗浄段階は、ジニトロトルエン相と水性洗浄媒体とを混合し、次いで水性洗浄媒体を除去することを含む、工程(i)で得られた粗生成物を後処理する工程;
(iii)工程(ii)で使用される水性洗浄媒体の除去の前または後に行う、電位を印加してジニトロトルエンを処理する工程;
(iv)電位を印加することにより処理されたジニトロトルエン出発物質を水素化する工程。
(i.1)有機相に対する水相の質量比を>2、好ましくは>3、特に好ましくは>3.5に維持し、かつ、有機相を水性相に分散させて、トルエンを混酸(nitrating acid)と反応させてモノニトロトルエンを形成し、モノニトロトルエン含有反応混合物を得;
(i.2)モノニトロトルエン含有反応混合物を、モノニトロトルエン含有有機相と硫酸含有水相とに分離し;
(i.3)有機相に対する水性相の質量比を>1.5、好ましくは>3、特に好ましくは>3.5に維持し、かつ、有機相を水性相に分散させて、モノニトロトルエン含有有機相と混酸とを反応させてジニトロトルエン含有反応混合物を得;
(i.4)ジニトロトルエン含有反応混合物を、ジニトロトルエン含有有機相と硫酸含有水相とに分離し;
トルエン1モル当たり合計2.06モル未満の硝酸が使用される。
DNTの水素化のために連続的に操作される反応器において、研究用グレードのDNTを、Niベース触媒の存在下で、反応器の容量に対して7質量%の割合で、24バール(絶対)の圧力および1.8時間の滞留時間で水素化した。反応を維持するために、平均して15時間ごとに触媒を添加する必要があった。
図1に示す設備を起動した(図に示すように、撹拌機を備えたミキサーの代わりに静的ミキサーを使用したことを除く)。ここで、DNT(1)1トン当たり50kgの水(2)を、静的ミキサーMで混合した。得られたDNT−水混合物を、電気凝集装置Eで400Vで1秒間処理し、得られた処理混合物を、分離装置Sにより、水(3)から分離した。実施例1において使用したものと同じ反応器、同じ圧力、触媒の種類、および触媒濃度の条件下、同じ滞留時間で、DNT(4)を水素化した。新鮮な触媒の添加は、平均して31時間ごとにのみ必要であった。
Claims (13)
- 電位を印加することにより処理されたジニトロトルエン出発物質を、触媒の存在下で水素化することによる、トルエンジアミンの製造方法。
- 前記電位を印加することにより処理されたジニトロトルエン出発物質が、90質量%〜99.5質量%のジニトロトルエン、0.5質量%〜10質量%の水を含有する、請求項1記載の方法。
- 50ボルト〜1000ボルトの直流電圧を、ジニトロトルエン出発物質に印加する電位として、1mm〜100mmの電極間隔を有するセル内で0.01秒〜100秒間使用する、請求項1または2に記載の方法。
- 以下の工程を含む、請求項1〜3のいずれか一項に記載の方法:
(i)トルエンをジニトロ化してジニトロトルエンを形成する工程;
(ii)(ii.1)水相を除去する工程、および、それに続く(ii.2)少なくとも一つの水性洗浄媒体により、工程(ii.1)で得られたジニトロトルエン相を少なくとも一段階洗浄する工程であって、各洗浄段階は、ジニトロトルエン相と水性洗浄媒体とを混合し、次いで水性洗浄媒体を除去することを含む、工程(i)で得られた粗生成物を後処理する工程;
(iii)工程(ii)で使用される水性洗浄媒体の除去の前または後に行う、電位を印加してジニトロトルエンを処理する工程;
(iv)電位を印加することにより処理されたジニトロトルエン出発物質を水素化する工程。 - 工程(ii.2)における洗浄が2〜4段階を含み、最終段階以外の少なくとも1段階の水性洗浄媒体が塩基を含有する、請求項4に記載の方法。
- 工程(ii.2)における洗浄が2〜6段階を含み、水性洗浄媒体がいずれかの段階でも塩基を含有しない、請求項4に記載の方法。
- 工程(iii)における処理が、工程(ii.2)における最後の洗浄段階中または後に、電位を印加することにより行われる、請求項4〜6のいずれか一項に記載の方法。
- 工程(ii.2)の最後の洗浄段階におけるジニトロトルエンと水性洗浄媒体との混合の後に、工程(iii)における電位の印加によるジニトロトルエンの処理のための電気凝集装置が続く、請求項7に記載の方法。
- 工程(iii)における電位の印加によるジニトロトルエンの処理のための電気凝集装置が、工程(ii.2)の最後の洗浄段階におけるジニトロトルエン相と水性洗浄媒体との混合に組み込まれる、請求項7に記載の方法。
- 工程(ii.2)の最後の洗浄段階における水性洗浄媒体の除去が、洗浄されたジニトロトルエン相を取り込むための下流の沈降槽を有する相分離装置内で行われ、前記沈降槽または前記沈降槽と前記相分離装置とを接続する管に、工程(iii)における電位の印加による処理のための電気凝集装置が設けられている、請求項7に記載の方法。
- 洗浄されたジニトロトルエン相に加えて水を沈降槽に供給し、沈降する水相を沈降槽から連続的または不連続的に除去する、請求項10に記載の方法。
- 水相を不連続的に除去する、請求項11に記載の方法。
- 前記触媒が、Pt、Pd、Rh、Ru、Ni、Co、Cuまたはこれらの混合物を含む触媒から選択され、前記触媒が、水素化における反応混合物の全質量に対して0.01質量%〜20質量%の濃度で使用される、請求項1〜12のいずれか一項に記載の方法。
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