CN1130613A - 储存和运输甲苯二胺的方法 - Google Patents
储存和运输甲苯二胺的方法 Download PDFInfo
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- CN1130613A CN1130613A CN95115666A CN95115666A CN1130613A CN 1130613 A CN1130613 A CN 1130613A CN 95115666 A CN95115666 A CN 95115666A CN 95115666 A CN95115666 A CN 95115666A CN 1130613 A CN1130613 A CN 1130613A
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- toluylenediamine
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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 26
- 238000000034 method Methods 0.000 title claims abstract description 20
- 230000008569 process Effects 0.000 title claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 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 19
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 11
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 9
- 230000009467 reduction Effects 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 9
- 239000006227 byproduct Substances 0.000 claims description 4
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 claims description 3
- 230000006837 decompression Effects 0.000 claims description 3
- ZMBQZWCDYKGVLW-UHFFFAOYSA-N 1-methylcyclohexa-3,5-diene-1,2-diamine Chemical compound CC1(N)C=CC=CC1N ZMBQZWCDYKGVLW-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000005194 fractionation Methods 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 238000002844 melting Methods 0.000 abstract description 7
- 230000008018 melting Effects 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 3
- 230000007774 longterm Effects 0.000 abstract description 2
- 238000004508 fractional distillation Methods 0.000 abstract 1
- 230000008014 freezing Effects 0.000 abstract 1
- 238000007710 freezing Methods 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 5
- 238000004821 distillation Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- FZZMTSNZRBFGGU-UHFFFAOYSA-N 2-chloro-7-fluoroquinazolin-4-amine Chemical compound FC1=CC=C2C(N)=NC(Cl)=NC2=C1 FZZMTSNZRBFGGU-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000004984 aromatic diamines Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000004998 toluenediamines Chemical class 0.000 description 2
- 125000005628 tolylene group Chemical group 0.000 description 2
- CNPURSDMOWDNOQ-UHFFFAOYSA-N 4-methoxy-7h-pyrrolo[2,3-d]pyrimidin-2-amine Chemical compound COC1=NC(N)=NC2=C1C=CN2 CNPURSDMOWDNOQ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
- C07C211/49—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring having at least two amino groups bound to the carbon skeleton
- C07C211/50—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring having at least two amino groups bound to the carbon skeleton with at least two amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/90—Stabilisation; Use of additives
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明涉及一种储存和运输、特别是长期储存或者在大容器(例如船运中的容器)中储存甲苯二胺的改进方法。本发明方法的改进之处在于可显著地降低由二硝基甲苯氢化产生的反应产物经分馏得到的无水甲苯二胺的熔点或凝固点。所述熔点降低是这样实现的：加入重量为甲苯二胺重量的5-15％的水并混合供储存和运输。向无水甲苯二胺中加入的水的量优选大约7-10％(重量)。
Description
本发明涉及制备能在液相状态下储存和运输的间甲苯二胺的方法。
甲苯二胺在工业上是通过将用混合酸法制得的二硝基甲苯氢化制备的。在该方法中，甲苯与硝酸在硫酸的存在下，在能够生成主要包含2，4-和2，6-二硝基甲苯异构体混合物(65-80％2，4-和20-35％2，6-)的反应产物的条件下接触。将二硝基甲苯回收，然后在氢化催化剂(例如镍催化剂)的存在下使其与氢接触。氢化完成后，将含有甲苯二胺的反应产物在减压和高温(360-390°F)下蒸馏，以除去所有轻馏分、水、甲苯胺、邻甲苯二胺和副产物。蒸馏之后，从大约390°F的塔底回收间甲苯二胺异构体混合物并送入产品冷却器中降温至大约230-250°F，并将压力升至大气压。所得间甲苯二胺异构体混合物被送去储存。
甲苯二胺是一种高熔点芳族二胺，其熔点约为105℃(220°F)。因为其熔点高，所以储存和运输变得困难，尤其是在大容器(例如船运中的大容器)中。如果将间甲苯二胺异构体混合物转变为固体，则芳族二胺在再熔化时可能由于传热差而发生降解。不仅有稳定性的问题，而且存在由于传热差而需要再熔化大的固体块的问题。人们已尝试过将甲苯二胺粒化供再熔用，但由于固体颗粒之间传热差，上述尝试仍然是不能接受的。于是，甲苯二胺异构体通常存放在小容器中，并用装备有能使甲苯二胺的温度保持在其熔点以上的装置的卡车或运输车辆运输。
在大容器如远洋货轮所用的容器中进行长期储存是极其困难的。与这种储存和/或运输有关的一个问题是缺少将储存的甲苯二胺保持在熔点温度之上所必需的装置。除了将甲苯二胺保持在其熔点温度之上所需的装置之外，还有在较长一段时间内将甲苯二胺的温度保持在其熔点以上所引起的操作能量成本问题。
本发明涉及生产间甲苯二胺异构体混合物的改进方法，所述混合物能储存和运输，特别是长期储存或在大容器(例如船用容器)中储存。基本过程包括：将甲苯二硝基化，得到含有2，4-和2，6-二硝基甲苯的反应产物；将含有2，4-和2，6-二硝基甲苯的反应产物氢化成2，4-和2，6-甲苯二胺；将氢化反应产物在减压和高温下蒸馏制得最终的基本上无水的富含2，4-和2，6-甲苯二胺的产物；将最终产物冷却，送去储存或装运。该方法的改进之处在于采用加入熔融态甲苯二胺的5-15％(重量)的水，混合并控制所得甲苯二胺-水混合物的温度使得甲苯二胺-水混合物的最终温度不超过沸点的方法明显地降低了富2，4-和2，6-甲苯二胺无水产物的熔点。最终产物可直接储存和运输。引入无水甲苯二胺中的水浓度优选大约7-10％(重量)。
本发明方法有几个显著的优点，它们包括：
能够明显降低间甲苯二胺的凝固点，方法是加入相对于间甲苯二胺为少量的水，以便储存和运输，特别是远洋货运。
能够降低由于长期储存或长途运输而将甲苯二胺保持液相状态的能量耗费；
能够将无水间甲苯二胺转变为适合于常规设备的较低熔点的间甲苯二胺；
能够在不引起变色、大量副产物生成和储存期的稳定性变化的情况下将间甲苯二胺转变为低熔点固体；
能够在低温下从间甲苯二胺中除去水，从而节省了高温蒸馏引起的能量耗费。
甲苯二胺通常是通过二硝基甲苯的氢化来生产的，二硝基甲苯又是通过用混合酸将甲苯硝化来生产的。将二硝基甲苯氢化得到的反应产物在真空下分馏，以除去轻(高挥发性)物质(例如去氨基化产物)、氨和残留水，它们是在反应中产生的。蒸馏除去反应产物中的副产物和残留水，从而生成主要由2，4-和2，6-甲苯二胺组成的、含有极少量杂质的无水间甲苯二胺。从蒸馏塔底回收的间甲苯二胺异构体混合物的温度一般为大约380-400°F。
我们发现，通过将间甲苯二胺的熔点由大约200-250°F降低可以在对储存中的产物不产生负面影响的情况下使得间甲苯二胺适合于长期储存和船运。熔点降低是通过将热的软化水、去离子水或蒸馏水在加压下加到200-250°F的间甲苯二胺中而实现的。混入可溶于甲苯二胺的水，能容易地将该混合物的凝固点降至大约145-165°F。本发明方法的显著优点之一是如果引入热(160-190°F)水，则仅将间甲苯二胺混合物的温度从220-250°F降至大约210-235°F。如果水是80-90°F，则降至大约200-225°F。在上述两种情况下，所得最终温度水平可较长时间地提供足够的内部热量，从而可不需要外部热源。主要的一点是间甲苯异构体混合物的最终温度应在泡点(即沸腾开始时的温度)以下。对于含有大约5％水的甲苯二胺混合物，温度大约为256℃而当甲苯二胺混合物含有大约10％水时，温度则降至大约242°F。然而，该最终温度仍远高于间甲苯二胺混合物的凝固点，从而为长期保持液相状态提供了大量的残留热。
可以使水浓度大于大约15％，以便将甲苯二胺的凝固点降至较低的温度，尽管这种凝固点的降低一般较小，不会影响能效率。由于水的热容高，所以水不仅降低了甲苯二胺的温度，随后蒸馏除去水所引起的能耗也增加。
实施例1
凝固点的测定
为测定水对于无水甲苯二胺的凝固点和稳定性的影响，我们在水存在下进行了一系列试验。这里所测定的凝固点是指结晶开始时的温度，不是指全部甲苯二胺成为固体时的温度。
将熔融态甲苯与不同量的水混合得到不同浓度的混合物，并将其缓慢冷却。随时间测取物料的温度。当温度恒定大约15分钟时，记录凝固点。下表给出了结果。
凝固点
温度(°F) 170 165 160 150
水(重量百分数) 3.4 4.9 5.6 10.1
甲苯二胺一溶质混合物可在185°F稳定30天，不发生相分离。
Claims (6)
1.制备可供装在大容器内储存和/或运输的间甲苯二胺的改进方法，所述改进包括：
向基本上无水的间甲苯二胺异构体混合物中加入5-15％(重量)的软化水，所述混合物是通过将二硝基甲苯氢化产生的反应产物于至少200°F分馏得到的；将水混合，以显著降低所述基本上无水的间甲苯二胺异构体混合物的凝固点；调节温度，使产物的最终温度在泡点以下。
2.权利要求1的方法，其中水的加入量为约7-10％(重量)。
3.权利要求2的方法，其中当加入水时，基本上无水的间甲苯二胺异构体混合物的温度是220-250°F。
4.权利要求3的方法，其中在向基本上无水的间甲苯二胺异构体混合物中加水时，水的温度为80-190°F。
5.权利要求4的方法，其中间甲苯二胺混合物包含大约65-80％2，4-甲苯二胺和大约20-35％2，6-甲苯二胺。
6.一种生产间甲苯二胺混合物的方法，其中在硫酸存在下，在能够生成主要包含2，4-和2，6-二硝基甲苯异构体混合物的反应产物的条件下，使甲苯与硝酸接触，回收二硝基甲苯，然后在氢化催化剂的存在下与氢气接触，将所得含有2，4-和2，6-甲苯二胺的反应产物在减压和高温条件下在塔中蒸馏，以除去任何轻质馏分、水、甲苯胺、邻甲苯二胺和副产物，从塔底回收基本上无水的间甲苯二胺异构体混合物，送入产品冷却器，在冷却器中温度被降至大约200-250°F，压力被升至至少大气压力，在将所得的间甲苯二胺异构体混合物制成能供储存和/或运输的最终间甲苯二胺异构体混合物方面的改进包括：
向温度至少为220°F的所述基本上无水的间甲苯二胺异构体混合物中加入5-15％(重量)的去离子水；
将水与所述基本上无水的间甲苯二胺异构体混合物混合，以及
调节最终温度，使得产品的温度在泡点温度以下。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US318,324 | 1981-11-05 | ||
| US318324 | 1994-10-05 | ||
| US08/318,324 US5449832A (en) | 1994-10-05 | 1994-10-05 | Process for storage and transport of toluenediamine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1130613A true CN1130613A (zh) | 1996-09-11 |
| CN1044806C CN1044806C (zh) | 1999-08-25 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95115666A Expired - Lifetime CN1044806C (zh) | 1994-10-05 | 1995-09-29 | 储存和运输甲苯二胺的方法 |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US5449832A (zh) |
| EP (2) | EP0705814B1 (zh) |
| JP (1) | JP2853614B2 (zh) |
| KR (1) | KR100191756B1 (zh) |
| CN (1) | CN1044806C (zh) |
| BR (1) | BR9504221A (zh) |
| CA (1) | CA2159441C (zh) |
| DE (2) | DE69506823T2 (zh) |
| MX (1) | MX185061B (zh) |
| TW (1) | TW315363B (zh) |
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| US5449832A (en) * | 1994-10-05 | 1995-09-12 | Air Products And Chemicals, Inc. | Process for storage and transport of toluenediamine |
| DE19528781A1 (de) * | 1995-08-04 | 1997-02-06 | Bayer Ag | Verfahren zur Herstellung von Toluylendiisocyanat, spezielle Gemische aus Toluylendiamin und Wasser und deren Verwendung zur Herstellung von Toluylendiisocyanat |
| US5714634A (en) * | 1996-06-25 | 1998-02-03 | Air Products And Chemicals, Inc. | Process for storage and transport of toluenediamine |
| US5693862A (en) * | 1996-12-18 | 1997-12-02 | Arco Chemical Technology, L.P. | Process for transport of toluenediamine |
| US6004482A (en) * | 1997-12-24 | 1999-12-21 | Bayer Corporation | Stable aromatic amine composition, and a process for preparing color stable aromatic amines |
| JP2002306518A (ja) * | 2000-12-21 | 2002-10-22 | Yuichi Mori | 体内留置用具 |
| US8524047B2 (en) * | 2007-11-27 | 2013-09-03 | Mitsui Chemicals Inc. | Method of dehydrating tolylenediamine and dehydrator |
| WO2014123226A1 (ja) * | 2013-02-08 | 2014-08-14 | 味の素株式会社 | １，５－ペンタジアミン又はその塩の保存方法、変色防止方法、および、容器入り１，５－ペンタジアミン又はその塩 |
| HUE054424T2 (hu) | 2017-01-27 | 2021-09-28 | Covestro Llc | Eljárás stabil toluol-diamin származék/víz elegyek elõállítására, kapcsolódó készítmények, és az elegyek üzemanyagként történõ alkalmazásának eljárásai |
| WO2021233887A1 (de) | 2020-05-19 | 2021-11-25 | Covestro Deutschland Ag | Verfahren zur aufarbeitung von toluylendiamin-gemischen |
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| DE2435818C3 (de) * | 1974-07-25 | 1982-02-25 | Bayer Ag, 5090 Leverkusen | Verfahren zur Herstellung aromatischer Diamine |
| US4239913A (en) * | 1977-10-25 | 1980-12-16 | Kabushiki Kaisha Veno Seiyaku Oyo Kenkyujo | Process for preparing 2-hydroxynaphthalenecarboxylic acids |
| US4585573A (en) * | 1981-12-09 | 1986-04-29 | Hitachi, Ltd. | Heat storage material and process for producing the same |
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| DE3513356A1 (de) * | 1985-04-15 | 1986-10-16 | Henkel KGaA, 4000 Düsseldorf | Neue ester ungesaettigter polymerisierbarer carbonsaeuren, daraus gewonnene oelloesliche homo- und copolymere, verfahren zu ihrer herstellung und ihre verwendung als stockpunktserniedriger |
| JPH062718B2 (ja) * | 1985-08-20 | 1994-01-12 | 三井東圧化学株式会社 | トリレンジアミンの連続的製造法 |
| US4906797A (en) * | 1988-09-12 | 1990-03-06 | The B.F. Goodrich Company | Liquid dicyclopentadiene feedstock for bulk polymerization |
| US5097903A (en) * | 1989-09-22 | 1992-03-24 | Jack C. Sloan | Method for recovering intractable petroleum from subterranean formations |
| US5449832A (en) * | 1994-10-05 | 1995-09-12 | Air Products And Chemicals, Inc. | Process for storage and transport of toluenediamine |
| US5714634A (en) * | 1996-06-25 | 1998-02-03 | Air Products And Chemicals, Inc. | Process for storage and transport of toluenediamine |
-
1994
- 1994-10-05 US US08/318,324 patent/US5449832A/en not_active Expired - Lifetime
-
1995
- 1995-06-26 TW TW84106538A patent/TW315363B/zh not_active IP Right Cessation
- 1995-09-28 CA CA002159441A patent/CA2159441C/en not_active Expired - Lifetime
- 1995-09-29 BR BR9504221A patent/BR9504221A/pt not_active IP Right Cessation
- 1995-09-29 DE DE69506823T patent/DE69506823T2/de not_active Expired - Lifetime
- 1995-09-29 CN CN95115666A patent/CN1044806C/zh not_active Expired - Lifetime
- 1995-09-29 EP EP95115420A patent/EP0705814B1/en not_active Expired - Lifetime
- 1995-09-29 DE DE69516187T patent/DE69516187T2/de not_active Expired - Lifetime
- 1995-09-29 EP EP98109981A patent/EP0866054B1/en not_active Expired - Lifetime
- 1995-10-04 JP JP7257297A patent/JP2853614B2/ja not_active Expired - Lifetime
- 1995-10-04 KR KR1019950033834A patent/KR100191756B1/ko not_active IP Right Cessation
- 1995-10-04 MX MX9504206A patent/MX185061B/es unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100338024C (zh) * | 2005-09-07 | 2007-09-19 | 无锡殷达尼龙有限公司 | 二元胺系列产品制成片胺的工艺方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0705814A1 (en) | 1996-04-10 |
| DE69506823D1 (de) | 1999-02-04 |
| MX185061B (es) | 1997-06-19 |
| CN1044806C (zh) | 1999-08-25 |
| EP0866054B1 (en) | 2000-04-05 |
| KR100191756B1 (ko) | 1999-06-15 |
| JP2853614B2 (ja) | 1999-02-03 |
| BR9504221A (pt) | 1996-08-06 |
| US5449832A (en) | 1995-09-12 |
| DE69516187T2 (de) | 2000-08-17 |
| EP0705814B1 (en) | 1998-12-23 |
| JPH08119910A (ja) | 1996-05-14 |
| DE69516187D1 (de) | 2000-05-11 |
| EP0866054A3 (en) | 1998-10-21 |
| DE69506823T2 (de) | 1999-05-20 |
| KR960014090A (ko) | 1996-05-22 |
| EP0866054A2 (en) | 1998-09-23 |
| TW315363B (zh) | 1997-09-11 |
| CA2159441C (en) | 1998-08-18 |
| CA2159441A1 (en) | 1996-04-06 |
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