CN1036576C - 从水合肼中除去杂质的方法 - Google Patents
从水合肼中除去杂质的方法 Download PDFInfo
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- CN1036576C CN1036576C CN94115836A CN94115836A CN1036576C CN 1036576 C CN1036576 C CN 1036576C CN 94115836 A CN94115836 A CN 94115836A CN 94115836 A CN94115836 A CN 94115836A CN 1036576 C CN1036576 C CN 1036576C
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- Prior art keywords
- hydrazine hydrate
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- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 title claims abstract description 35
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000012535 impurity Substances 0.000 title abstract description 8
- 239000003463 adsorbent Substances 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 238000004821 distillation Methods 0.000 claims abstract description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 230000007420 reactivation Effects 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 239000002594 sorbent Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- PFLUPZGCTVGDLV-UHFFFAOYSA-N acetone azine Chemical compound CC(C)=NN=C(C)C PFLUPZGCTVGDLV-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000007844 bleaching agent Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 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 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007516 brønsted-lowry acids Chemical class 0.000 description 1
- 150000007528 brønsted-lowry bases Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000011026 diafiltration Methods 0.000 description 1
- MYRTYDVEIRVNKP-UHFFFAOYSA-N divinylbenzene Substances C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000004476 plant protection product Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/16—Hydrazine; Salts thereof
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S203/00—Distillation: processes, separatory
- Y10S203/11—Batch distillation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
本发明涉及通过将水合肼减压蒸馏、使馏出物通过吸附剂并将蒸气冷凝而将有机杂质和溶解盐从水合肼及其水溶液中除去的方法。
Description
本发明涉及从水合肼及其水溶液中除去有机杂质和溶解盐的方法。
在目前通常用于合成水合肼的所谓酮法中，氨在水溶液中在酮如丙酮或甲基·乙基酮存在下与氧化剂如次氯酸钠或过氧化氢反应，生成相应的酮连氮(ketazine)，将其移出，然后水解。通常将该累积的肼溶液浓缩至肼含量为64％(重量)，这相当于100％水合肼。据其制备，用该方法制得的产物含少量有机次级成分和氯漂液用作氧化剂时的残留氯化物。在该水合肼中有机杂质的含量通常用TOC(总有机碳)值表示，对于酮法制备的商品品质而言，TOC在500和2000ppm之间。氯化物含量可能达到20ppm。
水合肼的典型应用在蒸汽循环的调节，发泡剂、植物保护剂和许多其它的化学制品的生产。对于诸如这些应用，常常需要进一步降低杂质含量。
已知水合肼中的类盐杂质可以通过吸附于离子交换树脂上来去除。为此，将水合肼用无机酸转化成相应的盐，然后使其与强酸性阳离子交换剂接触(US3458283)。用化学计算量的强碱洗脱来获得无盐产品。
该方法的缺点在于：在阳离子交换剂再生时额外需要酸和碱，以及产生盐的累积。
通过使水合肼依次以羟基形式通过强碱性阴离子交换剂和形式通过阳离子交换剂而使上述缺点减轻的变更方法在US3740436中进行了描述。
遗憾的是，上述这两个方法均无助于降低有机杂质的含量。
US4657751中描述了通过渗滤过聚合物吸附剂而从水合肼中除去有机杂质的方法。在该方法中，在水合肼中的TOC含量被降至200-350ppm的水平。但该方法不能降低氯化物的含量，因此还需要进行有花费的后处理步骤。
EP294100描述了基于蒸馏的在含盐辅助溶液存在下纯化水合肼的方法，用该方法，可将TOC含量降至50-230ppm的水平。关于该处理溶液的盐含量未提供任何数字。该方法的缺点是：一方面，涉及较多的设备，包括两个具有较高分离效率的蒸馏柱及相关的外围设备，另一方面，需要处理所用的辅助溶液。此外，关于能耗未提供精确的数字。然而，提供的那些数字表示它是值得考虑的。
因此，本发明提出的问题是提供能简便且廉价地使水合肼中的杂质含量降低但不存在任何已知方法的缺点的方法。
该问题已由本发明方法获得解决。
本发明涉及从水合肼及其水溶液中除去有机次级成分和溶解盐的方法，其特征在于：将水合肼或其水溶液在减压条件下蒸馏，使该水合肼蒸气通过吸附剂床，并在通过该床后将其冷凝，吸附剂可被任选地再生。
于是，如此纯化的水合肼可被进一步使用。
该水合肼最好在500-50000帕压力下蒸馏。相应于40至80℃的冷凝温度，5000-20000帕的压力特别有利。
在特别优选的实施方案中，蒸馏过程在不回流的情况下进行。在蒸馏过程中不回流，能耗最低。
所用的吸附剂最好选自在工作条件下具有足够的机械、热和化学稳定性的工业吸附剂。使用基于苯乙烯/二乙烯基苯的聚合物吸附树脂如Bayer LewatitOC 1062特别有利。
吸附树脂床最好是固定床的形式或者流化或部分流化床的形式。
吸附剂最好用在该水合肼生产过程中使用的液态或气态的物质来再生，特别是用丙酮和/或水来再生。
已惊人地发现，用本发明方法达到的50至150ppm的TOC含量比先有技术的低得多。约0.2ppm的氯化物含量也极低。水合肼可用本发明方法简便、经济且有效地来纯化。
本发明方法既可以分批实施，也可以连续实施。
本发明方法用下列实施例加以说明。
实施例1
将欲纯化的水合肼在真空设备中在约10000帕的压力下蒸馏。为此，使该气态水合肼通过带有烧结板的夹壁柱(长46cm，内径3cm)，所述柱的外套管用恒温控制的水加热至约70℃以防吸附树脂床中的水合肼蒸气冷凝。所用的吸附树脂是Bayer LewatitOC1062，为大孔的苯乙烯/二乙烯基苯共聚物，粒度范围为0.2至0.8mm，平均孔径110A，比表面积为500至600m2/g，该树脂预先已用水洗涤过。所述床的高度为约32cm。离开该柱顶端的水合肼蒸气在一倾斜的冷凝器中冷凝并被输送至接收器中。所用的水合肼是100％水合肼(2.11kg)，它通过用氯漂液在丙酮存在下氧化氨获得，并含有1250ppm TOC和9.2ppm氯化物。
得到总计2.08kg的TOC含量为130ppm的馏出液，相当于TOC值降低约90％。氯化物含量为0.2ppm。
实施例2
在实施例1所述的设备中及相同的条件下，在未再生或更换该吸附材料的情况下再蒸馏2.3kg水合肼(1700ppm TOc，10ppm氯化物)。在蒸馏过程中发现馏出物的T0c含量由150ppm增至900ppm，表明已达到该吸附剂的容量极限。
然后为再生，将该吸附树脂依次用水、丙酮和再次的水充分洗涤，最后将其干燥，在后来的更多的水合肼通过再生的吸附树脂床的蒸馏中，在实施例1所述的条件下获得含150ppm TOC和0.1ppm氯化物的馏出物。
应该懂得，本说明书和实施例说明但不限制本发明，而且本领域技术人员会提出本发明精神和范围内的其它实施方案。
Claims (3)
1.从水合肼及其水溶液中除去有机次级成分和溶解盐的方法，它包括在500-50000帕的低压下蒸馏水合肼或其水溶液，使该水合肼馏出物蒸气通过吸附剂床，所述的吸附剂床是一种基于苯乙烯/二乙烯基苯的树脂，通过该床后，将所述蒸气冷凝，并用丙酮、水或丙酮水溶液将该吸附剂再生。
2.权利要求1的方法，其中，所述蒸馏是在5000-20000帕压力下进行的。
3.权利要求1的方法，其中，蒸馏过程在无回流的情况下进行。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4329599.1 | 1993-09-02 | ||
| DE4329599A DE4329599C1 (de) | 1993-09-02 | 1993-09-02 | Verfahren zur Entfernung von Verunreinigungen aus Hydrazinhydrat |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1103104A CN1103104A (zh) | 1995-05-31 |
| CN1036576C true CN1036576C (zh) | 1997-12-03 |
Family
ID=6496639
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94115836A Expired - Fee Related CN1036576C (zh) | 1993-09-02 | 1994-09-02 | 从水合肼中除去杂质的方法 |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US5484511A (zh) |
| JP (1) | JP3529113B2 (zh) |
| CN (1) | CN1036576C (zh) |
| DE (1) | DE4329599C1 (zh) |
| FR (1) | FR2709481B1 (zh) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2778660B1 (fr) * | 1998-05-14 | 2000-06-23 | Atochem Elf Sa | Procede de preparation d'hydrate d'hydrazine |
| JP2009035467A (ja) * | 2007-08-06 | 2009-02-19 | Mitsubishi Gas Chem Co Inc | 金属微粉末製造に用いる水加ヒドラジンの製造方法 |
| KR101601271B1 (ko) | 2009-07-20 | 2016-03-08 | 주식회사 엘지화학 | 발광소자 봉지용 조성물, 발광 다이오드 및 액정표시장치 |
| KR101585270B1 (ko) | 2010-03-16 | 2016-01-13 | (주)엘지하우시스 | 점착 필름 및 터치패널 |
| CN105347319B (zh) * | 2015-11-17 | 2017-09-26 | 宜宾海丰和锐有限公司 | 一种去除酮连氮法水合肼有机杂质的方法 |
| CN109455683A (zh) * | 2018-11-23 | 2019-03-12 | 宜宾海丰和锐有限公司 | 一种纯化水合肼制备电子级水合肼的方法 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3458283A (en) * | 1966-05-26 | 1969-07-29 | Abcor Inc | Hydrazine purification |
| US3740436A (en) * | 1969-12-02 | 1973-06-19 | Olin Corp | Low impurity hydrazine |
| US4657751A (en) * | 1984-02-14 | 1987-04-14 | Atochem | Process for purifying aqueous hydrazine hydrate solutions |
| US4963232A (en) * | 1987-05-28 | 1990-10-16 | Mitsubishi Gas Chemical Company, Inc. | Process for producing a purified hydrazine hydrate |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2799631A (en) * | 1952-10-07 | 1957-07-16 | Fairmount Chem | Process of recovering hydrazine |
| NL230104A (zh) * | 1957-08-01 | |||
| GB1060065A (en) * | 1963-08-20 | 1967-02-22 | Whiffen & Sons Ltd | Improvements in or relating to hydrazine hydrate |
| US3652218A (en) * | 1969-12-02 | 1972-03-28 | Olin Corp | Low impurity hydrazine |
| EP0226686B1 (fr) * | 1985-12-20 | 1989-11-29 | Centre National D'etudes Spatiales | Procédé de préparation d'hydrazine anhydre à partir d'hydrate d'hydrazine |
| US4804442A (en) * | 1986-07-31 | 1989-02-14 | Olin Corporation | Ultrapure hydrazine production |
| US5035775A (en) * | 1986-07-31 | 1991-07-30 | Olin Corporation | Ultrapure hydrazine production |
| FR2655336B1 (fr) * | 1989-12-04 | 1993-05-21 | Atochem | Procede de vaporisation d'une solution d'hydrate d'hydrazine. |
-
1993
- 1993-09-02 DE DE4329599A patent/DE4329599C1/de not_active Expired - Lifetime
-
1994
- 1994-08-26 US US08/296,570 patent/US5484511A/en not_active Expired - Lifetime
- 1994-08-29 JP JP22609094A patent/JP3529113B2/ja not_active Expired - Fee Related
- 1994-09-01 FR FR9410520A patent/FR2709481B1/fr not_active Expired - Fee Related
- 1994-09-02 CN CN94115836A patent/CN1036576C/zh not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3458283A (en) * | 1966-05-26 | 1969-07-29 | Abcor Inc | Hydrazine purification |
| US3740436A (en) * | 1969-12-02 | 1973-06-19 | Olin Corp | Low impurity hydrazine |
| US4657751A (en) * | 1984-02-14 | 1987-04-14 | Atochem | Process for purifying aqueous hydrazine hydrate solutions |
| US4963232A (en) * | 1987-05-28 | 1990-10-16 | Mitsubishi Gas Chemical Company, Inc. | Process for producing a purified hydrazine hydrate |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3529113B2 (ja) | 2004-05-24 |
| CN1103104A (zh) | 1995-05-31 |
| DE4329599C1 (de) | 1995-03-16 |
| FR2709481B1 (fr) | 1997-06-13 |
| FR2709481A1 (fr) | 1995-03-10 |
| JPH0769610A (ja) | 1995-03-14 |
| US5484511A (en) | 1996-01-16 |
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