CN112093783A - Hydrazine hydrate purification process - Google Patents
Hydrazine hydrate purification process Download PDFInfo
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- CN112093783A CN112093783A CN202011055474.8A CN202011055474A CN112093783A CN 112093783 A CN112093783 A CN 112093783A CN 202011055474 A CN202011055474 A CN 202011055474A CN 112093783 A CN112093783 A CN 112093783A
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- hydrazine hydrate
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- temperature
- rectification
- distillation
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- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 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 78
- 238000000746 purification Methods 0.000 title claims description 13
- 238000004821 distillation Methods 0.000 claims abstract description 45
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 36
- 238000001179 sorption measurement Methods 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000012808 vapor phase Substances 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 239000003463 adsorbent Substances 0.000 claims description 4
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 claims description 2
- PFLUPZGCTVGDLV-UHFFFAOYSA-N acetone azine Chemical compound CC(C)=NN=C(C)C PFLUPZGCTVGDLV-UHFFFAOYSA-N 0.000 claims 1
- 239000012535 impurity Substances 0.000 abstract description 11
- 239000012141 concentrate Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 23
- 239000000047 product Substances 0.000 description 19
- 239000007788 liquid Substances 0.000 description 9
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 8
- 235000011121 sodium hydroxide Nutrition 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 229910017053 inorganic salt Inorganic materials 0.000 description 4
- 238000007599 discharging Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- -1 Na+<1ppm Chemical class 0.000 description 1
- TWLNVQNCJFIEEU-UHFFFAOYSA-N [N].CC(C)=O Chemical compound [N].CC(C)=O TWLNVQNCJFIEEU-UHFFFAOYSA-N 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011026 diafiltration Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- DKUAQOOKKHISJC-UHFFFAOYSA-N hydrazine;propan-2-one Chemical compound NN.CC(C)=O DKUAQOOKKHISJC-UHFFFAOYSA-N 0.000 description 1
- SWUZKHDVGQWXQT-UHFFFAOYSA-N hydrazine;propan-2-one;hydrate Chemical compound O.NN.CC(C)=O SWUZKHDVGQWXQT-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
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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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A process for purifying hydrazine hydrate, which comprises the following steps: 1) adding the crude hydrazine hydrate product as a raw material into a distillation tower, then adding a sodium hydroxide solution into the distillation tower, and controlling the temperature of a tower kettle of the distillation tower to be 117-125 ℃ and the pressure to be 0.01-0.02 MPa; 2) and (2) adsorbing a vapor phase discharged from the top of the distillation tower in the step 1) by an adsorption bed, and then, introducing the vapor phase into a rectification tower for rectification, controlling the temperature of the top of the rectification tower to be 98-100 ℃, the temperature of the bottom of the rectification tower to be 115-123 ℃, and obtaining a 100% hydrazine hydrate product at the bottom of the rectification tower. The invention can simply, conveniently and continuously concentrate and purify the crude hydrazine hydrate product, and simultaneously reduce the impurity content in the hydrazine hydrate to obtain the 100 percent purity hydrazine hydrate product.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to a hydrazine hydrate purification process.
Background
In the current acetone-hydrazine-hydrate process, ammonia is reacted in an aqueous solution with an oxidant, sodium hypochlorite, in the presence of excess acetone to produce relatively stable acetone-hydrazine, which is removed and then hydrolyzed to produce a hydrazine hydrate solution, which is typically concentrated to 80% hydrazine hydrate concentration and formulated to 40%, 55%, 64%, etc. for sale as commercial products. The hydrazine hydrate prepared by the acetone-nitrogen method contains a small amount of organic components due to the addition of acetone, and free chlorine in sodium hypochlorite and a byproduct sodium chloride thereof as well as alkaline earth metal added in the refining and purifying process also remain in the hydrazine hydrate in a small amount. With the technical progress and the further expansion of the application of hydrazine hydrate, part of novel high-added-value industries in downstream enterprises of hydrazine hydrate need to use high-purity hydrazine hydrate with the concentration of 100 percent due to the special production requirement of products, so that the prepared hydrazine hydrate needs to be further purified and concentrated.
The prior art discloses a method for removing hydrazine hydrate organic impurities by a ketone-hydrazine hydrate method, for example, Chinese patent CN201510786973, which adds alkaline earth metal hydroxide into a hydrazine hydrate solution to destroy the chemical structure and properties of the organic impurities and remove high-boiling-point organic impurities and nonvolatile impurities deposited at the bottom of an evaporator.
Patent US3740436 reduces the content of inorganic salt ions in hydrazine hydrate or hydrazine by passing a solution of hydrazine hydrate or pure hydrazine sequentially through a strongly basic anion exchanger and a cation exchanger, but does not mention a treatment method of trace organic matters, and does not mention a purification process of 100% hydrazine hydrate.
US467751 describes a process for the removal of organic impurities from water and hydrazine by diafiltration over a polymeric adsorbent. In this process, the TOC content in hydrazine hydrate is reduced to a level of 200-350 ppm. However, the method is only used for processing hydrazine hydrate solution or pure hydrazine product, and does not refer to a specific continuous purification process for producing 100 percent hydrazine hydrate.
Therefore, how to simply, conveniently and efficiently purify and concentrate hydrazine hydrate with high purity and concentration of 100 percent to meet the requirements of a part of novel high-added-value industries of hydrazine hydrate downstream enterprises is a problem to be solved by technical personnel in the field.
Disclosure of Invention
The invention aims to provide a hydrazine hydrate purification process aiming at the defects of the prior art, which can reduce the impurity content in hydrazine hydrate while simply and continuously concentrating and purifying a crude hydrazine hydrate product to obtain high-purity hydrazine hydrate with the concentration of 100%.
The technical scheme of the invention is as follows: a process for purifying hydrazine hydrate, which comprises the following steps:
1) adding the crude hydrazine hydrate product as a raw material into a distillation tower, then adding a sodium hydroxide solution into the distillation tower, and controlling the temperature of a tower kettle of the distillation tower to be 117-125 ℃ and the pressure to be 0.01-0.02 MPa;
2) and (2) adsorbing a vapor phase discharged from the top of the distillation tower in the step 1) by an adsorption bed, and then, introducing the vapor phase into a rectification tower for rectification, controlling the temperature of the top of the rectification tower to be 98-100 ℃, the temperature of the bottom of the rectification tower to be 115-123 ℃, and obtaining a 100% hydrazine hydrate product at the bottom of the rectification tower.
Preferably, the crude hydrazine hydrate in the step 1) is a hydrazine hydrate solution prepared by adopting an acetonitril method process, the concentration is 30-65 wt%, wherein the acetone content is less than 1 wt%, and the TOC value is 7000-15000 ppm.
Preferably, the concentration of the sodium hydroxide solution in the step 1) is 10-32 wt%, and the adding amount is 0.1-0.2% of the mass of the crude hydrazine hydrate.
Preferably, the concentration of the sodium hydroxide solution is 25 to 32 wt%.
Preferably, the temperature of the distillation column in the step 1) is 119-122 ℃, and the temperature of the top of the distillation column is 110-120 ℃.
Preferably, the adsorbent used in the adsorption bed in step 2) is a styrene/divinylbenzene polymeric adsorption resin.
Preferably, the adsorption temperature of the adsorption bed is 90-120 ℃.
Further, the condensate generated by the adsorption bed is refluxed to the distillation tower in the step 1).
Further, after the vapor phase discharged from the top of the rectifying tower in the step 2) is condensed, part of the vapor phase is taken as reflux liquid to reflux to the rectifying tower, and the temperature of the tower kettle is 120-123 ℃.
Preferably, the pressure of the bottom of the rectifying tower in the step 2) is 0.015-0.018 Mpa.
Adopt above-mentioned technical scheme to have following beneficial effect:
1. the invention adds a certain amount of sodium hydroxide solution into a distillation tower, controls the temperature of a tower kettle of the distillation tower at 117-. If other bases are used, e.g. KOH, Ca (OH)2While equivalent effects can be achieved with alkaline solutions, K+、Ca2+The ions and high-boiling residues formed at the bottom are recycled to a front-end system, so that impurity ions are introduced into the brine, and the brine cannot be used for ionic membrane caustic soda. The temperature of the tower kettle is controlled to be 117-125 ℃ and the pressure is 0.01-0.02MPa, so that the hydrazine hydrate solution can be ensured to be in a boiling state all the time, the hydrazine hydrate solution is distilled out of the distillation tower in a gas phase mode as far as possible, the yield of the hydrazine hydrate is ensured, and if the temperature is too high, part of high-boiling substances enter the rear end along with the gas phase, so that the product quality is influenced. And (3) adsorbing the vapor phase discharged from the top of the distillation tower by an adsorption bed, removing trace inorganic salt included in the vapor phase, reducing inorganic salt ions in the vapor phase entering the rectification tower to a trace level, separating small molecular organic matters and water vapor in the vapor phase entering the rectification tower from the top of the tower, obtaining a hydrazine hydrate product with the purity of 100% at the bottom of the tower, collecting the hydrazine hydrate product in the form of liquid at the bottom of the tower, and directly selling the hydrazine hydrate product as a commodity.
2. The adsorption temperature of the adsorption bed is controlled to be 90-120 ℃, and on the basis of ensuring the adsorption efficiency, the heat of a front-stage distillation tower can be utilized in the rectifying tower as much as possible, so that the energy consumption of hydrazine hydrate purification is reduced.
3. The condensate generated by the adsorption bed of the invention flows back to the distillation tower, thereby avoiding the impurity exceeding standard caused by entrainment of mist, ensuring the purity of the bottom liquid of the distillation tower and further ensuring the quality of hydrazine hydrate products.
4. The vapor phase discharged from the top of the distillation tower is condensed, and then partially flows back to the distillation tower, the temperature at the top of the tower is controlled at 100 ℃, so that the distillation of excessive hydrazine hydrate along with water is avoided, and the product yield is improved.
Proved by experiments of the applicant, the hydrazine hydrate product obtained by the purification process has the TOC content of less than 300ppm, high-boiling organic impurities of less than 200ppm and inorganic salt ions such as Na+＜1ppm，Fe2+＜ 1ppm，CI-Less than 1ppm and nonvolatile impurities less than 20ppm, which is superior to industrial hydrazine hydrate industry standard HG/T3259-2012.
The following description will be further described with reference to specific embodiments.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
Example one
The hydrazine hydrate starting material was purified according to the following steps:
1) continuously feeding hydrazine hydrate raw material solution into a distillation tower at a flow rate of 1280kg/h, wherein the concentration of hydrazine hydrate in the hydrazine hydrate raw material solution is 63 wt%, the concentration of the hydrazine hydrate in the hydrazine hydrate raw material solution contains 0.7 wt% of acetone, and the TOC is 11328ppm, and then continuously adding 32 wt% of sodium hydroxide solution into the distillation tower at a flow rate of 1 kg/h. Controlling the temperature of the distillation tower at 120 ℃, continuously evaporating under the pressure of 0.02MPa, and continuously discharging tower bottom liquid with the flow rate of 30 kg/h;
2) controlling the temperature at the top of the distillation column to be 90-120 ℃, and allowing the vapor phase discharged from the top of the distillation column to pass through an OC1062 type resin adsorption bed layer with the height of 130 cm;
3) the vapor phase after the adsorption of the adsorption bed layer enters a rectifying tower, the temperature of the tower bottom of the rectifying tower is controlled to be 123 ℃, the pressure is 0.013MPa, the flow rate of condensed reflux liquid is 800kg/h, the temperature of the tower top of the rectifying tower is 98 ℃, the product analysis of the tower bottom is as shown in the following table,
product analysis
Example two
The hydrazine hydrate starting material was purified according to the following steps:
1) continuously feeding a hydrazine hydrate raw material solution into a distillation tower at a flow rate of 1320kg/h, wherein the concentration of hydrazine hydrate in the hydrazine hydrate raw material solution is 67 wt%, the concentration of the hydrazine hydrate in the hydrazine hydrate raw material solution contains 0.9 wt% of acetone, and the TOC is 9328ppm, and then continuously adding 32 wt% of sodium hydroxide solution into the distillation tower at a flow rate of 0.5 kg/h. Controlling the temperature of the distillation tower at 120 ℃, continuously evaporating at the pressure of 0.018MPa, and continuously discharging tower bottom liquid at the flow rate of 27 kg/h;
2) controlling the temperature of the top of the distillation tower at 118 ℃, and allowing the vapor phase discharged from the top of the distillation tower to pass through an OC1062 type resin adsorption bed layer with the height of 130 cm;
3) the vapor phase after the adsorption of the adsorption bed layer enters a rectifying tower, the temperature of the tower bottom of the rectifying tower is controlled to be 123 ℃, the pressure is 0.018MPa, the flow of condensed reflux liquid is 810kg/h, the temperature of the tower top of the rectifying tower is 100 ℃, the product analysis of the tower bottom is as shown in the following table,
product analysis
EXAMPLE III
The hydrazine hydrate starting material was purified according to the following steps:
1) continuously feeding hydrazine hydrate raw material solution into a distillation tower at the flow rate of 1000kg/h, wherein the concentration of hydrazine hydrate in the hydrazine hydrate raw material solution is 59 wt%, the concentration of the hydrazine hydrate in the hydrazine hydrate raw material solution contains 0.5 wt% of acetone, and the TOC is 7378ppm, and then continuously adding 32 wt% of sodium hydroxide solution into the distillation tower at the flow rate of 0.68 kg/h. Controlling the temperature of the distillation tower at 120 ℃, continuously evaporating under the pressure of 0.017MPa, and continuously discharging tower bottom liquid with the flow rate of 20 kg/h;
2) controlling the temperature of the top of the distillation tower at 118 ℃, and allowing the vapor phase discharged from the top of the distillation tower to pass through an OC1062 type resin adsorption bed layer with the height of 130 cm;
3) the vapor phase after the adsorption of the adsorption bed layer enters a rectifying tower, the temperature of the tower bottom of the rectifying tower is controlled to be 123 ℃, the pressure is 0.018MPa, the flow rate of condensed reflux liquid is 740kg/h, the temperature of the tower top of the rectifying tower is 100 ℃, the product analysis of the tower bottom is as shown in the following table,
product analysis
Claims (10)
1. A purification process of hydrazine hydrate is characterized by comprising the following steps:
1) adding the crude hydrazine hydrate product as a raw material into a distillation tower, then adding a sodium hydroxide solution into the distillation tower, and controlling the temperature of a tower kettle of the distillation tower to be 117-125 ℃ and the pressure to be 0.01-0.02 MPa;
2) and (2) adsorbing a vapor phase discharged from the top of the distillation tower in the step 1) by an adsorption bed, and then, introducing the vapor phase into a rectification tower for rectification, controlling the temperature of the top of the rectification tower to be 98-100 ℃, the temperature of the bottom of the rectification tower to be 115-123 ℃, and obtaining a 100% hydrazine hydrate product at the bottom of the rectification tower.
2. A process for purifying hydrazine hydrate as claimed in claim 1, wherein the crude hydrazine hydrate in step 1) is a hydrazine hydrate solution prepared by the ketazine process with a concentration of 30-65 wt%, wherein the acetone content is less than 1 wt%, and the TOC value is 7000-15000 ppm.
3. A process for purifying hydrazine hydrate as claimed in claim 1, characterized in that the concentration of the sodium hydroxide solution in step 1) is 10-32 wt%, and the addition amount is 0.1-0.2% of the mass of the crude hydrazine hydrate.
4. A process for the purification of hydrazine hydrate as claimed in claim 3, wherein the concentration of the sodium hydroxide solution is 25-32% by weight.
5. A purification process of hydrazine hydrate as claimed in claim 1, wherein the temperature of the distillation column in step 1) is 119-122 ℃ and the temperature of the top of the distillation column is 110-120 ℃.
6. A process as claimed in claim 1, characterized in that the adsorbent used in step 2) is styrene/divinylbenzene polymeric adsorbent resin.
7. A process as claimed in claim 1 or 6, characterized in that the adsorption temperature of the adsorption bed is 90-120 ℃.
8. A process as claimed in claim 1 or 6, characterized in that the condensate generated by the adsorption bed is refluxed to the distillation column of step 1).
9. A purification process of hydrazine hydrate as claimed in claim 1, wherein the vapor phase discharged from the top of the distillation column in step 2) is condensed and then partially refluxed to the distillation column as reflux, and the temperature in the bottom of the column is 120-123 ℃.
10. A purification process of hydrazine hydrate as claimed in claim 1 or 9, characterized in that the still pressure of the rectification column in step 2) is 0.015-0.018 MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011055474.8A CN112093783A (en) | 2020-09-30 | 2020-09-30 | Hydrazine hydrate purification process |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202011055474.8A CN112093783A (en) | 2020-09-30 | 2020-09-30 | Hydrazine hydrate purification process |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4724133A (en) * | 1975-09-10 | 1988-02-09 | Atochem | Preparation of concentrated aqueous solution of hydrazine hydrate |
| JPH08208208A (en) * | 1995-02-03 | 1996-08-13 | Mitsubishi Gas Chem Co Inc | Recovery of hydrazine |
| JPH10236805A (en) * | 1997-02-28 | 1998-09-08 | Mitsubishi Gas Chem Co Inc | Production of refined hydrated hydrazine |
| CN103991851A (en) * | 2013-02-17 | 2014-08-20 | 赖中胜 | New process for green and cyclic production of hydrazine hydrate |
| CN105347319A (en) * | 2015-11-17 | 2016-02-24 | 宜宾海丰和锐有限公司 | Method for removing organic impurities in hydrazine hydrate prepared through ketazine method |
| CN209507590U (en) * | 2018-11-23 | 2019-10-18 | 宜宾海丰和锐有限公司 | A kind of purification device of pharmaceutical hydrazine hydrate |
-
2020
- 2020-09-30 CN CN202011055474.8A patent/CN112093783A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4724133A (en) * | 1975-09-10 | 1988-02-09 | Atochem | Preparation of concentrated aqueous solution of hydrazine hydrate |
| JPH08208208A (en) * | 1995-02-03 | 1996-08-13 | Mitsubishi Gas Chem Co Inc | Recovery of hydrazine |
| JPH10236805A (en) * | 1997-02-28 | 1998-09-08 | Mitsubishi Gas Chem Co Inc | Production of refined hydrated hydrazine |
| CN103991851A (en) * | 2013-02-17 | 2014-08-20 | 赖中胜 | New process for green and cyclic production of hydrazine hydrate |
| CN105347319A (en) * | 2015-11-17 | 2016-02-24 | 宜宾海丰和锐有限公司 | Method for removing organic impurities in hydrazine hydrate prepared through ketazine method |
| CN209507590U (en) * | 2018-11-23 | 2019-10-18 | 宜宾海丰和锐有限公司 | A kind of purification device of pharmaceutical hydrazine hydrate |
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Application publication date: 20201218 |