CN114292208B - Method for preparing methyl hydrazine by solid acid catalysis - Google Patents
Method for preparing methyl hydrazine by solid acid catalysis Download PDFInfo
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- CN114292208B CN114292208B CN202111614306.2A CN202111614306A CN114292208B CN 114292208 B CN114292208 B CN 114292208B CN 202111614306 A CN202111614306 A CN 202111614306A CN 114292208 B CN114292208 B CN 114292208B
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- hydrazine
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- methyl hydrazine
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- 238000000034 method Methods 0.000 title claims abstract description 43
- HDZGCSFEDULWCS-UHFFFAOYSA-N monomethylhydrazine Chemical compound CNN HDZGCSFEDULWCS-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000011973 solid acid Substances 0.000 title claims abstract description 19
- 238000007171 acid catalysis Methods 0.000 title claims description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 51
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 39
- BIVUUOPIAYRCAP-UHFFFAOYSA-N aminoazanium;chloride Chemical compound Cl.NN BIVUUOPIAYRCAP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 239000002244 precipitate Substances 0.000 claims description 22
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 18
- 229910052721 tungsten Inorganic materials 0.000 claims description 18
- 239000010937 tungsten Substances 0.000 claims description 18
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims description 15
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 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 claims description 12
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 239000012266 salt solution Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 229910002651 NO3 Inorganic materials 0.000 claims description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 8
- 229910052684 Cerium Inorganic materials 0.000 claims description 7
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 7
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims description 7
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 7
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 6
- 238000007069 methylation reaction Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- 238000000975 co-precipitation Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 230000011987 methylation Effects 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims 1
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- RHUYHJGZWVXEHW-UHFFFAOYSA-N 1,1-Dimethyhydrazine Chemical compound CN(C)N RHUYHJGZWVXEHW-UHFFFAOYSA-N 0.000 description 5
- QDHHCQZDFGDHMP-UHFFFAOYSA-N Chloramine Chemical compound ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 5
- STRCBAIOXBVIFS-UHFFFAOYSA-N O.NN.CO.Cl Chemical compound O.NN.CO.Cl STRCBAIOXBVIFS-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- -1 hydrazine carbonate dimethyl ester Chemical compound 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- BGNGWHSBYQYVRX-UHFFFAOYSA-N 4-(dimethylamino)benzaldehyde Chemical compound CN(C)C1=CC=C(C=O)C=C1 BGNGWHSBYQYVRX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 210000001124 body fluid Anatomy 0.000 description 2
- 239000010839 body fluid Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000004451 qualitative analysis Methods 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- KUBYTSCYMRPPAG-UHFFFAOYSA-N ytterbium(3+);trinitrate Chemical compound [Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUBYTSCYMRPPAG-UHFFFAOYSA-N 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
- GIKDYMRZQQJQFB-UHFFFAOYSA-N Methylhydrazine hydrochloride Chemical compound Cl.CNN GIKDYMRZQQJQFB-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229940045984 antineoplastic methylhydrazine Drugs 0.000 description 1
- CDYIVTJODJNCNP-UHFFFAOYSA-N benzaldehyde hydrazine hydrate Chemical compound C(C1=CC=CC=C1)=O.O.NN CDYIVTJODJNCNP-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- LIAWOTKNAVAKCX-UHFFFAOYSA-N hydrazine;dihydrochloride Chemical compound Cl.Cl.NN LIAWOTKNAVAKCX-UHFFFAOYSA-N 0.000 description 1
- GCWCHLULHAWMEH-UHFFFAOYSA-N hydrazine;methanol;hydrate Chemical compound O.OC.NN GCWCHLULHAWMEH-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for efficiently synthesizing methyl hydrazine, which comprises the following steps: in methanol aqueous solution, hydrazine hydrochloride is used as a raw material, and a solid acid catalyst is used for catalytic reaction, so that the methyl hydrazine is obtained. The method has the advantages of easily obtained raw materials, high product yield, easily separated catalyst, good reusability, simple operation, green and environment-friendly production process and the like, and is beneficial to industrial application.
Description
Technical Field
The invention discloses a method for preparing methyl hydrazine by solid acid catalysis, belonging to the technical field of organic synthesis.
Technical Field
Methyl hydrazine is an important chemical raw material and has wide application in the fields of aerospace, pesticides, medicines and the like. With the continuous development of social economy in China, the yield of methyl hydrazine is increased, and how to economically, efficiently and greenly synthesize the methyl hydrazine is a difficult problem which needs to be solved at present. Aiming at the synthesis of methyl hydrazine, the synthesis methods reported in the prior literature mainly comprise the following steps: a chlor-ammonia method, a hydrazine hydrate benzaldehyde condensation method, a hydrazine carbonate dimethyl ester method, a dimethyl sulfate hydrazine hydrate method, a hydrochloric acid methanol hydrazine hydrate method and the like.
The industrial production of methyl hydrazine in the current market mainly adopts a chloroammonia method and a hydrochloric acid methanol hydrazine hydrate method for synthesis. In US patent 4192819 a method for preparing methyl hydrazine by a chloroamine method is disclosed, firstly, chloramine is generated by reacting sodium hypochlorite with ammonia, and then chloramine is reacted with monomethylamine to form methyl hydrazine. The process is mature, but has large energy consumption, serious three wastes and low product selectivity in the production process. Further, japanese patent JP8298247 discloses a method for preparing methyl hydrazine by a methanol hydrazine hydrate method using hydrazine hydrochloride and methanol as raw materials, and forming methyl hydrazine under the catalysis of hydrazine dihydrochloride or methyl chloride. And after the reaction is finished, adding excessive hydrazine hydrate to free methyl hydrazine, and collecting a product through rectification. The method has low raw material cost, but low conversion rate and deviation of product selectivity. And the free hydrochloric acid in the reaction process is easy to corrode equipment, so that more and more hydrazine hydrochloride can be used, and the production efficiency is low.
Chinese patent CN105037196B discloses a new method for catalytic synthesis of methyl hydrazine under normal pressure. The method is characterized in that: hydrazine hydrate and chloromethane react with hydrochloric acid as a protective agent, silica gel as a catalyst and ethanol as a solvent at 70-74 ℃ under normal pressure to generate methyl hydrazine hydrochloride. The hydrazine free method is adopted, after the methyl hydrazine is free through hydrazine hydrate, the methyl hydrazine aqueous solution is obtained through the rectification process. The free byproduct hydrazine monohydrochloride can be recycled. According to the method, silica gel is used as a catalyst, so that corrosion of hydrochloric acid to equipment is avoided, but chloromethane is difficult to recover and process, and ethanol is easy to volatilize at the reaction temperature; and the raw materials are solid in the reaction system, so that the reaction effect can be reduced. The synthetic route of other methyl hydrazines is mainly limited by high raw material cost, and industrial application is difficult to further advance.
In conclusion, the existing synthesis method of methyl hydrazine cannot meet market demands in the aspects of efficiency, environmental protection, economy and the like, and the production process needs to be further optimized. In view of the low cost of raw materials and easy separation of products of the hydrochloric acid methanol hydrazine hydrate method, the invention provides a technical improvement of the hydrochloric acid methanol hydrazine hydrate method, and by using solid acid as a catalyst, the equipment requirement is reduced, the production efficiency is improved, and the environmental pollution is avoided.
Disclosure of Invention
The invention aims to provide a method for preparing methyl hydrazine by solid acid catalysis, which adopts a tungsten-based catalyst and is commercially available15 (ion exchange resin), gamma-Al 2 O 3 ZSM-5 molecular sieve is used for preparing methyl hydrazine by hydrazine hydrochloride methylation, and has higher hydrazine hydrochloride conversion rate and methyl hydrazine selectivity.
In a preferred embodiment, the solid acid catalyst is a tungsten-based catalyst. By using a tungsten-based catalyst, the hydrazine hydrochloride conversion and methyl hydrazine selectivity can be further improved.
In a preferred embodiment, the tungsten-based catalyst is prepared by a coprecipitation method from sodium tungstate, zirconyl nitrate and nitrate containing at least one of ytterbium, lanthanum and cerium.
In a preferred embodiment, the co-precipitation method comprises the steps of: preparing a salt solution containing sodium tungstate, zirconyl nitrate and nitrate containing at least one of ytterbium, lanthanum and cerium, and continuously stirring at room temperature until all substances are dissolved; adding ammonia water to regulate pH to form precipitate, and aging in oil bath; filtering and washing after aging to obtain a precipitate; the precipitate is dried, ground and calcined to obtain the tungsten-based catalyst.
In a preferred embodiment, the molar ratio of sodium tungstate to zirconyl nitrate is 1:10-20, and the molar ratio of zirconyl nitrate to nitrate of at least one of ytterbium, lanthanum and cerium is controlled to be 20-70:1.
The invention relates to a preparation method of a self-made tungsten-based catalyst and application of solid acid catalysis to preparation of methyl hydrazine, which comprises the following specific processes:
(1) The salt solution A containing sodium tungstate, zirconyl nitrate and nitrate containing at least one of ytterbium, lanthanum and cerium is prepared according to a certain proportion, and stirred at room temperature until the nitrate is completely dissolved. And adding ammonia water to regulate pH value to 9-10 to form precipitate, and ageing at 80-100 deg.c in oil bath for 12-24 hr. After the aging is finished, filtering and washing are carried out to obtain a precipitate B. Drying and grinding the precipitate B, and calcining the precipitate B in a muffle furnace at 700-900 ℃ to obtain the tungsten-based catalyst C.
(2) Mixing concentrated hydrochloric acid and hydrazine hydrate according to a molar ratio of 1:1, wherein after mixing, the pH=about 6, and removing water through reduced pressure distillation to obtain hydrazine hydrochloride solid. Then adding the synthesized hydrazine hydrochloride into a hydrothermal kettle, and adding methanol, wherein the dosage of the methanol is 0.8-1.2 times of the molar quantity of the hydrazine hydrochloride; then adding 5-60% of water by mass, and carrying out methylation reaction under the action of a tungsten-based catalyst C or a commercial catalyst;
(3) Filtering the mixture after the reaction is finished to remove the catalyst, adding a proper amount of hydrazine hydrate to free methyl hydrazine, and then separating the methyl hydrazine by rectification. The remainder is added with a small amount of hydrochloric acid to neutralize hydrazine hydrate and then returns to the methylation reaction step, and the catalyst can be reused.
In a preferred embodiment, the method is characterized by: the dosage of the methanol in the step (1) is 0.8 to 1.2 times of the molar quantity of the hydrazine hydrochloride.
In a preferred embodiment, the method is characterized by: the water consumption in the step (1) is 5-60% of the hydrazine hydrochloride mass.
In a preferred embodiment, the method is characterized by: in the step (1), the reaction temperature is controlled to be 115-135 ℃ and the reaction time is controlled to be 3-10 hours.
In a preferred embodiment, the method is characterized by: the dosage of the catalyst in the step (1) is 1-20% of the mass of hydrazine hydrochloride.
In a preferred embodiment, the yield of methylhydrazine is 40% or more, preferably 50% or more, and more preferably 55% or more.
In another preferred embodiment of the present invention, the 1, 1-dimethylhydrazine yield is 1% or less; preferably 0.5% or less.
In summary, the invention has the following advantages: (1) The solid acid catalyst is beneficial to separation, reduces the dosage of hydrazine hydrate in the step of methyl hydrazine free and the dosage of hydrazine hydrochloride in the later period, and improves the synthesis efficiency and selectivity. (2) The catalyst can be recycled, which is beneficial to reducing the cost, and the solid acid catalyst is unfavorable for the mass production of the byproduct 1, 1-dimethylhydrazine. (3) Compared with the hydrochloric acid methanol hydrazine hydrate method, the method greatly reduces the concentration of free acid in the reaction liquid and reduces the corrosion of equipment.
Detailed Description
The operation and effect of the present invention will be further illustrated by the following specific examples, but the present invention is not limited to the following examples, and any modifications made without departing from the technical principle of the present invention should be regarded as being within the scope of the claims of the present invention.
Example 1
The catalyst C-1 is prepared by the following steps:
1.423g of sodium tungstate, 19.522g of zirconyl nitrate and 0.632g of ytterbium nitrate were dissolved in 200ml of water, respectively, and stirred for 1 hour to prepare a salt solution A1. Ammonia water (40%) was slowly added dropwise to the beaker, ph=9 to 10 was adjusted, and stirring was carried out under an oil bath at 100 ℃ for 24 hours. After filtration and washing, precipitate B1 was obtained. The precipitate B1 was dried in an oven and ground to a powder, and finally calcined in a muffle furnace at 800℃for 3 hours to give a tungsten-based catalyst C-1.
Example 2
The catalyst C-2 is prepared by the following steps:
2.134g of sodium tungstate, 18.438g of zirconyl nitrate and 0.632g of ytterbium nitrate were each dissolved in 200ml of water and stirred for 1 hour to prepare a salt solution A2. Ammonia water (40%) was slowly added dropwise to the beaker, ph=9 to 10 was adjusted, and stirring was carried out under an oil bath at 100 ℃ for 24 hours. The precipitate B2 is obtained by filtration and washing. The precipitate B2 is dried in an oven and ground into powder, and finally calcined in a muffle furnace at 900 ℃ for 3 hours to obtain the tungsten-based catalyst C-2.
Example 3
The catalyst C-3 was prepared as follows:
1.423g of sodium tungstate, 19.522g of zirconyl nitrate and 0.758g of lanthanum nitrate were dissolved in 200ml of water, respectively, and stirred for 1 hour to prepare a salt solution A3. Ammonia water (40%) was slowly added dropwise to the beaker, ph=9 to 10 was adjusted, and stirring was carried out under an oil bath at 100 ℃ for 24 hours. After filtration and washing, precipitate B3 was obtained. The precipitate B3 was dried in an oven and ground to a powder, and finally calcined in a muffle furnace at 800℃for 3 hours to give a tungsten-based catalyst C-3.
Example 4
The catalyst C-4 was prepared as follows:
2.134g of sodium tungstate, 18.438g of zirconyl nitrate and 0.758g of lanthanum nitrate were each dissolved in 200ml of water and stirred for 1 hour to prepare a salt solution A4. Ammonia water (40%) was slowly added dropwise to the beaker, ph=9 to 10 was adjusted, and stirring was carried out under an oil bath at 100 ℃ for 24 hours. After filtration and washing, precipitate B4 was obtained. The precipitate B4 was dried in an oven and ground to a powder, and finally calcined in a muffle furnace at 900℃for 3 hours to give a tungsten-based catalyst C-4.
Example 5
The catalyst C-5 was prepared as follows:
1.423g of sodium tungstate, 19.522g of zirconyl nitrate and 1.438g of cerium nitrate were dissolved in 200ml of water, respectively, and stirred for 1 hour to prepare a salt solution A5. Ammonia water (40%) was slowly added dropwise to the beaker, ph=9 to 10 was adjusted, and stirring was carried out under an oil bath at 100 ℃ for 24 hours. After filtration and washing, precipitate B5 was obtained. The precipitate B5 was dried in an oven and ground to a powder, and finally calcined in a muffle furnace at 800℃for 3 hours to give a tungsten-based catalyst C-5.
Example 6
The catalyst C-6 was prepared as follows:
2.134g of sodium tungstate, 18.438g of zirconyl nitrate and 1.438g of cerium nitrate were each dissolved in 200ml of water and stirred for 1 hour to prepare a salt solution A6. Ammonia water (40%) was slowly added dropwise to the beaker, ph=9 to 10 was adjusted, and stirring was carried out under an oil bath at 100 ℃ for 24 hours. After filtration and washing, precipitate B6 was obtained. The precipitate B6 was dried in an oven and ground to a powder, and finally calcined in a muffle furnace at 900℃for 3 hours to give a tungsten-based catalyst C-6.
Example 7
788.24g (8.00 mol) of 37% concentrated hydrochloric acid was slowly added dropwise to 500g (8.00 mol) of 80% hydrazine hydrate, cooled to room temperature in an ice-water bath, and the pH of the solution was measured to be about 6. 547.8g of hydrazine monohydrochloride solid is obtained by distillation under reduced pressure, and the obtained solid is bottled for use.
Examples 8 to 13
To a 25ml polytetrafluoroethylene liner was added 5g of hydrazine hydrochloride, 0.5g of tungsten-based catalyst, 3g of water, 2.34g of methanol, and stirring seeds. After the hydro-thermal kettle is screwed up, the mixture is placed in an oil bath kettle for heating, and the reaction temperature is 130 ℃. After 8 hours of reaction, the hydrothermal kettle is taken out and placed in an ice water bath for cooling. The hydrothermal kettle is opened, the catalyst is filtered out, 0.1g of reaction solution is taken in a 15ml centrifuge tube, 2g of hydrochloric acid water (0.01 g/ml) and 2g of methanol are added, and finally, excessive p-dimethylaminobenzaldehyde (0.1 g/ml) solution is added dropwise, and ultrasonic treatment is carried out for 30min at 30 ℃. 2ml of post-treatment liquid is taken and is transferred into a sample injection bottle after being filtered, qualitative and quantitative analysis is carried out by adopting island body fluid phase, the reaction result is shown in table 1, and the yield is calculated based on the raw material hydrazine hydrochloride. The catalyst is filtered, the reaction liquid is combined, a proper amount of hydrazine hydrate is added to free methyl hydrazine, and the pure methyl hydrazine aqueous solution is obtained after rectification and collection at 100-107 ℃. The remainder is neutralized by adding a proper amount of hydrochloric acid and returned to the methylation step, and the catalyst can be reused.
TABLE 1
Examples 14 to 17
Into 25ml polytetrafluoroethyleneAdding 5g hydrazine hydrochloride and 0.5g C-2 or the like into the lining15、γ-Al 2 O 3 ZSM-5, 3g of water and 2.34g of methanol. After the hydro-thermal kettle is screwed up, the mixture is placed in an oil bath kettle for heating, and the reaction temperature is 130 ℃. After 8 hours of reaction, the hydrothermal kettle is taken out and placed in an ice water bath for cooling. The hydrothermal kettle is opened, 0.1g of the reaction solution is taken in a 15ml centrifuge tube, 2g of hydrochloric acid water (0.01 g/ml) and 2g of methanol are added, and finally an excessive amount of p-dimethylaminobenzaldehyde (0.1 g/ml) solution is added dropwise, and the mixture is subjected to ultrasonic treatment at 30 ℃ for 30min. 2ml of post-treatment liquid is taken and is transferred into a sample injection bottle after being filtered, qualitative and quantitative analysis is carried out by adopting island body fluid phase, and the reaction result is shown in table 2. The catalyst is filtered, the reaction liquid is combined, a proper amount of hydrazine hydrate is added to free methyl hydrazine, and the pure methyl hydrazine aqueous solution is obtained after rectification and collection at 100-107 ℃. The residue is neutralized with a proper amount of hydrochloric acid and returned to the methylation step, and the solid acid catalyst can be used continuously.
TABLE 2
Comparative examples 1 to 2
The specific reaction procedure was the same as in examples 14 to 17, except that hydrochloric acid and sulfuric acid were used as the catalyst instead of the solid acid. In view of the tendency of homogeneous acid catalysis to form excessive byproducts, data are provided for optimal reaction results when the amount of hydrochloric acid and sulfuric acid is 1% (in mol). The specific results are shown in table 3 below:
TABLE 3 Table 3
The above examples and comparative examples show that the present invention provides a new concept for the preparation of methylhydrazine. In aqueous methanol, hydrazine hydrochloride is methylated to methyl hydrazine using a solid acid as a catalyst. Compared with liquid acid catalysis, solid acid catalysis has the following advantages: the product has high selectivity, the catalyst is easy to separate and has good reusability, the requirement on equipment is low, the production process is environment-friendly, and the method is favorable for industrial application.
The foregoing describes preferred embodiments of the present invention, but is not intended to limit the invention thereto. Modifications and variations to the embodiments disclosed herein may be made by those skilled in the art without departing from the scope and spirit of the invention.
Claims (8)
1. The method for preparing methyl hydrazine by solid acid catalysis is characterized by comprising the following steps: in methanol aqueous solution, hydrazine hydrochloride is used as a raw material, and methyl hydrazine is obtained through reaction under the catalysis of a solid acid catalyst; the solid acid catalyst is selected from tungsten-based catalyst, gamma-Al 2 O 3 One or more combinations of ZSM-5 molecular sieves; the tungsten-based catalyst is prepared from sodium tungstate, zirconyl nitrate and nitrate containing at least one of ytterbium, lanthanum and cerium by a coprecipitation method.
2. The method of claim 1, the co-precipitation method comprising the steps of: preparing a salt solution containing sodium tungstate, zirconyl nitrate and nitrate containing at least one of ytterbium, lanthanum and cerium, and continuously stirring at room temperature until all substances are dissolved; adding ammonia water to regulate pH to form precipitate, and aging in oil bath; filtering and washing after aging to obtain a precipitate; the precipitate is dried, ground and calcined to obtain the tungsten-based catalyst.
3. The preparation method according to claim 2, wherein the molar ratio of sodium tungstate to zirconyl nitrate is 1:10-20, and the molar ratio of zirconyl nitrate to nitrate of at least one of ytterbium, lanthanum and cerium is controlled to be 20-70:1.
4. A process according to any one of claims 1 to 3, comprising the steps of:
(1) Adding a certain amount of hydrazine hydrochloride, methanol, water and a solid acid catalyst into a hydrothermal kettle, and reacting for more than 1 hour at a certain temperature;
(2) Cooling to room temperature after the reaction is finished, separating out a catalyst, adding hydrazine hydrate to free methyl hydrazine, and rectifying to obtain a methyl hydrazine aqueous solution;
(3) Adding hydrochloric acid into the rectification residual liquid to neutralize hydrazine hydrate, returning to the methylation step for reuse, and continuously recycling the solid acid catalyst.
5. The method of manufacturing according to claim 4, wherein: the dosage of the methanol in the step (1) is 0.8 to 1.2 times of the molar quantity of the hydrazine hydrochloride.
6. The method of manufacturing according to claim 4, wherein: the water consumption in the step (1) is 5-60% of the hydrazine hydrochloride mass.
7. The method of manufacturing according to claim 4, wherein: in the step (1), the reaction temperature is controlled to be 115-135 ℃ and the reaction time is controlled to be 3-10 hours.
8. The method of manufacturing according to claim 4, wherein: the dosage of the catalyst in the step (1) is 1-20% of the mass of hydrazine hydrochloride.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105037196A (en) * | 2015-08-10 | 2015-11-11 | 济南大学 | Novel method of catalytic synthesis of methylhydrazine under normal pressure |
| CN106543026A (en) * | 2016-10-31 | 2017-03-29 | 重庆锦杉科技有限公司 | A kind of preparation method of methyl hydrazine |
| CN109503418A (en) * | 2018-12-11 | 2019-03-22 | 河北合佳医药科技集团股份有限公司 | A kind of preparation process of methyl hydrazine |
| CN111320554A (en) * | 2019-12-11 | 2020-06-23 | 东力（南通）化工有限公司 | Improved technology of monomethylhydrazine production process |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105037196A (en) * | 2015-08-10 | 2015-11-11 | 济南大学 | Novel method of catalytic synthesis of methylhydrazine under normal pressure |
| CN106543026A (en) * | 2016-10-31 | 2017-03-29 | 重庆锦杉科技有限公司 | A kind of preparation method of methyl hydrazine |
| CN109503418A (en) * | 2018-12-11 | 2019-03-22 | 河北合佳医药科技集团股份有限公司 | A kind of preparation process of methyl hydrazine |
| CN111320554A (en) * | 2019-12-11 | 2020-06-23 | 东力（南通）化工有限公司 | Improved technology of monomethylhydrazine production process |
Non-Patent Citations (1)
| Title |
|---|
| 甲基肼的清洁生产工艺研究析;刘新元 等;《煤炭与化工》;第44卷(第9期);第135-137页 * |
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