CN1188348C - Catalytic hydrogenolysis of unsym-dimethyl hydrazine - Google Patents
Catalytic hydrogenolysis of unsym-dimethyl hydrazine Download PDFInfo
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- CN1188348C CN1188348C CNB001102346A CN00110234A CN1188348C CN 1188348 C CN1188348 C CN 1188348C CN B001102346 A CNB001102346 A CN B001102346A CN 00110234 A CN00110234 A CN 00110234A CN 1188348 C CN1188348 C CN 1188348C
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- dimethyl hydrazine
- unsymmetrical dimethyl
- catalytic hydrogenolysis
- unsymmetrical
- hydrogen
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- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The present invention relates to a catalytic hydrogenolysis method of unsymmetrical dimethylhydrazine. The present invention is characterized in that hydrogen gas reacts with unsymmetrical dimethylhydrazine to produce ammonia and dimethyl amine under the action of catalyst, and the catalyst is composed of a metal Pd as a main active component, Rh, Ru, Ir, Pt, Ni, Co as auxiliary agent components, and a supporter; the reaction temperature is from 100 to 300 DEG C, the feeding speed of the unsymmetrical dimethylhydrazine is 0.5 to 10 g of catalyst per hour, and the proportion of the hydrogen gas to the unsymmetrical dimethylhydrazine presents in a formula: H2 /UDMH=1-10 (mol/mol). The method of the present invention can make the unsymmetrical dimethylhydrazine decompose into useful ammonia and dimethylamine by catalytic hydrogenolysis, and has the advantages of simple and safe process, and realization of device miniaturization.
Description
The present invention relates to the protection of environment, provide a kind of catalytic hydrogenolysis of unsym-dimethylhydrazine to produce the method for ammonia and dimethylamine especially.
1, the 1-dimethylhydrazine claims unsymmetrical dimethyl hydrazine again, is colourless liquid, and irritating smell is arranged.In air, unsymmetrical dimethyl hydrazine easily is fuming and flavescence by slow oxidation.At present, unsymmetrical dimethyl hydrazine mainly is to adopt chloramine method production, and hypochlorous sodium, ammoniacal liquor and dimethylamine are raw material production.
The main application of unsymmetrical dimethyl hydrazine is the liquid fuel as rocket.The unsymmetrical dimethyl hydrazine of prolonged preservation can be generated a part of hydrazone by the air slow oxidation.
Oxidized unsymmetrical dimethyl hydrazine like this can not be used as rocket fuel again.Its processing is a very difficult problem.Because unsymmetrical dimethyl hydrazine nitrogen content height, the burning that acts as a fuel can produce a large amount of NO
X, cause serious atmospheric pollution.Because unsymmetrical dimethyl hydrazine is inflammable, explosive, also is difficult for length and handles again apart from being transported to original production factory.
The object of the present invention is to provide a kind of catalytic hydrogenolysis method of unsymmetrical dimethyl hydrazine, it can be useful ammonia and dimethylamine with catalytic hydrogenolysis of unsym-dimethylhydrazine, and method is simple and safe, and can realize device miniaturization.
The invention provides a kind of catalytic hydrogenolysis method of unsymmetrical dimethyl hydrazine, it is characterized in that: hydrogen and unsymmetrical dimethyl hydrazine generate ammonia and dimethylamine under catalyst action.
The inventive method and catalytic decomposition difference are reaction use hydrogen.Use hydrogen can improve the yield of ammonia and dimethylamine.Reaction is as shown in the formula expression:
Catalyzer used among the present invention is made up of main active ingredient, adjuvant component and carrier; Main activeconstituents is a palladium metal, and adjuvant component is selected from Rh, and Ru, Ir, Pt, Ni, one or more of Co metallic element, carrier are selected from one or more of silicon oxide, aluminum oxide, gac, diatomite carrier commonly used; Palladium metal content is preferably 0.5-5% (weight) in 0.1-30% (weight), and auxiliary agent content is preferably 0.05-5% (weight) in 0.01-10% (weight).Processing condition are temperature of reaction 100-300 ℃, the input speed of unsymmetrical dimethyl hydrazine: 0.5-10 gram/gram catalyzer hour, the ratio H of hydrogen and unsymmetrical dimethyl hydrazine
2/ UDMH=1-10 (mol/mol).
The carrier of catalyst system therefor can be selected ball-type, column type and sheet type for use among the present invention.Used catalyzer can be to use the solubility salt of palladium metal and auxiliary element as nitrate, the preparation of muriatic aqueous solution dipping carrier.The most handy hydrogen reducing before use, reduction temperature is 100-500 ℃, the recovery time is 0.5-14 hour.
The present invention also provides a kind of catalytic hydrogenolysis equipment that is specifically designed to the unsymmetrical dimethyl hydrazine of realizing aforesaid method, it is characterized in that: this equipment by unsymmetrical dimethyl hydrazine storage tank (1) through unsymmetrical dimethyl hydrazine pump (2), connect vaporizer (3) jointly with hydrogen making machine (7), connect reactor (4) again, reactor (4) outlet connects water cooler (5), separator (6) constitutes.The catalytic hydrogenolysis equipment of above-mentioned unsymmetrical dimethyl hydrazine can complete installation on an automobile.
Employed reactor can be one or several in parallel or series connection use among the present invention, or switches use.Reactor can be a shell and tube reactor, and this reactor can or be bordering under the isothermal condition at isothermal and move, and catalyzer is housed in the pipe, is thermal oil between pipe.Yet ordinary priority is selected adiabatic reactor for use, and is because it is lower than shell and tube reactor cost, easy for installation.
Technological operation of the present invention is described as follows: with pump the unsymmetrical dimethyl hydrazine in the storage tank quantitatively is transported in the vaporization mixing tank, the temperature of vaporization mixing tank generally maintains 100-200 ℃, make the unsymmetrical dimethyl hydrazine vaporization, simultaneously, hydrogen from hydrogen making machine also enters the vaporization mixing tank, realize mixing with the unsymmetrical dimethyl hydrazine of vaporization, gas mixture enters reactor through pipeline, the temperature of reactor generally maintains 100-300 ℃, the gasiform unsymmetrical dimethyl hydrazine contacts with catalyzer in reactor with hydrogen, and catalytic hydrogenolytic cleavage takes place, and generates products such as ammonia and dimethylamine, product is realized separating of ammonia and dimethylamine in separating tank through cooling.Entire reaction course is the normal pressure process, also can carry out having under the condition of certain pressure.
In a word, the present invention is useful ammonia and dimethylamine with catalytic hydrogenolysis of unsym-dimethylhydrazine, and method is simple and safe, and equipment can miniaturization, can be installed on the automobile, at the ground, storehouse of various a large amount of storage unsymmetrical dimethyl hydrazines on-the-spot disposal.Further be described by the following examples
Accompanying drawing 1 is to have the catalytic hydrogenolysis of unsym-dimethylhydrazine of a reactor to prepare the experimental installation simplified flow chart of ammonia and dimethylamine.
Example 1
Take by weighing carrier silicon-dioxide 49 grams, dispose 50 milliliters of aqueous hydrochloric acids that contain the Palladous chloride of 1.667 grams, with 50 milliliters that the configure aqueous hydrochloric acid dipping 49 gram silicon-dioxide that contain 1.667 gram Palladous chlorides, place, seasoning under the room temperature, then, 120 ℃ of dryings 2 hours, then, under hydrogen stream 300 ℃ the reduction 1 hour.Make silica supported palladium catalyst.
Example 2
Take by weighing 29.7 gram aluminium sesquioxide carriers, get 10 milliliters of Palladous chloride aqueous hydrochloric acids (0.05 gram PdCl
2/ ml) add 50 milliliter distilled water dilutings, with the aluminium sesquioxide carriers of above-mentioned 50 ml solns dipping, 29.7 grams, place, seasoning under the room temperature, then, and 120 ℃ of dryings 2 hours, then, 300 ℃ of reduction are 1 hour under hydrogen stream.Make the palladium catalyst that aluminium sesquioxide supports.
Example 3
Take by weighing carrier silicon-dioxide 49.45 grams, dispose 50 milliliters and contain 0.837 gram Palladous chloride and 0.103 gram ruthenium trichloride aqueous hydrochloric acid, contain the Palladous chloride of 0.837 gram and the aqueous hydrochloric acid dipping 49.45 gram silicon-dioxide of 0.103 gram ruthenium trichloride with 50 milliliters that configure, place, seasoning under the room temperature, then, 120 ℃ of dryings 2 hours, then, under hydrogen stream 300 ℃ the reduction 1 hour.Make the silica supported palladium catalyst that contains the ruthenium auxiliary agent.
Example 4
Adopt experimental installation as shown in drawings to carry out the catalytic decomposition of unsymmetrical dimethyl hydrazine.Reaction pressure is a normal pressure, and temperature of reaction is 160 ℃, and catalyzer is the made catalyzer of example 1, and catalyst levels is 10 grams, and the inlet amount of unsymmetrical dimethyl hydrazine is 28 milliliters/hour, and hydrogen flowing quantity is 300 ml/min, and experimental result is listed in the table 1.
Example 5
Adopt experimental installation as shown in drawings to carry out the catalytic decomposition of unsymmetrical dimethyl hydrazine.Reaction pressure is a normal pressure, and temperature of reaction is 170 ℃, and catalyzer is the made catalyzer of example 2, and catalyst levels is 10 grams, and the inlet amount of unsymmetrical dimethyl hydrazine is 28.2 milliliters/hour, and hydrogen flowing quantity is 300 ml/min, and experimental result is listed in the table 1.
Example 6
Adopt experimental installation as shown in drawings to carry out the catalytic decomposition of unsymmetrical dimethyl hydrazine.Reaction pressure is a normal pressure, and temperature of reaction is 170 ℃, and catalyzer is the made catalyzer of example 3, and catalyst levels is 10 grams, the inlet amount of unsymmetrical dimethyl hydrazine be 28.2 milliliters/hour, hydrogen flowing quantity is 300 ml/min, experimental result is listed in the table 1.
Table 1. experimental result
| Instance number | Unsymmetrical dimethyl hydrazine (ml/h) | H2/UDMH (mol/mol) | Temperature of reaction (℃) | Unsymmetrical dimethyl hydrazine transformation efficiency (mol%) | Ammonia yield (mol%) | Dimethylamine yield (mol%) |
| 4 | 28.2 | 2 | 160 | 100 | 23.3 | 72.1 |
| 5 | 28.2 | 2 | 170 | 100 | 22.0 | 68.2 |
| 6 | 28.2 | 2 | 170 | 100 | 30.1 | 77.4 |
Claims (8)
1. the catalytic hydrogenolysis method of a unsymmetrical dimethyl hydrazine, it is characterized in that: hydrogen and unsymmetrical dimethyl hydrazine generate ammonia and dimethylamine under catalyst action, used catalyzer is made up of main active ingredient, adjuvant component and carrier; Main active ingredient is a palladium metal, and adjuvant component is selected from Rh, and Ru, one or more of Ir metallic element, carrier are selected from one or more of silicon oxide, aluminum oxide, gac, diatomite; Palladium metal content is in 0.1-30% weight, and auxiliary agent content is in 0.01-10% weight.
2. according to the catalytic hydrogenolysis method of the described unsymmetrical dimethyl hydrazine of claim 1, it is characterized in that: processing condition are temperature of reaction 100-300 ℃, the input speed of unsymmetrical dimethyl hydrazine: 0.5-10 gram/gram catalyzer hour, the molar ratio H of hydrogen and unsymmetrical dimethyl hydrazine
2/ UDMH=1-10.
3. according to the catalytic hydrogenolysis method of the described unsymmetrical dimethyl hydrazine of claim 1, it is characterized in that: used palladium metal weight content is at 0.5-5%.
4. according to the catalytic hydrogenolysis method of the described unsymmetrical dimethyl hydrazine of claim 1, it is characterized in that: used auxiliary agent weight content is at 0.05-5%.
5. according to the catalytic hydrogenolysis method of the described unsymmetrical dimethyl hydrazine of claim 1, it is characterized in that: used carrier is selected ball-type, column type and sheet type for use.
6. according to the catalytic hydrogenolysis method of the described unsymmetrical dimethyl hydrazine of claim 1, it is characterized in that: used catalyzer is to prepare with the nitrate of palladium metal and auxiliary element or muriatic aqueous solution dipping carrier.
7. according to the catalytic hydrogenolysis method of the described unsymmetrical dimethyl hydrazine of claim 1, it is characterized in that: use hydrogen reducing before using, reduction temperature is 100-500 ℃, and the recovery time is 0.5-14 hour.
8. catalytic hydrogenolysis equipment that is specifically designed to the unsymmetrical dimethyl hydrazine of realizing the described method of claim 1 is characterized in that: this equipment is by unsymmetrical dimethyl hydrazine storage tank (1), unsymmetrical dimethyl hydrazine pump (2), hydrogen making machine (7), vaporizer (3), reactor (4), water cooler (5), and separator (6) constitutes; Equipment integral is installed on the automobile.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001102346A CN1188348C (en) | 2000-03-22 | 2000-03-22 | Catalytic hydrogenolysis of unsym-dimethyl hydrazine |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001102346A CN1188348C (en) | 2000-03-22 | 2000-03-22 | Catalytic hydrogenolysis of unsym-dimethyl hydrazine |
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| Publication Number | Publication Date |
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| CN1314305A CN1314305A (en) | 2001-09-26 |
| CN1188348C true CN1188348C (en) | 2005-02-09 |
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| CNB001102346A Expired - Fee Related CN1188348C (en) | 2000-03-22 | 2000-03-22 | Catalytic hydrogenolysis of unsym-dimethyl hydrazine |
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