CN107922191A - The cutting-off method of azine key, hydrazone key - Google Patents

Abstract

The present invention relates to the manufacture method of a kind of hydrazine hydrate, substitution hydrazine or amino-compound, it is characterized in that, by hydrolyzing ketone azine, hydrazone or schiff base compounds in the presence of subcritical, overcritical or liquid CO 2 state carbon dioxide, ketone and hydrazine hydrate or substitution hydrazine or carbazic acid or substitution carbazic acid or carbonyls and amino-compound or carbamic acid compound or substituted-amino formic acid are obtained.

Description

The cutting-off method of azine key, hydrazone key

Technical field

The present invention relates to a kind of manufacture method, it utilizes liquid CO 2, supercritical carbon dioxide, subcritical shape State carbon dioxide carry out the azine keies of azines, the hydrazone key of hydrazone compound, schiff bases azomethine key cut-out, with low energy Amount suppresses the generation of accessory substance and is readily obtained carbazic acid (hydrazine formic acid), hydrazine hydrate, substitution hydrazine, carbazic acid derivative, ammonia Base formic acid derivates, amino-compound.

Background technology

Hydration hydrazine is used for：Remove the oxygen that dissolves in boiler water with prevent the effect of boiler corrosion, resin foaming agent Raw material, high molecular polymerization initiator, the raw material of gas-forming agent of air bag, multi-medicament, the raw material of pesticide, rocket fuel, Artificial satellite gesture stability with fuel, the manufacture purposes of the metal particle of electronic material, circuit substrate etching reagent etc. very Wide scope, is important compound.In addition, substitution hydrazine, carbamic acid derivative and carbazic acid derivative are as medicine, agriculture The synthesis material and reaction reagent of medicine are important compounds.

[explanation of existing preparation method]

Illustrated herein centered on hydrazine hydrate and substitution hydrazine.The autofrettage of hydrazine hydrate and substitution hydrazine is long ago to open Hair and industrialized technology.The technology now used in production is the old technology of past exploitation, and there is no new promising Technology.Although also having carried out the small technological improvement of part, fundamental reaction does not improve thoroughly.Past, implemented now Manufacture method is essentially following shown methods.

As the 1st method, there is the method for being referred to as urea method.(non-patent literature 1)

It is following method：Urea is formed chlorination urea or substitution chlorination urea with the chlorinating agents such as sodium hypochlorite (oxidant), lead to Hoffmann rearrangement generation aminoisocyanate is crossed, hydrazine hydrate or substitution hydrazine (reaction equation 1) are then obtained by hydrolysis.The preparation method The disadvantage is that, product, that is, hydrazine hydrate or substitution hydrazine are the very strong compounds of reproducibility, therefore oxidant-hypochlorous acid in raw material When sodium is coexisted in system, the hydrazine hydrate or substitution hydrazine of generation can decompose immediately.Therefore glue etc. is added into reaction system to stablize Agent, in the case of hydrazine hydrate, it is necessary to stop reacting and being separated under the low concentration state below 4%.To this less than 4% Hydrazine hydrate or substitution hydrazine concentrated and the accessory substance with largely generating i.e. inorganic salts separate, the inorganic salts of by-product then become useless Gurry.And then in the case of hydrazine hydrate, it is necessary to be concentrated to the 60-100% of practical product concentration.In the case of anhydrous hydrazine, 100% hydrazine hydrate must first be obtained.Therefore need to consume substantial amounts of energy.Also have and inorganic acid is made in hydrazine hydrate or substitution hydrazine The method concentrated after salt, required hydrazine hydrate or substitution hydrazine in order to obtain, also have the hydrazine of generation is made inorganic salts and The method for stabilizing it, but inorganic salts must be neutralized and transform it into hydrazine hydrate or substitution hydrazine.Also generate at this time Substantial amounts of inorganic salts discarded object.

[reaction equation 1]

As the 2nd method, there is the following method for being referred to as drawing western (Raschig) method：With (the oxidation of the chlorinating agents such as sodium hypochlorite Agent) make ammonia or substitution amine generation chloramines, the chloramines is reacted at low temperature with ammonia or amine derivative, obtain hydrazine hydrate or substitution hydrazine (reaction equation 2).The hydrazine hydrate or substitution hydrazine generated in the reaction is very strong reducing agent, can be (secondary with oxidant, that is, chlorinating agent Sodium chlorate) react and decompose the hydrazine hydrate of generation or substitution hydrazine.In order to avoid such case, it is also desirable to added in the preparation method Glue etc. is stabilized, stops reaction and by-product under the low concentration that the hydrazine hydrate of generation or the concentration of substitution hydrazine are less than 4% Inorganic salts separation, be concentrated in the case of hydrazine hydrate usually used hydrazine hydrate or substitute the 60-100% of hydrazine concentration.This Outside, anhydrous hydrazine in order to obtain, it is necessary to first obtain 100% hydrazine hydrate.At this time, substantial amounts of energy, the substantial amounts of by-product salt of generation are expended The reason for as problem and public hazards.Also there is the method that inorganic salts and stabilizing it is made in the hydrazine of generation, but must be to nothing Machine salt is neutralized and transforms it into hydrazine hydrate or substitution hydrazine.Substantial amounts of inorganic salts discarded object (non-patent text is also generated at this time Offer 2).

[reaction equation 2]

Method as shown below is developed, it is improved in 1 method-urea method, 2 methods-Raschig process due to generation Hydrazine hydrate or substitution hydrazine by raw material oxidant, that is, chlorinating agent (sodium hypochlorite) decompose thus at low concentrations stop reaction and The shortcomings that only obtaining the hydrazine hydrate or substitution hydrazine of low concentration.

As the 3rd method, organic method or the preparation method of ketazine process are known as, is following method：In the reaction of Raschig process In, in the presence of large excess of ammonium hydroxide or amine derivative and large excess of acetone, low temperature, be vigorously stirred it is lower few every time The chlorinating agents such as oxidant, that is, sodium hypochlorite are added dropwise in amount ground, promote scattered, the diffusion of aqueous sodium hypochlorite solution, promote anti-with ammonia Should.The low concentration hydrazine hydrate or substitution hydrazine for making generation turn with being reacted with the reactive very high acetone of hydrazine or substitution hydrazine immediately It is changed into chemically stable acetone azine or acetone substitution hydrazone, so that agent (oxidant) oxidation is not chlorinated, but oxidant is i.e. secondary Decomposition reaction caused by sodium chlorate is fast, still cannot get positive effect (reaction equation 3).Acetone hydrazone only protects a side, therefore separately The free diazanyl of one side is same with hydrazine hydrate to be oxidized easily, therefore can't be the oxidants such as not oxidized dose i.e. sodium hypochlorite The protected compound of oxidation.If the diazanyl in two ends of hydrazine hydrate, substitution hydrazine does not react with acetone and forms ketazine Or the hydrazone of substitution hydrazine, then it can not avoid because of oxidant and the situation (patent document 1) of oxygenolysis.

[reaction equation 3]

But the problem of substantial amounts of there are by-product salt；And stabilize it in formation acetone azine or acetone substitution hydrazone Before, the hydrazine hydrate or the strong reducing property of substitution hydrazine and the reaction rate of chlorine system oxidant of generation are fast, the hydrazine hydrate of generation or substitution Hydrazine is decomposed due to the chlorine system oxidant of oxidant.Therefore, in the same manner as the 1st method, the 2nd method, in the situation of hydrazine hydrate Under, it is concentration limit that the concentration of ketazine or substitution hydrazone in reaction system is converted with 5% or so with hydrazine hydrate.Acetone azine is Water solubility, after reaction, evaporation recycling excess of ammonia, the excessive acetone of low boiling point is recycled in then evaporation, finally, due to acetone a word used for translation Piperazine understands azeotrope with water and makes its azeotropic, separation.The bottom of destilling tower can remain salinity height, the aqueous solution containing impurity, usually It is discarded, become public hazards reason.The concentration conversion of the acetone azine obtained herein is up to 20% or so for hydrazine hydrate.Acetone hydrazone or Acetone substitution hydrazone is not soluble in water, also not azeotrope with water.The separation of acetone azine, method of purification need other methods.Ketazine process Problem is to be characterized in that being formed the azine or substitution hydrazone of the stabilization not aoxidized by oxidant i.e. chlorinating agent, but in order to obtain Required object-hydrazine hydrate or substitution hydrazine, it is necessary to the ketazine or hydrazone that make or the hydrolysis of substitution hydrazone come obtain hydrazine hydrate or Substitute hydrazine, be hydrolyzed and be relatively easy to using strong acid such as sulfuric acid, hydrochloric acid.But for obtained product, it is only capable of to be hydrated Hydrazine, hydrazine derivate with these etc. salt obtain.Free hydrazine hydrate, hydrazine be in itself in order to obtain, it is necessary to is neutralized.Its result It is to need extra alkali raw material and the substantial amounts of by-product salt of generation.Stable ketazine, hydrazone, substitution hydrazone without using strong acid etc. then very Difficulty is hydrolyzed.Other ketones do not show the so high reactivity of acetone, therefore do not have the protectant effect of hydrazine, it is impossible to make With.It is most of industrial if not making ketone azine, hydrazone and acetone substitution hydrazone hydrolysis and obtaining high concentration hydrazine hydrate and substitution hydrazine It cannot be used in way.Also there is using low concentration hydrazine hydrate or substitutes the example of hydrazine in special circumstances.As without using strong acid etc. and Make acetone azine, the method for acetone hydrazone hydrolysis, it is contemplated that the method hydrolyzed under high temperature, but it is hydrolysis and the change after hydrolysis Compound in conjunction with balanced reaction, its mutual reaction rate is almost identical, therefore obtains object by pyrohydrolysis and be also Extremely difficult.High-temperature-hot-water solution method is applied in the hydrolysis of ketone azine, hydrazone and acetone the substitution hydrazone obtained by the preparation method When, it is necessary to 150-160 DEG C or so of high-temperature-hot-water solution, object is obtained using minimum equilibrium constant difference bit by bit, With efficiency is excessively poor, the serious problems of the substantial amounts of energy of consumption.But substantial amounts of accessory substance will not be generated, not become public affairs by having The advantages of the reason for evil.For this method, will describe in detail thereafter.

Developed as the 4th method, be known as the method (patent document 2) (patent document 3) of hydrogen peroxide method.

Any method all generates substantial amounts of by-product salt in 1st method, the 2nd method, the 3rd method, so that as public hazards Reason.In addition, in order to avoid product is decomposed due to oxidants such as the sodium hypochlorite in raw material, it is necessary to stop at low concentrations Reaction.As the method for not generating substantial amounts of by-product salt, the method using hydrogen peroxide as oxidant is developed.Although reaction Mechanism is not disclosed, but based on chemical reaction knowledge from the point of view of, it is the reaction entirely different with the reaction mechanism of conventional preparation method, can be with Easily speculate its reaction mechanism.But it is not to say that and simply mixes ammonia or amine derivative with hydrogen peroxide.At present There is no any document to carry out reaction intermediates and confirmation, the explanation of reaction mechanism.It is presumed that：The reaction of presumption is preferably first Ketone is set to be reacted with ammonia and generate stable ketimide (ketimine).Preferably, generate ketimide (ketimine) ketone with It is on the contrary stable compound that ammonia or amine derivative, which have reactivity, the ketimide (ketimide) generated by the reaction with ketone,. The acetone generation acetone imine used in 3rd method, but acetone imine or acetone imine derivative are unstable, therefore it is tired from operation Hardly possible, yield, side reaction, decomposition reaction set out and evade acetone imine or acetone imine derivative.In the technology, as long as generation The ketone of stable ketimide can be any ketone, but the ketimide oxidation of 2 molecules is generated ketone azine with hydrogen peroxide or is taken For hydrazone.The problem of the problem of producing with shown in the 3rd method is identical.When hydrolyzing ketone azine with strong acid, obtain hydrazonium salt or take For hydrazonium salt.It is desirable that the by-product salt for the reason for not generating as public hazards, without using causing the increased strong acid of cost, but use High-temperature-hot-water solution method obtains hydrazine hydrate or substitution hydrazine.Viewpoint when from ketazine and substituting the high-temperature-hot-water solution of hydrazone with post processing Set out, make methyl ethyl ketone and ammonia or amine derivative reaction and obtain stable Methylethyl ketimide (ketimine), containing In the presence of having the catalyst (tetramethyldiarsine) of supervirulent arsenic compound, ketimide is aoxidized with hydrogen peroxide, makes the ketone of 2 molecules The NH structures of imines with reference to and generate N-N keys, so as to generate ketone azine；Or ketimide and substitution amine are made by same reaction With reference to, obtain substitution hydrazone；Therefore obtained methyl ethyl ketone azine or substitution hydrazone is and acetone azine or acetone hydazone derivative phase More stable ketone azine or hydrazone or substitution hydrazone than further.The hydrazine hydrate of target or substitution hydrazine in order to obtain, it is necessary to obtaining herein To ketone azine and substitution hydrazone be hydrolyzed (reaction equation 4).

[reaction equation 4]

Make the stabilization ketone azine hydrazone or substitution hydrazone high-temperature-hot-water solution and obtain hydrazine hydrate or substitution hydrazine for the 3rd preparation method It is difficult to realize with for the 4th preparation method.In the 3rd method and the 4th method, when the hydrazone to generation carries out high-temperature hot hydrolysis When, when hydrolysis, is transformed into the accessory substance or the accessory substance of hydrazone and reactive ketone of more inner molecular reaction.Formation, stabilization from imines Property, the viewpoint such as reactivity and from the ketone azine after reaction or substitute that the heating of hydrazone is water-disintegrable, is regenerated as ketone etc. by hydrolysis Harmony set out, the ketone used in the 4th method mainly use methyl ethyl ketone etc..Methyl ethyl ketone azine therefrom Methylethyl hydrazone or Methylethyl substitution hydrazone etc. it is not soluble in water, therefore have the advantages that easily to separate with water layer, no The advantages of producing the inorganic salts discarded objects such as salt, but catalyst and needs using supervirulent arsenic are needed at 190 DEG C or so High-temperature-hot-water solution, for this method also in the same manner as the 3rd method, the reaction of high temperature thermal decomposition is balanced reaction, utilizes the equilibrium constant Subtle differences obtain bit by bit hydrazine hydrate and substitution hydrazine.Therefore, because generated when wasting substantial amounts of energy, high-temperature heating Accessory substance and the problem of make color articles etc., and be more difficult to carry out.And then when using the ketone more than carbon number, the height of ketazine Warm hydrolysis is almost impossible.Its hydrolysis will describe in detail in following items.

[obtain the ketazine in the preparation method of ketazine or hydrazone or substitution hydrazone or hydrazone or substitute the high-temperature-hot-water solution method of hydrazone Illustrate]

In the 3rd preparation method (organic method, ketazine process), before formation acetone azine stabilizes, the hydrazine hydrate of generation Or the reproducibility of substitution hydrazine is very strong, therefore easily due to chlorinating agents such as oxidant, that is, sodium hypochlorite in raw material and by oxidation point Solution, therefore be the hydrazine hydrate of generation or substitution hydrazine is transformed to stable acetone azine before being decomposed by oxidant or acetone takes For hydrazone, so as to the method for not oxidized decomposition.In acetone hydrazone, on the one hand, diazanyl is free state, therefore is easily aoxidized by raw material Agent aoxidizes and cannot form stabilisation material.On the other hand, although hydrazine hydrate or substitution hydrazine may achieve mesh under low concentration state , but with the increase of acetone azine or acetone hydrazone or the concentration of acetone substitution hydrazone, the hydrazine hydrate substantially generated later or take For hydrazine all since decomposition fast with the reaction rate of the chlorine system oxidant such as sodium hypochlorite and caused by the oxidant preferentially occurs is anti- Should.Therefore, it is also required to stop reacting at low concentrations when acetone azine or acetone substitute hydrazone method.Final required product removes It is substantially hydrazine hydrate beyond specific use or substitutes the high concentration product of hydrazine, it is therefore desirable to makes ketone azines or substitution hydrazone Hydrolyze and concentrate, the hydrazine hydrate or substitution hydrazine of high concentration is made.

For the 4th preparation method (hydrogen peroxide method), consider from presumption reaction mechanism, it is contemplated that following scheme：Make methyl second Base ketone and ammonia or the reaction of substitution amine and first generate methyl ethyl ketone imines, with hydrogen peroxide by methyl in the presence of arsenic series catalysts Ethyl ketimide aoxidizes and generates N-N keys, is initially being transformed to methyl ethyl ketone azine or Methylethyl substitution hydrazone.Due to reaction Initially do not generate hydrazine hydrate or substitution hydrazine, therefore there is no oxidant, that is, hydrogen peroxide make hydrazine hydrate or substitute hydrazine decompose ask Topic.The concentration of methyl ethyl ketone azine or Methylethyl substitution hydrazone can be improved, but these compounds are the compounds of stabilizer pole. Final goal product is hydrazine hydrate or the high concentration product of substitution hydrazine, it is therefore desirable to substitutes methyl ethyl ketone azine or Methylethyl Hydrazone compound is hydrolyzed into hydrazine hydrate or substitutes hydrazine and recycle methyl ethyl ketone, carries out hydrazine hydrate or substitute the concentration of hydrazine.

For the 3rd preparation method, the 4th preparation method both preparation methods, due to obtaining ketone azine or substituting the stable material of hydrazone, It must carry out ketone azine or substitute the hydrolysis of hydrazone.Can easily it be hydrolyzed using inorganic acid etc. as catalyst, but obtain Compound is hydrazine or the inorganic acid salt of substitution hydrazine, it is necessary to neutralized once again with alkali and forms hydrazine hydrate or substitution hydrazine, therefore further The reason for generating substantial amounts of by-product salt and becoming public hazards, simultaneously because causing cost to improve using extra neutralization raw material.

In order to avoid these, high-temperature-hot-water solution is taken in actual production, this method will not be connected by the high ketone of stability Nitrogen or substitution hydrazone generation by-product salt.But the ketone that is generated of high-temperature-hot-water solution and hydrazine hydrate or substitution hydrazine in conjunction with reaction Velocity constant also becomes larger.It is the indiscriminate balanced reaction of reaction rate.Also it is only capable of obtaining even if selection optimum condition minimal amount of Hydrazine hydrate or substitution hydrazine (reaction equation 5).

When at a higher temperature carry out pyrohydrolysis reaction when hydrolysis constant become larger, but ketone with dissociate hydrazine hydrate or take Also become larger for the reaction rate constant of hydrazine, be the condition of contradiction each other.There are the equilibrium constant slightly difference in high-temperature-hot-water solution Temperature spot, therefore the hydrazine hydrate as obtained from high-temperature-hot-water solution that can isolate or substitute the amount of hydrazine few, Bu Guoshi Make ketazine at such high temperatures or substitute hydrazone ad infinitum to circulate progress pyrohydrolysis, the hydrazine hydrate for obtaining low concentration or substitution hydrazone.When When further gradually stepping up hydrolysis temperature, the difference of reaction rate constant will not correspondingly become larger.Acetone azine or acetone substitution hydrazone The minimum temperature for being also required to 150-160 DEG C or so of hydrolysis of (the 3rd preparation method), methyl ethyl ketone azine or methyl ethyl ketone substitution hydrazone The temperature of (the 4th preparation method) then 180-190 DEG C or so of subsistence level.Other ketone can hardly then carry out ketazine or substitute the life of hydrazone Into the pyrohydrolysis with these compounds.Hydrazine hydrate or substitution hydrazine are obtained due to long-time circulation progress high-temperature-hot-water solution, can be produced Give birth to substantial amounts of energy dissipation and hydrazone is generated due to incomplete reaction when synthesizing ketone azine during ketone azine, and warmed in height During hydrolysis incomplete decomposing and in conjunction with when generate hydrazone.Hydrazone occurs disproportionated reaction when heated and forms ketone azine and hydrazine hydrate, The hydrazone of hydrazine hydrate and ketone is unstable compound, can be by inner molecular reaction or with the reaction of ketone and in the high-temperature heating course Generate substantial amounts of pyrazoline, other accessory substances.In addition, ketone in itself also due to long-time high temperature course and generate condensation product.This Outside, these accessory substances are the reason for causing the purity of product reduce, colour.It is very big with energy expenditure to be heated at high temperature method for hydrolysis So as to it is less economical, be only capable of obtaining containing impurity, there is the problem of low-quality product of coloring.On passing through height during ketazine process Concentration of hydrazine hydrate that warm water's solution obtains, the salt of by-product, its separation method, method for concentration etc., referring to the record of its project.Appoint The rectifying again that one method is required to distillation purifying and carries out as needed.

[reaction equation 5]

K1, K2 represent dissociation constant.

Prior art literature

Patent document

Patent document 1:Ger.P.1,082,889(June 9,1960)

Patent document 2:FR.P.2260569(November,5,1975)

Patent document 3:US.P.4093656(June.6.1978)

Non-patent literature

Non-patent literature 1:J.Fischer,J.Jander,Z.Anorg.Allgem.Chem.,313,14(1961)

Non-patent literature 2:J.E.Troyan,Ind.Eng.Chem.,45,2608(1953)

Non-patent literature 3:Lin Hong, Synthetic Organic Chemistry association will, page 33,451 (1975)

Non-patent literature 4:Japanese industries medical gas association " liquefied carbon dioxide Handling materials " (in September, 2015,54 Page)

The content of the invention

Problems to be solved by the invention

The problem of the present invention is, there is provided a kind of hydrazine hydrate or the autofrettage for substituting hydrazine, it is catalyzed without using inorganic acid etc. Agent, therefore generate accessory substance and discarded object, consumed energy it is few, under the low temperature such as room temperature with high yield, efficient method into The hydrolysis of row ketazine (ketone azine) or hydrazone, substitution hydrazone or schiff base compounds, economically produces high-purity, high concentration, any The hydrazine hydrate or substitution hydrazine of concentration.Furthermore it is possible to widely using the ketone as raw material, aldehyde etc. has the compound of carbonyl.Made Carbon dioxide being capable of cycling and reutilization.In addition, in conventional method, make in the case of without using catalyst such as inorganic acids Ketone azines or ketone substitution hydrazone compound hydrolysis and generate hydrazine hydrate or substitute hydrazine method in need high-temperature-hot-water solution, because The ketone compound that this essence can use is only limitted to acetone or methyl ethyl ketone.In addition, if allow a large amount of generation by-product salt, then It can be hydrolyzed using inorganic acid, be neutralized again after obtaining the inorganic acid salt of hydrazine to obtain hydrazine hydrate or substitution hydrazine.But The conclusive shortcomings such as economical poor, the reason for producing substantial amounts of by-product salt and becoming public hazards.Although it can use wider The carbonyls of scope, but be difficult to use as substantive working system.

The method of the present invention is entirely different hydrolysis mechanism, therefore can use the carbonyls of wide scope.

The solution used to solve the problem

The present inventor to solve the above-mentioned problems, to ketone azine, hydrazone, substitution hydrazone or schiff base compounds hydrolysis in can The exploration and its application method for expecting the compound of catalytic effect have made intensive studies, as a result, in lewis acid, common carbon Sour water or pressurization and make under the acid degree of the degree of carbon dioxide solubility, although it is low to carry out the hydrolysis interconversion rate, be only capable of Obtain the hydrazine hydrate or substitution hydrazine of low concentration.When improving the temperature of hydrolysis, reaction obtains a degree of promotion, but secondary Reaction also aggravates.The purpose of the present invention cannot be reached.Needed as not generating stable salt with hydrazine hydrate or substitution hydrazine, also not generating The acid of salt to be separated and discarded, we consider carbonic acid, but the pH of carbonated water is 6.35 under room temperature, normal pressure, when pressurization improves Though pH also declines during solubility, the limit is pH=2.9 or so.Under the acid degree of the degree, azine or hydrazone or substitution hydrazone Hydrolysis is very weak.Even if improving temperature under elevated pressure to improve reactivity to carry out, also increase only accessory substance, target The hydrazine hydrate of thing substitutes the generation of hydrazine then less to increase.As hereinafter described in detail, carbon dioxide can correspond to pressure Carbon dioxide state, the region of subcritical state, supercriticality, liquid CO 2 state is presented with temperature.Make us anticipating It is outer, find the subcritical, supercritical carbon dioxide under the conditions of minimum pressure and and then phasor in liquid two Under the conditions of carbonoxide and in the presence of water, azine, hydrazone, substitution hydrazone or schiff base compounds are successfully made successfully to hydrolyze and not have Impurity produces, can in a short time with high yield, the hydrazine hydrate of high efficiency generation object, substitution hydrazine or carbonyls And amino-compound.

It was found that in order to be hydrolyzed using subcritical, supercritical carbon dioxide and liquid CO 2 and by ketone a word used for translation Piperazine, hydrazone, substitution hydrazone or schiff base compounds form hydrazine hydrate, substitution hydrazine, carbonyls or amino-compound, will be with hydrate Form add the water of amount more than required water and amount needed for hydrolysis solution and dispersion 40 DEG C of grades with Under temperate condition under be stirred, obtained well so as to efficiency high-purity, high concentration, form by adjusting water Hydrazine hydrate, carbazic acid (hydrazine formic acid), substitution hydrazine, substitution carbazic acid, carbamic acid derivative or carbonyl for any concentration Based compound and amino-compound.

Although reaction mechanism outside the anticipation assumes that, but the association of liquid CO 2 and be neither gas nor be The supercritical carbon dioxide of liquid is not monomolecular gas when carrying out microscopic observation, but the state of multiple molecular associations, It is electron transmission mechanism or proton transfer mechanism based on this that can speculate mechanism of action.The mixing with water is used in the present invention Thing, it can be considered that the end of association carbon dioxide is carboxylic acid.According to above-mentioned association mechanism, thus it is speculated that the proton shows strong acid Property.It was found that generation hydrazine hydrate or the carbazic acid or substitution carbazic acid that substitute hydrazine and carbon dioxide reaction and generate, lead to Cross and be heated to 40-70 DEG C and be easily safely decomposed into hydrazine hydrate or substitution hydrazine and carbon dioxide, high-purity, highly concentrated can be obtained Degree, by using water and as any concentration hydrazine hydrate or substitution hydrazine as product.Needing to obtain low concentration When the condition of product is to carry out, water is evaporated with destilling tower first, is distilled under the azeotropic state with hydrazine hydrate and obtains 80% Hydrazine hydrate, and then only evaporate water and concentrated, distill then can obtain 100% hydrazine hydrate.In addition, also carry out at this time pure Change.By confirming to these facts, so as to complete the present invention.

[detailed description of the solution used to solve the problem]

In the present invention, by by needed for subcritical carbon dioxide, supercritical carbon dioxide, liquid CO 2 and hydrate The water wanted, the required water of hydrolysis amount more than the water of amount be stirred 40 DEG C such as the following (being not limited to the temperature), and make After reaction is hydrolyzed in ketone azine, hydrazone, substitution hydrazone or schiff base compounds shown in following reaction equations (6), subcritical titanium dioxide Carbon and the state that supercritical carbon dioxide is the property with two side of gas and liquid, the cluster associated for carbon dioxide are disperseed State.Therefore, subcritical carbon dioxide, supercritical carbon dioxide are changed to liquid-phase condition after reaction, with liquid CO 2 Merging forms liquid phase.Standing then becomes these carbon dioxide liquid layers and the separated state of water layer.The carbon dioxide dissolved in water Concentration and the water dissolved in liquid CO 2 amount it is as shown in Figure 2.Supercritical carbon dioxide has the property of organic solvent Matter, therefore it is used as extracting the solvent of useful organic matter from natural materials.But liquid dioxy is not found in each document Change the report that carbon shows organic solvent sample property.Although visible alcohol on supercritical carbon dioxide and low mole prop0rtion and organic The data to balance each other of solvent, but the parsing to the detailed results on organic reaction is the fact that found first in the present invention. Under any state in subcritical carbon dioxide, supercritical carbon dioxide and liquid CO 2, ketazine (the ketone a word used for translation of raw material Piperazine) and the generated ketone of hydrolysis and the slightly water-soluble of generation substitution hydrazine be dissolved in and can be described as subcritical the two of liquid condition on microcosmic Carbon-coating, supercritical carbon dioxide layer and liquid CO 2 layer are aoxidized, the ketone dissolved in water is also dissolved in these liquid titanium dioxides Carbon-coating.Hydrazine hydrate, substitution hydrazine and amino-compound soluble easily in water is dissolved in water, therefore is dissolved in water layer.

As shown in data (1), the proportion of liquid CO 2 is according to temperature and makes its liquefied pressure and different.Liquid two The critical point of carbonoxide is 31.1 DEG C, 7.38MPa.Density of the liquid CO 2 under each temperature, pressure such as data (1) institute Show.The solvent used in the present invention is subcritical carbon dioxide, supercritical carbon dioxide and liquefied carbon dioxide and water, is reacted After, temperature or/and pressure are adjusted, subcritical carbon dioxide and supercritical carbon dioxide are transformed to liquid dioxy Change carbon.As shown in Fig. 2, the liquefied carbon dioxide dissolved in the water and water that are dissolved in liquefied carbon dioxide under low temperature is non- Often low concentration.The water and liquefied carbon dioxide that cannot be dissolved each other are discrete state.Even if due to molten in water or liquefied carbon dioxide Ketone azine or ketone hydrazone or ketone the substitution hydrazone and hydrazine hydrate of solution substitute the materials such as hydrazine, carbazic acid or substitution carbazic acid and show Show solidification point reduction, can also freeze when water becomes more and reaches low-down temperature.Under agitation, water layer forms solid, because This becomes the slurry state that solidified water layer occurs in liquid CO 2 layer.Liquid CO 2 when more than -10 DEG C Proportion reach less than 1, when with preferable reaction condition implement the present invention method when, due to being liquid CO 2 and water Mixed system, therefore liquid CO 2 layer can be moved to upper strata, water layer is then moved to lower floor.When use can be dissolved in liquefaction During the above raw material of carbon dioxide and water, stock dispersion is formed in the state or formation liquefaction dioxy of liquefied carbon dioxide and water Change carbon, water, 3 layers of raw material.Raw material and product can cause solidification point to reduce, in addition can be to occurring in liquid CO 2 layer The slurry state thing of solidified water layer is handled, but from viewpoints such as reactivity, the thermal efficiency, post processings, preferably -30 DEG C or so more than and less than 40 DEG C of temperature under reacted.Further preferably more than -10 DEG C and at less than 30 DEG C of temperature Reacted.Relative to volume and the filling of liquid CO 2 filled of the pressure dependence of these temperature in pressure vessel Measure (filling constant), will illustrate in the project of Fig. 4.The solidification point of 60% hydrazine hydrate is -70.7 DEG C, 100% hydrazine hydrate Solidification point be -51.7 DEG C.It is however not limited to above-mentioned reaction condition.

(non-patent literature 4)

[table 1]

Relative to the amount of the azine of raw material, hydrazone, substitution hydrazone or schiff base compounds, the liquid dioxy of arbitrary proportion can be used Change carbon.With the progress of hydrolysis, ketone azine, hydrazone, substitution hydrazone or the schiff base compounds of raw material are hydrolyzed to hydrazine hydrate, take For hydrazine, carbazic acid, substitution carbazic acid, carbamic acid, carbamic acid derivative, amino-compound and ketone or carbonyl compound Thing.Hydrazine hydrate, substitution hydrazine, carbazic acid and the substitution carbazic acid of the water ease of solubility generated are dissolved in water layer, ketone, indissoluble It is dissolved in the substitution hydrazine and substitution carbazic acid of water in liquid CO 2.Schiff base compounds are broken down into carbonyl compound Thing and amino-compound or carbamic acid derivative, are also dissolved in liquid CO 2 layer or water layer.

The hydrolysis carried out using this technology does not occur at ketone with being sent out in the reaction of hydrazine hydrate or hydrazone or substitution hydrazine completely The raw reaction for returning to azine or hydrazone or substituting hydrazone, does not produce the accessory substances such as the condensation product of ketone completely yet.Adjustment temperature after the reaction Degree or pressure, in the case of being subcritical, supercritical carbon dioxide, are transformed to liquid CO 2, so as to be separated into liquid two Aoxidize carbon-coating and water layer.By the way that water layer is heated to 30-100 DEG C, preferably 40-70 DEG C, remaining with carbazic acid or can be taken Hydrazine hydrate or substitution hydrazine and carbon dioxide (reaction equation are easily and safely decomposed into for compound existing for carbazic acid form 7).It is however not limited to the condition.In the case of schiff base compounds similarly.

Hydrazine hydrate substitutes the concentration dependant of hydrazine in the water added, addition and the target of hydrazine hydrate in hydrolysis The corresponding water of product concentration, can directly obtain the hydrazine hydrate close to aimed concn.Usually used is the dense of 60-100% The hydrazine hydrate of degree.Certain user also uses the hydrazine hydrate of 5-60% sometimes, can be with regulating pondage to reach the concentration.It is being set to essence During close product concentration, the concentration of obtained rough hydrazine hydrate is analyzed and be added as needed on high concentration hydrazine hydrate or Water is added, so as to be adjusted to defined concentration.

And then when needing the hydrazine hydrate of high-purity, rectifying can be carried out to obtained high concentration hydrazine hydrate and obtained. When carrying out rectifying with 100% hydrazine hydrate, the hydrazine hydrate of any concentration can be adjusted to by dilution, so as to tackle various concentration Product.Moreover it is possible to it is enough in the concentration for adjusting rough hydrazine hydrate.In addition, in the case where needing anhydrous hydrazine, can pass through It is dehydrated by 100% hydrazine hydrate and is distilled and obtained as needed.Hydrazine hydrate azeotrope with water at 80%, therefore with altogether Boiling product will obtain 80% hydrazine hydrate when being fractionated, if will be set to the hydrolysis of azine or hydrazone for the water of reaction in advance The following amount of amount necessary to required water and the hydrazine hydrate of formation 80%, then can obtain more than 80% hydrazine hydrate The hydrazine hydrate of any high concentration.Substitution hydrazine does not form hydrate, therefore adds the water hydrolyzed more than required water.It is logical Cross the boiling point for being heated to water and water is only evaporated from these, then fractionate out 100% hydrazine hydrate concentrated or substitution hydrazine i.e. Can.When distilling hydrazine hydrate, the decomposition caused by the oxygen in decomposition, air in order to avoid hydrazine hydrate in nitrogen etc., it is necessary to not live Sprinkle and distilled in gas.In addition, substitution hydrazine is more unstable, it is therefore desirable in inactive gas and the addition for being suitable for substituting hydrazine Distilled in agent.

[reaction equation 6]

[chemical formula 1]

Ketone azine

Compound (1) in reaction equation (6) represents ketazine (ketone azine), and compound (2) represents ketone.Compound (3) table Show the ketone identical with compound (2) or the ketone of other species.Compound (4) represents hydrazine hydrate (hydrazine hydrate, hydrazine Hydrate).The R of chemical formula 1₁、R₂、R₃、R₄Can be identical or respectively different, it can be combined in addition, in addition R₁With R₂And R₃、R₄ It can be bonded.Not only there is carbon, there can also be the hetero atoms such as hydrogen atom, nitrogen-atoms, oxygen atom, sulphur atom.Can also have Substituent.As substituent, for alkyl, alkynyl, alkenyl, aralkyl, alkylidene, aryl, pi-allyl, condensed ring radical, there is miscellaneous original The group of these sub grades, can also have will not produce dysgenic halogen, nitro, OH in addition when generating ketone azine or hydrazone The substituents such as base, sulfydryl.It is however not limited to these grade substituents.Primary condition is that at least have and R₁、R₂、R₃、R₄The 1 of bonding The structure that a carbonyl and hydrazine bonding forms.

[chemical formula 2]

Ketone (1)

Represent the ketone of the condition shown in chemical formula (1).R₁、R₂It is identical with the content described in chemical formula (1).

[chemical formula 3]

Ketone (2)

Represent the ketone of the condition shown in chemical formula (1).R₃、R₄It is identical with the content described in chemical formula (1).

[chemical formula 4]

Hydrazine hydrate (hydrazine hydrate, hydrazine hydrate)

H₂NNH₂·H₂O

[chemical formula 5]

Hydrazone

Represent the hydrazone of the condition shown in chemical formula (1).R₁、R₂、R₃、R₄It is identical with the content described in chemical formula (1).R₅、 R₆Also with the R of chemical formula (1)₁、R₂、R₃、R₄Described in content it is identical.

[chemical formula 6]

Carbazic acid (hydrazine formic acid)

H₂NNH-COOH

[chemical formula 7]

Substitute hydrazine

R in chemical formula (7)₅、R₆It is identical with the content described in chemical formula (5).

[reaction equation 7]

The hydrolysis of carbazic acid (hydrazine formic acid)

[chemical formula 14]

H₂NNH-COOH+H₂O→H₂NNH₂·H₂O+CO₂

The effect of invention

The present invention is following method：Make aforementioned Chemistry Figure (1) and ketone azine or hydrazone or substitution hydrazone shown in chemical formula (5) In the case of without using proton catalysts such as inorganic acid etc., under the low temperature such as room temperature in subcritical carbon dioxide, overcritical two Hydrolyzed in carbonoxide and liquid CO 2, substantially with 1 section react do not generated accessory substance high-purity and high concentration or The hydrazine hydrate of any concentration or substitution hydrazine, make liquid CO 2 layer (including change temperature and pressure and be transformed into it is subcritical, Supercriticality) separated with water layer progress layer, by method reliably and securely with cheap, no coupling product, saving energy and nothing The method manufacture hydrazine hydrate or substitution hydrazine of public hazards.It is that used liquid CO 2, ketone or aldehyde for raw material does not occur Side reaction and the manufacture method that recycling, the hydrazine hydrate recycled or substitution hydrazine can be easily separated.

It is unlimited the purpose of the present invention is obtaining hydrazine hydrate or substitution hydrazine, but from the presumption reaction mechanism of above-mentioned record In the hydrolysis of ketone azine, hydrazone, which also can be used in the chemical combination with imido key (- C=N-) shown in the structures such as schiff bases The hydrolysis of thing.

Brief description of the drawings

Fig. 1 shows CO₂The pH of the water of saturation.

Fig. 2 shows CO₂Relative to the solubility and water of water relative to CO₂Solubility.

Fig. 3 shows CO₂State diagram.

Fig. 4 shows the CO in pressure vessel₂State.

Embodiment

The present invention described further below.

The present invention is by the mixing to subcritical carbon dioxide or supercritical carbon dioxide or liquid CO 2 and water Ketone azine or hydrazone or substitution hydrazone are added in system, more than -56.6 DEG C and less than 60 DEG C, preferably -30 DEG C~40 DEG C, it is further excellent Choosing -10~30 DEG C at be stirred and make ketone azine or hydrazone or substitution hydrazone hydrolysis so that with high efficiency, high concentration be transformed to ketone and Hydrazine hydrate substitutes the hydrazine hydrate of hydrazine or substitutes the manufacture method of hydrazine.Describe in detail referring to " solution used to solve the problem it is detailed Thin declaratives ".It is believed that if the detailed parsing for carrying out reaction result according to reaction equation (6) and (9) shown in reaction Come carry out.And then if detailed resolving reaction formula (6), also confirms the reaction and reaction of reaction equation (8) and reaction equation (7) Product.After hydrolysis, adjustment subcritical carbon dioxide layer, the temperature and pressure of supercritical carbon dioxide layer, preferably whole shapes Separated after into liquid CO 2 layer, raw ketone is confirmed when being analyzed with gas-chromatography, liquid chromatogram.If make Liquid CO 2 titanium dioxide from liquid CO 2 layer is carbonized and gasifies, then confirms the residual of ketone.At low temperature will The water layer isolated, which is concentrated under reduced pressure or adds methanol etc. and is dissolved in the poor solvent of water, can then separate out partial crystals.With IR and liquid phase Chromatography confirms the crystal, is accredited as carbazic acid (hydrazine formic acid) or substitution carbazic acid.Carbazic acid or substitution diazanyl Formic acid is unstable compound, when being heated to 40 DEG C~60 DEG C or so of temperature, reliably and securely, is fully decomposed into water Close hydrazine or substitution hydrazine and carbon dioxide.Bubble can be produced when heating the water layer of this reaction, is clearly carbon dioxide through analysis.

[hydrolysis in the existing preparation method of acetone azine or acetone hydrazone]

Formed in the existing preparation method of acetone azine, first by the composition after reaction, i.e. ammonia, acetone, acetone azine, acetone Volatile material such as hydrazone, hydrazine hydrate, water all temporarily evaporates, and salt is concentrated in distillation tower bottom, divides as an aqueous solution From, remove.Ammonia is recycled from volatile ingredient at the same time, then separates ketone.Aqueous solution containing acetone azine and acetone hydrazone is existed Heat resolve reaction is incorporated into hydrolysis tower.

On R₁、R₂、R₃、R₄For the hydrolysis of the acetone azine of methyl, by the third of the bottom tank of the hydrolysis tower of more column plate modes (acetone azine and water show azeotropic to ketone azine aqueous solution.Hydrazine hydrate and water also azeotropic) it is heated to make the K1 shown in reaction equation (1) Just over 130-150 DEG C of K2, excessive water is evaporated first, and then to avoid passing through the hydration that high-temperature-hot-water solution generates Hydrazine and acetone are evaporated in conjunction with and by minimal amount of free acetone, make it is unhydrolysed, in conjunction with and the acetone azine that generates into Row cyclic high-temperature pyrohydrolysis, acetone is evaporated bit by bit from tower top.The hydrazine hydrate of generation then remains in bottom of towe.Consumption is a large amount of Steam and acetone azine is circulated for a long time, obtain the hydrazine hydrate aqueous solution of 20-30%.Since acetone azine is sudden and violent for a long time High temperature is exposed to, the accessory substance such as pyrazoline of the acetone hydrazone that is hydrolyzed by side generation, the accessory substance such as condensation product of acetone can increase. In order to avoid the low concentration hydrazine hydrate of the obtained 20-30% of bottom of towe is decomposed due to the oxygen in air, in addition in order to ensure Security, rectifying is separately carried out in the presence of the inactive gas such as nitrogen, water is evaporated first and is concentrated, then with hydrazine hydrate Rectifying is carried out with the azeotropic mixture form of water, obtains 80% hydrazine hydrate.Nonetheless impurity is still contained.When needing high-purity and height During the hydrazine hydrate of concentration, aoxidize, in addition in order to ensure security, evaporated first in the presence of the addition such as nitrogen property gas in order to prevent Remove water and improve concentration, carry out rectifying again.100% hydrazine hydrate in order to obtain, aoxidizes and does not live in nitrogen etc. in order to prevent In the presence of sprinkling gas, water is evaporated from tower top first, 100% hydrazine hydrate is obtained in bottom of towe, its rectifying once again is obtained from tower top 100% hydrazine hydrate.

When obtaining substitution hydrazine, since it is unstable compound, it is impossible to obtained by the processing same with hydrazine hydrate. Need the special environmental condition of the distillation for substituting hydrazine.

[hydrolysis in the existing preparation method of hydrogen peroxide method]

Methyl ethyl ketone is used in existing hydrogen peroxide method.It is not known in patent, document etc. and records hydrogen peroxide method Reaction process, reaction mechanism, but consider from the situation and chemical knowledge of the embodiment of patent, in hydrogen peroxide method firstly the need of Methyl ethyl ketone and ammonia is set to react and generate Methylethyl ketimide.In the case of acetone, due to acetone imine it is unstable without Use acetone.On hydrogen peroxide method, recorded in patent：Starting is mixed from the methyl ethyl ketone and ammonia of raw material, is as a result generated Methyl ethyl ketone azine.Methyl ethyl ketone azine is not soluble in water, has the advantages that can be easily separated, but methyl ethyl ketone azine is phase To stable compound, it more difficult to hydrolyze, although it is also that balance shown in reaction equation (5) is anti-to carry out the high-temperature-hot-water solution reaction Should.During high-temperature-hot-water solution, the difference of equilibrium constant K 1 and K2 it is minimum, make K2 more than the temperature of K1 constants be 180-200 DEG C of height Temperature.The theoretical amount of the required water of pyrohydrolysis of externally heated methyl ethyl ketone azine and the required water of hydrate of hydrazine with On water mixture or be blown into 180-200 DEG C of high-temperature vapour and heated, by each very small amount from the tower of hydrolysis tower The methyl ethyl ketone of ground dissociation evaporates, and the hydrazine hydrate aqueous solution of generation residues in bottom of towe.Consume substantial amounts of energy and long-time Ground make undecomposed methyl ethyl ketone azine and methyl ethyl ketone and hydrazine hydrate in conjunction with into methyl ethyl ketone azine it is mixed Compound ad infinitum circulates, and obtains hydrazine hydrate.Hydrolysis of the energy that hydrolysis in the preparation method is consumed much larger than acetone azine is disappeared The energy of consumption.Due to making methyl ethyl ketone azine be exposed to for a long time under the high temperature, (most components is pyrazoline to accessory substance The condensation product of class, ketone) generation increase, due to the reason such as these, the problem of color articles are also serious.In addition, the preparation method needs Will be as the catalyst for being referred to as tetramethyldiarsine of supervirulent arsenic derivative.The recovery method of the catalyst, needed for it into This becomes problem.

It is other that there is R₁、R₂、R₃、R₄、R₅、R₆The big carbonyl of molecular weight compound azines class and hydrazone chemical combination In the case of species, it is impossible to heating hydrolysis.It is only capable of enough strong acid and is hydrolyzed to make its dissociation.Although also disclose using hexichol first Ketone, cyclohexanone, but what is obtained with strong acid hydrolysis such as sulfuric acid is sulfate of hydrazine etc..In order to obtain hydrazine hydrate and with alkaline matter With, exist produce substantial amounts of salt accessory substance the problem of (non-patent literature 3).

[explanation of the situation of hydrazone]

Confirm the conduct incomplete reaction thing for stopping at the midway state to form ketazine stable in the reaction system When the hydrazone and pyrohydrolysis of matter by ketone and hydrazine hydrate in conjunction with into a small amount of hydrazone for being used as incomplete reaction material. On the other hand, in the reaction with substituting hydrazine, raw material is to substitute amine and ammonia, therefore can be as the change in the mixture of various products One of compound and obtain.Substitution hydrazone from the amine with substituent does not have reproducibility without free diazanyl, is steady Fixed.Be only capable of utilize by sodium hypochlorite when oxidant make the mixture of ketone and ammonia generation hydrazine hydrate when incomplete reaction thing, And the hydrazone formed on the hydrazine hydrate of generation in conjunction with the ketone of 1 molecule, formed with the ketone of 2 molecules and the hydration hydrazine reaction of 1 molecule Ketazine, the preparation method for generating stable compound are different, have with the 1st preparation method, the 2nd preparation method is same the problem of.In subcritical state During carbon dioxide, supercritical carbon dioxide when, liquid CO 2 when hydrazone have dissolubility to water, but substitute hydrazone in water, liquid Dissolubility in carbon dioxide is also low, therefore is not particularly advantageous.In original synthetic reaction, the ketazine of generation or substitution Hydrazone sometimes with hydrazone or substitute the state of hydrazone and comprising therefore in pyrohydrolysis, the liquid CO 2 (including subcritical two of the present invention Carbonoxide, supercritical carbon dioxide system) under pyrohydrolysis when be transformed to hydrazine hydrate or substitution hydrazine, although less be also considered as reaching Purpose, contribute to obtain object.In addition, hydrazone compound occurs disproportionated reaction and forms azines and hydrazine.Generation Hydrazine be decomposed due to oxidant.

Intermediate as the processing of the present invention, it is contemplated that there is a possibility that of hydrazone compound, course.Between in the reaction When stage is confirmed with liquid chromatogram, the peak for being estimated as hydrazone compound has been confirmed.In addition, in pyrohydrolysis process, liquid is used Phase chromatography has also confirmed the presence of hydrazone compound in the reaction solution in interstage.It is not present in the processing reaction solution of the present invention Oxidant, it is taken as that there may be hydrazone compound.Think that it is not decomposed either, as midway completely in pyrohydrolysis processing Catabolite and generate.When isolating the hydrazone compound for the stabilization being dissolved in water and the processing method of the application present invention, energy Enough effects for playing the present invention, hydrolyze to obtain hydrazine hydrate without generating accessory substance in the same manner as azines.

[situations of schiff base compounds]

For the azomethine key of schiff base compounds for stabilizing carbonyls or amino-compound and being commonly used Equivalent to a half structure of the ketone azine used in the present invention.Carbonyls or amination are retrieved in order to hydrolyze it Compound, the Conventional treatments of those skilled in the art are hydrolyzed using inorganic acid.And have the shortcomings that during ketone azine it is same, Problem.Due to the half structure with ketone azine, it can be said that equivalent, identical with the hydrolysis of ketone azine.As solution The method of the problem, method of the invention, be hydrolyzed using subcritical, overcritical, liquid CO 2 be it is effective, this Any is self-evident.

[solubility between carbon dioxide and water]

Ideally carbonic acid shows acid-hydrolyzed effect, still, in carbonated water, the Pk of carbonic acid₁=3.60, Pk₂= 10.25, the Pk=6.35 of carbonic acid, are very weak acid, do not show the function for the acid catalyst for promoting hydrolysis.Carbon dioxide exists When temperature is lower, pressure is higher, solubility in water more increases, and the pH value of aqueous solution becomes lower (Fig. 1).

But pH value cannot preferentially cause ketazine or hydrazone for the carbonic acid of the degree or substitute the hydrolysis of hydrazone.It is hydrolyzed Ketazine is few, is the acidic catalyst generation of more accessory substance of carbonic acid on the contrary.Carbon dioxide relative to water solubility such as Fig. 2 It is shown.It is high concentration to be dissolved in the state of high temperature of the amount in supercriticality of the water of carbon dioxide, high pressure, but due to for height Temperature, side reaction preferentially occur, and cannot get hydrazine hydrate or substitution hydrazine.Although solubility of the water in the liquid CO 2 of low temperature It is low, but the water dissolved is critically important.In order to increase the contact probability of the dissolving of new water, raising and liquid CO 2, it is necessary to Sufficiently stirring.

[behavior of carbon dioxide, solubility (gas, subcritical, overcritical, liquid)]

The state diagram of carbon dioxide is as shown in Figure 3.In the presence of water, even in central area in each region of phasor etc. and The hydrolysis of ketazine is carried out under at higher temperature, higher pressure subcritical and supercritical carbon dioxide state, it is also unconfirmed to good Ketazine hydrolysis.It is due to the acid catalytic effect of carbonic acid on the contrary, has been catalyzed the generation of more accessory substance.In liquid two The problem is then not present in oxidation carbon phase.

When be liquid CO 2 in the state diagram in carbon dioxide, under conditions of the state of supercritical carbon dioxide, When carrying out ketazine or hydrazone in the presence of water or substituting the hydrolysis of hydrazone, water layer is separated, to existing except hydrazine hydrate or substitution hydrazine When carbazic acid or substitution carbazic acid in addition is heated, heated and made its hydrolysis, equally with high yield, efficiently Rate obtains the hydrazine hydrate or substitution hydrazine of high concentration, has no that the Asia under the high concentration carbon sour water of high-pressure trend, hot conditions is faced completely The generation of the pyrazoline, the condensation product of ketone that are easily generated when being reacted under boundary's carbon dioxide, supercritical carbon dioxide state.Using When subcritical carbon dioxide and supercritical carbon dioxide, improve temperature then show it is bad as a result, therefore close to critical point Good hydrolysis effect is shown when being handled at low temperature as far as possible.

[situation in pressure vessel]

There are during air inside pressure reacting container, air is driven out of with carbon dioxide in advance, put with carbon dioxide Change, the volume of pressure reacting container is needed for following capacity：Relative to be filled liquid CO 2, the ketazine of raw material or Filling constant more than hydrazone or the capacity of substitution hydrazone and water, exists suitable for the more than needed of operation.Gas blanket is almost by titanium dioxide Carbon occupies.State diagram is approximate in pressure vessel when situation inside pressure is considered as with being only filled with liquid CO 2.Pressure Temperature change and pressure change in container depend on the filling constant of liquid CO 2, when below critical-temperature, liquid Carbon dioxide and the carbon dioxide to aerify are in equilibrium state in the phasor of Fig. 3, on boiling point curve.It is normal corresponding to filling Number, when the temperature rise in pressure vessel liquid CO 2 in corresponding temperatures force container be full of State, if temperature further raises, as shown in figure 4, pressure steeply rises and is in supercriticality.

The line of black represented when filling constant 1.34, is reached at about 22 DEG C and is full of, and shows that temperature further raises When liquid and supercriticality under pressure change.The line of grey represented when filling constant 1.6, is reached at 29 DEG C and is full of, Show the pressure change under supercriticality when temperature further raises.In liquid CO 2 and gas shape carbon dioxide The state being then under conditions of equilibrium state on boiling line.

[using the hydrolysis of the azines of liquid carbonic acid, the detailed description of operation]

For the azine, hydrazone, substitution hydrazone that are used as raw material, it is appropriate that compound when raw material is filled for liquid passes through Method is filled, and when being solid, is opened the lid of reaction pressure vessel and is filled necessary amount.It is noted as above, is filling The air in reaction vessel is replaced into carbon dioxide completely in advance before liquid CO 2.Even if solid material is not exclusively molten Solution also can gradually be dissolved in liquid CO 2 with the progress of reaction.

In subcritical carbon dioxide, supercritical carbon dioxide, liquid CO 2, rub relative to 1 mole of addition 3 of azine Water more than you, make azinium moiety hydrolyze obtained from the case of hydrazone, relative to the water of 1 mole of hydrazone, more than 2 moles of addition, liquid Body carbon dioxide is not particularly limited relative to azine, hydrazone, preferably large excess of amount.On the amount of water, rub relative to azine 1 You for more than 3 moles amount, relative to 1 mole of hydrazone be more than 2 moles amount, when to substitute hydrazone, rub relative to hydrazone 1 is substituted You can also be the water adjusted to hydrazine hydrate or the aimed concn for substituting hydrazine, it is necessary to more than 2 moles of water, without especially Limitation.

For the temperature of liquid it is -56.6 DEG C to 31.1 in the state diagram of the carbon dioxide shown in Fig. 3 on reaction condition DEG C, pressure be 0.52MPa with up to more than 7.38MPa, be desired for -20 DEG C to 31 DEG C, pressure be 2.0MPa with up to 7.4MPa More than, more preferably -10 DEG C to 20 DEG C and 2.8MPa with up to more than 5.8MPa, relative to the pressure position of the temperature such as these In on the boiling line of the state diagram of liquefied carbon dioxide and dependent on filling constant, filled up when in high temperature side and pressure vessel When, the pressure that the minor variations of temperature this may result in drastically rises.Therefore in order to select the liquid two in pressure reacting container The situation that the filling constant and answering pressure of carbonoxide rise, voltage endurance capability, which can for example have as 10MPa, has more than needed.In advance It is most important installed in the safety valve that pressure is discharged into outside system when reaching higher pressure.But the resistance to pressure of pressure vessel Not limited to this.It is overcritical under subcritical carbon dioxide state and more than 31.1 DEG C of temperature and the pressure of more than 7.38MPa During carbon dioxide, 31.1 DEG C to less than 80 DEG C of temperature and the pressure of more than 7.38MPa under preferably corresponding filling constant Power.It is identical when the resistance to pressure of pressure vessel is with liquid CO 2.The container and application method of liquid CO 2 are with reference to high pressure Flue logos and the operating instruction of manufacturer.This in supercritical carbon dioxide, liquid CO 2 state temperature and After the hydrolysis that azine is carried out under pressure, change temperature and be transformed to whole carbon dioxide including supercritical carbon dioxide Liquid CO 2 layer, forms 2 layers of liquid CO 2 layer and water layer and separates each layer.When maintaining low temperature, deposited in water layer In hydrazine hydrate and carbazic acid.When being warming up to more than 30 DEG C, carbazic acid produces carbon dioxide, forms hydrazine hydrate.Diazanyl first Preferred 40-60 DEG C of the safe decomposition temperature of acid.In subcritical carbon dioxide and during supercritical carbon dioxide, the influence of temperature is non- Chang great, low temperature is desired for due to the purpose of this hydrolysis, it is therefore desirable for selecting 31.1 DEG C close to critical point, the bar of 7.38MPa Part.It is however not limited to these numerical value, condition, to be suitable for operation, the temperature of operation, pressure.

The usual commercially available liquefied carbon dioxide storage bottle with siphon pipe is sold with the liquid status that seethe with excitement.Large-scale, a large amount of In use, carried out in the container with vacuum heat-insulating layer of insulating bottle type with -20 DEG C of low-temperature liquefaction form of carbon dioxide Sale, since heat transfer is not zero, low temperature is kept by the evaporation of internal liquid carbon dioxide.

It is dense by the material that can be dissolved according to temperature and each on the separation of liquid CO 2 layer and water layer Spend and the reverse of layer occurs, therefore cannot uniformly show.Measuring to get off to be separated with the liquid level meter of belt sensor.Trip From ketone solubility it is different according to the species of ketone, but the amount for being dissolved in liquid CO 2 layer is more.Although also according to ketone Species and acetone usually used in different but present manufactures, methyl ethyl ketone are easily dissolved in liquid CO 2, especially It is methyl ethyl ketone, its is not soluble in water.It is molten in the case where using substantial amounts of liquid CO 2 relative to azine or substitution hydrazone The liquid CO 2 that solution has these ketone can be used with the cycle of states dissolved with these ketone.In subcritical carbon dioxide or super In the case of being reacted in critical carbon dioxide and water layer, water layer is separated.But it is not limited to this mode.

When dissolving of the ketone in liquid CO 2 becomes slow or difficult, by subcritical carbon dioxide, overcritical two Carbonoxide, liquid CO 2 gasifier gases are simultaneously discharged into outside system, and ketone is then remained as raffinate.The recycling ketone can With direct reuse, when needing purifying, rectifying can be carried out and purified.Arbitrarily selected according to the situation of operation, operation.

If it is desired to efficiently use thermal energy in whole reaction system, then liquid CO 2 is being aerified with gasifier When, it can be cooled down due to heat of gasification, by cold and heat recovery in the form of hypothermic saline while heating with brine etc., and be used for Cooling liquid in the distillation of ketone or for other cooling segments.When the carbon dioxide of aerification is by aerification cooling heat and Cooling carries out cooling liquid when nearby separately having Cooling and Heat Source with its cooled carbon dioxide, is then pressurizeed and liquid with compressor Change.Efficiency when being compressed, liquefied with compressor can be improved when in advance cooling down carbon dioxide, compressor can be suppressed Used electric energy.Meeting heat release when being compressed with compressor, and heat is discharged into outside.Using this caused recuperation of heat as Heat energy when concentration, purifying or the distillation of ketone of hydrazine hydrate utilizes.It is recommended that by using these effective energies (exergy) energy expenditure is ideally suppressed.It is however not limited to these are operated.

Shown in R₁、R₂、R₃、R₄、R₅、R₆Identical substituent is represented in each compound.R₁、R₂、R₃、R₄、R₅、R₆Can Think identical group, can be the group that part is identical, part is different, can also all different groups.Can also be R₁、 R₂And R₃、R₄It is bonded the cyclic structure formed.If it is considered that recycle, it is generally desirable to, the compound and chemistry of chemical formula (2) The compound of formula (3) is the same compound.R₁、R₂、R₃、R₄、R₅、R₆Represent：Hydrogen；Can be formed side chain, can have not with ammonia, two The reactions such as carbonoxide, hydrazine it is substituent, can have heteroatomic alkyl, alkenyl, alkynyl, alkylidene, aralkyl, alkenylene, Arlydene, ester ring type group, aryl, pi-allyl, heterocyclic radical, condensed ring radical, these etc. diyl etc..It is however not limited to these.

As R₁、R₂、R₃、R₄、R₅、R₆Specific example, the alkyl such as hydrogen, methyl, ethyl, isopropyl, isobutyl group are shown.Show Go out the cyclic alkyls such as cyclopenta, cyclohexyl.The ring-type alkane such as cyclopenta including the carbon of structural formula of compound, cyclohexyl are shown Base.The alkenyls such as vinyl, pi-allyl are shown.The cycloalkenyl groups such as cyclopentenyl, cyclohexenyl group are shown.Show to include structural formula of compound Carbon including cyclopentenyl, the cycloalkenyl group such as cyclohexenyl group.The aromatic series ring group such as phenyl, naphthyl is shown.Pyrazolyl, pyrazoles are shown The heterocyclic radicals such as quinoline base, imidazole radicals, imidazolinyl, pyridine radicals, pyrrole radicals, triazolyl, oxazolyls, pyrazinyl, quinolyl.And then Can have on these groups not the alkoxy with the reaction such as ammonia, carbon dioxide, hydrazine, halogen group, nitro, amino, aryloxy group, The substituents such as aromatic series ring group, heterocyclic radical.Preferably hydrogen, methyl, ethyl, isobutyl group, aryl, cycloheptane ring, cyclohexane ring etc.. Specifically, if represented with chemical formula (2), chemical formula (3), for aldehyde such as acetaldehyde, isopropyl aldehyde, benzaldehyde, naphthaldehyde, furfurals Class, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), methylcyclopentyl ketone, cyclopentanone, cyclohexanone, furanone, acetophenone, hexichol Ketone, anthraquinone, naphthoquinones, Fluorenone, fluorenyl ketone (fluorenyl ketone) etc..It is however not limited to these.

Embodiment

The present invention is described in more detail with embodiment below, but the present invention limits from these embodiments.

[analysis of hydrazine hydrate, quantitative approach]

The analysis method of the hydrazine hydrate obtained in following embodiment.

The analysis of hydrazine hydrate can be carried out by gas-chromatography, preferably accurately be analyzed by titration.

[the Hydrazine Hydrate Analyzing method for utilizing titration]

Reagent

1) hydrochloric acid (3+2)

Deionized water 200ml is added into white hydrochloric acid 300ml.

2) chloroform (reagent is superfine)

3) M/40 potassium iodate solutions (5.35g KIO₃/l)

By Potassiumiodate (capacity analysis standard reagent) 130 DEG C heating 2 it is small when after, in drier place cooling, with Be accurate to 0.1mg degree measure carry out normalization after be 10.701g amount, be transferred in 2000ml volumetric flasks, spend from Constant volume { being prepared in the way of the factor (F) reaches 1.000 } after sub- water dissolving.

Operation

1) accurate weighing corresponds to the sample collection amount (*) of concentration, is put into 500ml volumetric flasks, is determined with deionized water Hold.

2) 10ml therein is taken exactly, is transferred in the flask (volume 300ml) with plug, is added hydrochloric acid (3+2) 50ml.

3) titrated with M/40 potassium iodate solutions, chloroform 5ml is added when close to terminal, acutely concussion, is titrated to chloroform layer It is red disappear untill, acutely concussion repeatedly.

Content is obtained by following formula.

[number 1]

M/40 Potassiumiodate 1=0.0012515g N2H4H2O

Remarks

[table 2]

The sample collection capacity that (*) corresponds to concentration is as described above.

[synthesis of standard test raw material]

[synthesis of acetone azine]

At room temperature, to acetone 2, the hydrazine hydrate 100g (2 moles) of the middle additions 100% of 320g (40 moles).At this time due to Reaction heat, temperature rise.Then when the scope stirring 2 of 40~50 DEG C of temperature is small inside.After reaction, after cooling to room temperature, strong Anhydrous potassium carbonate 828g (6 moles) is slowly added under strong stirring, be directly stirred at room temperature 2 it is small when and remove the moisture of by-product. At this time, if stirring is insufficient, potassium carbonate can consolidate sometimes, should be noted.

Potassium carbonate is filtered out after drying, the potassium carbonate filtered out is fully washed with acetone.Remaining acetone is evaporated under reduced pressure Afterwards, the rectifying of acetone azine is carried out by being evaporated under reduced pressure.

[synthesis of methyl ethyl ketone azine]

Under 60 DEG C of heating, 100% hydration is added dropwise into methyl ethyl ketone Isosorbide-5-Nitrae 40g (20 moles) with vigorous stirring Hydrazine 100g (2 moles).Heated in dropwise addition from outside so that reach 80 DEG C during completion of dropwise addition.Methyl ethyl ketone is not easy With being hydrated hydrazine reaction.After completion of dropwise addition, when reaction 10 is small at 80 DEG C with vigorous stirring.Methyl ethyl ketone and 100% water It is immiscible to close hydrazine, therefore forms 2 layers.The methyl ethyl ketone layer on upper strata is isolated, is dehydrated with anhydrous sodium sulfate, is dry.Filter out sulphur After sour sodium, decompression evaporates remaining methyl ethyl ketone, and the rectifying of methyl ethyl ketone azine is carried out by being evaporated under reduced pressure.

Embodiment 1

The volume 400ml with mixer, pressure-resistant 20MPa the autoclave with safety valve on installation with siphon pipe Liquefied carbon dioxide storage bottle, apparatus for supercooling, high pressure constant displacement pump, autoclave is impregnated in thermostat.In advance into autoclave Carbon dioxide is passed through, the air in autoclave is thoroughly replaced.Make generally 20 DEG C of autoclave in 20 DEG C of thermostat. Height is injected into after the solution that acetone azine 28g (0.25 mole) is dissolved with water 31.5g (1.75 moles) is adjusted to 20 DEG C Press in kettle.Made under agitation with high-pressure fluid constant displacement pump by subcooler from liquid CO 2 storage bottle on this basis Carbon dioxide 213g (4.84 moles) is slowly injected into autoclave, in order to avoid aerify quickly when importing liquefied carbon dioxide. The weight change two of autoclave after amount and liquid filling body carbon dioxide that the liquid CO 2 amount origin of injection self-quantitatively pumps Person measures.Pressure in autoclave is shown as about 5.7MPa.At this moment valve is closed, when stirring 12 is small at 20 DEG C.In storage bottle The liquid component of liquid CO 2 and water and acetone azine accounts for about 270ml, and the volume of gaseous state accounts for about 130ml, is to be located at State on the boiling line of state diagram.

After reaction, since the proportion of liquid CO 2 at 20 DEG C is less than water, the water layer portion of lower floor is taken out extremely Pressure vessel, from the carbon dioxide of gas release valve release dissolving, is then slowly heated to 55 DEG C.Make the hydrazine for being present in water layer Base formic acid resolves into hydrazine hydrate and carbon dioxide, and carbon dioxide is discharged into outside system from relief valve.Sampled from water layer, by upper The titrimetry stated calculates the amount of hydrazine hydrate.From the result of titrimetry, hydrazine hydrate (is received for 11.75g (0.235 mole) Rate 94%).On the concentration of hydrazine hydrate, due to be dissolved at this temperature and pressure liquefied carbon dioxide water amount very It is few, therefore be the hydrazine hydrate solution of about 38.4% concentration.

Embodiment 2

Temperature is set to 10 DEG C, water is set to 22.5g (1.25 moles), in addition, carries out similarly to Example 1 anti- Should, it handle.When carrying out the titrimetry of water layer, the hydrazine hydrate for 0.24 mole is calculated.Yield is 96%.It is about 55.7% The hydrazine hydrate solution of concentration.

Embodiment 3

Temperature is set to 0 DEG C, water is set to 22.5g (1.25 moles), in addition, carries out similarly to Example 1 anti- Should, it handle.When carrying out the titrimetry of water layer, the hydrazine hydrate for 0.246 mole is calculated.Yield is 98.4%.It is about The hydrazine hydrate solution of 57.2% concentration.

Embodiment 4

The liquefaction dioxy with siphon pipe is installed on the top of the volume 400ml with mixer, the autoclave of pressure-resistant 20MPa Change carbon storage bottle, carbon dioxide storage tank, subcooler, high pressure constant displacement pump, autoclave is impregnated in thermostat.In advance to autoclave In be passed through carbon dioxide, the air in autoclave is thoroughly replaced.Make autoclave generally 32 in 32 DEG C of thermostat ℃.It is injected into after the solution that acetone azine 28g (0.25 mole) is dissolved with water 22.5g (1.25 moles) is adjusted to 32 DEG C In autoclave.It will be stored up under agitation with high-pressure fluid constant displacement pump by subcooler from liquid CO 2 on this basis The liquid CO 2 219g (4.98 moles) of bottle is slowly injected into autoclave.The internal pressure of autoclave is shown as about 9MPa. If it is assumed that all liquid CO 2s of liquid component, then the filling constant of carbon dioxide is equivalent to about 1.6, due to filled with The liquid component in addition to liquid CO 2 of about 50g, therefore cannot say that filling constant is 1.6 exactly.At this moment valve is closed Door, when stirring 12 is small at 32 DEG C.At 32 DEG C, the pressure in autoclave is about 9MPa.Make usually as liquid CO 2 With in the storage bottle of purpose, the liquid CO 2 in storage bottle is below 31.1 DEG C of critical points, on the boiling line in state diagram State.Under the conditions of the filling constant, at about 29 DEG C as no gas blanket, hydraulically full state in carbon dioxide storage bottle Critical carbon dioxide state.Even if having small temperature change in reaction autoclave, it can also steeply rise pressure, therefore for Security consideration, the autoclave of the 200MPa with safety valve is used in order to keep supercritical carbon dioxide layer.

After reaction, autoclave and content are cooled to 10 DEG C, take out the water layer portion of heavy lower floor to pressure-resistant In container, from the carbon dioxide of gas release valve release dissolving, 55 DEG C are then slowly heated to.Make the diazanyl for being present in water layer Formic acid resolves into hydrazine hydrate and carbon dioxide, and carbon dioxide is discharged into outside system from relief valve.Sampled from water layer, by above-mentioned Titrimetry calculate the amount of hydrazine hydrate.From the result of titrimetry, hydrazine hydrate is 0.205 mole (yield 82%).Close It is considerably less due to being dissolved in the amount of water of liquefied carbon dioxide at this temperature and pressure in the concentration of hydrazine hydrate, it is about The hydrazine hydrate solution of 47.3% concentration.

Embodiment 5

The liquefaction dioxy with siphon pipe is installed on the top of the volume 400ml with mixer, the autoclave of pressure-resistant 20MPa Change carbon storage bottle, gasifier, carbon dioxide storage tank, subcooler, high pressure constant displacement pump, autoclave is impregnated in thermostat.Xiang Gao Carbon dioxide is passed through in pressure kettle, the air in autoclave is thoroughly replaced.Make autoclave overall in 20 DEG C of thermostat For 20 DEG C.The solution that methyl ethyl ketone azine 35g (0.25 mole) is dissolved with water 22.5g (1.25 moles) is adjusted to 20 It is injected into after DEG C in autoclave.The liquid dioxy of subcooler will be passed through with high-pressure fluid constant displacement pump under agitation on this basis Change carbon 215g (4.9 moles) to be slowly injected into autoclave.Valve is closed herein, when stirring 12 is small at 20 DEG C.Liquid dioxy The filling constant for changing carbon is about 1.6.Under the filling constant, in common liquid CO 2 storage bottle, there are liquid in storage bottle Carbon dioxide and gas carbon dioxide layer.It is the state on the boiling line in state diagram of equilibrium state below 29 DEG C. At 20 DEG C, the pressure in autoclave shows about 5.9MPa.

Even the temperature more than temperature, the state seethed with excitement on line of state diagram is also in untill 29 DEG C.Instead Even if answering in autoclave has small temperature change, in order to ensure safety, also using keeping carrying for supercritical carbon dioxide layer 200 pressure-resistant autoclaves of safety valve.

After reaction, the proportion of liquid CO 2 is smaller than water at 20 DEG C, thus by the water layer portion of lower floor take out to Pressure vessel, from the carbon dioxide of gas release valve release dissolving, is then slowly heated to 55 DEG C.Make the hydrazine for being present in water layer Base formic acid resolves into hydrazine hydrate and carbon dioxide, and carbon dioxide is discharged into outside system from relief valve.Sampled from water layer, by upper The titrimetry stated calculates the amount of hydrazine hydrate.From the result of titrimetry, hydrazine hydrate is 0.233 mole (yield 93%). It is considerably less due to being dissolved in the amount of water of liquefied carbon dioxide at this temperature and pressure on the concentration of hydrazine hydrate, be The hydrazine hydrate solution of about 54.0% concentration.

Embodiment 6

As raw material, benzophenone azine 72g (0.20 mole), liquid CO 2 188g (4.27 moles), water are used 31.5g (1.75 moles), filling constant is about 1.58.Processing similarly to Example 1 is carried out, obtains hydrazine hydrate 9.1g (0.182 Mole).Yield is 91%, concentration of hydrazine hydrate 29.8%.

Embodiment 7

From the survey for the autoclave weight for adding separation and the liquid CO 2 preserved in autoclave in embodiment 1 The weight of acetone of liquid CO 2 can be dissolved in by determining the supposition that result subtracts the weight of initial empty autoclave, hydrolysis generates Amount, and the amount of the remaining liquid CO 2 of estimation is 203g.Water 27g (1.5 moles) and acetone azine 28g is filled on this basis (0.25 mole), carries out reaction, processing similarly to Example 1.Constant is filled close to about 1.7.Analysis result is display hydration Hydrazine 10.4g (0.208 mole) yield is 83%.

Claims (8)

1. the manufacture method of a kind of hydrazine hydrate, substitution hydrazine or amino-compound, it is characterised in that by subcritical, overcritical Or make ketone azine, hydrazone or schiff base compounds hydrolysis in the presence of the carbon dioxide of liquid CO 2 state, obtain ketone and hydration Hydrazine or substitution hydrazine or carbazic acid or substitution carbazic acid or carbonyls and amino-compound or carbamic acid Compound or substituted-amino formic acid.

2. the manufacture method of hydrazine hydrate according to claim 1, substitution hydrazine or amino-compound, under the conditions of it is following Manufacture method, the condition are：

It will be less than 60 DEG C and more than -56.6 DEG C in the temperature of the carbon dioxide and the pressure of the carbon dioxide is 0.52MPa subcritical carbon dioxides formed above, supercritical carbon dioxide, the temperature of liquid CO 2 state, pressure, filling The condition that coefficient is composed.

3. the manufacture method of hydrazine hydrate according to claim 1 or 2, substitution hydrazine or amino-compound, it is following condition Under manufacture method, the condition is：

By the temperature of the carbon dioxide be -30 DEG C~40 DEG C and the pressure of the carbon dioxide be more than 1.4MPa~ The bar that 7.38MPa subcritical, overcritical, liquid CO 2 state temperature formed above, pressure, fill factor are composed Part.

4. according to the manufacture method of hydrazine hydrate according to any one of claims 1 to 3, substitution hydrazine or amino-compound, wherein,

The carbon dioxide can recycle.

5. the manufacture method of hydrazine hydrate according to any one of claims 1 to 4, substitution hydrazine or amino-compound, wherein, Further comprise following steps：

Heat the carbazic acid or substitution carbazic acid and be decomposed into hydrazine hydrate or substitution hydrazine and carbon dioxide.

6. according to the manufacture method of hydrazine hydrate according to any one of claims 1 to 5, substitution hydrazine or amino-compound, wherein,

The ketone azine is the compound shown in chemical formula (1)：

In formula,

R¹~R⁴It is separately hydrogen atom, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl group, aromatic series ring group or heterocyclic radical, Here, these groups can according to circumstances be chosen free alkyl, alkenyl, alkynyl, halogen group, alkoxy, amino, nitro, sulfydryl, More than 1 substituent substitution in the group of aryloxy group, aromatic series ring group and heterocyclic radical composition, or

R¹And R²Ring structure is formed together with the carbon atom being bonded with them, here, the ring structure group according to circumstances can be by conduct Substituent is selected from by alkyl, alkenyl, alkynyl, halogen group, alkoxy, amino, nitro, sulfydryl, aryloxy group, aromatic series ring group Substitute with the substituent in the group of heterocyclic radical composition, or

R³And R⁴Ring structure is formed together with the carbon atom being bonded with them, here, the ring structure group according to circumstances can be by conduct Substituent is selected from by alkyl, alkenyl, alkynyl, halogen group, alkoxy, amino, nitro, sulfydryl, aryloxy group, aromatic series ring group With the substituent substitution in the group of heterocyclic radical composition.

7. according to the manufacture method of hydrazine hydrate according to any one of claims 1 to 5, substitution hydrazine or amino-compound, wherein,

The hydrazone is the compound shown in chemical formula (7)：

In formula,

R¹、R²、R⁵、R⁶It is separately hydrogen atom, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl group, aromatic series ring group or heterocycle Base, here, these groups can according to circumstances be chosen free alkyl, alkenyl, alkynyl, halogen group, alkoxy, amino, nitro, mercapto More than 1 substituent substitution in the group that base, aryloxy group, aromatic series ring group and heterocyclic radical form, or

R¹And R²Ring structure is formed together with the carbon atom being bonded with them, here, the ring structure group according to circumstances can be by conduct Substituent is selected from by alkyl, alkenyl, alkynyl, halogen, alkoxy, amino, nitro, sulfydryl, aryloxy group, aromatic series ring group and miscellaneous Substituent substitution in the group of ring group composition, or

R⁵And R⁶Ring structure is formed together with the nitrogen-atoms being bonded with them, here, the ring structure group according to circumstances can be by conduct Substituent is selected from by alkyl, alkenyl, alkynyl, halogen group, alkoxy, amino, nitro, sulfydryl, aryloxy group, aromatic series ring group With the substituent substitution in the group of heterocyclic radical composition.

8. according to the manufacture method of hydrazine hydrate according to any one of claims 1 to 5, substitution hydrazine or amino-compound, wherein,

The schiff bases is the compound shown in chemical formula (9)：

In formula,

R¹、R²、R⁷It is separately hydrogen atom, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl group, aromatic series ring group or heterocycle Base, here, these groups can according to circumstances be chosen free alkyl, alkenyl, alkynyl, halogen group, alkoxy, amino, nitro, mercapto More than 1 substituent substitution in the group that base, aryloxy group, aromatic series ring group and heterocyclic radical form, or

R¹And R²Ring structure is formed together with the carbon atom being bonded with them, here, the ring structure group according to circumstances can be by conduct Substituent is selected from by alkyl, alkenyl, alkynyl, halogen group, alkoxy, amino, nitro, sulfydryl, aryloxy group, aromatic series ring group With the substituent substitution in the group of heterocyclic radical composition.