TWI237016B - Method and apparatus for preparing hydrazodicarbonamide using urea as starting material - Google Patents

Abstract

The present invention relates to a method and apparatus for preparing hydrazodicarbonamide using urea as starting material economically and environmentally desirably. The apparatus includes a pyrolysis furnace to obtain biuret and ammonia by pyrolyzing urea; a recrystallization reactor to purify the biuret obtained from the pyrolysis furnace; a first reactor to obtain an metal monohalobiuret salt by reacting the biuret with metal hypohalogen compound or with halogen and base; a second reactor to synthesize the hydrazodicarbonamide by reacting the monohalobiuret metal salt with ammonia; and an ammonia evaporator to separate the excess ammonia from hydrazodicarbonamide and to supply the separated ammonia to an ammonia concentrator.

Description

1237016 A7 B7 V. Description of the invention () Field of the invention: The present invention relates to a method and equipment for preparing azidomethoxamine using urea as a starting material. Specifically, the present invention relates to a method for generating bipyridine with urea and reacting the generated (biple spleen and ammonium generated during the synthesis of biphosphine) with each other to economically and environmentally produce azidomethamine. BACKGROUND OF THE INVENTION: Azido Tamine (hydrazodicarbonamide, HDCA) is a very useful starting material for the preparation of azomethamine, and azomethamine is a widely used bubble bed As shown in Reaction Formula 1, azomethoxamine (2) can be obtained by oxidizing azidomethoxamine (1) with an appropriate oxidant. [Action formula 1] ........... ............. Order (Please read the notes on the back before filling this page) [〇1 〇〇II II h2n-c-nh-nh-c-nk ⑴ h2n-cn = nc -nh2 (2) The traditional method for preparing azidomethoxamine by the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs includes (i) starting with hydrazine '(ii) direct synthesis with urea, (iii) urea To prepare a semicarbazide ', and then convert the prepared semicarbazide to azidemethoxamine, and (iv) bisplendium as the starting material. In the preparation method using hydrazine as the starting material ( Application formula 2) 'Azomethanamine is prepared by reacting 1 mole of hydrazine (3) and 2 mole of urea (4). The first paper size applies Chinese National Standard (CNS) A4 Specifications (210X297) Chu 1237016 A 7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention () [Reaction formula 2] 0 0 0 H2NNH2 4. H2N-C-NH2 --- H2N-C-NH -NH-C-NH2 + 2 nh3 (3) (4) ^ The advantage of the above reaction formula is that the process is simple, but the disadvantage is that the starting material used is hydrazine, which is expensive and difficult to synthesize. Can be prepared Typical methods of hydrazine include the Rasehing process and the method using ketazine. However, the hydrazine obtained by these methods also needs to be concentrated and hydrolyzed before it can be used. Therefore, the manufacturing process is caused The energy consumption required is too high, which results in increased production costs. In addition, hydrazine can also be prepared by the urea method that reacts urea with steel hypochlorite and sodium hydroxide. However, this method requires the use of excess hydrogen Sodium oxide, which is too expensive to remove by-products of sodium carbonate, and requires many chemicals The reaction by-products can only be removed. Therefore, this method is considered to be incompatible with environmental protection and economic benefits. The following reaction formula 3 represents a method for directly synthesizing azidomethoxamine from urea. As shown in reaction formula 3, 3 moles of urea and The reaction of 4 mole sodium hydroxide and 1 mole chlorine can obtain 1 mole of azidomethanamine. However, this method also has its disadvantages' because it requires the use of excess reagents and the manufacturing process is complicated, so the cost is too high. Another One problem is that many byproducts of ammonia that are not environmentally friendly are produced. (Please read the precautions on the back before filling this page) Packing-then fill in this one. F The top paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 1237016 A7 B7 V. Description of the invention ([Reaction Formula 3;)? H2N-C-NH2 + 4Na〇H + a ο 9 II 丨 丨 H NC-NH-NH-C-NH. + 2 NaCl + 2 H2 〇 + called 03 + 2 NH] The following reaction formula 4 shows another method for synthesizing azidomethoxamine. The present method includes a step of preparing semicarbazide from urea, and then a step of converting the obtained semicarbazide to azidomethoxamine. As shown in reaction formula 4, the reaction between urea and sodium hypochlorite can obtain the sodium monochloride urea, and the sodium monochloride urea reacts with excess ammonia in the presence of a catalyst to obtain the intermediate-semicarbazide, which will be known later <The amino spleen reacts with urea to obtain the final product, azidomethoxamine. [Reaction formula 4] Please read the notes on the back first and then fill in this page. H2N-C-NH2 4- NaOC! H2N-C-NH-NH «NaCI -f · H2 〇

〇 II H ^ NC-NH-NH ο II h2n-c-nh2 oou 丨 I II H2N-0-NH-NH-C-NHo + NHn Intellectual Property Bureau, Ministry of Economic Affairs, Employee Consumer Cooperative Printed Base 5 The prescription requires the salt to urge the steel to make the expensive urine, and the gas is used to make the unit demand is single or per unit. Therefore, it should also be reversed, but the amount of ammonia is increased by oo. The change is blue. The length of the head Mi is very different, and the second question will be shortened, and the test will be displayed separately. To make 5 benefits, the formula is to use the amine symbol instead of nitrogen. Tian «Urea is the next page. The size of this paper applies the Chinese National Standard (CNS) A4 specification (210X 297 public copy) 1237016 A7 B7 V. Description of the invention () PCT7KR8 8/0 1 8 0) Method for synthesizing azidomethoxamine. It comprises the steps of reacting biuret with a metal hypohalide (MOX) to form a monohalide biuret metal salt, and subsequently reacting the obtained monodentate biuret metal salt with ammonia to prepare azidomethyl siamine. step. [Reaction formula 5] 0 0 0 0 〇 9 II \\ II ί! II 11 H2N-C-NH-C-NH2 -f ΜΟχ —H2N-C-N-C-NH or H2N-C-N-C-NH + h2 0

X

0 0 H2N.CNC-NH or η, ν-cnc-nh + nh3 III i XM MX? H2n-c-nh-nh-c-nh2 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, but 'the above is biuret The method for preparing azidomethoxamine as a starting material also has disadvantages in that the bispyrolysis as a starting material is expensive or contains many impurities, and the reaction of preparing biazidine with biuret and ammonia A lot of extra ammonia is needed, so this law is not environmentally friendly and economical. Disclosure of the Invention One of the objects of the present invention is to provide a method for economically and environmentally-friendly preparation of azidomethoxamine using urea, which is cheap and easily available, as a starting material. Another object of the present invention is to provide a method and apparatus for preparing azidomethoxamine which can use the least starting materials and produce the least by-products. Another object of the present invention is to provide a method and apparatus for preparing azidomethoxamine by continuously performing a process to obtain a high yield. In order to achieve the above-mentioned objects, the present invention provides a method for preparing azidomethoxamine. Page 5

1237016 A7 B7 5. The method of the invention description (), which comprises the steps of pyrolyzing urea to prepare biuret and ammonia of formula 1; letting the biuret and the hypohalide metal compound (or halogen And a step of reacting) to obtain a mono-bilated bisplen metal salt of Formula 2 or Formula 3; and a step of reacting the obtained mono-functional biuret metal salt with ammonia. [Formula 1] 〇 〇

II II h2n ^ c-nh-c-nh2 [Formula 2]

HaN-〇-N-〇-fs4H X Μ [Formula 3]

H2N-0-N-C-NH In the above formulae 2 and 3, M represents a metal and X represents an i prime. The pyrolysis temperature of urea is preferably between 100 ° C and 300 ° C, and the pyrolysis process is preferably performed when ammonia is removed, and the removed ammonia and the monodentate biuret metal salt reaction. The present invention further provides a device for preparing azidomethoxamine, which includes the paper size on page 6 which is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page) , Τ f Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1237016 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (a pyrolysis furnace that can pyrolyze urea to obtain biuret and ammonia; The first reactor in which the obtained biuret is reacted with a secondary metal compound (or! I and a base) to obtain a monohalogenated biuret metal salt; a monorehalable biuret metal salt can be obtained A second reactor that reacts with ammonia to synthesize azidomethoxamine; and an ammonia volatilizer that separates excess ammonia from azidomethoxamine and directs the separated ammonia to an ammonia concentrator. Preferably, the excess ammonia and the ammonia generated in the pyrolysis furnace can be concentrated, and the concentrated ammonia can be provided to the second reactor for use. The pyrolysis furnace may include a gas injection port capable of injecting an inert gas, the Inert gas system will not The isocyanate reaction in the furnace, and the pyrolysis furnace can also include a means to reduce the pressure so that ammonia can be removed from the pyrolysis furnace. BRIEF DESCRIPTION OF THE DRAWINGS The invention and its understanding will be better understood from the following drawings. Advantages, of which: Fig. 1 is a flow chart showing a device for preparing azidomethoxamine according to an embodiment of the present invention. Drawing No. Comparative Description 10 12 20 30 32, 54 Reconcentration of ammonia concentrator in gas injection port of pyrolysis furnace The paper size of the dehydrator is applicable to the Chinese national standard (CNS) A4 specification (210 × 297 mm) 1237016 A 7 B7 V. Description of the invention () 40 First reactor 50 Second reactor (please read the note on the back first) Please fill in this page again for details) 52 Detailed description of the ammonia volatilizer invention The following detailed description only lists the preferred embodiments of the present invention, so as to explain the best mode for implementing the present invention. It should be noted that the present invention can make many improvements and changes. These improvements and changes should still be regarded as the scope of the present invention, so the drawings and detailed description of the present invention are only for the purpose of illustrating the present invention, and the scope of the present invention is not limited to this. Preparation of azidomethanamine according to the present invention, First, urea is pyrolyzed at a temperature higher than the melting point of urea to produce biuret and ammonia of formula 1. In general, biuret is widely used as a precursor for drugs, herbicides, and analytical reagents. It is also widely used as a feed for tooth decay animals, and is widely used in various plastic resin fields. In addition, some biuret derivatives are also known to have the function of physiological healing agents or chemotherapeutics. The following reaction formula 6 shows the heat Production process of biuret by decomposing urea. [Reaction 6] Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy 9 9 〇〇II il heat II || H2N-C-NH2 + H2N-C-NH2-h2n- c-nh-c-nh2 + nh3 As shown in the reaction formula 6, it can pyrolyze 2 moles of urea and remove ammonia, which can be produced on page 8. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 1237016 A7 B7 V. Description of the invention (biuret. Specifically, as shown in the following reaction formula 7, it is generally assumed that when urea is pyrolyzed, isocyanate and ammonia are first produced, and then the target product, biuret, is produced. [Reaction formula 7] heat H-N = C-0 + NH, please read the meanings on the back first

HN = c = 0 + H2N-C-NH oo II II h2n-c-nh-c-nh2 The method of printing pyrolytic urea to synthesize biuret by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs has the advantage that the reaction operation is easy. However, the disadvantage is that the conversion of urea into bisplenism is low. In the reaction process of biuret formation, due to the reaction between biuret acid, hybrid conversion rates such as triuret and cyanuric acid are too high. low. If the reaction temperature is increased and the conversion rate is increased, the impurities such as triuret and cyanuric acid will also increase. If the reaction temperature is lowered to reduce the amount of impurities, the rate will be slowed down, making it economically ineffective. In the present invention, in order to reduce the yield of diurea and reduce the amount of impurities, the reaction temperature is preferably maintained between ° C and 300 ° c, and the optimal temperature is maintained between 130 ° c and i7 (rc again, if the By-products such as air and nitrogen, which are not injected into the reactor with an atmosphere and / or the pressure of the reactor is reduced, ammonia can be effectively increased from the reactor tg after the reaction rate And the impurity quality will also be reduced. At the same time, page 9 This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm). The ratio is too simple to be isocyanate, and the concentration of elongation is reflected in the reaction. At the reaction of 100% acid, the reaction of Titanium is removed. The reaction is 1237016 A7 B7. 5. Description of the invention (under the high temperature of the device, the liquid-phase organic compounds can be changed to inert gas and can be used as an inert gas source. If necessary, a catalyst may also be used to increase the pyrolysis reaction rate. It is preferable to use a beam acid catalyst such as nitric acid, hydrochloric acid, and sulfuric acid 'an acid-type catalyst such as thionyl chloride, and Sulfur-containing substances such as sodium Catalyst. The amount of the catalyst is preferably about 0.1 to 0.5 mole per 1 mole of urea, and more preferably about 0.01 to 0.3 mole per mole of urea. The following formula 2 Or the bidentate biuret metal salt of formula 3 can be prepared by reacting the obtained biphosphine with a hypo-metal compound or a pixel with a base. [Formula 2] 〇 〇II || Μ Please read the back first Precautions for S [Eq. 3]

ο ο Printed by II II H2N-C-N-C-NH Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs In the above formulas 2 and 3, M represents a metal and X represents a letter. The method for directly preparing the single-drawing biuret metal salt is carried out by reacting bifurcate with a subhalogenated metal compound as shown in Reaction Formula 8. The paper standard is applicable to Chinese National Standard (CNS) A4 Specifications (210X297 mm) 1237016 V. Description of the invention () An example is shown in reaction formula 9. [Reaction formula 8] A7 B7 0 0I! I 丨 H, N-C-NH-C-NH, +

M0X

0 0II II H W-C-N-C-NH or ο οII II μ N-C-N-C-NH + Η, 〇 X Μ

M X In the above reaction formula, M represents a metal and X represents a tooth element. [反应 式 9] 〇 ο 丨 I II + NaOCl

NH oyc- 善 —α Q = -c- N- 2 H

Na or N- 2 Η o = c-a 善 —Na o = c- ΝΗ ο 2 Η

C f Please read the notes on the back before writing this page} Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Refer to the above reaction formula 9, biuret reacts with sodium hypochlorite to form a vaporized biuret sodium salt. Since the above reaction system is an exothermic reaction, the reaction system is preferably maintained at a low temperature. However, the obtained sodium biuret chloride is quite stable for a moderate degree of yield, and therefore it can be prepared at room temperature. The preferred reaction temperature is below 60 ° C, and more preferably between -10. (: To ° C, the best is between -5 ° C to 3 5 ° C. In consideration of economic benefits and operating equipment, the molar response ratio of chemical reaction per 1 mole of urea is better It is between 0.1 and 2. When the molar reaction ratio is lower than 1 molar, the excess biuret can be recovered and reused. In the above reaction, page 11 of this paper applies the Chinese national standard (CNS ) A4 size (210X297 mm) 1237016

V. Description of the invention () In the formula, when the molar reaction ratio is lower than 0 1 or the reaction temperature is lower than − i 0C, the reaction time will become too long. And if the Mohr reaction ratio is higher than 2 or more, it will increase the production cost and may produce by-products. Furthermore, if the reaction temperature is above 60 ° C, the monohalogenated biuret metal salt product is decomposed because it is unstable at high temperatures. The sodium bichloride obtained in the above case can be used directly or stored for the next reaction. Reaction formula 10 shows a method for preparing a monohalogenated biuret metal salt of the above formula 2 or 3 by reacting biuret with a prime and a base. As shown in Reaction Formula 10, "After the biuret is reacted with an autogen or a pigment compound such as chlorine", a monodentate biuret (5) can be obtained. As for the monodentate biuret metal salt, only metal hydrogen such as metal hydrogen can be added. Oxide (such as sodium hydroxide, potassium hydroxide, calcium hydroxide) and other bases can be obtained by the obtained monofunctional biuret (5). [反应 式 10] .......—----- Order (Please read the precautions on the back before filling this page) 〇 οιι ιι Η N-C-NH-C-NH + Χ2

Ο Ο II II h2n-c-n-c-nh2 + μοη X

ο ο II II H2N-CNC-NH2 -f Η × 'k (5) ο ο II 丨 I HN-CNC-NH 2 II Printed in the above reaction formula 10, M represents the metal and X stands for pixels. The reaction system for generating monofunctional biuret (5) is an exothermic reaction, so the inverse temperature is preferably maintained at a low temperature, that is, below 60 ° C, and preferably between -10 ° C and 60t; The best range is between -5 ° C and 30 ° C, in order to maintain a stable anti-page. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 1237016 A7 B7 Employees ’Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs Printed 5. Description of the invention () Response rate and stability of reaction. Alternatively, a monofunctional biuret metal salt can be prepared by first mixing a metal hydroxide with bisplenol 'and then reacting the element with the obtained product. Therefore, the reaction is also an exothermic reaction, so the reaction temperature should also be maintained at a low temperature, preferably between ^ and 60.匸; the best range is -51 to 30. (: Between. In the above reaction, when the reaction temperature is lower than 1 (TC), the reaction time will be too long; if the reaction temperature is higher than 60 ° C, the monofunctional biuret metal salt may be due to It decomposes due to its thermal instability. As shown in Reaction Formula u, the obtained monohalogenated biuret metal salt can be a 3-mono-biuret metal salt (6) or a 1-monohalobiuret metal salt (7). [Reaction formula 1 1]??? MOX h2n-c-nh-c-nh2 + or-1 2 3 4 5 ten 2Λ / Ι0Η (6) (7) In order to produce azidomethanamine, The obtained monofunctional biuret metal salt is reacted with ammonia generated when urea is pyrolyzed. It is generally estimated that the reaction mechanism is the same as the Favorskii reaction shown in Reaction Formula 12 or the reaction shown in Reaction Formula 13. Hoffman rearrangement reaction is similar to 〇H,

0 Ο II II, Ν-CNC-NH_ 1 I page 13 This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before ringing this page) Ben 0Γ 〇 0 II II h2n-cnc-nh 1237016 Λ7 B7 V. Description of the invention ([Reaction formula 1 2] 〇 〇Η 丨 I h2n-cnc-nh (8) H2N-〇-N ^ f

H NH.

〇 II H2N-C-NT ο

MX o 〇 II II H2N-C-NH-NH-C-NH2 (Please read the precautions on the back before writing this page) Install and repeat this one [Reaction formula 1 3]

ο ο if II H0N-CNC-NH ο! l H2N-C ^ 5: 〇NH3 I? I? H2N-C-NH-NH-C-NH., τ Refer to the above reaction formula 1 2 ' The intermolecular reaction of an anionic nitrogen atom on the bisplenic metal salt (8), through the formation of a nitrogen-nitrogen bond and the removal of the metal functional compound ', produces an unstable diaziridinone (9). The azide derivative (9) can be easily reacted with highly reactive ammonia, and thus azidomethanamine can be produced. In addition, referring to the above reaction formula 1 3 ', it is generally assumed that the mono-bicondensate metal drug will be converted into a compound containing isocyanate hydrazone, and the converted isocyanate compound will react with highly reactive ammonia, And azide methylamine is formed. In the reaction of the monofunctional biuret metal salt with ammonia (a by-product when pyrolyzing urea), in consideration of its reaction rate and benefits, it is preferred to maintain the reaction telemetry between 0 ° C and 150 ° C. More preferably, it is maintained between 30 ° c and i50 ° C. Page 14 This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 印 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1237016 A7 B7 Five invention instructions () When the reaction temperature is lower than 0 ° C the reaction rate will be It becomes too slow to lose economic benefits, but when the reaction temperature is higher than 15t, the equipment cost will increase due to the need to redesign the equipment to withstand the high internal pressure caused by volatilization of the gas. In addition, you can use the self-propelled four-shaped complaint package platform — Dan | j 便 assets, such as ammonia, liquid ammonia or ammonium hydroxide. It is preferred to use a suitable amount of ammonia to increase the reaction rate. The amount of ammonia required per mole of mono-biuret biuret metal medicine is between t and 1,000 moles, more preferably between 2 and 500 moles, and most preferably between 5 1 and 100. Mole Room ... Except for the reaction of Mole gas with 1 Mole monochemically reduced spleen metal salt, excess ammonia can be recovered: it can be used in subsequent reactions. Excessive reaction temperature due to the use of a large amount of ammonia can increase the pressure of the reaction system to prevent ammonia from being circulated. This can change the reaction rate and # 安 择 焱 此 』汉. The yield and pressure are preferably between i and 100 kgf / cm2. According to the present invention, the reaction for preparing azidomethylamine from urea is shown in the reaction formula. In addition, according to the preferred embodiment of the present invention, The equipment for preparing azidomethoxamine is shown in the figure. [Reaction formula 14] (Please read the precautions on the back before writing this page.) Binding · -Order · Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 2 H2N-C-NH2 + 2MOH + &amp; --- HDCA + 2 MX + 2 H2 0 As shown in FIG. 1, the equipment for preparing azidomethacamine according to a preferred embodiment of the present invention includes a pyrolysis furnace 1 0, which can pyrolyze urea to obtain shrinkage. Page 15 This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) 1237016 A7 B7 V. Description of the invention (Urea and ammonia printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Pyrolysis furnace 10 preferably contains 1 The gas injection port 12 is capable of injecting an inert gas into the pyrolysis furnace 10; or includes various means for reducing the pressure in the pyrolysis furnace 10 so that ammonia can be easily removed from the pyrolysis furnace 10. The Examples of the inert gas are not limited to air, nitrogen, and liquid organic compounds that can be changed to inert gas in the pyrolysis furnace 10, which does not react with isocyanic acid. Ammonia removed from the pyrolysis furnace 10 It is preferably supplied to an ammonia concentrator 20 whose function is to concentrate The ammonia in the pyrolysis furnace 10 and the excess ammonia still present after the formation of azidomethanamine. The biuret present in the pyrolysis furnace 10, impurities such as triuret and cyanuric acid can be obtained by The recrystallization means (including the recrystallizer 30 and the dehydrator 32 such as a centrifuge) separates it and then supplies it to the first reactor 40. The purified biuret is sent to the first reactor. In 40, it is then reacted with a metal halide (for example, NaOC1) or a halogen (for example, chlorine) to produce a monodentate biuret metal salt, which is then supplied to the second reactor 50. Rong Dan _The reaction of biuret metal salt with ammonia can generate azidomethoxamine ', and the ammonia participating in the reaction is preferably provided by an ammonia concentrator 20. The obtained azidomethoxamine and excess ammonia will It is then led to the ammonia volatilizer 52. The ammonia volatilizer 52 can volatilize the excess ammonia, and the volatilized ammonia will be sent to the ammonia concentrator 20. The azidomethanamine separated from the excess ammonia can be borrowed Purified by a dehydrator 5 4 such as filter paper. As shown in FIG. 1 and reaction formula 13, according to the present invention, a continuous process can be performed Urea was prepared starting from methyl acyl azide amines. Thus the entire process train is continuously performed, so the process efficiency can be improved. P. 16 (Read Notes on the back and then fill the page)

1237016 A7

V. Description of the invention () (Please read the notes on the back before filling out this page} In addition, the reaction of the mono-biuret metal salt with the reaction by-product _ ammonia (thereby greatly reducing the amount of raw materials, and also indirectly production Cost is reduced. Therefore, this process can produce azidomethanamine more environmentally friendly by reacting with ammonia, a by-product that is less environmentally friendly. The following provides preferred embodiments and manufacturing examples of the present invention to help readers understand the present invention However, the scope of the present invention is not limited to the described examples. Basket Example _: Preparation of two-packed flasks. Inject 500 grams (8.33 moles) of urea into a four-necked round-bottomed flask and vigorously fall. Air was injected into the bottom of the flask at the rate shown in Table 1. The reaction was performed simultaneously for 5 hours, and the reaction temperature was maintained at 14 ° C by heating. After the reaction was completed, the composition of the obtained solid was analyzed by liquid chromatography. The results are shown in the following Table 1. Table 1 Example of the rate of air injection (liters / minute) Amount of urea (% by weight) Amount of biuret (% by weight) Cyanuric acid and other solids (% by weight) 1 0 62 35 3 2 1 41 55 4 3 2 38 60 2 4 4 37 61 2 Printed by Manufacturing Cooperative of Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Example 5-7: Preparation of biuret Basically the method of manufacturing example 1 is used to prepare biuret 'but the reaction only takes 3 hours, and the reaction temperature is changed and the air is removed. The injection rate is maintained at 2 liters / page 17. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 1237016 A7 B7 V. Description of the invention () minutes. After the reaction is completed, it is analyzed by liquid chromatography The composition of the solids, the results are shown in the following Table 2. Table 2 Example reaction temperature ΓΟ Amount of urea (% by weight) Amount of biuret (% by weight) Cyanuric acid and other solids (% by weight) 4 ------ -150 47 50 3 5 160 38.5 57 4.3 6 170 28 65 7 Manufacturing Example 8-10: Basically, the diminution solution was prepared according to the method of Manufacturing Example 1, but the reaction was under the low pressure caused by the vacuum pump shown in Table 3 below. Perform the injection instead of air. After the reaction is completed, the composition of the solid obtained is analyzed by liquid chromatography, and the results are disclosed in the table below 3 ° (Please read the precautions on the back before filling this page) Bureau employee consumer cooperative seal Tab. 3 Example Pressure (mmHg) Urea (wt%) Biuret (wt%) Cyanuric acid and other solids (wt%) 8 380 56 50 4 9 190 41.5 55 3.5 10 100 40 57 3 Manufacturing Example 11 -1 3: Preparation of Biuret Biuret is basically prepared according to the method of Manufacturing Example 1, but the reaction is performed under various types of catalyst per 0.05 mole of urea and air is injected. Page 18 This paper size applies to Chinese National Standard (CNS) A4 (210X 297 mm) ί 1237016 A7

V. Description of the invention () The rate is maintained at 2 liters / minute. After completion of the reaction, the composition of the obtained solid was analyzed by liquid chromatography, and the results are shown in Table 4 below. --7 --- Table 4 Amount of urea (wt.%) Of biuret (wt.%) Of cyanuric acid and other solids (wt.%) __21 sulfuric acid 34 62 4 12 sodium scale 36 36 Sulfuryl chloride 35 62 3 ΙϋΑ 14: Synthetic gasification biuret sodium salt. A 2 liter glass reactor was charged with 423.1 g (0.287 mol) of a 7% biuret slurry solution, stirred and cooled. To 5. (:. In this reactor, add a 12% aqueous sodium chloride solution to maintain the reaction temperature of the system below 5 ° C. After the reaction is completed, analyze the composition of the resulting solution by iodometric titration and liquid chromatography. The available chlorine is 3.3 7%. This corresponds to a yield of 98%. Production Example 15 ·· Synthetic Biuret Chloride Test In a 2 liter glass reactor, 423.1 grams (0.287 moles), 7% shrinking mud-like solution, stir and cool to 5. (:. In this reactor, add 223 g (0.575 mol) of 10.3% sodium hydroxide aqueous solution 'and add 20.3 g (0.287 mol) 〇%。 Equivalent to the yield of chlorine, the reaction temperature of the system was maintained at 10. (: below. After the reaction is complete, the composition of the solution obtained is analyzed by iodometric titration and liquid chromatography. The available chlorine is 3.0%. For page 19, this paper size applies the Chinese National Standard (CNS) A4 specification (210 &gt; &lt; 297 mm) (Please read the precautions on the back before writing this page) Printed 1237016 A7 B7 V. Description of the invention () 98% 〇1 Example 16: Synthetic gasification shrinkage A diurea sodium salt was charged in a 2 liter glass reactor with 423.1 g (0.287 mol) of a 7% biuret slurry solution, stirred and cooled to 5 ° C. In this reactor, 20.3 was added Grams (0.287 moles) of chlorine gas to maintain the reaction temperature of the system below 10 ° C. After the chlorine gas was added, 223 grams (0.575 moles) of a 10 · 3% sodium hydroxide aqueous solution was added while vigorously carrying Stir and maintain the reaction temperature below 5 ° C. After the reaction is complete, analyze the composition of the resulting solution by dish titration and liquid chromatography. The available chlorine is 300 /. The equivalent yield is 98% . (Please read the precautions on the back of the 4th chapter before filling out this page}

f Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, page 20 This paper size applies to China National Standard (CNS) A4 (210X297 mm) ^ 37016

'Explanation of the invention (Example 1) 9: Synthetic azide. Job: Inject 593 "of a biseptic urea flask into a 2 liter sterile flask. The sodium biuret chloride salt prepared according to the above Production Example 14 was stirred and cooled to 10%. r. Maintain the reaction temperature below 10 ° C, while adding 600 grams (8.8 mol) of 25% liquid ammonia solution, while vigorously stirring. The reaction is carried out at various temperatures and times. After the reaction is completed, the reaction will be unreacted. The ammonia was removed, and the reaction solution was filtered to obtain azidomethanamine, which is insoluble in water. The yield is calculated and shown in Table 5. Poor 5 Example reaction conditions (temperature, hour-130 ° C, 1 Hour 2 30 ° C, 2 hours 1 330 ° C, 3 hours 4 60 ° C, 1 hour 5 60 ° C, 2 hours 66 (TC, 3 hours 7 90 ° C, 1 hour 8 90 ° C, 2 hours 9 90 ° C, 3 hours (Please read the precautions on the back before filling this page)

Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs page 21 This paper size applies to China National Standard (CNS) A4 (210X297 mm)

Order 1237016 A7 B7 V. Description of the invention () Example 10-18: Synthesis of azidomethoxamine In addition to adding various catalysts shown in Table 6, the synthesis was basically carried out according to the method of Example 4. After the reaction is completed, the reaction solution is filtered to obtain amine azide insoluble in water. The yield is calculated and shown in Table 6. Table 6 Catalyst yield (%) used in the examples 10 ZnCl3 94 11 Zn (OH) 2 92 12 A1C13 90 13 B aC 12 91 14 CdCl2 92 15 ZnS04 93 16 ZnCl2 + A1C13 (0.025 moles each) 96 17 ZnCl2 + BaCl2 (0.025 moles each) 94 18 ZnCl2 + CdCl2 (0.025 moles each) 96 Please read the notice on the back -C before filling out this page. Printed by the Employees ’Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Page 22 This paper applies to China National Standard (CNS) A4 specification (210X 297 mm) 1237016 A7 B7 V. Description of the invention (Example 19 · 27: Synthetic i-nitrocarbamate face) In a 2 liter sterile flask, 593.1 g prepared according to the above-mentioned manufacturing example 0 was injected. Chlorinated sodium bisulfate 'and stirred to cool to 10 ° C. The reaction temperature of Lu Duweifu is below 10 ° C. While adding 600 g (8.8 mole) 25% liquid ammonia solution, stir vigorously The reaction is carried out at various temperatures and times. After the reaction is completed, the unreacted ammonia is removed, and the water-insoluble azidomethanamine can be obtained by anti-deer solution. The yield is calculated and shown in Table 7 Table 7

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Example Response conditions (temperature, time) Yield (%) 19 30 ° C, 1 hour 78 20 3 0 ° C, 2 hours 89 21 30 ° C, 3 hours 89 22 6 0 ° C, 1 hour 88 23 60 ° C, 2 hours 90 24 60 ° C, 3 hours 90 25 90 ° C, 1 hour 87 26 90 ° C, 2 hours 86 27 90 ° C, 3 hours 89 __ Page 23 This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm). Order · ί 1670 3 12 Five A7 B7 Description of the invention () Column 28-36: Synthetic gas, in addition to formamide The various catalysts shown in Figure 8 (0.05 moles) were synthesized basically according to the method of Example 22. After the reaction is completed, unreacted ammonia is removed, and the reaction solution is filtered to obtain water-insoluble azidomethanamine. The yield is calculated and shown in Table 8. Table 8 Read the notes on the back before filling out this page Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs on page 24 Example ----- Yield of catalyst used (%) __28 ZnCl3 94 Zn (OH) 2 91 30 A1C13 89 31 BaCl2 91 32 CdCl2 93 33 ZnS04 92 34 ZnCl2 + A1C13 (0.025 mol each) 97 35 ZnCl2 + BaCl2 (0.025 mol each) 93 36 ZnCl2 + CdCl2 (0.025 mol each) 96 This paper is applicable to China National Standard (CNS) A4 specification (210X297 mm) 1237016 A7 B7 V. Description of the invention () Examples 37-45: Synthetic azide was injected into a 2 liter bacteria-control flask 5 9 3 · 1 g according to the above-mentioned manufacturing example 16 The prepared sodium salt of bisphosphonium chloride was cooled to 10X with stirring. While maintaining the reaction temperature below 10 ° C, 600 g (8.8 mol) of 25% liquid ammonia solution was added while vigorously stirring. The reaction is carried out at various temperatures and times. After the reaction is completed, unreacted ammonia is removed, and the reaction solution is filtered to obtain water-insoluble azidomethamine. The yield is calculated and shown in Table 9. Table 9 Example printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Reaction conditions (temperature, time) Yield (%) 37 30 ° C, 1 hour 79 38 3 0 C, 2 hours 88 39 3 0 C, 3 hours 89 40 60 ° C, 1 hour 89 41 6 0 C, 2 hours 90 42 6 0 ° C, 3 hours 91 43 90 ° C, 1 hour 88 44 90 ° C, 2 hours 88 45 90 ° C, 3 hours 89 Page 25 This paper size applies Chinese National Standard (CNS) A4 specification (210 × 297 mm) (Please read the precautions on the back before filling this page)-, τ 1237016 V. Description of the invention (: In addition to the addition of Table 10 The various catalysts shown below (0.05 moles were synthesized basically according to the method of Example 40. After the reaction was completed, unreacted ammonia was removed, and the reaction solution was filtered to obtain water-insoluble azidomethanamine The yield is calculated and shown in Table 丨 〇. Table 10 Yield (please read the notes on the back before filling this page)

Order

The catalyst used by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, page 26, the catalyst used in the first example 46 ZnCl3 93 47 Zn (〇H) 2 48 A1C1, 90__ 49 BaCl, 50 CdCl, _- 51 ZnS04 52 ZnCl2 + A1C13 (each 0.025 Moore, 53 '------------___ ZnCl2 + BaCl2 (0.025 moles each) 54 ZnCl2 + CdCl2 (0.025 moles each, this paper size applies Chinese National Standard (CNS) A4 specifications (210X297 mm ) τ-r 70 3 12 6 、 1 Mingfa Λ 5

4 The preparation solution should be able to produce 1 temperature-soluble reaction liquid. In a 2 liter sterile flask, inject 5933 grams of the vaporized sodium bisulfate according to the above-mentioned manufacturing example 14, and stir to cool to 1 (rc. Maintain the reaction in the lot. Next, while adding liquid ammonia of each content shown in Table n, the mixture is vigorously stirred for 1 hour. After the reaction is completed at various temperatures and times, the unreacted ammonia is removed and the reaction is filtered to obtain a water-insoluble stack. Azamethoxamine. Its yield is calculated and shown in Table 11. Table 11

Cases — 丨 6 forks; 8 Molar ratio of ammonia and gasification shrinkage sodium salt (%) Yield (%) 15 75 30 87 60 90 90 89 @ Ll9-62: Synthetic azide The Consumer Cooperative of the Ministry of Intellectual Property Bureau printed 593 · 1 g of the sodium biuret chloride according to the above-mentioned manufacturing example 14 into a 2 liter sterile flask prepared by the preparation and flour mixing and heating plant, and stirred Cool to 10. (: Maintain the reaction &amp; below 10 ° C, while adding various organic solvents shown in Table 12, the volume is 0.5 times the weight of water. Maintain the reaction temperature below i0 ° c, add 600 grams (8.8 Mo) Ear) 25% liquid ammonia solution, one side is violent for 1 hour. The reaction is performed at various temperatures and times. After the reaction is completed, page 27 This paper applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm) 1237016

Description of the invention (50% of the 丸 V pill 味 taste 嫕 嫕 reaction solution can be obtained ranformamidine. The yield is calculated and shown in Table 12. j 5 6 1-6 6 丄 2 Table 12 Solvent ^ ~ ------ Yield (%) Methanol 90 Dimethylformamide ~ __ 94 Tetrahydrofuran --- ---__ One---- ------- 90 Acetonitrile ----- ^ _ --- 88 ---- For example, the above-mentioned method and preparation for the preparation of azidomethanamine according to the present invention are prepared by the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs and the Ministry of Economic Affairs of the Intellectual Property Bureau of the Ministry of Economic Affairs. Urea, which is easily obtained, is used as the starting # to prepare methyl green amine. In addition, the present invention also uses by-products as raw materials to minimize the amount of the product, and uses an effective continuous process to produce azide, which can be used to prepare azide in an environmentally friendly manner. Methylamine. The description is only a detailed description of the present invention. It should be noted that the present invention can have various changes. These changes and improvements should still be regarded as a paradigm shift of the present invention. Page 28 This paper applies the Chinese National Standard (CNS) A4 size (210X297 mm)

Claims (1)

1237016 y, V A:-B3, C8, D8, No. P patent, amended in September, P. 'i 1. A method for preparing azidomethoxamine, which comprises the following steps: Pyrolysis of urea to obtain biuret and ammonia of formula 1; [Formula 1] 〇〇II Η II Η2Ν-C-N- C-ΝΗ2 reacts the obtained biuret with a secondary metal compound or element and a base to obtain a mono-biuret metal salt of formula 2 or formula 3; [Formula 2] 〇II II H2N-C One NC-NH X Μ (Please read the notes on the back before writing this page) • One and one cloud [Formula 3] 〇 Ⅱ II H2N-CNC-NΗ Μ X-ray Ministry of Economy Intellectual Property Bureau Bei X Consumer Cooperative Printed in Formulas 2 and 3, M represents a metal and X represents a halogen; the resulting mono-biuret metal salt is allowed to react with ammonia generated when the urea is derived from pyrolysis, and the mono-biuret The molar ratio of metal salt to total ammonia is between 1: 1 and 1: 1000. 2. The method for preparing azidomethoxamine according to item 1 of the scope of the patent application, wherein the temperature of the pyrolyzed urea is between 100 ° C and 300 ° C. Page 29 This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 1237016 B8 C8 D3 VI. Application for patent scope 3. The method for preparing azidomethoxamine as described in item 1 of the patent scope, ( Please read the notes on the back before filling this page) * Among them, ammonia is removed from the reaction system when performing the pyrolysis urea reaction. 4. The method for preparing azidomethoxamine as described in item 1 of the scope of the patent application, wherein when performing the pyrolysis urea reaction, a process of inert gas injection and / or a process of reducing system pressure can be performed at the same time. 5. The method for preparing azidomethoxamine according to item 1 of the scope of the patent application, wherein the pyrolysis urea reaction is performed in the presence of at least one catalyst selected from the group consisting of an inorganic acid catalyst and an acid catalyst, and In a group of substances including phosphorus. 6. The method for preparing azidomethoxamine as described in item 1 of the scope of the patent application, wherein the molar ratio of the biuret to the hypothesizing metal compound is between 1: 0.1 and 1: 2. Member of the Intellectual Property Bureau of the Ministry of Economic Affairs, X Consumer Cooperative, printed the method for preparing azidomethoxamine as described in item 1 of the scope of patent application, in which the singulated bifurcate metal salt is obtained by mixing the metal hydride with the biform of formula 1 Urea is then prepared by reacting the resulting product with a prime, or by reacting the two legs of Formula 1 with an iS prime gas and then reacting the resulting product with a base. Page 30 This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) «888 CBCD 1237016 6. Application for patent scope 8. The method for preparing azidomethoxamine as described in item 1 of the patent scope, where The process for obtaining the monohalogenated biuret metal salt is performed at a temperature below 60 ° C. 9. The method for preparing azidomethoxamine as described in item 1 of the scope of patent application, wherein ammonia means liquid ammonia, ammonia gas or ammonium water. 10. The method for preparing azidomethoxamine as described in item 1 of the scope of the patent application, wherein the reaction between the monohalogenated biuret metal salt and ammonia is performed at a temperature ranging from 0 ° C to 150 ° C. 1 1. The method for preparing azidomethoxamine as described in item 1 of the scope of patent application, wherein the reaction solvent is a mixture of water and a second solvent, and the second solvent is a polar solvent, which is Selected from the group consisting of water, methanol, ethanol, propanol, isopropanol, and mixtures thereof; or the second solvent is an aprotic solvent, which is selected from the group consisting of dimethylformamide and dimethylformamide In the group consisting of sulfoximine, dimethylacetamide and mixtures thereof. 1 2. A device for preparing azidomethoxamine, which comprises: a pyrolysis furnace, which can pyrolyze urea to obtain shrinkage and ammonia; a recrystallizer, which can be purified and obtained from pyrolysis Biuret in the furnace; a first reactor, which can make bipyridine react with secondary metal compounds or biuret with _ prime and alkali to produce mono-condensation page 31 of this paper Standards apply to the National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling out this page) --5T »Line-* &gt; Member of the Intellectual Property Bureau of the Ministry of Economy X Printed by Consumer Cooperatives 5 8 8 8: BCD 1237016 VI. Patent application scope Diurea metal salt; a second reactor, which is capable of reacting a single iS biuret metal salt with ammonia to synthesize amine azide; and an ammonia volatilizer, which The system can separate excess ammonia from azidomethoxamine and supply the separated ammonia to an ammonia concentrator, where the ammonia concentrator can concentrate the excess ammonia and ammonia from the pyrolysis furnace. This concentrated ammonia was supplied to a second reactor. 1 3. The equipment for preparing azidoamine as described in item 12 of the scope of the patent application, wherein the pyrolysis furnace has a gas injection port for injecting inert gas, and the inert gas system will not interact with the pyrolysis furnace. Isocyanate reaction. 14. The apparatus for preparing azidomethoxamine as described in item 12 of the scope of the patent application, wherein the pyrolysis furnace has a device capable of reducing the pressure to remove ammonia in the pyrolysis furnace. (Please read the precautions on the back before filling out this page), τ LINE LINE Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy