CN111393328A - Waste TNT conversion and recycling process - Google Patents
Waste TNT conversion and recycling process Download PDFInfo
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- CN111393328A CN111393328A CN202010266130.5A CN202010266130A CN111393328A CN 111393328 A CN111393328 A CN 111393328A CN 202010266130 A CN202010266130 A CN 202010266130A CN 111393328 A CN111393328 A CN 111393328A
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- tnt
- triphosgene
- triaminotoluene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C263/00—Preparation of derivatives of isocyanic acid
- C07C263/10—Preparation of derivatives of isocyanic acid by reaction of amines with carbonyl halides, e.g. with phosgene
Abstract
The invention discloses a waste TNT conversion and recycling process which comprises the following steps of preparing 2,4, 6-triaminotoluene by catalytic hydrogenation in a high-pressure reaction kettle by taking waste TNT as a raw material, Pd/C as a catalyst, hydrogen as a reducing agent and one of methanol, chloroform, toluene and acetone as a solvent, and reacting at normal temperature to obtain 2,4, 6-triaminotoluene hydrochloride. Using triaminotoluene hydrochloride and triphosgene as raw materials, using chlorobenzene as a solvent, firstly dissolving the triphosgene in chlorobenzene (the chlorobenzene is dehydrated by a molecular sieve in advance), adding a triphosgene solution into the triaminotoluene hydrochloride solution, cooling to room temperature, filtering, and distilling under reduced pressure to obtain the TTI. The process method for converting waste TNT into toluene-2, 4, 6-triisocyanate (TTI) can solve the problem that the normal service guarantee of an army is influenced by the accumulation of a large amount of waste TNT in a storehouse, and can convert waste TNT without utilization value into a high-value chemical product, thereby improving the economic benefit.
Description
Technical Field
The invention relates to a waste TNT conversion and recycling process, and belongs to the technical field of organic synthesis.
Background
TNT (2,4, 6-trinitrotoluene) is an energetic compound which is most widely applied in China and is widely used in military various ammunitions and civil explosive devices. With the continued use of new higher energy energetic compounds, the amount of TNT used has been gradually reduced in the military field. However, TNT-based ammunition which is equipped in early stage of China continuously enters the retired period, and a large amount of waste TNT is poured out of the metal shell through a heating melting method. The recycling value of the waste TNT is too low, and the recycling cost is even higher than the manufacturing cost of the TNT; secondly, the TNT energy is too low, and in addition, the TNT has no relevant recycling standard, so that the TNT cannot be recycled in the military field; thirdly, the early TNT open-air incineration disposal method is forbidden due to serious environmental pollution; fourthly, toxic products after TNT explosion seriously affect the ecological environments of surrounding atmosphere, water sources, soil and the like, and are eliminated by the civil field. Therefore, the waste TNT is accumulated in the army storeroom in a large amount due to no recycling way, so that not only is serious potential safety hazard brought, but also a large amount of manpower, material resources and financial resources are consumed, and the normal service guarantee of the army is seriously influenced. Therefore, a safe and environment-friendly TNT conversion path is found, and a great amount of waste TNT is converted into a high-value and high-demand chemical product, which becomes a problem to be solved urgently.
Shevelev discloses a process for converting TNT to 2,4, 6-triaminotoluene hydrochloride (synthetic communications,2001,31(17): 2557-2561.). The process takes ferric chloride and carbon powder as catalysts, uses excess hydrazine hydrate to reduce TNT into 2,4, 6-triaminotoluene, and then reacts with hydrochloric acid to generate a target compound. Kashaev discloses a process for converting TNT to 2,4, 6-triaminotoluene (thermal considerations of chemical engineering,2008,42(5): 650-. The process takes Pd/C as a catalyst, and uses hydrogen to reduce TNT into a target compound. Kastens et al disclose a process for converting TNT to 1,3, 5-trihydroxybenzene (phloroglucinol) (Industrial and engineering chemistry 1950,42(3): 402-. The process uses Na2Cr2O7TNT is first oxidized into TNBA, nitro is then reduced with iron powderMeanwhile, the m-benzenetriamine is obtained by decarboxylation under the acidic condition, and the phloroglucinol is obtained by hydrolysis under the condition of hydrochloric acid/water heating.
2,4, 6-triaminotoluene and hydrochloride thereof are low in price, and reagents used in the conversion process are toxic or expensive, so that the conversion value of the processes is low; sodium dichromate and the like used in a process for converting 1,3, 5-trihydroxybenzene (phloroglucinol) cause serious environmental pollution and are strictly prohibited in developed countries such as europe and the united states. In addition, both 2,4, 6-triaminotoluene and hydrochloride thereof and 1,3, 5-trihydroxybenzene (phloroglucinol) have limited market demand, so that the problem that a large amount of waste TNT accumulation storehouses cannot be met and cannot be treated is solved.
Disclosure of Invention
The invention aims to solve the technical problems of limited market demand and low conversion value of target compounds in the background technology, and provides a method for converting waste TNT into a chemical product with high demand and high conversion value.
In order to realize the purpose of the invention, the invention adopts the technical scheme that:
a process for converting waste TNT into toluene-2, 4, 6-triisocyanate (TTI) comprises the following steps:
the method comprises the steps of taking waste TNT as a raw material, taking Pd/C as a catalyst, taking hydrogen as a reducing agent, taking one of methanol, chloroform, toluene and acetone as a solvent, carrying out catalytic hydrogenation in a high-pressure reaction kettle to prepare 2,4, 6-triaminotoluene, reacting for 1-4 h at normal temperature, filtering, adding 5-20 ml of concentrated hydrochloric acid into filtrate after filtering, freezing, filtering, and leaching to obtain 2,4, 6-triaminotoluene hydrochloride, wherein the structural formula is shown as (II). Wherein the mass ratio of TNT to Pd/C is (5-15): 1, and the mass ratio of TNT to solvent is 1: (5-10). The hydrogen pressure is 1-5 MPa. And secondly, using triaminotoluene hydrochloride and triphosgene as raw materials, using chlorobenzene as a solvent, dissolving the triphosgene in chlorobenzene (the chlorobenzene is dehydrated by a molecular sieve in advance), adding a triphosgene solution into the triaminotoluene hydrochloride solution, stirring at room temperature for 5-30 h, refluxing for 5-30 h, cooling to room temperature, blowing argon for 40min, filtering, and distilling under reduced pressure to obtain TTI, wherein the structural formula is shown as (III). Wherein the mass ratio of the triaminotoluene hydrochloride to the triphosgene is (0.3-0.5): 1;
the preferred TNT conversion toluene-2, 4, 6-triisocyanate (TTI) process method comprises the following steps:
preparation of triaminotoluene hydrochloride: the method comprises the steps of taking waste TNT as a raw material, Pd/C as a catalyst, hydrogen as a reducing agent and absolute methanol as a solvent, preparing 2,4, 6-triaminotoluene through catalytic hydrogenation in a high-pressure reaction kettle, reacting for 2 hours at normal temperature, filtering, adding 15ml of concentrated hydrochloric acid into filtrate, freezing, filtering, and washing with the absolute methanol to obtain the 2,4, 6-triaminotoluene hydrochloride. Wherein the mass ratio of TNT to Pd/C is 9:1, and the mass ratio of TNT to solvent is 1: 7. The hydrogen pressure was 2.5 MPa.
Preparation of toluene-2, 4, 6-triisocyanate (TTI): using triaminotoluene hydrochloride and triphosgene as raw materials, using chlorobenzene as a solvent, firstly dissolving the triphosgene in chlorobenzene (the chlorobenzene is dehydrated by a molecular sieve in advance), adding a triphosgene solution into the triaminotoluene hydrochloride solution, stirring at room temperature for 24 hours, refluxing for 24 hours, cooling to room temperature, blowing argon for 40min, filtering, and distilling under reduced pressure to obtain TTI. Wherein the mass ratio of the triaminotoluene hydrochloride to the triphosgene is 0.3: 1.
The invention has the beneficial effects that:
the toluene-2, 4, 6-triisocyanate (TTI) obtained by the process method for converting waste TNT into toluene-2, 4, 6-triisocyanate (TTI) is an analogue of TDI which is a raw material with the largest demand for Polyurethane (PU) materials, compared with TDI, one more isocyanate group in TTI can provide a larger branching degree, and can be used as a curing agent and a crosslinking agent, can be used as a curing agent in 2K coating, and can be used as a performance regulator of TDI to partially replace TDI. The sale price of TDI is 12000 yuan/ton-55000 yuan/ton, and the annual demand is about 500 ten thousand tons. Waste TNT is converted into TTI, so that the problem that the normal service guarantee of an army is influenced by a large number of waste TNT stacked storehouses can be solved, waste TNT without utilization value can be converted into high-value chemical products, and economic benefits are improved. In the comparison document, no matter the waste TNT is converted into the 2,4, 6-triaminotoluene and the hydrochloride thereof, or the 1,3, 5-trihydroxybenzene (phloroglucinol), the market demand is limited, the converted product is not high in price, and the problem that a large amount of waste TNT cannot be treated is solved.
Detailed Description
The present invention will be described in further detail with reference to examples. It should be noted that these embodiments are preferable examples, and are mainly used for understanding the present invention, but the present invention is not limited to these embodiments.
Example 1
(1) 4.54g (20mmol) of 2,4, 6-trinitrotoluene, 0.5g of palladium carbon and 40ml of anhydrous methanol are sequentially added into a reaction kettle, hydrogen is pressurized to 2.5MPa, the mixture is stirred for 2 hours at room temperature and filtered, 15ml of concentrated hydrochloric acid is dropwise added into the filtrate, the mixture is frozen and filtered, and a filter cake is washed by methanol to obtain 4.43g of a reddish brown solid with the yield of 90 percent.
And (3) structural identification:
infrared spectrum: IR (KBr, cm)-1),υ：3485cm-1And 3587cm-1(N-H)；2878cm-1(NH3 +)；1497cm-1(benzene ring); 1094cm-1(C-N)；868cm-1(C-H)；
Nuclear magnetic spectrum:1HNMR (DMSO-d6,400MHz,): 7.09(s, 2H, H-3, 5); 2.19(s, 3H, CH 3); the active hydrogen contained in the amino hydrochloride is shown at 8.75, showing a broad peak.
The above structural identification data confirmed that the resulting material was indeed triaminotoluene hydrochloride.
(2) Taking 3g (12.16mmol) of triaminotoluene hydrochloride, adding 10ml of chlorobenzene, dissolving 10g of triphosgene in 40ml of chlorobenzene (the chlorobenzene is dehydrated by a dried molecular sieve in advance), adding the triphosgene solution into the triaminotoluene hydrochloride solution, stirring for 24h at room temperature, refluxing for 24h at 130 ℃, stopping heating, blowing argon for 40min, filtering the obtained solution, and distilling under reduced pressure to obtain 1.36g of white solid powder. The yield thereof was found to be 52%.
And (3) structural identification:
infrared spectrum: IR (KBr, cm)-1),υ：2274cm-1(N＝C＝O)；1596cm-1(benzene ring); 1013cm-1(C-H)；854cm-1(C-H)；
Nuclear magnetic spectrum:1HNMR(DMSO-d6,400MHz,)：7.09(s，2H，H-3,5)；2.19(s，3H，CH3) (ii) a The active hydrogen contained in the amino hydrochloride is shown at 8.75, showing a broad peak.
The above structural identification data confirmed that the resulting material was indeed toluene-2, 4, 6-triisocyanate.
Example 2
(1) 4.54g (20mmol) of 2,4, 6-trinitrotoluene, 0.3g of palladium carbon, 30ml of toluene and hydrogen are sequentially added into a reaction kettle, the mixture is pressurized to 2.5MPa, stirred for 2 hours at room temperature, filtered, 15ml of concentrated hydrochloric acid is dropwise added into the filtrate, the filtrate is frozen and filtered, and a filter cake is washed by methanol to obtain 4.15g of a red brown solid with the yield of 84%.
(2) Taking 3g (12.16mmol) of triaminotoluene hydrochloride, adding 10ml of chlorobenzene, dissolving 6g of triphosgene in 40ml of chlorobenzene (the chlorobenzene is dehydrated by a dried molecular sieve in advance), adding the triphosgene solution into the triaminotoluene hydrochloride solution, stirring for 8h at room temperature, refluxing for 24h at 130 ℃, stopping heating, blowing argon for 40min, filtering the obtained solution, and distilling under reduced pressure to obtain 0.85g of white solid powder. The yield thereof was found to be 32%.
Example 3
(1) 4.54g (20mmol) of 2,4, 6-trinitrotoluene, 0.9g of palladium carbon and 50ml of anhydrous methanol are sequentially added into a reaction kettle, hydrogen is pressurized to 2.5MPa, the mixture is stirred for 2 hours at room temperature and filtered, 15ml of concentrated hydrochloric acid is dropwise added into the filtrate, the mixture is frozen and filtered, and a filter cake is washed by methanol to obtain 4.48g of a reddish brown solid with the yield of 91 percent.
(2) Taking 3g (12.16mmol) of triaminotoluene hydrochloride, adding 10ml of chlorobenzene, dissolving 8g of triphosgene in 40ml of chlorobenzene (the chlorobenzene is dehydrated by a dried molecular sieve in advance), adding the triphosgene solution into the triaminotoluene hydrochloride solution, stirring for 12h at room temperature, refluxing for 12h at 130 ℃, stopping heating, blowing argon for 40min, filtering the obtained solution, and distilling under reduced pressure to obtain 1.18g of white solid powder. The yield thereof was found to be 45%.
Example 4
(1) 4.54g (20mmol) of 2,4, 6-trinitrotoluene, 0.5g of palladium carbon and 40ml of toluene are sequentially added into a reaction kettle, hydrogen is pressurized to 1MPa, the mixture is stirred for 3 hours at room temperature, and then filtered, 5ml of concentrated hydrochloric acid is dropwise added into the filtrate, the mixture is frozen and filtered, and a filter cake is washed by methanol to obtain 3.89g of a reddish brown solid with the yield of 79 percent.
(2) Taking 3g (12.16mmol) of triaminotoluene hydrochloride, adding 10ml of chlorobenzene, dissolving 10g of triphosgene in 40ml of chlorobenzene (the chlorobenzene is dehydrated by a dried molecular sieve in advance), adding the triphosgene solution into the triaminotoluene hydrochloride solution, stirring for 8h at room temperature, refluxing for 8h at 130 ℃, stopping heating, blowing argon for 40min, filtering the obtained solution, and distilling under reduced pressure to obtain 1.03g of white solid powder. The yield thereof was found to be 39%.
Example 5
(1) 4.54g (20mmol) of 2,4, 6-trinitrotoluene, 0.5g of palladium carbon and 40ml of anhydrous methanol are sequentially added into a reaction kettle, hydrogen is pressurized to 5MPa, the mixture is stirred for 2 hours at room temperature, the mixture is filtered, 15ml of concentrated hydrochloric acid is dropwise added into the filtrate, the mixture is frozen and filtered, and a filter cake is washed by methanol to obtain 4.03g of a red brown solid with the yield of 82 percent.
(2) Taking 3g (12.16mmol) of triaminotoluene hydrochloride, adding 10ml of chlorobenzene, dissolving 8g of triphosgene in 40ml of chlorobenzene (the chlorobenzene is dehydrated by a dried molecular sieve in advance), adding the triphosgene solution into the triaminotoluene hydrochloride solution, stirring at room temperature for 30h, refluxing at 130 ℃ for 30h, stopping heating, blowing argon for 40min, filtering the obtained solution, and distilling under reduced pressure to obtain 1.36g of white solid powder. The yield thereof was found to be 49%.
Claims (2)
1. A process for converting waste TNT into toluene-2, 4, 6-triisocyanate TTI is characterized by comprising the following steps of,
the method comprises the steps of firstly, preparing 2,4, 6-triaminotoluene by taking waste TNT as a raw material, Pd/C as a catalyst, hydrogen as a reducing agent and any one of anhydrous methanol, chloroform, toluene and acetone as a solvent through catalytic hydrogenation in a high-pressure reaction kettle, reacting for 1-4 hours at normal temperature, filtering, adding 5-20 ml of concentrated hydrochloric acid into filtrate after filtering, freezing, filtering and leaching to obtain 2,4, 6-triaminotoluene hydrochloride;
wherein the mass ratio of the TNT to the Pd/C is 5-15: 1, and the mass ratio of the TNT to the solvent is 1: 5-10, and the hydrogen pressure is 1-5 MPa;
secondly, taking 2,4, 6-triaminotoluene hydrochloride and triphosgene as raw materials, taking chlorobenzene as a solvent, firstly dissolving the triphosgene in the chlorobenzene to obtain a triphosgene solution, wherein the chlorobenzene needs to be dehydrated by a molecular sieve in advance; adding a triphosgene solution into a 2,4, 6-triaminotoluene hydrochloride solution, stirring at room temperature for 5-30 h, refluxing for 5-30 h, cooling to room temperature, blowing with argon for 40min, filtering, and distilling under reduced pressure to obtain TTI; wherein the mass ratio of the 2,4, 6-triaminotoluene hydrochloride to the triphosgene is 0.3-0.5: 1.
2. the process for converting waste TNT into toluene-2, 4, 6-triisocyanate TTI as claimed in claim 1, comprising the following steps,
firstly, taking waste TNT as a raw material, Pd/C as a catalyst, hydrogen as a reducing agent, and anhydrous methanol as a solvent, preparing 2,4, 6-triaminotoluene by catalytic hydrogenation in a high-pressure reaction kettle, reacting for 2 hours at normal temperature, filtering, adding 15ml of concentrated hydrochloric acid into filtrate after filtering, freezing and filtering, and obtaining 2,4, 6-triaminotoluene hydrochloride after the anhydrous methanol is washed by water; the mass ratio of the TNT to the Pd/C is 9:1, the mass ratio of the TNT to the solvent is 1:7, and the hydrogen pressure is 2.5 MPa;
secondly, taking 2,4, 6-triaminotoluene hydrochloride and triphosgene as raw materials, taking chlorobenzene as a solvent, and firstly dissolving the triphosgene in chlorobenzene to obtain a triphosgene solution, wherein the chlorobenzene needs to be dehydrated by a molecular sieve in advance; adding triphosgene solution into 2,4, 6-triaminotoluene hydrochloride solution, stirring at room temperature for 24h, refluxing for 24h, cooling to room temperature, blowing with argon for 40min, filtering, and distilling under reduced pressure to obtain TTI; wherein the mass ratio of the 2,4, 6-triaminotoluene hydrochloride to the triphosgene is 0.3: 1.
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| CN112125826A (en) * | 2020-09-16 | 2020-12-25 | 北京理工大学 | Preparation method of 2,4, 6-toluene triisocyanate |
| CN113072907A (en) * | 2021-03-09 | 2021-07-06 | 北京理工大学 | Environment-friendly adhesive and preparation method and application thereof |
| CN115490597A (en) * | 2022-09-19 | 2022-12-20 | 西安近代化学研究所 | Synthetic method of fluorotoluene derivatives |
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| CN113072907A (en) * | 2021-03-09 | 2021-07-06 | 北京理工大学 | Environment-friendly adhesive and preparation method and application thereof |
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Application publication date: 20200710 |