CN110498724B

CN110498724B - Fuming composition capable of reducing initial reaction temperature, preparation method and application

Info

Publication number: CN110498724B
Application number: CN201910545763.7A
Authority: CN
Inventors: 徐云; 郭晓文; 柳林; 库丽加那提·帕提汗; 周鑫; 王玉三; 魏敏; 程万影; 董国军; 韩莎莎; 王�锋; 周永斌
Original assignee: Chinese People's Liberation Army 69080
Current assignee: Chinese People's Liberation Army 69080
Priority date: 2019-06-22
Filing date: 2019-06-22
Publication date: 2021-01-29
Anticipated expiration: 2039-06-22
Also published as: CN110498724A

Abstract

The invention relates to the use of ammonium dihydrogen phosphate for reducing the decomposition temperature of potassium chlorate and the initial reaction temperature of fuming compositions containing potassium chlorate. The invention also relates to a fuming composition for reducing the initial reaction temperature, which comprises the following components in parts by mass: 35 parts of potassium chlorate, 23 parts of ammonium chloride, 42 parts of crude anthracene and 6-15 parts of ammonium dihydrogen phosphate. Preferably, the mass ratio of the additive ammonium dihydrogen phosphate is 10. The method of making a smoking composition comprises the steps of: mixing the components according to the mass ratio at normal temperature and normal pressure, stirring uniformly, weighing the mixture quantitatively, and packaging into a smoke generating pot. The invention solves the problems that the smoke generating tank is not easy to ignite in plateau and winter and is easy to catch fire and burn in summer. The invention also relates to a new application of the smoke agent in interference of middle infrared rays of 3-5 mu m.

Description

Fuming composition capable of reducing initial reaction temperature, preparation method and application

Technical Field

The invention relates to a smoking composition, a method of making and use thereof.

Background

The invention takes an anthracene mixed smoke tank which is put on the market in a large quantity in Heilongjiang Jianhua machinery factory as a research object, and the smoke tank is used for shielding visible light and is hereinafter referred to as the smoke tank. According to the information disclosed in the specification, the smoke pot has two problems in practical use. Firstly, the ignition time is long or the ignition is difficult to occur under severe cold weather conditions, and sometimes the ignition time is prolonged from 30s to 120 s; secondly, the fire is easy to catch fire under the condition of hot weather.

The main charge of the fuming can contains crude anthracene, potassium chlorate and ammonium chloride, which are short for anthracene mixed fuming agent. In order to eliminate the combustion problem of the smoke generating pot and improve the safety, manufacturers require a smoke generating method which comprises the steps of inserting an awl into a central hole to a depth of about 80mm, then taking out the awl, and puncturing sealing films on the other 10 smoke spraying holes, namely 11 action links, so that not only is time wasted, but also when the battlefield situation changes or the wind direction and the wind speed change are not suitable for smoke generation, the opened smoke generating pot can only be scrapped, in addition, the method also increases the time of the toxic action of a user and the exposure possibility of enemy fire, and therefore, related units adopt a measure of adding sodium bicarbonate on a filling mode, but have small actual effect. Therefore, through physical and chemical analysis and filling tests, the problems that the smoke tank is difficult to ignite and is ignited and burnt are solved, especially the influence of the additive on the ignition and fuming effects of the smoke tank is discussed, the formula process of the smoke agent is improved, the additive or the catalyst for decomposing potassium chlorate is developed, and the method has very important significance for providing an effective way for preparing the smoke agent which is easy to ignite, efficient and stable in fuming.

Disclosure of Invention

In order to solve the above problems of the prior art, the present invention provides a smoking composition which is easily ignitable and has the effect of preventing the ignition and burning of the smoking process.

The invention further provides a method of making the smoking composition.

The invention also provides a new application of the smoking composition in interference of the middle infrared ray of 3-5 mu m.

Specifically, the invention provides an anthracene mixed smoke agent which reduces the initial reaction temperature, brings easy ignition and has the effect of preventing ignition, and is characterized in that the smoke agent comprises the following components in parts by mass:

preferably, the smoke agent comprises the following components in parts by mass:

the invention also provides a preparation method of the fuming composition, which is characterized in that the components are mixed and stirred uniformly at room temperature, and then the mixture is used as a detonator or a main fuming agent to be quantitatively packaged into a fuming tank.

The invention further provides a new application of the smoke agent in interference of infrared light of 3-5 microns.

Drawings

FIG. 1 is a smoke agent differential thermogram. In the figure: 1 primary smoke agent, 2 smoke agent added with 10% ammonium dihydrogen phosphate; 3 adding 25% sodium bicarbonate smoke agent.

Figure 2 is a poor heat map of the addition of 4% analytically pure ammonium dihydrogen phosphate smoking agent.

Figure 3 is a poor heat map of 4% commercial ammonium dihydrogen phosphate smoking agent addition.

Figure 4 is a difference heat map of the addition of different mass percentages of ammonium dihydrogen phosphate smoking agent.

FIG. 5 is a thermogravimetric analysis chart of 8 samples each of which was added with ammonium dihydrogen phosphate as a smoke agent. The left column 4 shows the addition of 0%, 4%, 6%, and 8% by mass, and the right column 4 shows the addition of 10%, 12%, 16%, and 25% by mass.

FIG. 6 is a graph of the effect of varying mass percentages of ammonium dihydrogen phosphate on the effective smoke producing amount of a smoking agent.

FIG. 7 is an infrared spectrum of a primary smoke agent without the addition of ammonium dihydrogen phosphate.

FIG. 8 is an infrared spectrum of a smoke generator with 10% ammonium dihydrogen phosphate added thereto.

Detailed Description

The invention will be further understood from the following illustrative examples.

Example 1

A fuming composition for reducing the initial reaction temperature comprises the following components in parts by mass:

the preparation method of the smoke agent comprises the following steps: weighing 3500g of potassium chlorate, 2300g of ammonium chloride, 4200g of crude anthracene and 1000g of ammonium dihydrogen phosphate at room temperature, mixing, stirring uniformly, and quantitatively packaging into a smoke generating pot as an ignition agent or a main smoke generating agent.

Example 2

Different smoking compositions were tested in a thermal analysis test.

The procedure for making different compositions and weight fractions of the smoke agent was the same as in example 1.

Thermal analysis test tests are now performed.

Preparation of anthracene mixture containing

Analytically pure additive LP1 in ammonium dihydrogen phosphate number, and industrial additive LP2 in ammonium dihydrogen phosphate number are ground and weighed. For convenience of presentation, ammonium dihydrogen phosphate is sometimes replaced with the LP code in the present invention. The components specified in the examples in Table 1 were weighed and mixed at room temperature under normal temperature and pressure and stirred uniformly for use. Before pilot test, each canned sample is 300g and naturally compacted.

Test equipment for the capsule wall: DTA1700 thermal system analyzer, manufactured by P.E usa; the aluminum can is used in the middle test, and conforms to GB 15266-94. Electric heating jacket, thermometer, stopwatch and analytical balance. KCLO₃And analyzing and purifying; anthracene, third-class product.

⒊ test results

In the prior art, in order to prevent organic matters in the smoke agent from being excessively decomposed, control the combustion time and eliminate flame, 20% -30% of sodium bicarbonate is added into the smoke agent as a cooling agent. Sodium bicarbonate and industrial ammonium dihydrogen phosphate are selected as LP2 additives for comparison tests, and a differential thermal analysis chart of the original anthracene mixed smoke agent of the smoke pot and the smoke agent added with 10% of LP2 and the smoke agent added with 25% of sodium bicarbonate is prepared, and is shown in figure 1. In the figure, curve 1 represents the primary anthracene mixed smoke agent without any additives, curve 2 represents the addition of 10% LP2 smoke agent, and curve 3 represents the addition of 25% sodium bicarbonate smoke agent.

As can be seen in figure 1, the LP2 additive reduced the initial reaction temperature of the original smoking composition from 225 ℃ to 183 ℃, indicating that the initial reaction temperature of the smoking composition with the addition of monoammonium phosphate was reduced by 42 ℃ compared to the smoking composition without the addition of monoammonium phosphate.

The control sample with sodium bicarbonate should be discarded because it absorbs a lot of heat when decomposed, which is not good for ignition of the smoke agent.

Experiment on interaction of components of LP additive and smoke agent

LP lowers the reaction initiation temperature of the anthracene mix smoke agent. The primary anthracene mixed smoke agent consists of potassium chlorate, ammonium chloride and crude anthracene. Ammonium chloride is heated to 100 ℃ and begins to volatilize obviously, is dissociated into ammonia and hydrogen chloride when heated to 337.8 ℃, is recombined to generate ammonium chloride with extremely small particles after being cooled to form white dense smoke, and is heated to 350 ℃ to sublimate and has a boiling point of 520 ℃. Thus, the interaction of LP with ammonium chloride can be eliminated. Anthracene is both a smoke-forming and a flammable agent. To ascertain whether LP reacts with anthracene or potassium chlorate, we performed a differential thermal test of groups for the effect that LP may have on each component. The results are shown in Table 1.

TABLE 1 LP fuming agent Effect test results

As can be seen from Table 1, the additive was only to KCI0 in the smoke agent₃And triggered by the LP 1-initiated decomposition reaction, the addition of 4% ammonium dihydrogen phosphate reduced the decomposition initiation temperature of potassium chlorate from 340 ℃ to 180 ℃ to a reduction of 160 ℃.

Comparative example

With the problem that other catalysts are more favorable for the decomposition of potassium chlorate, the catalysts such as CuO and the like recorded in the textbook of chemical chemistry in middle school are selected for experiments, and the results are shown in Table 2.

TABLE 2 Effect of various additives on the decomposition temperature of Potassium chloride

As seen in table 2, the above metal oxide, most notably 4% manganese dioxide, catalyzes potassium chlorate, which lowers the initial reaction temperature of potassium chlorate from 340 c to 320 c, i.e., by 20 c. The reaction effect is not significant. The new application of the additive ammonium dihydrogen phosphate which is obtained by the invention is shown, and the new application is 8 times of the temperature reduction amplitude of manganese dioxide.

Comparative example

Effect of LP purity on fuming agent performance.

In order to reduce the cost, ammonium dihydrogen phosphate of an analytical pure reagent and industrial ammonium dihydrogen phosphate are respectively added into a smoke agent according to the same proportion, differential thermal analysis tests are respectively carried out, the results are respectively shown in attached figures 2 and 3, the two test curves are basically consistent, and the result shows that the purity of the ammonium dihydrogen phosphate has no influence on the performance of the smoke agent basically, in other words, the interference effect of impurities contained in the ammonium dihydrogen phosphate is eliminated.

Example 3

And (4) selecting an experiment according to the optimal addition ratio of LP.

Differential thermal analysis experiments are respectively carried out according to the addition ratios of 0%, 2%, 4%, 10% and 16% LP, and corresponding differential thermal maps are analyzed and compared in sequence, see figure 4, and for simplifying the graph, the 10% LP curve is omitted from figure 4 so as not to be repeated with the above contents.

We have found that an increase in the proportion of additive causes a gradual change in the differential thermal profile and a left shift in the exotherm peak, and restores the original exotherm peak characteristics between 4% and 10%.

We added LP2 to the smoke agent at a ratio of 0%, 4%, 6%, 8%, 10%, 12%, 16%, 25%, respectively, and performed thermogravimetric analysis experiments thereon, respectively, see fig. 5, in which the first 4 samples are listed in the left column from top to bottom, and the last 4 samples are listed in the right column from top to bottom. Through a thermogravimetric experiment and an actual fuming experiment, the weight of the sample at the first inflection point after the rapid weight reduction section on the thermogravimetric graph of the sample is the same as the residual weight of the sample after the actual fuming. Therefore, we defined the weight lost at this point of the sample at room temperature as the effective smoke generation amount, and collate the thermogravimetric analysis experimental data to obtain the relationship between the additive ratio and the effective smoke generation amount, see table 3.

TABLE 3 Effect of LP additive ratio on effective smoke generation

As is clear from Table 3, the increase of the additive reduced the reaction completion, and part of the smoke generating agent was converted to a residue without forming smoke and being released.

For ease of analysis, the data in Table 3 were plotted as FIG. 6.

To clarify the practical significance of the curve of FIG. 6, we performed a series of test tube heating tests.

The OA section shown in the figure 6 is an easily-ignited area, the detonation and ignition phenomena exist in the test tube, and the additive content of the section is less than 6 percent. Because a large amount of smoke substances are consumed in the process of ignition, the smoke amount is reduced, the pipe wall is blackened, and residues are dried and loosened. In the BC section, the additive content is more than 15 percent, which is an easy-to-smoke region, only partial ignition smoke is generated, and the self-termination is realized, and the rest part of the sample is soaked by the syrup-like liquid and does not participate in the reaction. In the AB section, the additive content is between 6% and 15%, the stable smoke generating area is formed, the ignition is rapid, the smoke generating is stable, the smoke generating efficiency is high, and the smoke generating agent is basically exhausted. The residue is black and white, has clear micropores and is moist and hard after being cooled.

Therefore, from the analysis of chemical characteristics, the proportion of the additive is preferably selected to be between 6% and 15%, and the optimal smoking effect is achieved by adding 10%.

Example 4

High and low temperature pilot test.

We added LP to the smoke agent system at 0%, 5% ratio, ignited to smoke in fume hood at room temperature and-20 ℃ respectively; and then adding the LP into a smoke agent system according to the proportion of 0 percent, 6 percent and 10 percent, and igniting and fuming outdoors. The results are shown in Table 4.

TABLE 4 smoking conditions in pilot scale at different temperatures

No. 4 sample is directly buried into a large-energy fire-drawing tube of a certain smoke-generating grenade for combustion.

Experimental results show that the anthracene mixed smoke agent prepared by adding LP2 has the following 3 characteristics.

The ignition temperature is reduced, and the ignition performance is improved.

Secondly, the ignition of the smoke generating tank can be effectively inhibited, and the smoke generating time and the smoke generating quality are ensured.

And the smoke is sensitive and the smoke volume is large.

Example 5

Resistance to mid-infrared spectroscopic analysis.

The same weight of anthracene mixed smoke agent is taken, and infrared spectrum analysis is carried out without adding 10 percent ammonium dihydrogen phosphate and adding 10 percent ammonium dihydrogen phosphate respectively. The results are shown in FIGS. 7 and 8.

Compared with the prior art, the smoke agent added with ammonium dihydrogen phosphate has a plurality of strong absorption peaks in the most sensitive military mid-infrared range of 3-5 microns, and the smoke agent has a new anti-mid-infrared interference function on the basis of the original visible light. The new application of adding ammonium dihydrogen phosphate into the fuming tank is brought by the change of components and fuming performance.

The smoke test mechanism for the smoke pot was analyzed as follows.

The smoking mechanism of the smoke generating pot is that the ignition rod provides energy to enable KCI0₃Decomposing, releasing oxygen and heat, oxidizing anthracene by the released oxygen, and releasing a great deal of heat while oxidizing anthracene, wherein the heat promotes NH₄The Cl and unoxidized anthracene sublime to form a smoke. KCl0₃Heat released by decomposition and anthracene oxidation, one part of which maintains the continued reaction after the ignition rod is extinguished, and the other part of which is used for making NH react₄Cl and anthracene sublime.

The chemical reactions and thermal effects of the fuming process are as follows:

first oxidant KCI0₃Decomposition of

2KCI0₃→2KCl+3O₂···········①

△H＝-89.71kJ/mol

The oxidation of anthracene and phenanthrene (isomers of anthracene)

When the oxygen amount is insufficient, the reaction products are CO and H₂O

C₁₄H₁₀+19/2O₂→14CO+5H₂O············②

Wherein when anthracene is oxidized, delta H is-2826.7 kJ/mol;

when phenanthrene is oxidized, delta H-2867.5 kJ/mol

When the amount of oxygen is sufficient, the reaction product is CO₂And H ₂0, the reaction is as follows:

C₁₄H_l0+33/20₂→14C0₂+5H ₂0············③

wherein when anthracene is oxidized, delta H is-6788.7 kJ/mol;

when phenanthrene is oxidized, Δ H ═ 6829.5kJ/mol.

Therefore, the heat released by the complete oxidation of anthracene and phenanthrene is far greater than the heat generated by CO, and the reaction II and III are controlled by the reaction I. When the temperature of the system reaches the ignition point of anthracene, a proper amount of oxygen causes reaction III, and a large amount of heat generated by the reaction III accelerates the reaction I, so that the circulation is realized, and the combustion is not stopped.

The mechanism analysis of the additive effective inhibition smoke pot ignition test is as follows:

addition of NH₄H₂P0₄Then, the following reaction first occurs at its melting point temperature:

NH₄H₂P0₄→NH₃+H₃P0₄············④

△H＝111.05kJ/mol

decomposition of the resulting NH₃And (4) escaping. Above 150 ℃, phosphoric acid loses bound water to generate pyrophosphoric acid H₄P₂0₇(ii) a If the temperature is increased to 290-300 ℃,to produce easily sublimable HPO metaphosphate₃The reaction is as follows:

H₃P0₄→HPO₃+H₂O·············⑤

ΔH＝97.96kJ/mol

the melting points of phosphoric acid, pyrophosphoric acid and metaphosphoric acid are very low, 42.3 deg.C, 61 deg.C and 38 deg.C-41 deg.C, respectively.

We believe that the flame retardant effect of LP is mainly 3 points: first, an endothermic effect. The reactions of the fourth and fifth are endothermic reactions, each mole of ammonium dihydrogen phosphate is decomposed to absorb 111.05kJ energy; each mole of phosphoric acid is dehydrated to generate metaphosphoric acid, and 97.96kJ energy is absorbed. Second, dilution is effected. The non-combustible gas such as ammonia gas generated by decomposition dilutes the oxygen concentration in the combustion zone and the combustible gas concentration generated by heating the smoke agent, so that the combustion performance and speed are reduced. Third, the covering effect. The surplus phosphoric acid combines with the reaction product to block the pores and cover the surface, thereby playing a role in heat insulation.

The reactions (iv) and (v) also cause an increase in the amount of smoke generated after addition of LP.

Example 6

To examine the effect of the rapid ignition method on the ignition time of a smoke canister, two comparative tests were performed in winter. The results are given in Table 5 below.

TABLE 5 comparison of ignition effect before and after omitting 11 operation links

The test uses a primary smoke canister and only compares two different ignition methods.

The invention has the beneficial effects that:

1. the energy provided by the ignition rod enables the smoke agent to reach the ignition temperature at normal temperature of the primary smoke tank. Under severe cold conditions, the environmental heat dissipation is increased, and the energy obtained by the smoke agent from the ignition rod in the same time is less than that at normal temperature, so that the time for reaching the ignition temperature is prolonged. After the addition of LP, the ignition temperature of the smoke agent is reduced to 183 ℃, and the time for reaching the ignition temperature is shorter, so that the required ignition energy is correspondingly reduced, the time is shortened, and the ignition reliability is improved. Considering that the situation of minus 42 ℃ rarely occurs in all parts of China in winter, the ignition temperature of the invention is reduced by about 42 ℃, which shows that the problem of prolonging the ignition time of the primary smoke tank is basically eliminated.

2. The temperature of the fuming system is reduced by 42 ℃ as a whole, the safety temperature difference between the system temperature and the ignition point of the fuming agent in the fuming process is widened, and the two factors act together to solve the ignition problem of the fuming tank.

⒊ the real reason of the smoke tank combustion explosion is caused by the high smoke initiation ignition temperature and the small safety temperature difference with the ignition point of the smoke agent formula, and the 11 action links of the required smoke method of pricking the awl into the center hole to prick the depth about 80mm, then taking out the awl and pricking the sealing film on the other 10 smoke spraying holes are redundant in order to prevent the smoke tank combustion explosion problem and improve the safety, which not only wastes time, but also can only scrap the opened smoke tank when the battlefield situation changes or the wind direction and the wind speed change are not suitable for smoke generation, in addition, the method also increases the time of the poison effect of the soldier and the opportunity of exposing under the enemy fire, so the 11 action operation links can be omitted, and the related problems can be thoroughly solved.

⒋ after the 11 operation links are omitted, because the smoke pot is in a sealed state during ignition, the energy dissipation of the smoke pot from the ignition rod to the environment is obviously reduced, so the problem of ignition time delay under severe cold conditions in plateau is obviously improved, and in fact, the problem that ignition can not be realized by adopting the new ignition method for reducing 11 operation links is not found.

⒌ the method is advantageous for equipment protection, delay reuse and withdrawal when the battlefield requirement changes suddenly because 10 smoke spraying holes are not opened.

⒍ the quick ignition method is favorable for shortening the ignition time and improving the tactical performance of the smoke pot in adverse weather conditions such as severe cold in plateau.

⒎ the smoke generated by the added smoke agent enhances the interference ability to near infrared light.

⒏ the anthracene mixed smoke agent is not only smoke agent but also combustible agent for converting heat energy required by smoke generation, and the smoke amount of the generated smoke is large when the converted heat energy is small. The temperature of the fuming tank system is reduced in the fuming process, the temperature difference is reduced, so that the fuming tank can emit heat energy to the environment to reduce, the heat energy supply is reduced by the two factors, the effective fuming amount is improved, and the function of the fuming composition is changed.

According to Stephen-Boltzmann law, radiation energy of an object is in direct proportion to the fourth power of temperature, reaction temperature is obviously reduced, and the radiation capability of target exposure and infrared reconnaissance monitoring and tracking striking of an enemy is greatly reduced.

⒑ the invention discloses the catalysis and promotion effect of ammonium dihydrogen phosphate on the decomposition reaction of potassium chlorate, which is 8 times of the temperature difference effect of the most effective catalyst manganese dioxide provided by the textbook of middle school. The breakthrough of the invention in basic research can be further applied to chemical industry, national defense, industry, agriculture, science and technology industry and related departments of national production.

Claims

1. Use of monoammonium phosphate for reducing the initial reaction temperature of a potassium chlorate-containing fuming composition.

2. A fuming composition added with ammonium dihydrogen phosphate comprises the following components in parts by mass:

potassium chlorate 35

Ammonium chloride 23

Crude anthracene 42

6-15 parts of ammonium dihydrogen phosphate.

3. A process for preparing the smoking composition of claim 2, characterized in that the process comprises the steps of: mixing the components by mass at normal temperature and normal pressure, stirring uniformly, weighing quantitatively and packaging into a smoke generating pot.