Fire extinguishing composition containing transition metal compound

Abstract

The disclosure relates to a fire extinguishing composition containing a transition metal compound, comprising a salt of an organic acid of the fourth period elements in a subgroup and the group VIII; and using a pyrotechnic agent as a heat source and a power source, reacting through heat emitted by igniting the pyrotechnic agent to burn and outputting a fire extinguishing material. In the disclosure, a transition metal compound is selected as a primary ingredient, then an amine and/or organic amine salt is added to assist in fire extinguishing, a fire extinguishing aerosol is formed by using the fire extinguishing material generated by heating and decomposing the transition metal compound, and meanwhile the amine and/or organic amine salt is heated and decomposed to generate a great quantity of gas, thereby increasing the concentration and the air pressure strength of the fire extinguishing aerosol, improving the injection strength of the fire extinguishing material, and greatly improving the fire extinguishing performance of the fire extinguishing composition.

Claims

1. A fire extinguishing composition containing a transition metal salt of an organic acid and a pyrotechnic agent; and the fire extinguishing composition adopts the pyrotechnic agent as a heat source and a power source, reacts and releases a fire extinguishing material through heat emitted by igniting and burning the pyrotechnic agent, the mass percentage of the transition metal salt of the organic acid is 65 wt % to 95 wt %, the fire extinguishing composition further includes an auxiliary fire extinguishing agent in a mass percentage of 5 wt % to 35 wt %, the auxiliary fire extinguishing agent is an amine and/or organic amine salt; wherein the transition metal salt of the organic acid is a ferric salt of an organic acid, a manganese salt of an organic acid, a nickel salt of an organic acid, a copper salt of an organic acid, a zinc salt of an organic acid or a cobalt salt of an organic acid; wherein the ferric salt of the organic acid is one or more of ferric citrate, ferric oleate, ferric linoleate, ferric stearate, ferric benzoate, ferric acetate, ferric salicylate and ferric gluconate; wherein the manganese salt of the organic acid is one or more of manganous acetate, manganous benzoate, manganese salicylate and manganese gluconate; wherein the nickel salt of the organic acid is one or more of nickel oleate, nickel benzoate, and nickel salicylate; wherein the copper salt of the organic acid is one or more of copper formate, copper oleate, copper linoleate, copper stearate, copper tartrate, copper 2-hydroxybutanedioate, copper iso-octoate, copper benzoate, and copper salicylate; wherein the zinc salt of the organic acid is one or more of zinc oleate, zinc citrate, zinc benzoate, zinc methacrylate, zinc salicylate and zinc gluconate; wherein the cobalt salt of the organic acid is one or more of cobalt acetate, cobalt citrate, cobalt iso-octoate, cobalt benzoate, and cobalt salicylate; wherein the organic amine salt includes an organic amine hydrochloride and an organic amine sulphate; wherein the organic amine salt is one or more of 2-methylaniline hydrochloride, 3,3′-dimethylbenzidine dihydrochloride, N′N-dimethyl-p-phenylenediamine sulphate, N,N′-dimethyl-p-phenylenediamine monohydrochloride, N′N-diethyl-p-phenylenediamine sulphate, N,N′-diethyl-p-phenylenediamine monohydrochloride, 1-naphthylamine hydrochloride, aniline hydrochloride, 3-hydroxyphenylamine hydrochloride, diphenylamine hydrochloride, dimethylamine hydrochloride, diethylamine hydrochloride, cyclohexylamine hydrochloride, benzidine sulfate, benzidine phydrochloride, trimethylamine hydrochlorate, ethylenediamine hydrochloride, m-phenylenediamine hydrochloride, o-phenylendiamine hydrochloride, o-bromoaniline hydrochloride, N(1-naphthyl)ethylenediamine hydrochloride and triethanolamine hydrochloride.

2. The fire extinguishing composition containing a transition metal compound according to claim 1, wherein the organic amine sulfate is one or more of m-phenylenediamine sulfate, hydroxylamine sulfate, o-phenylenediamine sulfate, 3-hydroxyphenylamine sulfate, ethylenediamine sulfate and diethylamine sulfate.

3. The fire extinguishing composition containing a transition metal compound according to claim 1, wherein the amine is one or more of o-nitroaniline, methacrylamide, salicylanilide, p-toluenesulfonamide, p-phenetidine, N-hydroxymethylbenzene sulfonamide, phthalimide and N,N′-methylenebisacrylamide.

4. The fire extinguishing composition containing a transition metal compound according to claim 1, wherein the fire extinguishing composition further includes a performance additive; the performance additive is hydroxy propyl methyl cellulose, talc or a combination thereof; the mass percentage of the performance additive ranging from larger than 0 to smaller than or equal to 15%.

5. The fire extinguishing composition containing a transition metal compound according to claim 4, wherein ingredients and mass percentage thereof in the fire extinguishing composition are as follows: the salt of the organic acid of the fourth period transition metals: 75 wt % to 90 wt %; auxiliary fire extinguishing agent: 5 wt % to 20 wt %; performance additive: 5 wt %.

Description

DETAILED DESCRIPTION OF THE EMBODIMENTS

(1) A fire extinguishing composition of the disclosure will be further described in combination with specific examples below:

(2) the fire extinguishing composition includes a salt of an organic acid of the fourth period transition metal elements in a subgroup and the group VIII, adopts a pyrotechnic agent as a heat source and a power source, reacts and releases a fire extinguishing material in use of heat emitted by igniting and burning the pyrotechnic agent. Wherein the salt of the organic acid in the subgroup mainly involves a salt of an organic acid of a transition metal element in the group IB, the group IIB or the group VIIB. The salt of the organic acid of the fourth period transition metal elements in the subgroup and the group VIII mainly includes one or more of a ferric salt of an organic acid, a manganese salt of an organic acid, a nickel salt of an organic acid, a copper salt of an organic acid, a zinc salt of an organic acid and a cobalt salt of an organic acid. The ferric salt of the organic acid is ferric citrate, ferric oxalate, ferric oleate, ferric linoleate, ferric stearate, ferric benzoate, ferric acetate, ferric salicylate or ferric gluconate etc.; the manganese salt of the organic acid is manganous acetate, manganese oxalate, manganese citrate, manganous benzoate, manganese salicylate or manganese gluconate etc.; the nickel salt of the organic acid is nickel acetate, nickel oxalate, nickel oleate, nickel citrate, nickel benzoate, nickel salicylate or nickel aminosulfonate etc.; the copper salt of the organic acid is copper acetate, copper formate, copper oxalate, copper oleate, copper linoleate, copper stearate, copper citrate, copper tartrate, copper 2-hydroxybutanedioate, copper iso-octoate, copper benzoate, or copper salicylate etc.; the zinc salt of the organic acid is zinc acetate, zinc oxalate, zinc oleate, zinc stearate, zinc citrate, zinc benzoate, zinc methacrylate, zinc salicylate or zinc gluconate etc.; the cobalt salt of the organic acid is cobalt acetate, cobalt oxalate, cobalt citrate, cobalt iso-octoate, cobalt benzoate, cobalt salicylate or cobalt amino-sulfonate etc.

(3) An auxiliary fire extinguishing agent may be further added, i.e. an amine and/or organic amine salt. Wherein the organic amine salt includes an organic amine hydrochloride and an organic amine sulfate; the organic amine hydrochloride may be one or more of 2-methylaniline hydrochloride, 3,3′-dimethylbenzidine dihydrochloride, N′N-dimethyl-p-phenylenediamine sulphate, N,N′-dimethyl-p-phenylenediamine monohydrochloride, N′N-diethyl-p-phenylenediamine sulphate, N,N′-diethyl-p-phenylenediamine monohydrochloride, 1-naphthylamine hydrochloride, aniline hydrochloride, 3-hydroxyphenylamine hydrochloride, diphenylamine hydrochloride, dimethylamine hydrochloride, diethylamine hydrochloride, cyclohexylamine hydrochloride, benzidine sulfate, benzidine hydrochloride, trimethylamine hydrochlorate, triethylamine hydrochlorate, ethylenediamine hydrochloride, m-phenylenediamine hydrochloride, o-phenylendiamine hydrochloride, o-bromoaniline hydrochloride, N-(1-naphthylethyl)enediamine hydrochloride and triethanolamine hydrochloride. The organic amine sulfate may be one or more of m-phenylenediamine sulfate, hydroxylamine sulfate, o-phenylenediamine sulfate, 3-hydroxyphenylamine sulfate, ethylenediamine sulfate and diethylamine sulfate. The amine may be one or more of o-nitroaniline, methacrylamide, salicylanilide, p-toluenesulfonamide, p-phenetidine, N-hydroxymethylbenzene sulfonamide, phthalimide and N,N′-methylenebisacrylamide.

(4) In order to facilitate processing or production, a performance additive and an adhesive may be further added, and prepared according to specific ingredients.

(5) The materials above were used for preparing fire extinguishing compositions and tests were carried out, and fire extinguishing experiments were carried out together with a commercially available K-type aerosol fire extinguishing agent in the same conditions, specifically as follows:

Example 1

(6) In the present example, 75 wt % of ferric oxalate and 20 wt % of diethylamine hydrochloride were applied as a coolant, 2.5 wt % of hydroxy methyl propyl cellulose was added as an adhesive, industrial alcohol was applied as a solvent, after pelleting with a 20-mesh sieve, 2.5% of magnesium stearate was added as a release agent, all the above materials were mixed uniformly and then passed through a 15-mesh sieve, and shaped into a honeycomb shape by using processes including pelleting, mould pressing and extruding etc. and loaded to a fire extinguishing apparatus.

Example 2

(7) In the present example, 95 wt % of ferric oxalate was applied and 2.5 wt % of hydroxy methyl propyl cellulose was applied as an adhesive, and other coating processing etc. was the same as that in the first example.

Example 3

(8) In the present example, 85 wt % of nickel citrate and 10 wt % of triethylamine hydrochlorate were applied, and other coating processing etc. was the same as that in the first example.

Example 4

(9) In the present example, 95 wt % of nickel citrate was applied as a coolant, 2.5 wt % of hydroxymethyl propyl cellulose was added as an adhesive, industrial alcohol was used as a solvent, after pelleting with a 20-mesh sieve, 2.5 wt % of magnesium stearate was added as a release agent, all the above materials were mixed uniformly and then passed through a 15-mesh sieve, and shaped into a bar shape by using processes including pelleting, mould pressing and extruding etc. and loaded to a fire extinguishing apparatus.

Example 5

(10) The major difference from the first example is that 65 wt % of cobalt salicylate and 20 wt % of cobalt acetate were used and diethylamine hydrochloride in a mass percentage of 10% was used as an auxiliary fire extinguishing agent; other adhesive, release agent, content thereof and composition preparation etc. were the same as the first example.

Example 6

(11) In the present example, 65 wt % of cobalt salicylate and 30 wt % of cobalt acetate were used, 2.5 wt % of hydroxy methyl propyl cellulose was added as an adhesive, industrial alcohol was used as a solvent, after pelleting with a 20-mesh sieve, 2.5 wt % of magnesium stearate was added as a release agent, all the above materials were mixed uniformly and then passed through a 15-mesh sieve, and shaped into a tablet shape by using processes including pelleting, mould pressing and extruding etc. and loaded to a fire extinguishing apparatus.

(12) After preparing and shaping 50 g of the fire extinguishing compositions of the first example to the sixth example in tests, the fire extinguishing compositions were loaded to a fire extinguishing apparatus containing 50 g of a K-type aerosol generator, and 8B fire extinguishing tests were carried out on 3 fires in each group; specific test methods, test models and evaluation methods are as follows, and results are recorded in Table 1:

(13) test model: the oil disk is a GA86-2009 8B circular disk (diameter 570 mm, internal depth 150 mm and approximate area 0.25 m.sup.2);

(14) test method: 500 mm of water was added to the oil disk, then 2 mm of 93# gasoline was added, the oil disk was pre-burning for 1 min and then began fire extinguishment;

(15) evaluation standard: it is considered that fire extinguishment is successful if there is no after-combustion 1 min after flame extinction and there is still gasoline remaining in the oil disk.

Comparison Experiment 1

(16) A fire extinguishing test was performed for a fire extinguishing apparatus sample containing 100 g of a commercially available K-type hot aerosol fire extinguishing agent according to the same experiment model and experiment method as those in the examples above, and test results are as shown in Table 1.

(17) TABLE-US-00001 TABLE 1 Test records of fire extinguishing compositions containing a salt of an organic acid of elements of group VIII Ingredient content of examples (mass percentage) Comparison Ingredient 1 2 3 4 5 6 1 K type agent • • • • • • • Ferric oxalate 75 95 — — Cobalt salicylate 65 65 Cobalt acetate 20 30 Nickel citrate 85 95 Diethylamine 20 10 hydrochloride Triethylamine 10 hydrochloride Hydroxy methyl 2.5 2.5 2.5 2.5 2.5 2.5 propyl cellulose Magnesium 2.5 2.5 2.5 2.5 2.5 2.5 stearate Fire extinguishing 6.2 7.0 6.0 6.0 6.0 6.2 time(s) Fire extinguishing 2 extinguished 1 extinguished 2 extinguished 1 extinguished All 1 extinguished Not situation in 3 in 3 in 3 in 3 extinguished in 3 extinguished

(18) It can be clearly seen from Table 1 that the fire extinguishing compositions containing a salt of an organic acid of the fourth period transition metals in group VIII can meet basic fire extinguishing requirements of national standard GA86-2009 and there are no naked flames at all nozzles; the fire extinguishing performance is obviously better than that of the first comparison example and the fire extinguishing time is short.

Example 7

(19) In the present example, 90 wt % of manganese acetate, 5 wt % of methacrylamide and 2.5 wt % of hydroxy methyl propyl cellulose were mixed, industrial alcohol was used as a solvent, after pelleting with a 20-mesh sieve, 2.5 wt % of magnesium stearate was added as a release agent, all the above materials were mixed uniformly and then passed through a 15-mesh sieve, and shaped into a ball shape by using processes including pelleting, mould pressing and extruding etc. and loaded to a fire extinguishing apparatus containing 50 g of a K-type hot aerosol generator, a 93# gasoline fire extinguishing test of an oil disk having an area of 0.25 m.sup.2 was carried out; test results are as shown in Table 2 of test records.

Example 8

(20) In the present example, 95 wt % of manganese acetate and 2.5 wt % of hydroxy methyl propyl cellulose were mixed, industrial alcohol was used as a solvent, after pelleting with a 20-mesh sieve, 2.5 wt % of magnesium stearate was added as a release agent, all the above materials were mixed uniformly and then passed through a 15-mesh sieve, and shaped into a ball shape by using processes including pelleting, mould pressing and extruding etc. and loaded to a fire extinguishing apparatus containing 50 g of a K-type hot aerosol generator, a 93# gasoline fire extinguishing test of an oil disk having an area of 0.25 m.sup.2 was carried out; test results are as shown in Table 2 of test records.

Example 9

(21) In the present example, 78 wt % of copper tartrate, 17 wt % of N,N′-methylenebisacrylamide and 2.5 wt % of hydroxy methyl propyl cellulose were mixed, industrial alcohol was used as a solvent, after pelleting with a 20-mesh sieve, 2.5 wt % of magnesium stearate was added as a release agent, all the above materials were mixed uniformly and then passed through a 15-mesh sieve, and shaped into a ball shape by using processes including pelleting, mould pressing and extruding etc. and loaded to a fire extinguishing apparatus containing 50 g of a K-type hot aerosol generator, a 93# gasoline fire extinguishing test of an oil disk having an area of 0.25 m.sup.2 was carried out; test results are as shown in Table 2 of test records.

Example 10

(22) In the present example, 95 wt % of copper tartrate, and 2.5 wt % of hydroxymethyl propyl cellulose were mixed, industrial alcohol was used as a solvent, after pelleting with a 20-mesh sieve, 2.5 wt % of magnesium stearate was added as a release agent, all the above materials were mixed uniformly and then passed through a 15-mesh sieve, and shaped into a ball shape by using processes including pelleting, mould pressing and extruding etc. and loaded to a fire extinguishing apparatus containing 50 g of a K-type hot aerosol generator, a 93# gasoline fire extinguishing test of an oil disk having an area of 0.25 m.sup.2 was carried out; test results are as shown in Table 2 of test records.

Example 11

(23) In the present example, 87 wt % of zinc acetate, 8 wt % of methacrylamide and 2.5 wt % of hydroxy methyl propyl cellulose were mixed, industrial alcohol was used as a solvent, after pelleting with a 20-mesh sieve, 2.5 wt % of magnesium stearate was added as a release agent, all the above materials were mixed uniformly and then passed through a 15-mesh sieve, and shaped into a ball shape by using processes including pelleting, mould pressing and extruding etc. and loaded to a fire extinguishing apparatus containing 50 g of a K-type hot aerosol generator, a 93# gasoline fire extinguishing test of an oil disk having an area of 0.25 m.sup.2 was carried out; test results are as shown in Table 2 of test records.

Example 12

(24) In the present example, 95 wt % of zinc acetate, and 2.5 wt % of hydroxy methyl propyl cellulose were mixed, industrial alcohol was used as a solvent, after pelleting with a 20-mesh sieve, 2.5 wt % of magnesium stearate was added as a release agent, all the above materials were mixed uniformly and then passed through a 15-mesh sieve, and shaped into a ball shape by using processes including pelleting, mould pressing and extruding etc. and loaded to a fire extinguishing apparatus containing 50 g of a K-type hot aerosol generator, a 93# gasoline fire extinguishing test of an oil disk having an area of 0.25 m.sup.2 was carried out; test results are as shown in Table 2 of test records.

Example 13

(25) In the present example, 60 wt % of manganese acetate, 35 wt % of cupric acetate and 2.5 wt % of hydroxymethyl propyl cellulose were mixed, industrial alcohol was used as a solvent, after pelleting with a 20-mesh sieve, 2.5 wt % of magnesium stearate was added as a release agent, all the above materials were mixed uniformly and then passed through a 15-mesh sieve, and shaped into a ball shape by using processes including pelleting, mould pressing and extruding etc. and loaded to a fire extinguishing apparatus containing 50 g of a K-type hot aerosol generator, a 93# gasoline fire extinguishing test of an oil disk having an area of 0.25 m.sup.2 was carried out; test results are as shown in Table 2 of test records.

Example 14

(26) In the present example, 94.7 wt % of manganese acetate, and 5.3 wt % of methacrylamide were mixed, industrial alcohol was used as a solvent, after pelleting with a 20-mesh sieve, 2.5 wt % of magnesium stearate was added as a release agent, all the above materials were mixed uniformly and then passed through a 15-mesh sieve, and shaped into a ball shape by using processes including pelleting, mould pressing and extruding etc. and loaded to a fire extinguishing apparatus containing 50 g of a K-type hot aerosol generator, a 93# gasoline fire extinguishing test of an oil disk having an area of 0.25 m.sup.2 was carried out; test results are as shown in Table 2 of test records.

Comparison Experiment 2

(27) A 93# gasoline fire extinguishing test was performed on an oil disk having an area of 0.25 m.sup.2 for a fire extinguishing apparatus sample containing 100 g of a commercially available K-type hot aerosol fire extinguishing agent, and test results are as shown in Table 2.

(28) TABLE-US-00002 TABLE 2 Test records of fire extinguishing compositions containing a salt of an organic acid of elements of a subgroup Ingredient content of examples (mass percentage) Comparison Ingredient 7 8 9 10 11 12 13 14 2 K type agent • • • • • • • • • Manganese acetate 90 95 60 94.7 Copper acetate 35 Copper tartrate 78 95 Zinc acetate 87 95 Methacrylamide 5 8 5.3 N,N′-methylene- 17 bisacrylamide Hydroxy methyl 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 propyl cellulose Magnesium stearate 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Fire extinguishing 4.0 4.0 5.0 5.0 5.0 6.0 5.0 5.0 time(s) Fire extinguishing All All All 2 extiguished All All All All Not situation extinguished extinguished extinguished in 3 extinguished extinguished extinguished extinguished extinguished

(29) It can be clearly seen from Table 2 that the fire extinguishing compositions containing an organic salt of transition metals in the group IB, the group IIB, and the group VIIB can completely meet basic fire extinguishing requirements of national standard GA86-2009 and there are no naked flames at all nozzles; the fire extinguishing performance is obviously better than that of the second comparison example and the fire extinguishing time is short. The fire extinguishing compositions containing an organic salt compound of transition metals in the group IB, the group IIB, and the group VIIB can meet ideal fire extinguishing requirements without addition of an auxiliary fire extinguishing ingredient in a certain mass percentage. However, by comprehensively considering aspects including spraying time, fire extinguishing time, the size of nozzle gas flows, spraying stability and processing etc.; a certain amount of an auxiliary fire extinguishing ingredient is added optimally.