CN115894138A - Method for recycling waste copper nitrate containing guanidine alkali and application - Google Patents
Method for recycling waste copper nitrate containing guanidine alkali and application Download PDFInfo
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- CN115894138A CN115894138A CN202211026848.2A CN202211026848A CN115894138A CN 115894138 A CN115894138 A CN 115894138A CN 202211026848 A CN202211026848 A CN 202211026848A CN 115894138 A CN115894138 A CN 115894138A
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- copper nitrate
- gas
- guanidine
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- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 title claims abstract description 118
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 239000002699 waste material Substances 0.000 title claims abstract description 63
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 title claims abstract description 59
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000004064 recycling Methods 0.000 title claims abstract description 18
- 239000003513 alkali Substances 0.000 title claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 88
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 75
- 239000002585 base Substances 0.000 claims abstract description 40
- 239000007800 oxidant agent Substances 0.000 claims abstract description 28
- 239000011230 binding agent Substances 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 230000001590 oxidative effect Effects 0.000 claims abstract description 15
- 239000000654 additive Substances 0.000 claims abstract description 10
- 230000000996 additive effect Effects 0.000 claims abstract description 10
- NDEMNVPZDAFUKN-UHFFFAOYSA-N guanidine;nitric acid Chemical compound NC(N)=N.O[N+]([O-])=O.O[N+]([O-])=O NDEMNVPZDAFUKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000003831 tetrazolyl group Chemical group 0.000 claims abstract description 6
- 238000005422 blasting Methods 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 116
- 239000000463 material Substances 0.000 claims description 83
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims description 26
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical group [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 25
- 238000001291 vacuum drying Methods 0.000 claims description 24
- 229910000831 Steel Inorganic materials 0.000 claims description 20
- 239000010959 steel Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 18
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 18
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 18
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 239000004033 plastic Substances 0.000 claims description 10
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 claims description 9
- 229910001487 potassium perchlorate Inorganic materials 0.000 claims description 9
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 claims description 8
- 235000010333 potassium nitrate Nutrition 0.000 claims description 8
- 239000004323 potassium nitrate Substances 0.000 claims description 8
- 238000005550 wet granulation Methods 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- 238000007908 dry granulation Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 239000004570 mortar (masonry) Substances 0.000 claims description 5
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 5
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 5
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 4
- 239000002910 solid waste Substances 0.000 abstract description 5
- 239000003518 caustics Substances 0.000 abstract 2
- 239000000306 component Substances 0.000 description 13
- 229920003123 carboxymethyl cellulose sodium Polymers 0.000 description 7
- 229940063834 carboxymethylcellulose sodium Drugs 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 150000001540 azides Chemical class 0.000 description 3
- -1 azines Chemical class 0.000 description 3
- 239000008358 core component Substances 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- OFZKYQYOBLPIPO-UHFFFAOYSA-N guanidine;hydrate Chemical compound O.NC(N)=N OFZKYQYOBLPIPO-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 206010039203 Road traffic accident Diseases 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
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Abstract
The invention provides a method for recycling waste copper nitrate containing guanidine alkali, which comprises the following steps: step one, mixing waste copper nitrate containing guanidine base with a combustible agent tetrazolium salt; step two, adding an additive into the gas generating agent component to prepare a gas generating agent composition capable of generating gas; the main components of the guanidine base-containing copper nitrate are basic copper nitrate and guanidine nitrate; the additive comprises an auxiliary oxidant and a binder. According to the invention, the combustible agent and the additive are added into the waste copper nitrate containing guanidine caustic to prepare the gas generating agent composition capable of generating gas, so that the waste copper nitrate containing guanidine caustic is recycled. Meanwhile, the gas generant composition prepared by the invention can be used for inflation equipment, high-pressure gas blasting devices and the like, plays the roles of fully utilizing dangerous solid wastes, saving energy and protecting environment, and has excellent performance and wide application field.
Description
Technical Field
The invention relates to the technical field of dangerous solid waste utilization, in particular to a method for recycling waste copper nitrate containing guanidine alkali and application thereof.
Background
Automotive airbags are an important component of passive safety systems. In recent years, with the improvement of road conditions and the improvement of automobile technologies, the driving speed of automobiles is faster and faster, the traffic density is higher and higher, and the traffic safety problem is more and more urgent, so that road traffic accidents become the first killer of various safety accidents, and account for about 80%. Airbags are also receiving increasing attention as protection devices in automobiles. The core component of the automobile safety air bag is a gas generator, and the core component of the gas generator is a gas generating agent, namely a gas producing medicine. The safety airbag has the working principle that after the gas generator receives a pulse electric signal, an electric ignition tube in the ignition system is excited to detonate, ignition powder is ignited by heat generated by ignition of ignition powder in the electric ignition tube, gas production powder is ignited after the ignition powder is combusted, a large amount of gas generated by combustion of the gas production powder fills the gas bag, and the filled gas bag has a buffering effect, so that the purpose of protecting passengers is achieved.
Early gas generants for air bags used sodium azide as the fuel, which had gradually exited the market due to the high toxicity of sodium azide. At present, nitrogen-containing organic matters are widely used as non-azide gas generating agents of fuels. The research on non-azide gas generants has been focused mainly on non-azides such as azoles, azines, guanidines, and azos. Wherein, the guanidine gas production medicament has the characteristics of high chemical stability, large gas production, easily obtained raw materials and the like. Many current gas generants use basic copper nitrate/guanidine nitrate systems, i.e., basic copper nitrate and guanidine nitrate as the primary components.
Basic Copper Nitrate (BCN), a known oxidizer, has been widely used as an oxidizer because it lowers the combustion temperature and suppresses the amount of NO generated due to low heat of combustion, and thus has a purifying effect on the emitted gas and also improves ignition and combustion properties.
In the industrial production, the situations that the granulation of the gas-producing medicament of the safety air bag fails and the product quality cannot meet the factory standard exist, and a mixture of waste basic copper nitrate and guanidine nitrate is generated. Based on the method, the waste mixture of guanidine nitrate and basic copper nitrate is used as one of the components of the gas generating agent composition to prepare the gas generating agent with gas generating capacity, so that the recovery and the utilization of dangerous solid wastes are realized.
Disclosure of Invention
In view of the above, the present invention is directed to recycling waste copper nitrate containing guanidine hydroxide by adding a combustible agent and an additive to the waste copper nitrate containing guanidine hydroxide to prepare a gas generant composition capable of generating gas.
The invention adopts the following technical scheme: a method for recycling waste copper nitrate containing guanidine alkali is characterized by comprising the following steps: the method comprises the following steps:
step one, mixing waste copper nitrate containing guanidine base with a combustible agent tetrazolium salt;
step two, adding an additive into the gas generating agent component to prepare a gas generating agent composition capable of generating gas;
wherein:
the main components of the guanidine base-containing copper nitrate are basic copper nitrate and guanidine nitrate;
the additive comprises an auxiliary oxidant and a binder;
the oxygen balance of the gas generant composition is-0.2 to 0;
the gas generating agent composition comprises the following components in percentage by mass:
further, the waste copper nitrate containing guanidine alkali comprises the following components in percentage by mass:
further, the tetrazolium salt of the flammable agent comprises 5-aminotetrazole.
Further, the auxiliary oxidizer comprises one or more of perchlorate and nitrate, the perchlorate comprises ammonium perchlorate and potassium perchlorate, and the nitrate comprises potassium nitrate and ammonium nitrate.
Further, the binder is sodium carboxymethylcellulose, and the mass percentage of the binder is 1-5% of the total mass of the gas generating agent.
Further, the preparation method of the gas generant composition comprises wet granulation and dry granulation.
Further, the specific preparation method of the wet granulation comprises the following steps:
directly mixing waste copper nitrate containing guanidine base, a combustible agent, an auxiliary oxidant and a binder to obtain a first material;
putting the first material into a plastic bottle, adding absolute ethyl alcohol until the material is submerged, adding 30 steel balls with different particle sizes, stirring for 12 hours by a machine, and removing the steel balls to obtain a second material after the stirring is finished;
putting the second material into a vacuum drying oven at 60 ℃, and performing vacuum drying for 24 hours to obtain a third material;
step four, putting the third material into a self-made mould
The mixture was pelletized by a hand hydraulic press to obtain a molded gas generant composition.
Further, the specific preparation method of the dry granulation comprises the following steps:
step one, mixing combustible agents in three batches into waste guanidine-base-containing copper nitrate, and grinding the mixture by using a mortar to obtain a first material;
step two, mixing the auxiliary oxidant and the binder into the first material in three batches, and grinding the mixture by using a mortar to obtain a second material;
putting the second material into a vacuum drying oven at 60 ℃, and performing vacuum drying for 12h to obtain a third material;
step four, putting the third material into a self-made mould
The mixture was pelletized by a hand hydraulic press to obtain a molded gas generant composition.
The invention also provides a gas generant composition prepared by the method for recycling the waste copper nitrate containing guanidine alkali.
The invention also provides application of the gas generating agent composition, and the gas generating agent composition is applied to inflation equipment, a high-pressure gas blasting device or a driver seat airbag gas generator.
Has the advantages that: compared with the prior art, the gas generating agent composition capable of generating gas is prepared by adding the combustible agent and the additive into the waste copper nitrate containing guanidine caustic soda, so that the waste copper nitrate containing guanidine caustic soda is recycled. Meanwhile, the gas generant composition prepared by the invention can be used for inflation equipment, high-pressure gas blasting devices and the like, plays the roles of fully utilizing dangerous solid wastes, saving energy and protecting environment, and has excellent performance and wide application field.
Drawings
FIG. 1 is a graph showing the relationship between the pressure of a container and time in examples 1 to 7 of the present invention.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the accompanying drawings. The invention may be embodied in different forms and is not limited to the embodiments described herein. Rather, the embodiments are provided so that this disclosure will be thorough and complete.
The embodiment of the application provides a method for recycling waste copper nitrate containing guanidine base, which comprises the following steps: step one, mixing waste guanidine base-containing copper nitrate with a combustible agent tetrazolium salt; and step two, adding an additive into the gas generating agent component to prepare the gas generating agent composition capable of generating gas.
The waste guanidine-containing alkali copper nitrate can be used as an oxidizing agent of the composition, mainly contains basic copper nitrate and guanidine nitrate, and needs to be dried before mixing; the combustible agent contains a nitrogen-containing compound, and the nitrogen-containing compound is 5-aminotetrazole; the auxiliary oxidant is one or more of ammonium perchlorate, potassium perchlorate, ammonium nitrate and potassium nitrate, and is used for improving the oxidability of the waste guanidine base-containing copper nitrate; the binder is sodium carboxymethyl cellulose, which is used for improving the bonding strength among the components.
The content of the components in percentage by mass is as follows: 50% -85% of the waste guanidine-base-containing copper nitrate; 15 to 50 percent of flammable agent; the auxiliary oxidant is 5-30%; 1 to 5 percent of binder. Preferably, the content of each component is 54-78% of the waste basic copper nitrate; 16 to 46 percent of flammable agent; 5-25% of auxiliary oxidant and 5% of binder.
In the gas generating composition produced as described above, the mass percentage of the guanidine base-containing copper nitrate to be discarded may be, but is not limited to, 66%, 61%, 67%, 72%, 74%, 77%, 81%, 83%, 89%.
In the gas generant composition formed as described above, the mass percentage of the combustible agent when 5-aminotetrazole is used may be, but not limited to, 18%, 25%, 27%, 32%, 33%, 38%, 36%, 38%, 41%.
In the gas generant composition produced as described above, the mass percentage of the auxiliary oxidizer in the case of ammonium perchlorate may be, but not limited to, 9%, 11%, 13%, 15%, 17%.
In the gas generant composition produced as described above, the auxiliary oxidizer may be, but is not limited to, potassium perchlorate in an amount of 9, 11, 15, 20 or 25% by mass.
In the gas generating composition produced as described above, the mass percentage of the auxiliary oxidizing agent selected from ammonium nitrate may be, but is not limited to, 7%, 8%, 10%, 16%, 20%.
In the gas generant composition produced as described above, the auxiliary oxidizer may be selected from potassium nitrate in a range of, but not limited to, 7%, 8%, 10%, 13%, 15% and 18% by mass.
In the gas generating composition, the binder may be sodium carboxymethylcellulose in an amount of, but not limited to, 1%, 2%, 4% or 5% by mass.
The components of the gas generant compositions of the embodiments of the present application desirably are within the above-described ranges and have an oxygen balance 0B value of-0.20 to 0.05, alternatively an oxygen balance of-0.15 to 0, and further alternatively-0.15. In the above-described gas generant composition, the oxygen balance of the gas generant composition may be, but is not limited to, 0.05, 0, -0.05, -0.10, -0.15, -0.2.
As an embodiment, the gas generant composition consists of waste guanidine base-containing copper nitrate, 5-aminotetrazole, perchlorate/nitrate, and the composition of the gas generant composition refers to the composition of the active ingredient, impurities and moisture inevitably introduced during the storage and mixing stages.
It should be noted that the gas generant composition refers to a product that can be used in a gas generator for an automobile airbag, and that is generally molded. For example, the gas generating agent has a circular or elliptical sheet structure, a circular or elliptical columnar structure, a special-shaped sheet or columnar structure, a circular or elliptical single-pore structure, a circular or elliptical porous structure, or a special-shaped single-pore or porous structure.
In laboratory experiments, the diameter of the gas generating agent with a circular sheet structure is generally 10-15 mm, and the height is generally 2-5 mm; the diameter of the gas generating agent with a circular columnar structure is generally 4-8 mm, and the height is generally 5-10 mm; the inner diameter of the gas generating agent with a circular single-hole structure is generally 0.5-2.5 mm, the outer diameter is generally 3-15 mm, and the height is generally 3-15 mm; the inner diameter of the gas generating agent with an oval single-hole structure is generally 0.5-2.5 mm, the major diameter is generally 3-20 mm, the minor diameter is generally 2-12 mm, and the height is generally 3-15 mm.
In the embodiment of the present application, the gas generant composition can be prepared by wet granulation and dry granulation. As an implementation mode for the case of preparing the gas generating agent by wet granulation which is simple in process and easy to realize, the specific preparation method of the gas generating agent comprises the following steps:
directly mixing waste guanidine base-containing copper nitrate, a combustible agent, an auxiliary oxidant and a binder to obtain a first material;
putting the first material into a plastic bottle, adding absolute ethyl alcohol until the material is submerged, adding 30 steel balls with different particle diameters, stirring for 12 hours by a machine, and taking out the steel balls after the stirring is finished to obtain a second material;
step three, placing the second material into a vacuum drying oven at 60 ℃, and performing vacuum drying for 24 hours to obtain a third material;
step four, putting the third material into a self-made mould
The mixture was pelletized by a hand hydraulic press to obtain a molded gas generant composition.
The first step of the preparation method of the gas generating agent composition can be mixing by a mixer or grinding and mixing by a mortar, and the mixing time is more than 30min.
This example provides a gas generant composition that is produced by the above-described method of recycling waste guanidine base-containing copper nitrate and can include single-hole cylindrical, porous cylindrical, granular and flaky shaped bodies according to the desired shape of the shaped bodies.
The embodiment also provides application of the gas generating agent composition, and the gas generating agent composition and a formed body prepared from the gas generating agent composition are applied to the fields of inflation equipment, high-pressure gas blasting devices and the like.
The features and properties of the present application are described in further detail below with reference to examples.
Example 1
This example provides a gas generant composition in the form of a 6mm diameter 10mm thick column composed of waste copper nitrate containing guanidine base, 5-aminotetrazole as a combustible agent, and sodium carboxymethylcellulose as a binder. According to the mass percentage, 77 percent of waste copper nitrate containing guanidine base, 22 percent of 5-aminotetrazole and 1 percent of sodium carboxymethylcellulose. The gas generant composition has an oxygen balance of about 0.
The preparation process of the gas generating agent comprises the following steps:
directly mixing waste guanidine base-containing copper nitrate, combustible agent 5-aminotetrazole and adhesive carboxymethyl cellulose sodium to obtain a first material; putting the first material into a 80mL plastic bottle, adding absolute ethyl alcohol until the material is submerged,adding 30 steel balls with different particle diameters, stirring for 12 hours by a machine, and taking out the steel balls after finishing stirring to obtain a second material; putting the second material into a vacuum drying oven at 60 ℃, and performing vacuum drying for 24h to obtain a third material; putting the third material into a self-made mould
The mixture was pelletized by a hand hydraulic press to obtain a molded gas generant composition.
Example 2
This example provides a gas generant composition in the form of a 6mm diameter, 10mm thick column composed of waste copper nitrate containing guanidine base, 5-aminotetrazole as a flammable agent, and sodium carboxymethylcellulose as a binder. According to the mass percentage, 72 percent of waste copper nitrate containing guanidine base, 27 percent of 5-aminotetrazole and 1 percent of sodium carboxymethylcellulose are used. The gas generant composition has an oxygen balance of about-0.05.
The preparation process of the gas generating agent comprises the following steps:
directly mixing waste guanidine base-containing copper nitrate, combustible 5-aminotetrazole and adhesive carboxymethyl cellulose sodium to obtain a first material; putting the first material into a 80mL plastic bottle, adding absolute ethyl alcohol until the material is submerged, adding 30 steel balls with different particle sizes, stirring for 12 hours by a machine, and taking out the steel balls after the stirring is finished to obtain a second material; putting the second material into a vacuum drying oven at 60 ℃, and performing vacuum drying for 24 hours to obtain a third material; putting the third material into a self-made mould
The mixture was pelletized by a hand hydraulic press to obtain a molded gas generant composition.
Example 3
This example provides a gas generant composition in the form of a 6mm diameter 10mm thick column composed of waste copper nitrate containing guanidine base, 5-aminotetrazole as a combustible agent, and sodium carboxymethylcellulose as a binder. According to the mass percentage, the waste basic copper nitrate is 66 percent, the combustible agent is 5-amino tetrazole is 33 percent, and the sodium carboxymethyl cellulose is 1 percent. The gas generant composition has an oxygen balance of about-0.10.
The preparation process of the gas generating agent comprises the following steps:
directly mixing waste guanidine base-containing copper nitrate, combustible agent 5-aminotetrazole and adhesive carboxymethyl cellulose sodium to obtain a first material; putting the first material into a 80mL plastic bottle, adding absolute ethyl alcohol until the material is submerged, adding 30 steel balls with different particle sizes, stirring for 12 hours by a machine, and taking out the steel balls after the stirring is finished to obtain a second material; putting the second material into a vacuum drying oven at 60 ℃, and performing vacuum drying for 24h to obtain a third material; putting the third material into a self-made mould
The mixture was pelletized by a hand hydraulic press to obtain a molded gas generant composition.
Example 4
This example provides a gas generant composition in the form of a 6mm diameter 10mm thick column composed of waste copper nitrate containing guanidine base, 5-aminotetrazole as a combustible agent, and sodium carboxymethylcellulose as a binder. According to the mass percentage, 59 percent of waste copper nitrate containing guanidine base, 39 percent of combustible agent 5-aminotetrazole and 2 percent of sodium carboxymethyl cellulose. The gas generant composition has an oxygen balance of about-0.15.
The preparation process of the gas generating agent comprises the following steps:
directly mixing waste guanidine base-containing copper nitrate, combustible agent 5-aminotetrazole and adhesive carboxymethyl cellulose sodium to obtain a first material; putting the first material into a 80mL plastic bottle, adding absolute ethyl alcohol until the first material submerges the material, adding 30 steel balls with different particle sizes, stirring for 12 hours by a machine, and taking out the steel balls after the stirring is finished to obtain a second material; putting the second material into a vacuum drying oven at 60 ℃, and performing vacuum drying for 24 hours to obtain a third material; putting the third material into a self-made mould
The mixture was pelletized by a hand hydraulic press to obtain a molded gas generant composition.
Example 5
This example provides a gas generant composition in the form of a 6mm diameter 10mm thick column composed of waste copper nitrate containing guanidine base, 5-aminotetrazole as a combustible agent, and sodium carboxymethylcellulose as a binder. 53 percent of waste guanidine base-containing copper nitrate, 45.5 percent of combustible agent 5-aminotetrazole and 2 percent of sodium carboxymethylcellulose. The gas generant composition has an oxygen balance of about-0.20.
The preparation process of the gas generating agent comprises the following steps:
directly mixing waste guanidine base-containing copper nitrate, combustible agent 5-aminotetrazole and adhesive carboxymethyl cellulose sodium to obtain a first material; putting the first material into a 80mL plastic bottle, adding absolute ethyl alcohol until the material is submerged, adding 30 steel balls with different particle sizes, stirring for 12 hours by a machine, and taking out the steel balls after the stirring is finished to obtain a second material; putting the second material into a vacuum drying oven at 60 ℃, and performing vacuum drying for 24h to obtain a third material; putting the third material into a self-made mould
The mixture was pelletized by a hand hydraulic press to obtain a molded gas generant composition.
Example 6
This example provides a gas generant composition in the form of a 6mm diameter, 10mm thick column composed of waste guanidine base-containing copper nitrate, 5-aminotetrazole as a flammable agent, potassium perchlorate as an auxiliary oxidizer, and sodium carboxymethylcellulose as a binder. According to the mass percentage, 45.3 percent of waste copper nitrate containing guanidine base, 30.2 percent of combustible agent 5-aminotetrazole, 24 percent of auxiliary oxidant potassium perchlorate and 1 percent of sodium carboxymethylcellulose. The oxygen balance of the gas generant composition is about 0.
The preparation process of the gas generating agent comprises the following steps:
directly mixing waste guanidine base-containing copper nitrate, combustible 5-aminotetrazole, auxiliary oxidant potassium perchlorate and binder carboxymethylcellulose sodium to obtain a first material; putting the first material into a 80mL plastic bottle, adding absolute ethyl alcohol until the material is submerged, adding 30 steel balls with different particle sizes, stirring for 12 hours by a machine, and taking out the steel balls after the stirring is finished to obtain a second material; putting the second material into a vacuum drying oven at 60 ℃, and performing vacuum drying for 24h to obtain a third material(ii) a Putting the third material into a self-made mould
The mixture was pelletized by a hand hydraulic press to obtain a molded gas generant composition.
Example 7
This example provides a gas generant composition in the form of a 6mm diameter 10mm thick column composed of waste guanidine base-containing copper nitrate, 5-aminotetrazole as a combustible agent, ammonium perchlorate and potassium nitrate as auxiliary oxidants, and sodium carboxymethylcellulose as a binder. According to the mass percentage, 41.7 percent of waste copper nitrate containing guanidine base, 28.4 percent of combustible agent 5-aminotetrazole, 15.3 percent of auxiliary oxidant ammonium perchlorate, 13.1 percent of potassium nitrate and 1 percent of sodium carboxymethylcellulose. The oxygen balance of the gas generant composition is about 0.
The preparation process of the gas generating agent comprises the following steps:
directly mixing waste guanidine base-containing copper nitrate, combustible 5-aminotetrazole, auxiliary oxidants ammonium perchlorate and potassium nitrate and binder carboxymethylcellulose sodium to obtain a first material; putting the first material into a 80mL plastic bottle, adding absolute ethyl alcohol until the material is submerged, adding 30 steel balls with different particle sizes, stirring for 12 hours by a machine, and taking out the steel balls after the stirring is finished to obtain a second material; putting the second material into a vacuum drying oven at 60 ℃, and performing vacuum drying for 24h to obtain a third material; putting the third material into a self-made mould
The mixture was pelletized by a hand hydraulic press to obtain a molded gas generant composition. />
TABLE 1
Note: BCN, KP, AP and KN are respectively basic copper nitrate, potassium perchlorate, ammonium perchlorate and potassium nitrate
Table 1 shows the weight of each component in examples 1 to 7; as shown in FIG. 1, the pressure change during constant volume combustion in examples 1 to 7 was examined by using a closed explosion device. As can be seen from the P-t curves of the closed explosions of examples 1 to 5, the pressure rise rate was the highest in example 4 in which no additional oxidant was added; from the P-t curves of the sealed detonators of examples 1 to 7, it can be seen that the rate of pressure increase is highest when potassium perchlorate is added in the case where an auxiliary oxidizer is added. In conclusion, the waste copper nitrate containing guanidine base is used as a raw material to prepare the gas generating agent, solid waste is fully utilized, energy is saved, the environment is protected, and the prepared gas generating agent has excellent performance. Provides a reliable idea for resource utilization of waste gas producing medicaments.
All functions may be implemented in the above embodiments, or a part of the functions may be implemented as necessary.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
Claims (10)
1. A method for recycling waste copper nitrate containing guanidine alkali is characterized by comprising the following steps: the method comprises the following steps:
step one, mixing waste copper nitrate containing guanidine base with a combustible agent tetrazolium salt,
step two, adding an additive into the gas generating agent component to prepare a gas generating agent composition capable of generating gas;
wherein:
the main components of the guanidine base-containing copper nitrate are basic copper nitrate and guanidine nitrate;
the additive comprises an auxiliary oxidant and a binder;
the oxygen balance of the gas generant composition is-0.2 to 0;
the gas generating agent composition comprises the following components in percentage by mass:
2. the method for recycling waste copper nitrate containing guanidine alkali as claimed in claim 1, wherein the method comprises the following steps: the waste guanidine base-containing copper nitrate comprises the following components in percentage by mass:
3. the method for recycling waste copper nitrate containing guanidine alkali according to claim 1, wherein the method comprises the following steps: the tetrazolium salt of the flammable agent includes 5-aminotetrazole.
4. The method for recycling waste copper nitrate containing guanidine alkali as claimed in claim 1, wherein the method comprises the following steps: the auxiliary oxidizer comprises one or more of perchlorate and nitrate, the perchlorate comprises ammonium perchlorate and potassium perchlorate, and the nitrate comprises potassium nitrate and ammonium nitrate.
5. The method for recycling waste copper nitrate containing guanidine alkali as claimed in claim 1, wherein the method comprises the following steps: the binder is sodium carboxymethylcellulose, and the mass percentage of the binder is 1-5% of the total amount of the gas generating agent.
6. The method for recycling waste copper nitrate containing guanidine alkali according to claim 1, wherein the method comprises the following steps: the preparation method of the gas generant composition comprises wet granulation and dry granulation.
7. The method for recycling waste copper nitrate containing guanidine alkali as claimed in claim 6, wherein the method comprises the following steps: the specific preparation method of the wet granulation comprises the following steps:
directly mixing waste copper nitrate containing guanidine base, a combustible agent, an auxiliary oxidant and a binder to obtain a first material;
putting the first material into a plastic bottle, adding absolute ethyl alcohol until the material is submerged, adding 30 steel balls with different particle sizes, stirring for 12 hours by a machine, and removing the steel balls to obtain a second material after the stirring is finished;
putting the second material into a vacuum drying oven at 60 ℃, and performing vacuum drying for 24 hours to obtain a third material;
step four, putting the third material into a self-made mould
The mixture was pelletized by a hand hydraulic press to obtain a molded gas generant composition.
8. The method for recycling waste copper nitrate containing guanidine alkali as claimed in claim 6, wherein the method comprises the following steps: the preparation method of the dry granulation comprises the following steps:
step one, mixing combustible agents in three batches into waste guanidine-base-containing copper nitrate, and grinding the mixture by using a mortar to obtain a first material;
step two, mixing the auxiliary oxidant and the binder into the first material in three batches, and grinding the mixture by using a mortar to obtain a second material;
putting the second material into a vacuum drying oven at 60 ℃, and performing vacuum drying for 12h to obtain a third material;
step four, putting the third material into a self-made mould
The mixture was pelletized by a hand hydraulic press to obtain a molded gas generant composition.
9. A gas generant composition, characterized by: the method for recycling the waste copper nitrate containing guanidine alkali as claimed in any one of claims 1 to 8.
10. Use of a gas generant composition in accordance with claim 9 wherein: the gas generating agent composition is applied to inflation equipment, high-pressure gas blasting devices and the like.
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| CN202211026848.2A CN115894138A (en) | 2022-08-25 | 2022-08-25 | Method for recycling waste copper nitrate containing guanidine alkali and application |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002012493A (en) * | 1999-10-08 | 2002-01-15 | Daicel Chem Ind Ltd | Gas generator composition |
| CN1609080A (en) * | 2003-10-20 | 2005-04-27 | 大赛璐化学工业株式会社 | Gas generating composition |
| CN1651360A (en) * | 2005-03-28 | 2005-08-10 | 张根发 | Gas producing composition and its preparation method |
| TWI238145B (en) * | 1999-09-27 | 2005-08-21 | Daicel Chem | Gas generator composition |
| CN1918086A (en) * | 2004-02-10 | 2007-02-21 | Snpe巨能材料公司 | Gas-generating pyrotechnical compositions and pyrotechnical compounds for automotive safety |
| CN104744185A (en) * | 2013-12-30 | 2015-07-01 | 比亚迪股份有限公司 | Gas generating agent composition and preparation method thereof |
| CN107840772A (en) * | 2017-03-02 | 2018-03-27 | 湖北航天化学技术研究所 | A kind of high burn rate gas-forming agent and its granulating process |
-
2022
- 2022-08-25 CN CN202211026848.2A patent/CN115894138A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI238145B (en) * | 1999-09-27 | 2005-08-21 | Daicel Chem | Gas generator composition |
| JP2002012493A (en) * | 1999-10-08 | 2002-01-15 | Daicel Chem Ind Ltd | Gas generator composition |
| CN1609080A (en) * | 2003-10-20 | 2005-04-27 | 大赛璐化学工业株式会社 | Gas generating composition |
| CN1918086A (en) * | 2004-02-10 | 2007-02-21 | Snpe巨能材料公司 | Gas-generating pyrotechnical compositions and pyrotechnical compounds for automotive safety |
| CN1651360A (en) * | 2005-03-28 | 2005-08-10 | 张根发 | Gas producing composition and its preparation method |
| CN104744185A (en) * | 2013-12-30 | 2015-07-01 | 比亚迪股份有限公司 | Gas generating agent composition and preparation method thereof |
| CN107840772A (en) * | 2017-03-02 | 2018-03-27 | 湖北航天化学技术研究所 | A kind of high burn rate gas-forming agent and its granulating process |
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