Safe and environment-friendly porous granular ammonium nitrate fuel oil explosive and preparation method thereof

Abstract

The invention relates to the technical field of ammonium nitrate fuel oil explosives in industrial explosives, in particular to a safe and environment-friendly porous granular ammonium nitrate fuel oil explosive and a preparation method thereof. The safe and environment-friendly porous granular ammonium nitrate fuel oil explosive comprises the following components in percentage by mass: 3-9% of porous granular ammonium nitrate and 91-97% of biomass oil, the biomass oil is cashew nut shell oil or a cashew nut shell oil derivative; the preparation method comprises the following steps: S1, weighing; s2, loading materials; and S3, mixing. The porous granular ammonium nitrate fuel oil explosive is prepared by compounding the renewable and high-flash-point biomass oil containing a plurality of polar groups in the molecular structure with the porous granular ammonium nitrate, renewable resources are fully utilized, resource waste is avoided, pollution of petrochemical resources to the environment is reduced, and the explosive production cost can also be reduced. And the explosive prepared by the invention has excellent thermal stability and explosion performance, and has a good application prospect.

Description

Technical Field

[0001] The present application relates to the technical field of ammonium nitrate oil explosives in industrial explosives, and more specifically, to a safe and environmentally friendly porous granular ammonium nitrate oil explosive and a preparation method thereof. Background Art

[0002] The "Civil Explosives Industry Development Plan" (2016-2020) clearly states that industrial explosives should develop from packaged to bulk and on-site mixed explosives, and develop and promote safe, environmentally friendly, high-performance industrial explosives and their products. With the change of blasting operations from packaging to on-site mixing, the use of on-site mixed porous granular ammonium oil explosives in open-pit mining has increased year by year.

[0003] Porous granular ammonium nitrate oxidant and diesel reductant are the main components of porous granular ammonium nitrate oil explosive, and the thermal stability, storage stability and explosion performance of porous granular ammonium nitrate oil explosive are all related to the oil. Diesel oil is a kind of petroleum resource, along with the pressure of resource exhaustion and environmental protection, price is also rising gradually, because finished diesel oil flash point is lower, volatility is also very strong, cause its porous granular ammonium oil-fuel oil explosive prepared is not suitable for use in high temperature fire zone blasting environment, easily cause safety quality accident, such as this type of explosive in patent CN102942427A and CN101973827A, is not suitable for use in high temperature fire zone; A kind of heat-resistant porous granular ammonium oil-fuel oil explosive is disclosed in patent CN104844396B, what its oil phase adopts is base oil, belongs to petroleum resource, and price is higher, need to add antioxidant in its oil phase material simultaneously; Although patents such as patent CN 101475828A, CN1063727B openly use vegetable oil to prepare porous granular ammonium oil-fuel oil explosive oil phase, this type of vegetable oil belongs to edible oil, and price is relatively high.

[0004] Today, the environmental pollution caused by the shortage of oil resources and the extensive use of petrochemical resources is getting worse and worse. People pay more attention to the environment in which they live. Under this high-pressure situation, how to develop green and renewable bio-based resources at low cost has become a development trend and an urgent problem to be solved in today's era. Summary of the invention

[0005] In view of the existing status quo and problems, in order to improve the deficiencies of the above-mentioned prior art, the present application provides a safe and environmentally friendly porous granular ammonium oil explosive and a method thereof.

[0006] In the first aspect, the safe and environmentally friendly porous granular ammonium oil-fuel explosive provided by the present application adopts the following technical scheme: A safe and environmentally friendly porous granular ammonium oil explosive, comprising porous granular ammonium nitrate and biomass oil, wherein the mass percentage of the biomass oil is 3% to 9%, and the mass percentage of the porous granular ammonium nitrate is 91% to 97%; The biomass oil is cashew nut shell oil or a cashew nut shell oil derivative. The cashew nut shell oil is obtained by separating cashew nut shells through multi-stage precipitation and filtration; the cashew nut shell oil derivative is obtained by modifying the cashew nut shell oil.

[0007] Preferably, the cashew nut shell oil derivative includes a polar group, and the polar group includes a phenolic hydroxyl group, a carboxyl group, an amino group, an epoxy group or an ester group.

[0008] Preferably, the modification treatment comprises one or more of deacidification, epoxidation, hydrogenation and esterification.

[0009] Preferably, the molecular weight of the cashew nut shell liquid and cashew nut shell liquid derivative is 300-350, and the density is 0.9100-0.9500 g / cm 3 , the flash point is not less than 210℃. Biomass oil has a higher flash point, which is beneficial to improve the safety of ammonium nitrate explosive.

[0010] Preferably, the percentage of the biomass oil is 6% to 8%, and the percentage of the porous granular ammonium nitrate is 92% to 94%.

[0011] Preferably, the biomass oil accounts for 7% and the porous granular ammonium nitrate accounts for 93%.

[0012] Through the above technical scheme, the oil phase material in the present application, i.e., the biomass oil, has a high flash point, which can improve the thermal stability of the porous granular ammonium nitrate oil explosive; at the same time, the polar groups in the molecular structure can increase the adsorption between the oil phase material and the porous granular ammonium nitrate, and improve the oil absorption rate of the porous granular ammonium nitrate. The porous granular ammonium nitrate oil explosive of the present application has good storage stability and explosive performance; the flash point of cashew nut shell oil and its derivatives is not less than 210° C., so that the porous granular ammonium nitrate oil explosive has good thermal stability.

[0013] At the same time, cashew nut shell liquid is a widely distributed and abundant agricultural by-product, but unlike soybean oil, peanut oil and corn oil, it is a non-edible oil. Due to its unique molecular structure, cashew nut shell liquid is now a green, environmentally friendly, natural renewable resource with extremely high application value. It can replace petrochemical raw materials. Developing its utilization value can avoid waste of resources and get rid of dependence on oil resources.

[0014] Cashew nut shell liquid is a non-edible biomass, a natural renewable resource, and its cost is between 3,000 and 4,000 yuan per ton, which is inexpensive. Developing its application in porous granular ammonium nitrate oil explosives can reduce the current dependence of porous granular ammonium nitrate oil explosives on petroleum resources, expand the utilization field of non-edible biological oil resources, avoid resource waste, have environmental significance, and have certain economic and social benefits.

[0015] In a second aspect, the present application provides a method for preparing a safe and environmentally friendly porous granular ammonium nitrate oil explosive, comprising the following steps: S1. Weighing: accurately weigh the biomass oil and porous ammonium nitrate particles according to the specified ratio; S2. Loading: Add porous granular ammonium nitrate into the device Internal, biomass oil adding device In; the device is a stirring device, the device It is a device with heating and jetting functions; S3, Mixing: Heat the biomass oil to the specified temperature and start the device Mixing and equipment The spray feed switch is turned on, and porous granular ammonium oil-fired explosive is obtained after sufficient mixing.

[0016] Preferably, in step S3, the specified temperature is 25°C to 80°C.

[0017] In summary, this application has the following beneficial effects: 1. The porous granular ammonium nitrate oil-fuel oil of the present application is derived from the vegetable oil squeezed from the discarded cashew nut shells of nature, and is separated by multi-stage precipitation filtration. The cashew nut shell oil is modified and refined, and the molecular structure of the cashew nut shell oil derivative contains polar groups, which can enhance the adsorption of the oil and the porous granular ammonium nitrate. The prepared porous granular ammonium nitrate oil-fuel oil has good storage stability and explosion performance; the flash point of cashew nut shell oil and its derivatives is not less than 210°C, so that the porous granular ammonium nitrate oil-fuel oil has good thermal stability; 2. Cashew nut shell liquid is a non-edible biomass, a natural renewable resource, and its cost is 3,000 to 4,000 yuan per ton, which is low in price. Developing its application in porous granular ammonium nitrate oil explosives can reduce the current dependence of porous granular ammonium nitrate oil explosives on petroleum resources, expand the utilization field of non-edible biological oil resources, avoid waste of resources, have environmental protection significance, and have certain economic and social benefits.

[0018] 3. The preparation method of the present application is simple, easy to operate and has good application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 It is a flow chart of the method provided by this application. DETAILED DESCRIPTION

[0020] The present application is further described in detail below with reference to the embodiments.

[0021] Example 1 Take the production of 1 ton of porous granular ammonium oil-fuel explosive as an example: the safe and environmentally friendly porous granular ammonium oil-fuel explosive is prepared from 30 kg of cashew nut shell oil and its derivatives and 970 kg of porous granular ammonium nitrate, and is specifically prepared as follows: S1. Weighing: accurately weigh the biomass oil and porous granular ammonium nitrate according to the above masses; S2. Loading: Add porous granular ammonium nitrate into a stirring device. In the device with heating and spraying function, cashew nut shell oil and its derivatives are added Inside; S3, Mixing: Heat the cashew nut shell liquid and its derivatives to 25°C and start the device Mixing and equipment Switch on the spray feeder to obtain porous granular ammonium oil explosive after sufficient mixing.

[0022] The cashew nut shell liquid and its derivatives are refined cardanol, with a flash point of 210°C, a molecular weight of about 300, and a density of 0.9345 g / cm 3 .

[0023] Bag the explosives or drive them directly into the blasthole at room temperature.

[0024] According to the test method and storage test of oil absorption rate in HG / T 3280-2011 "Porous Granular Ammonium Nitrate", the oil absorption rate of porous granular ammonium nitrate is 15.2%, indicating that refined cardanol has good adsorption to porous granular ammonium nitrate; the thermal stability test of porous granular ammonium oil-fuel explosive adopts the isothermal thermal weight loss method, and the specific method is as follows: place the flat weighing bottle containing the explosive sample in a constant temperature box (100°C), and record the thermal weight loss of the first 48 hours and the second 48 hours respectively. Other relevant performance test methods are carried out in accordance with GB 17582-1998 "Porous Granular Ammonium Oil-fuel Explosive" and GB / T 13228-2015 "Determination Method of Detonation Velocity of Industrial Explosives", and the blasting test and other performance test data are as follows: Example 2 Taking the production of 1 ton of porous granular ammonium oil-fuel oil explosive as an example: the fully environmentally friendly porous granular ammonium oil-fuel oil explosive is prepared from 60 kg of cashew nut shell oil and its derivatives and 940 kg of porous granular ammonium nitrate. The specific preparation method is the same as that in Example 1, except that the cashew nut shell oil and its derivatives are heated to 80 ° C, that is, fully stirred at 80 ° C until the oil phase material is evenly distributed in the pores of the porous granular ammonium nitrate (about 20 minutes), and the porous granular ammonium oil-fuel oil explosive is obtained.

[0025] The cashew nut shell liquid and its derivatives are hydrogenated cashew nut shell liquid, with a flash point of 230°C, a molecular weight of about 315, and a density of 0.9100 g / cm 3 .

[0026] When the temperature of the explosives cools down to below 40°C, bag the explosives or drive them directly into the blasthole.

[0027] The oil absorption rate of porous granular ammonium nitrate tested according to the relevant method in Example 1 is 13.5%, indicating that hydrogenated cashew nut shell liquid has good adsorption capacity for porous granular ammonium nitrate; other relevant performance test data are as follows: Example 3 Taking the production of 1 ton of porous granular ammonium oil-fuel oil explosive as an example: the fully environmentally friendly porous granular ammonium oil-fuel oil explosive is prepared from 80 kg of cashew nut shell oil and its derivatives and 920 kg of porous granular ammonium nitrate. The specific preparation method is the same as that in Example 1, except that the cashew nut shell oil and its derivatives are heated to 50 ° C, that is, fully stirred at 50 ° C until the oil phase material is evenly distributed in the pores of the porous granular ammonium nitrate (about 20 minutes), and the porous granular ammonium oil-fuel oil explosive is obtained.

[0028] The cashew nut shell liquid and its derivatives are epoxidized cashew nut shell liquid, with a flash point of 215°C, a molecular weight of 335, and a density of about 0.9500 g / cm 3 .

[0029] When the temperature of the explosives cools to below 40°C, bag the explosives or drive them directly into the blast hole.

[0030] The oil absorption rate of porous granular ammonium nitrate tested according to the relevant method in Example 1 is 14.6%, indicating that epoxidized cashew nut shell liquid has good adsorption capacity for porous granular ammonium nitrate; other relevant performance test data are as follows: Example 4 Taking the production of 1 ton of porous granular ammonium oil oil explosive as an example: the fully environmentally friendly porous granular ammonium oil oil explosive is prepared from 50 kg of cashew nut shell oil and its derivatives and 950 kg of porous granular ammonium nitrate. The specific preparation method is the same as that in Example 1, except that the cashew nut shell oil and its derivatives are heated to 60 ° C, that is, fully stirred at 60 ° C until the oil phase material is evenly distributed in the pores of the porous granular ammonium nitrate (about 20 minutes), and the porous granular ammonium oil oil explosive is obtained.

[0031] The cashew nut shell liquid and its derivatives are esterified cashew nut shell liquid, with a flash point of 230°C, a molecular weight of about 350, and a density of 0.9450 g / cm 3 .

[0032] When the temperature of the explosives cools to below 40°C, bag the explosives or drive them directly into the blast hole.

[0033] The oil absorption rate of porous granular ammonium nitrate tested according to the relevant method in Example 1 is 14.1%, indicating that the esterified cashew nut shell liquid has good adsorption capacity for porous granular ammonium nitrate; other relevant performance test data are as follows: Example 5 Take the production of 1 ton of porous granular ammonium oil oil explosive as an example: the fully environmentally friendly porous granular ammonium oil oil explosive is prepared from 70 kg of cashew nut shell oil and its derivatives and 930 kg of porous granular ammonium nitrate. The specific preparation method is the same as that in Example 1. The mixture is fully stirred at 25 ° C until the oil phase material is evenly distributed in the pores of the porous granular ammonium nitrate (about 20 minutes) to obtain a porous granular ammonium oil oil explosive.

[0034] The cashew nut shell liquid and its derivatives are cashew nut shell liquid, with a flash point of 210°C, a molecular weight of about 300, and a density of 0.9459 g / cm 3 .

[0035] Bag the explosives or drive them directly into the blasthole at room temperature.

[0036] The oil absorption rate of the porous granular ammonium nitrate tested according to the relevant method in Example 1 is 15.5%, indicating that cashew nut shell liquid has good adsorption capacity for porous granular ammonium nitrate; other relevant performance test data are as follows: Example 6 Taking the production of 1 ton of porous granular ammonium oil-fuel oil explosive as an example: the fully environmentally friendly porous granular ammonium oil-fuel oil explosive is prepared from 90 kg of cashew nut shell oil and its derivatives and 910 kg of porous granular ammonium nitrate. The specific preparation method is the same as that in Example 1, except that the cashew nut shell oil and its derivatives are heated to 50 ° C, that is, fully stirred at 60 ° C until the oil phase material is evenly distributed in the pores of the porous granular ammonium nitrate (about 20 minutes), and the porous granular ammonium oil-fuel oil explosive is obtained.

[0037] The cashew nut shell liquid and its derivatives are hydrogenated cashew nut shell liquid, with a flash point of 230°C, a molecular weight of about 315, and a density of 0.9100 g / cm 3 .

[0038] When the temperature of the explosives cools to below 40°C, bag the explosives or drive them directly into the blast hole.

[0039] The oil absorption rate of the porous granular ammonium nitrate tested according to the relevant method in Example 1 is 13.5%, indicating that cashew nut shell liquid has good adsorption capacity for porous granular ammonium nitrate; other relevant performance test data are as follows: The application is not limited to the above-mentioned specific embodiments, and it should be understood that those of ordinary skill in the art can make a lot of modifications on the basis of technical scheme of the present invention without creative work, including that biomass oil in the application is composited with oil phase material in existing porous granular ammonium nitrate oil explosive preparation technology. Therefore, all those skilled in the art should be within the protection scope determined by claims according to the concept of the present invention by logical analysis, reasoning or limited experimental obtainable technical inventions or schemes on the basis of prior art.

Claims

1. A safe and environmentally friendly porous granular ammonium nitrate oil explosive, comprising porous granular ammonium nitrate and biomass oil, characterized in that: The mass percentage of the biomass oil is 3% to 9%, and the mass percentage of the porous granular ammonium nitrate is 91% to 97%; The biomass oil is cashew nut shell oil or a cashew nut shell oil derivative. The cashew nut shell oil is obtained by separating cashew nut shells through multi-stage precipitation and filtration; the cashew nut shell oil derivative is obtained by modifying the cashew nut shell oil.

2. safety and environment-friendly porous granular ammonium oil-fuel explosive according to claim 1, it is characterized in that: The cashew nut shell oil derivative includes polar groups, and the polar groups include phenolic hydroxyl groups, carboxyl groups, amino groups, epoxy groups or ester groups.

3. according to the safety and environmental protection type porous granular ammonium oil-fuel mixture described in any one of claim 1-2, it is characterized in that: The modification treatment includes one or more of deacidification, epoxidation, hydrogenation and esterification.

4. safety and environment-friendly porous granular ammonium oil-fuel explosive according to claim 2, it is characterized in that: The molecular weight of the cashew nut shell liquid and cashew nut shell liquid derivative is 300-350, and the density is 0.9100-0.9500 g / cm 3 , the flash point is not less than 210℃.

5. The safe and environment-friendly porous granular ammonium oil-fuel explosive according to claim 1, wherein: The percentage of the biomass oil is 6% to 8%, and the percentage of the porous granular ammonium nitrate is 92% to 94%.

6. The safe and environment-friendly porous granular ammonium oil-fuel explosive according to claim 1, wherein: The percentage of the biomass oil is 7%, and the percentage of the porous granular ammonium nitrate is 93%.

7. according to the preparation method of the described safe and environmentally friendly porous granular ammonium nitrate oil explosive of claim 1-6 any one, it is characterized in that, The steps include: S1. Weighing: accurately weigh the biomass oil and porous ammonium nitrate particles according to the specified ratio; S2. Loading: Add porous granular ammonium nitrate into the device Internal, biomass oil adding device In; the device is a stirring device, the device It is a device with heating and jetting functions; S3, Mixing: Heat the biomass oil to the specified temperature and start the device Mixing and equipment The spray feed switch is turned on, and porous granular ammonium oil-fired explosive is obtained after sufficient mixing.

8. the preparation method of safety and environment-friendly porous granular ammonium nitrate oil explosive according to claim 7 is characterized in that: In step S3, the specified temperature is 25°C to 80°C.

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