CN106316727B - A kind of porous particulated ammonium oil explosive and preparation method thereof - Google Patents
A kind of porous particulated ammonium oil explosive and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of porous particulated ammonium oil explosive and preparation method thereof, wherein porous particulated ammonium oil explosive is by mass percentage, composed of the following components：Ammonium nitrate 93%~97%, biomass fuel 3%~7%；The boiling range of the wherein described biomass fuel is at 170 DEG C or more.The preparation method of porous particulated ammonium oil explosive is, hydrogenated oil and fat is subjected to fast pyrolysis in catalyst presence, the biomass fuel that light yellow clear is obtained after pyrolysis product is purified, porous particulated ammonium oil explosive is obtained after which is mixed in proportion with ammonium nitrate.Porous particulated ammonium oil explosive storage stability of the present invention is strong, and explosion property is more preferable, and preparation method is simple for process, and raw materials used is regenerative resource, while environmental pollution is small, is conducive to industrialized production.
Description
Technical field
The present invention relates to a kind of porous particulated ammonium oil explosives and preparation method thereof, and in particular to a kind of to utilize hydrogenation oil-breaking
Produce porous particulated ammonium oil explosive and preparation method thereof prepared by hydrocarbon fuels oil.
Background technology
Porous particulated ammonium oil explosive, since its component is simple, only ammonium nitrate and diesel oil are easy to operate,
Only need porous particulated ammonium oil explosive, while ammonium nitrate to obtain the final product after ammonium nitrate and diesel oil are simply mixed
It is of low cost with diesel oil so that porous particulated ammonium oil explosive cost is relatively low, therefore porous particulated ammonium oil explosive is worldwide
It is widely used, also clearly proposes to greatly develop porous particulated ammonium oil explosive in the planning of China's civil explosive industry.It is more
Hole ANFO explosives prill is the mixture of ammonium nitrate oxidizing agent and diesel oil reducing agent, the exhaustion with fossil energy and world wide
The continuous exacerbation of environment pollution problem and the continuous fluctuation of diesel-fuel price, it is necessary to which Development of Novel recyclable fuel replaces
Dai Pin substitutes the diesel fuel composition of porous particulated ammonium oil explosive, and porous particulated ammonium oil explosive is made to have reproducible characteristic.
With the problem of environmental pollution getting worse during the increasingly depleted of fossil energy and fossil energy use, hair
Exhibition regenerative resource obtains the extensive approval of countries in the world, and development renewable biomass fuel technology has obtained more and more weights
Depending on and study.
Since the carbon number in the carbon number and fossil diesel fuel in animal and plant fat is close, while grease is as renewable resource,
Raw material sources are extensive, and the attention of people has been first subjected in renewable resource evolution, at present ester-interchange method and cracking process
That studies is the most extensive, and patent CN 101475828A disclose a kind of biological in ZSM-5 catalyst actions cracking system by vegetable oil
The method of diesel oil, this method directly use vegetable oil for raw material, and cost is very high, and the biodiesel stability that cracking is produced is poor, and
And the problem of needing to cope with catalyst inactivation.Patent CN 101935593A disclose a kind of Supercritical methanol continuous processing system
The method of standby biodiesel, this method need to carry out at high temperature under high pressure, and the requirement to consersion unit is harsh, while energy consumption is larger.
Patent CN104342198 reports the Chinese tallow method that cracking prepares biomass fuel under the conditions of microwave radiation technology, due to this
Reaction is made of microwave method, and to equipment requirement height, while energy consumption is very big.Patent CN 1861750A disclose a kind of use
The method that Bronsted acid ion liquid catalysts prepare biodiesel, this method are difficult to remove there are ionic-liquid catalyst
Problem.It opens space etc. and reports method (Zhang Yu, Zhang Xiu that the cracking of enuatrol under microwave condition obtains hydrocarbon biomass fuel
Celery, Zhang Zhongqiang wait enuatrol microwave cracking decarboxylations to prepare comparative study [J] Chinese oils of HC fuel, 2015,40 (1):
69-73).The biodiesel of the ester-exchange technology production developed at present is since solidification point is relatively high and production of biodiesel
It is more demanding to raw material, limit biodiesel further applying as petrochemical industry oil-producing substitute.Furthermore with animals and plants
Grease Direct Pyrolysis causes pyrolysis product small molecular chain content of material very high due to the presence of double bond in vegetable fat, cracking
Mainly gasolene ingredient, the diesel fuel composition for generating substance are seldom.Gasoline flash-point is relatively low, is security consideration, Direct Pyrolysis method
The biomass fuel of generation is not suitable for the diesel oil substitute in porous and granular explosive and directly uses.Also there is stalk life at present simultaneously
Substance cracking generates the report of biomass fuel, such as CN101602954A, CN103980921A, CN101613613A, etc. all
It reports stalk biomass cracking and generates biomass fuel method, CN103965533A is that carrier reports stalk with fuse salt
The method of biolobic material cracking.Since this biolobic material itself is cellulose, hemicellulose and lignin all at, oxygen content compared with
Height keeps the fuel oil acid value in pyrolysis product high, and viscosity is big, and oxidation stability is poor, and hydrophily is strong and aldehydes matter content is high
The shortcomings of, it limits such renewable fuel oil and is used in commercial explosive as fossil diesel fuel substitute.
Although plant oil-breaking is directly obtained renewable fuel oil, molecular weight is small, is not suitable for using in commercial explosive,
But it is to produce the effective ways of biomass fuel by plant decarboxylation acid cleavage.Compared to biodiesel, the combustion obtained through cracking
Material oil has better stability and high heating value.
Invention content
The object of the present invention is to provide a kind of environmental protection is renewable, stability is strong, the better porous and granular ammonium oil of explosion property
Explosive and preparation method thereof, this method is reacted as raw material through depickling using hydrogenated oil and fat is converted to hydrogenated oil and fat and nature of petroleum and component
Similar hydrocarbon obtains porous grain after being mixed according to a certain percentage with ammonium nitrate using the hydrocarbon
Shape ammonium nitrate-fuel oil mixture.
Realize that the technical solution of the object of the invention is：
A kind of porous particulated ammonium oil explosive, it is by mass percentage, composed of the following components：Ammonium nitrate 93%
~97%, biomass fuel 3%~7%；The boiling range of the wherein described biomass fuel is at 170 DEG C or more.
Preferably, a kind of porous particulated ammonium oil explosive, it is by mass percentage, composed of the following components：Porous and granular nitre
Sour ammonium 94%, biomass fuel 6%.
The present invention also provides a kind of preparation methods of porous particulated ammonium oil explosive, specifically comprise the following steps：
Step 1: under nitrogen protection, hydrogenated oil and fat is heated to 350 DEG C~450 DEG C progress cracking reactions, is 30 DEG C with boiling range
Evaporation removes petroleum ether after~60 DEG C of petroleum ethers collect cooling pyrolysis product, and gained pyrolysis product is carried out distillation separation, collects
Biomass fuel of the boiling range at 170 DEG C or more；
Step 2: obtaining porous and granular ammonium oil after biomass fuel obtained by step 1 is mixed with ammonium nitrate
Explosive, wherein mass percent shared by biomass fuel are 3%~7%, and mass percent is shared by ammonium nitrate
93%~97%.
In above-mentioned steps, the hydrogenated oil and fat is oil with hydrogenated soybean, and hydrogenated palm oil is any one in hydrogenated rapeseed oil
Kind.
In above-mentioned steps, catalyst can also be added in the cracking reaction of the step 1, the addition of catalyst is hydrogenation
Oil and the 0.1%~2% of catalyst gross mass, catalyst are potassium carbonate, potassium hydroxide, sodium hydroxide, zirconium oxide, calcium oxide,
One kind in magnesia.
In above-mentioned steps, the petroleum ether can be recycled after evaporation detaches, and further, the petroleum ether recycling exists
It is carried out under condition of negative pressure.
Compared with prior art, the present invention its remarkable advantage is：
1, porous particulated ammonium oil explosive of the invention in component due to using bio-oil instead of traditional fossil bavin
Oil so that explosive has the characteristics that reproducible, and toxic gas content significant decrease after explosion, characteristic of environmental protection is apparent.
2, porous particulated ammonium oil explosive of the invention uses 93%~97% ammonium nitrate by mass percentage
It being mixed to prepare with 3%~7% biomass fuel, explosion property is remarkably reinforced compared with conventional explosives, more preferably,
94% ammonium nitrate is taken to be mixed with 6% biomass fuel, the explosive charge produced under this optimum proportioning
It can be more preferable.
3, bio-oil is obtained first with hydrogenation oil-breaking in the preparation method of explosive of the present invention, due to pyrolysis product
Macromolecular chain content of material higher, and main component is based on diesel oil, therefore be suitble to use in porous particulated ammonium oil explosive, together
When products therefrom oxygen content it is low, good fluidity, stability is strong, more conducively industrialized production.
4, in the preparation method of explosive of the present invention after hydrogenated oil and fat cracking reaction, condensed, distillation separation collects boiling range and exists
170 DEG C or more of biomass fuel, improves oil flash point so that the production security of porous particulated ammonium oil explosive is also therewith
It improves.Oil phase material and the isolated inhibition of ammonium nitrate, porous particulated ammonium oil explosive storage stability also obtain significantly simultaneously
Reinforce.
Specific implementation mode
Technical scheme of the present invention is further described with reference to embodiment, but should not be as the limitation present invention
Protection domain.
Embodiment 1
The first step；The preparation of biomass fuel
It is 99.9 by mass ratio under nitrogen protection：0.1 hydrogenated palm oil with potassium carbonate after evenly mixing, in pyrolysis furnace
Middle carry out fast pyrolysis, cracking temperature are 350 DEG C, are that will be mixed after 30~60 DEG C of petroleum ethers collect cooling pyrolysis product with boiling range
It closes after object evaporates separation petroleum ether under 45 DEG C of condition of negative pressure and recycles.The pyrolysis product of above-mentioned gained is subjected to heating distillation
Biomass fuel oil component of the boiling range at 170 DEG C or more is collected in separation, is used as preparing ammonium nitrate oil phase material after cooling
Expect raw material.
Second step；The preparation of ammonium nitrate
It is 94 in mass ratio by ammonium nitrate and biomass fuel：6 mixed after obtain the present invention it is more
Hole ANFO explosives prill.Diesel oil is proportionally uniformly mixed with coal dust to obtain common porous ANFO explosives prill.With reference to porous
Ammonium nitrate-fuel oil mixture explosion velocity test method tests explosion velocity, and porous particulated ammonium oil explosive explosion velocity of the invention is 2950m/s, with petrifaction diesel
It is 2730m/s for the common porous ANFO explosives prill explosion velocity of fuel.
Embodiment 2
The first step；The preparation of biomass fuel
It is 98 by mass ratio under nitrogen protection：2 oil with hydrogenated soybean and potassium hydroxide after evenly mixing, in pyrolysis furnace into
Row fast pyrolysis, cracking temperature are 450 DEG C, are that 30~60 DEG C of petroleum ethers are collected mixture after cooling pyrolysis products with boiling range
It is recycled after evaporation separation petroleum ether under 45 DEG C of condition of negative pressure.The pyrolysis product of above-mentioned gained is subjected to distillation separation, is received
Collect biomass fuel oil component of the boiling range at 170 DEG C or more, is used as preparing ammonium nitrate oil phase material raw material after cooling.
Second step；The preparation of ammonium nitrate
It is 94 in mass ratio by ammonium nitrate and biomass fuel：6 mixed after obtain the present invention it is more
Hole ANFO explosives prill.Diesel oil is proportionally uniformly mixed with coal dust to obtain common porous ANFO explosives prill.With reference to porous
Ammonium nitrate-fuel oil mixture explosion velocity test method tests explosion velocity, and porous particulated ammonium oil explosive explosion velocity of the invention is 3020m/s, with petrifaction diesel
It is 2730m/s for the common porous ANFO explosives prill explosion velocity of fuel.
Embodiment 3
The first step；The preparation of biomass fuel
It is 99 by mass ratio under nitrogen protection：1 hydrogenated rapeseed oil with sodium hydroxide after evenly mixing, in pyrolysis furnace
Fast pyrolysis is carried out, cracking temperature is 400 DEG C, and being with boiling range will mixing after 30~60 DEG C of petroleum ethers collect cooling pyrolysis product
Object recycles after evaporating separation petroleum ether under 45 DEG C of condition of negative pressure.The biomass fuel of above-mentioned gained is subjected to distillation point
From biomass fuel oil component of the collection boiling range at 170 DEG C or more is used as preparing ammonium nitrate oil phase material after cooling
Raw material.
Second step；The preparation of ammonium nitrate
It is 94 in mass ratio by ammonium nitrate and biomass fuel：6 mixed after obtain the present invention it is more
Hole ANFO explosives prill.Diesel oil is proportionally uniformly mixed with coal dust to obtain common porous ANFO explosives prill.With reference to porous
Ammonium nitrate-fuel oil mixture explosion velocity test method tests explosion velocity, and porous particulated ammonium oil explosive explosion velocity of the invention is 3080m/s, with petrifaction diesel
It is 2730m/s for the common porous ANFO explosives prill explosion velocity of fuel.
Embodiment 4
The first step；The preparation of biomass fuel
It is 99 by mass ratio under nitrogen protection：1 hydrogenated palm oil with zirconium oxide after evenly mixing, in pyrolysis furnace into
Row fast pyrolysis, cracking temperature are 390 DEG C, are that 30~60 DEG C of petroleum ethers are collected mixture after cooling pyrolysis products with boiling range
It is recycled after evaporation separation petroleum ether under 45 DEG C of condition of negative pressure.The pyrolysis product of above-mentioned gained is subjected to distillation separation, is received
Collect biomass fuel oil component of the boiling range at 170 DEG C or more, is used as preparing ammonium nitrate oil phase material raw material after cooling.
Second step；The preparation of ammonium nitrate
It is 94 in mass ratio by ammonium nitrate and biomass fuel：6 mixed after obtain the present invention it is more
Hole ANFO explosives prill.Diesel oil is proportionally uniformly mixed with coal dust to obtain common porous ANFO explosives prill.With reference to porous
Ammonium nitrate-fuel oil mixture explosion velocity test method tests explosion velocity, and porous particulated ammonium oil explosive explosion velocity of the invention is 2960m/s, with petrifaction diesel
It is 2730m/s for the common porous ANFO explosives prill explosion velocity of fuel.
Embodiment 5
The first step；The preparation of biomass fuel
It is 99.5 by mass ratio under nitrogen protection：0.5 oil with hydrogenated soybean with calcium oxide after evenly mixing, in pyrolysis furnace
Middle carry out fast pyrolysis, cracking temperature are 420 DEG C, are that will be mixed after 30~60 DEG C of petroleum ethers collect cooling pyrolysis product with boiling range
It closes after object evaporates separation petroleum ether under 45 DEG C of condition of negative pressure and recycles.The pyrolysis product of above-mentioned gained is subjected to distillation point
From biomass fuel oil component of the collection boiling range at 170 DEG C or more is used as preparing ammonium nitrate oil phase material after cooling
Raw material.
Second step；The preparation of ammonium nitrate
It is 94 in mass ratio by ammonium nitrate and biomass fuel：6 mixed after obtain the present invention it is more
Hole ANFO explosives prill.Diesel oil is proportionally uniformly mixed with coal dust to obtain common porous ANFO explosives prill.With reference to porous
Ammonium nitrate-fuel oil mixture explosion velocity test method tests explosion velocity, and porous particulated ammonium oil explosive explosion velocity of the invention is 3050m/s, with petrifaction diesel
It is 2730m/s for the common porous ANFO explosives prill explosion velocity of fuel.
Embodiment 6
The first step；The preparation of biomass fuel
It is 98.5 by mass ratio under nitrogen protection：1.5 hydrogenated palm oil with magnesia after evenly mixing, in pyrolysis furnace
Middle carry out fast pyrolysis, cracking temperature are 400 DEG C, are that will be mixed after 30~60 DEG C of petroleum ethers collect cooling pyrolysis product with boiling range
It closes after object evaporates separation petroleum ether under 45 DEG C of condition of negative pressure and recycles.The pyrolysis product of above-mentioned gained is subjected to distillation point
From biomass fuel oil component of the collection boiling range at 170 DEG C or more is used as preparing ammonium nitrate oil phase material after cooling
Raw material.
Second step；The preparation of ammonium nitrate
It is 93 in mass ratio by ammonium nitrate and biomass fuel：7 mixed after obtain the present invention it is more
Hole ANFO explosives prill.Diesel oil is proportionally uniformly mixed with coal dust to obtain common porous ANFO explosives prill.With reference to porous
Ammonium nitrate-fuel oil mixture explosion velocity test method tests explosion velocity, and porous particulated ammonium oil explosive explosion velocity of the invention is 2690m/s, with petrifaction diesel
It is 2730m/s for the common porous ANFO explosives prill explosion velocity of fuel.
Embodiment 7
The first step；The preparation of biomass fuel
Under nitrogen protection, hydrogenated palm oil is subjected to fast pyrolysis in pyrolysis furnace, cracking temperature is 400 DEG C, with boiling
After mixture is is evaporated separation petroleum ether by journey after 30~60 DEG C of cooling pyrolysis products of petroleum ethers collection under 45 DEG C of condition of negative pressure
It recycles.The pyrolysis product of above-mentioned gained is subjected to distillation separation, collect boiling range 170 DEG C or more biomass fuel at
Point, it is used as preparing ammonium nitrate oil phase material raw material after cooling.
Second step；The preparation of ammonium nitrate
It is 97 in mass ratio by ammonium nitrate and biomass fuel：3 mixed after obtain the present invention it is more
Hole ANFO explosives prill.Diesel oil is proportionally uniformly mixed with coal dust to obtain common porous ANFO explosives prill.With reference to porous
Ammonium nitrate-fuel oil mixture explosion velocity test method tests explosion velocity, and porous particulated ammonium oil explosive explosion velocity of the invention is 3070m/s, with petrifaction diesel
It is 2730m/s for the common porous ANFO explosives prill explosion velocity of fuel.
Claims (8)
1. a kind of porous particulated ammonium oil explosive, which is characterized in that by mass percentage, composed of the following components：
Ammonium nitrate 93%~97%, biomass fuel 3%~7%；The wherein described biomass fuel passes through such as
Lower section method is made：Under nitrogen protection, hydrogenated oil and fat is heated to 350 DEG C~450 DEG C progress cracking reactions, is 30 DEG C~60 with boiling range
Evaporation removes petroleum ether after DEG C petroleum ether collects cooling pyrolysis product, and gained pyrolysis product is carried out distillation separation, collects boiling range
In 170 DEG C or more of biomass fuel.
2. a kind of porous particulated ammonium oil explosive according to claim 1, which is characterized in that by mass percentage, by with
The following group is grouped as：Ammonium nitrate 94% and biomass fuel 6%.
3. a kind of a kind of preparation method of porous particulated ammonium oil explosive as described in claim 1, which is characterized in that including as follows
Step：
Step 1: under nitrogen protection, hydrogenated oil and fat is heated to 350 DEG C~450 DEG C progress cracking reactions, is 30 DEG C~60 with boiling range
Evaporation removes petroleum ether after DEG C petroleum ether collects cooling pyrolysis product, and gained pyrolysis product is carried out distillation separation, collects boiling range
In 170 DEG C or more of biomass fuel；
Step 2: it is fried to obtain porous and granular ammonium after biomass fuel obtained by step 1 is mixed with ammonium nitrate
Medicine, wherein mass percent shared by biomass fuel are 3%~7%, and mass percent is shared by ammonium nitrate
93%~97%.
4. a kind of preparation method of porous particulated ammonium oil explosive according to claim 3, it is characterised in that：The hydrogenated oil and fat
For oil with hydrogenated soybean, hydrogenated palm oil, any one in hydrogenated rapeseed oil.
5. a kind of preparation method of porous particulated ammonium oil explosive according to claim 3, it is characterised in that：The step 1
Cracking reaction in be added catalyst, the addition of catalyst is the 0.1%~2% of hydrogenated oil and fat and catalyst gross mass.
6. a kind of preparation method of porous particulated ammonium oil explosive according to claim 5, it is characterised in that：The catalysis
Agent is potassium carbonate, potassium hydroxide, sodium hydroxide, zirconium oxide, calcium oxide, one kind in magnesia.
7. a kind of preparation method of porous particulated ammonium oil explosive according to claim 3, which is characterized in that the petroleum ether
It can be recycled after evaporation detaches.
8. a kind of preparation method of porous particulated ammonium oil explosive according to claim 7, which is characterized in that the petroleum ether
Recycling carries out under condition of negative pressure.
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