CN107937029A - A kind of method and system of coal base calcium carbide acetylene - Google Patents
A kind of method and system of coal base calcium carbide acetylene Download PDFInfo
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- CN107937029A CN107937029A CN201711406332.XA CN201711406332A CN107937029A CN 107937029 A CN107937029 A CN 107937029A CN 201711406332 A CN201711406332 A CN 201711406332A CN 107937029 A CN107937029 A CN 107937029A
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- calcium carbide
- acetylene
- coal
- gas
- calcium
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- 239000005997 Calcium carbide Substances 0.000 title claims abstract description 93
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 62
- 239000003245 coal Substances 0.000 title claims abstract description 43
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 claims abstract description 80
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 55
- 239000000463 material Substances 0.000 claims abstract description 45
- 239000000843 powder Substances 0.000 claims abstract description 29
- 230000008569 process Effects 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 230000007062 hydrolysis Effects 0.000 claims abstract description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 20
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 20
- 239000011575 calcium Substances 0.000 claims description 20
- 229910052791 calcium Inorganic materials 0.000 claims description 20
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 15
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 239000000292 calcium oxide Substances 0.000 claims description 11
- 235000012255 calcium oxide Nutrition 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 8
- 229910021532 Calcite Inorganic materials 0.000 claims description 7
- 235000013312 flour Nutrition 0.000 claims description 7
- 239000002817 coal dust Substances 0.000 claims description 6
- 239000012778 molding material Substances 0.000 claims description 5
- 229920002472 Starch Polymers 0.000 claims description 4
- 239000002283 diesel fuel Substances 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 235000000346 sugar Nutrition 0.000 claims description 4
- 235000019738 Limestone Nutrition 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 3
- 239000006028 limestone Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000003350 kerosene Substances 0.000 claims description 2
- 239000011269 tar Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 6
- 238000003723 Smelting Methods 0.000 abstract description 5
- 239000007789 gas Substances 0.000 description 76
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 20
- 238000004519 manufacturing process Methods 0.000 description 14
- 239000000571 coke Substances 0.000 description 11
- 229910052786 argon Inorganic materials 0.000 description 10
- 238000009413 insulation Methods 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 238000004587 chromatography analysis Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 239000003595 mist Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 5
- 238000007493 shaping process Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 241001417490 Sillaginidae Species 0.000 description 4
- 241001062472 Stokellia anisodon Species 0.000 description 4
- JETSKDPKURDVNI-UHFFFAOYSA-N [C].[Ca] Chemical compound [C].[Ca] JETSKDPKURDVNI-UHFFFAOYSA-N 0.000 description 4
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 4
- 239000003830 anthracite Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000004939 coking Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000002657 fibrous material Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000000443 aerosol Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000010891 electric arc Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000007770 graphite material Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000010742 number 1 fuel oil Substances 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000026676 system process Effects 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10H—PRODUCTION OF ACETYLENE BY WET METHODS
- C10H19/00—Other acetylene gas generators
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10H—PRODUCTION OF ACETYLENE BY WET METHODS
- C10H21/00—Details of acetylene generators; Accessory equipment for, or features of, the wet production of acetylene
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10H—PRODUCTION OF ACETYLENE BY WET METHODS
- C10H21/00—Details of acetylene generators; Accessory equipment for, or features of, the wet production of acetylene
- C10H21/10—Carbide compositions
Abstract
The invention discloses a kind of preparation method and system of coal base calcium carbide acetylene.The method includes the steps：Fine is carried out after the material is sufficiently mixed in proportion to grind to obtain superfine powder, superfine powder carries out forming processes, then carry out microwave heating smelting and obtain solid-state calcium carbide, solid-state calcium carbide and the water of generation are reacted, calcium carbide obtains acetylene gas after hydrolysis is contacted with water.
Description
Technical field
The invention belongs to technical field of coal chemical industry.Relate more specifically to a kind of coproduction one at the same time of coal base calcium carbide acetylene to aoxidize
The method and system of carbon.
Background technology
The energy resource structure in China has the characteristics that few gas rich in coal and poor in oil, and it is China's Sustainable development policies to greatly develop coal chemical industry
Important technique measure.Coal base calcium carbide acetylene is the important component of China's coal chemical industry, is provided for organic chemical industry's industry
Acetylene raw material.Traditional coal base calcium carbide acetylene is by synthesizing calcium carbide reproduction acetylene by coal.The industrial calcium carbide life in China at present
For production technology using electric arc heated method, the calcium carbide of production is liquid molten phase, is needed for liquid calcium carbide cold by calcium carbide pot
But, program, complex process, the dust pollution such as the demoulding, broken are serious.In addition, contain more impurity, the electricity of generation in the calcium carbide of generation
Phase inversion process of the stone Jing Guo high-temperature fusion, material structure is relatively closer, it is necessary to calcium carbide progress break process, could enter acetylene
Synthesis procedure, so not only causes dust pollution serious, and calcium carbide exposure in atmosphere, tends to have acetylene generation during this,
Environmental pollution is so not only caused, but also the danger that easily sets off an explosion.In short, industrial coal base calcium carbide acetylene coal carbide acetylene
Method there is technological process length, high energy consumption, it is seriously polluted the problems such as.Acetylene is produced to traditional one coking of coal through calcium carbide by coal dust
The complicated technology route of one calcium carbide, one acetylene proposes challenge.
Therefore, there is an urgent need in the art to provide the coal base calcium carbide acetylene that a kind of cooling energy-saving, technique are simple, environmentally protective
Preparation method.
The content of the invention
The present invention is directed to the shortcoming of prior art route, it is desirable to provide one kind is by coal base preparation of ethyne by carbide co-production
The technique of carbon monoxide, which smelts generation solid-state calcium carbide using coal as raw material, by microwave calcium carbide stove heat, by consolidating for generation
State calcium carbide is sent into acetylene generator to be reacted with water, and the acetylene gas of generation obtains pure acetylene gas by purifier.
During this at the same time co-producing high-purity carbon monoxide.
In the first aspect of the present invention, there is provided a kind of method of coal base calcium carbide acetylene, the method includes the steps：
(1) microwave heating will be carried out containing the mixed-forming material of coal and calcium source, reaction obtains solid-state calcium carbide；The shaping
Material is to obtain the mixture containing coal and calcium source of 30-1000 nanometers of granularity through forming processes；With
(2) the solid-state calcium carbide of generation is contacted in acetylene generator with water, acetylene gas is obtained through hydrolysis.
In another preference, the coal is less than 5 centimetres of coal dust for particle diameter；The calcium source is selected from quick lime or lime stone
(calcite), 5 centimetres of powder is less than for particle diameter.
In another preference, the molar ratio of coal dust and calcium source powder in the mixture containing coal and calcium source (with carbon,
Calcium constituent meter) it is 2-4:1.
In another preference, the forming processes are uniformly mixed by the mixture containing coal and calcium source or with binding agent
It is compressing afterwards；The addition of binding agent is 2-25%；The binding agent is selected from following one or more：Tar, coal
Oil, diesel oil, sugar, flour, starch, water.
In another preference, the microwave heating temperature is 1400-2000 DEG C, reaction pressure 0.03-1.1atm, instead
30-180min between seasonable.
In another preference, the step (1) obtains carbon monoxide content while solid-state calcium carbide is obtained and is more than
95% gas.
In another preference, solid-state calcium carbide described in step (2) is without broken process, and directly in acetylene generator
React to obtain acetylene gas with water.
In the second aspect of the present invention, there is provided a kind of system for the method that can be achieved to provide present invention as described above,
The system comprises powder crushing process unit, material plastotype forming unit, calcium carbide generation unit, acetylene generation unit and carbon monoxide
Cogeneration unit.
Accordingly, the present invention provides a kind of cooling energy-saving, the coal base calcium carbide acetylene preparation side that technique is simple, environmentally protective
Method.
Brief description of the drawings
Fig. 1 is the method schematic diagram for preparing solid-state calcium carbide.
Fig. 2 is coal base calcium carbide acetylene coproduction carbon monoxide system process flow chart.
Embodiment
Inventor has found the mixture containing coal and calcium source being refined as nano level powder by in-depth study extensively
Last, through forming processes, the molding materials of acquisition can obtain solid-state calcium carbide, while co-producing high-purity using microwave heating smelting
Carbon monoxide；The solid-state calcium carbide obtained just can directly get angry without disintegrating process and produce acetylene.On this basis, this is completed
Invention.
Specifically, the method provided by the invention using coal base preparation of ethyne by carbide includes step：
The first step, material forming
Feed coal and calcium source are subjected to break process first, fine is carried out after being then sufficiently mixed in proportion and grinds to obtain
Superfine powder, superfine powder carry out forming processes, obtain certain particle size and the molding materials of shape.
Second step, calcium carbide synthesis
Material after shaping is placed in microwave furnace of calcium carbide and carries out heating smelting, obtains the solid-state calcium carbide of high-purity, it is in parallel
The CO gas of production of high purity.
3rd step, acetylene synthesis
The solid-state calcium carbide generated in second step is sent into acetylene generator and is reacted with water, calcium carbide contacts hydrolysis with water
After obtain acetylene gas.
Feed coal described in the above-mentioned first step is selected from following one or more：Anthracite, lignite, jet coal,
Coking coal, metallurgical coke, petroleum coke and semi-coke, through crushing and being sized to particle diameter less than 5 centimetres, obtain feed coal powder；The calcium
Source is selected from quick lime or lime stone (calcite), through broken and screening, obtains the calcium source powder that particle diameter is less than 5 centimetres.
According to molar ratio (in terms of carbon, calcium constituent) it is 2-4 by coal dust end and calcium source powder:After 1 is mixed, by feeding machine
Milling machine host is delivered to, the granular material that granularity is 30-1000nm is worn into machine host being milled, filter bag is sent into through air-introduced machine
Middle collection, obtains superfine powder.Superfine powder is directly carried out to forming processes under the action of tablet press machine, some can be used normal
Rule method carries out forming processes, such as, but not limited to, above-mentioned powder pressing shaping；Or add Jiao that mass content is 2-25%
One or two kinds of above in oil, kerosene, diesel oil, sugar, flour, starch, water is pressed into after mixing after being used as binding agent
Type.The molding materials can have any shape, such as, but not limited to, granular pattern, cylinder, spherical, disc and clover
Type.By being compressed plastotype to mixed material, mixed material contact can be made close, the mass transfer between fortified mixture material, from
And improve calcium carbide production efficiency.
In one embodiment of the invention, in above-mentioned second step, the molding materials of acquisition are initially positioned in crucible,
Then crucible is placed in insulation barrel.The crucible can be made of materials such as boron nitride, graphite, aluminium oxide, mullites.It is described
Insulation barrel is made of the material with transmission microwave and heat insulation, includes but not limited to alumina silica refractory, aluminium oxide
One or more in fibrous material, graphite material, zirconia nanopowder fibrous material, carbon aerosol are made.
Microwave furnace of calcium carbide described in above-mentioned second step is sealed furnace, its structure includes microwave furnace of calcium carbide furnace wall, furnace bottom turns
Disk, microwave source, microwave introduce the composition such as window, water-cooling system, heat-insulation system, infrared radiation thermometer, gas inlet and outlet.Thing will be held
The insulation barrel of material is placed on furnace bottom turntable, and the rotation of furnace bottom driven by rotary disc material makes it uniformly receive microwave, the furnace bottom turntable
Rotating speed is 5-20 revs/min, is driven by motor；The microwave calcium carbide furnace bottom has gas feed, and top has gas
Outlet.
In one embodiment of the invention, calcium carbide microwave reaction stove is evacuated first in above-mentioned second step or
Ventilation is handled, and removes the air in microwave furnace of calcium carbide, then carries out heat temperature raising, temperature to reacting furnace by adjusting microwave power
For 1400-2000 DEG C, reaction pressure 0.3-1.1atm, reaction time 30-180min, smelt reaction and terminate 400- to be cooled to
At less than 450 DEG C, solid-state calcium carbide product is obtained.
In one embodiment of the invention, calcium carbide microwave reaction furnace exhaust gas is discharged by gas exhaust piping in above-mentioned second step
Reacting furnace, by adsorption filter, removes the impurity such as tar in tail gas, then by desulfurizer remove inorganic sulfur in tail gas and
Organic sulfur, can obtain the gas that CO contents are 95-99%, carbon monoxide basin or next workshop section is sent into after purified.
In one embodiment of the invention, above-mentioned 3rd step can be electric by the solid-state generated in second step by batcher
Stone is sent into acetylene generator, and the acetylene gas of generation is after the gases such as hydrogen phosphide, hydrogen sulfide are fallen in the removing of peace and quiet tower, then removes second
Acid mist and moisture in alkynes gas obtain pure acetylene gas.
Present invention also offers a kind of system using coal base preparation of ethyne by carbide coproduction carbon monoxide, it includes crushing system
Powder unit, material plastotype forming unit, calcium carbide generation unit, acetylene generation unit and carbon monoxide cogeneration unit.
The powder crushing process unit includes crusher and flour mill.The crusher is equipped with inlet port and outlet port, carbon
Plain raw material and calcareous material difference enters crusher by feed inlet after mixing, and it is below 5cm to obtain granularity after crushing
Raw material.The flour mill is made of feeding machine, host, filter bag, air-introduced machine.It is above-mentioned it is broken after granularity be less than the thing of 5cm
Material directly or after mixing by feeding machine is sent into host, and the powder that granularity 30-1000nm is worn into host is sent into filter by air-introduced machine
Collected in bag.
The material plastotype forming unit is made of tablet press machine.By above-mentioned powder under the action of tablet press machine direct pressing
Shaping, or it is one or more in the tar of 2-25%, sugar, flour, starch, water as binding agent to add mass content
It is uniformly mixed afterwards and is then pressed into type.Material after shaping can be cylindrical, spherical, cloverleaf pattern, disc etc., its external form
Size is 2-50mm.By being compressed plastotype to mixed material, mixed material contact can be made close, between fortified mixture material
Mass transfer, so as to improve calcium carbide production efficiency.
The calcium carbide generation unit includes microwave furnace of calcium carbide, and the microwave furnace of calcium carbide is sealed furnace, its structure includes
Microwave furnace of calcium carbide furnace wall, furnace bottom turntable, microwave source, microwave introduce window, water-cooling system, heat-insulation system, infrared radiation thermometer, gas
The composition such as inlet and outlet.The furnace bottom driven by rotary disc material rotation makes it uniformly receive microwave, its rotary speed is 5-20 revs/min
Clock, is driven by motor；The microwave source device, for producing microwave, introduces window, into microwave furnace of calcium carbide via microwave
In；The microwave introduces window, it is made of the material of admitting microwaves, so as to which microwave is introduced into microwave furnace of calcium carbide；It is affiliated
Infrared temperature measurement device at the top of the microwave furnace of calcium carbide, its measurable 300-3000 DEG C high temperature；Microwave vacuum furnace bottom has gas
Body import, top have offgas outlet；Thermal insulation material in the micro-wave oven has the spy of transmission microwave and heat insulation
Point, by based in alumina silica refractory, alumina fibre material, graphite material, zirconia nanopowder fibrous material, carbon aerosol
One or more be made.The mixed-forming material is sent into microwave furnace of calcium carbide, and smelting is carried out to the mixed material
Refining is handled, so as to obtain solid-state calcium carbide.
The carbon monoxide cogeneration unit includes gas discharge pipe system and purifier, in microwave furnace of calcium carbide reaction process
The tail gas of generation discharges furnace of calcium carbide by gas exhaust piping, is sent into carbon monoxide basin or next work after purification by purifier
Section.
The acetylene generation unit includes batcher, acetylene generator, peace and quiet tower and neutralizing tower, the solid-state calcium carbide of generation
Acetylene generator is sent into by batcher, generator lower part sets acetylene gas outlet, and the acetylene gas of generation takes off by peace and quiet tower
After removing the gases such as hydrogen phosphide, hydrogen sulfide, then respectively enter caustic neutralizer column removing fall acetylene gas in acid mist, remove acid mist after
Acetylene gas removes moisture after supercharging and condensation and obtains the acetylene gas of high-purity.
Compared with prior art, the beneficial effects of the present invention are：
1st, coke can be replaced using a variety of coals, eliminates coking link, not only reduce production cost, and simplify
Technological process.
2nd, feed coal and calcic Raw material processing are the superfines of 30-1000nm into granularity, and carry out compression forming, make to mix
The contact of compound material is close, the specific surface area and contact area of material can be dramatically increased, so that the mass transfer between dramatically increasing raw material
Ability and reduction reaction temperature simultaneously improve calcium carbide production efficiency.
3rd, microwave technology is introduced into calcium carbide production technology, substitutes traditional electric arc heated method with microwave heating, reduce
The reaction temperature of calcium carbide synthesis, and shorten the reaction time.In addition, the process can directly generate solid-state calcium carbide product, it is not required to
The complicated process such as calcium carbide pot cooling, the demoulding, broken, not only saving energy, lowering energy consumption and reducing pollutants discharge are undergone, but also enormously simplify calcium carbide production
Technological process.The carbon monoxide of co-producing high-purity at the same time, can couple to form multi-production process, significantly with other techniques of coal chemical industry
Improve environment and technical economic benefit.
4th, the solid-state calcium carbide of microwave smelting production is lower than the calcium carbide product consistency that arc process produces, and can be not required to broken process
It is directly used in and produces acetylene, and raising rate is fast, so as to simplify calcium carbide generation acetylene flow, improves production efficiency.
In short, different from the complicated technology route of its traditional one coking of coal, one calcium carbide, one acetylene, the present invention proposes one
The method of the new coal base calcium carbide acetylene of kind, this method have the advantages that technological process is short, energy consumption is low, pollution is small, low emission, together
When co-producing high-purity CO gas, production can be coupled with C1 chemical industry routes, realize carbon monoxide appreciate utilize, improve work
The economy of skill entirety.
The features described above that the present invention mentions, or the feature that embodiment is mentioned can be in any combination.Disclosed in this case specification
All features can be used in combination with any composition form, each feature disclosed in specification, any can provide it is identical,
The alternative characteristics substitution of impartial or similar purpose.Therefore except there is special instruction, revealed feature is only impartial or similar spy
The general example of sign.
With reference to specific embodiment, the present invention is further explained.It is to be understood that these embodiments are merely to illustrate the present invention
Rather than limit the scope of the invention.The experimental method of actual conditions is not specified in the following example, usually according to conventional strip
Part or according to the condition proposed by manufacturer.Unless otherwise stated, otherwise all percentage, ratio, ratio or number is pressed
Weight meter.The unit in percent weight in volume in the present invention is well-known to those skilled in the art, such as is referred to 100
The weight of solute in the solution of milliliter.Unless otherwise defined, all professional and scientific terms used in text and this area are ripe
It is identical to practice meaning known to personnel.In addition, any method similar or impartial to described content and material all can be applied to
In the method for the present invention.The preferred methods and materials described herein are for illustrative purposes only.
Embodiment 1
Referring to Fig. 2.According to carbon calcium molar ratio it is 2.8 by metallurgical coke and quick lime:By flour mill (1) and ground after 1 mixing
It is fine into mixing superfine powder of the particle diameter distribution between 30-80nm.The Industrial Analysis of metallurgical coke is as shown in table 1, fixed carbon content
For 84.73%, the content of calcium oxide is more than 99% in quick lime.Mixing superfine powder is fed through material inlet (10) tablet press machine
(2) in, pressure obtains a diameter of 40mm, highly the cylindrical piece material material for 10-15mm for 6MPa lower sheetings.By the material
It is placed on the microwave voluntarily developed by material inlet (11) to smelt in furnace of calcium carbide (3), argon gas is passed through micro- through gas feed (13)
Ripple smelts furnace of calcium carbide (3), carries out atmosphere displacement.Then microwave is heated to 1750 DEG C and maintains 1h in argon gas atmosphere, instead
The tail gas produced during answering enters purified point of purification separation device (5) by offgas outlet (12) into discharge duct (16)
It is 98.4% through gas chromatographic analysis CO contents, the argon gas isolated recycles from the gas products of high CO contents are obtained.Instead
Microwave emission power supply is closed after answering, microwave is opened when temperature of charge is reduced to below 450 DEG C and smelts furnace of calcium carbide outlet valve
(14), solid-state calcium carbide is obtained, is detected through gas generating device, gas forming amount can reach 239L/kg.By the calcium carbide of generation through material outlet
(14) material inlet (15) is sent into be reacted with water in acetylene generator (4), generator temperature control at 80 DEG C, generation it is thick
Acetylene gas is sent into peace and quiet tower (6) and neutralizing tower (7) through peace and quiet tower entrance (19), and the gases such as hydrogen phosphide, hydrogen sulfide are fallen in removing respectively
Acetylene gas is obtained with the acid mist in acetylene gas and moisture, is 98.9% through gas chromatographic analysis acetylene content.
The Industrial Analysis of 1 metallurgical coke of table
| Moisture (Mad) | Ash content (Aad) | Volatile matter (Vad) | Fixed carbon (Cad) |
| 1.31% | 12.41% | 1.55% | 84.73% |
Embodiment 2
Metallurgical coke and calcite are fine into the metallurgical coke superfines that particle diameter is 80-120nm by two level pulverising mill respectively
With calcite superfines.The Industrial Analysis of wherein metallurgical coke is as shown in table 1, and the content of calcium carbonate is more than 97% in calcite.
It is 4.5 that the superfines of above-mentioned metallurgical coke and calcite is pressed carbon calcium molar ratio:1 ratio, and mass parts rate is added as 3%
Diesel oil is sent into in roller tablet press after mixing, pressure be made under 6.5MPa a diameter of 5mm, be highly 10mm cylindricality
Granular material.The material is placed on to the microwave voluntarily developed to smelt in furnace of calcium carbide, carries out atmosphere displacement with argon gas first.So
Microwave is heated to 1680 DEG C in argon gas atmosphere afterwards, maintains 1h, and the tail gas produced in reaction process is passed through into discharge duct
The gas products of high CO contents are obtained after separator, are 97.8% through gas chromatographic analysis CO contents, the argon gas isolated follows
Ring uses.Microwave emission power supply is closed after reaction, is opened insulation barrel when temperature of charge is reduced to below 450 DEG C, is obtained
Solid-state calcium carbide, is detected through gas generating device, and gas forming amount can reach 231L/kg.The calcium carbide of generation is sent into acetylene generator and water
Reacted, at 80 DEG C, the acetylene gas of generation falls the gases such as hydrogen phosphide, hydrogen sulfide by the removing of peace and quiet tower for generator temperature control
Afterwards, then remove acid mist in acetylene gas and moisture obtains pure acetylene gas, be 97.8% through gas chromatographic analysis content.
Embodiment 3
Anthracite and quick lime are fine into the anthracite superfine powder and life that particle diameter is 100-150nm by two level pulverising mill
Lime superfine powder.Wherein anthracitic Industrial Analysis is as shown in table 2, and the content of calcium oxide is more than 99% in quick lime.Will be upper
The anthracite and the superfine powder of quick lime stated are 3 by carbon calcium molar ratio:1 ratio after mixing, is sent into tablet press machine, pressure
The globular material of a diameter of 5mm is made under power 6.5MPa.The material is placed on to the microwave voluntarily developed and smelts furnace of calcium carbide
In, first atmosphere displacement is carried out with argon gas.Then microwave is heated to 1800 DEG C in argon gas atmosphere and constant temperature maintains 1h, instead
The tail gas produced during answering enters the gas products that discharge duct obtains high CO contents after separator, through gas-chromatography point
It is 95.6% to analyse CO contents, and the argon gas isolated recycles.Microwave emission power supply is closed after reaction, treats that temperature of charge drops
It is low to less than 450 DEG C when open insulation barrel, obtain solid-state calcium carbide, detected through gas generating device, gas forming amount can reach 202L/kg.Will
The calcium carbide of generation is sent into acetylene generator to be reacted with water, and at 80 DEG C, the acetylene gas of generation passes through for generator temperature control
After the gases such as hydrogen phosphide, hydrogen sulfide are fallen in the removing of peace and quiet tower, then remove acid mist in acetylene gas and moisture obtains pure acetylene
Gas, is 96.4% through gas chromatographic analysis content.
2 anthracitic Industrial Analysis of table
| Moisture (Mad) | Ash content (Aad) | Volatile matter (Vad) | Fixed carbon (Cad) |
| 7.59% | 16.95% | 25.76% | 49.70% |
Comparative example
According to carbon calcium molar ratio it is 2.8 by metallurgical coke and quick lime:1 mix and be finely ground to particle diameter distribution for 20-60 μm it
Between mixing superfine powder.Mixing superfine powder to be sent into tablet press machine, pressure obtains a diameter of 36mm for 5.0MPa lower sheetings,
Highly it is the cylindrical piece material material of 12mm.The material is placed on to the microwave voluntarily developed to smelt in furnace of calcium carbide, reaction behaviour
Make step as described in Example 1, be 89.9% through gas chromatographic analysis CO contents, the argon gas isolated recycles.Obtain
Calcium carbide gas forming amount can reach 189.4L/kg.The calcium carbide of generation is sent into acetylene generator and is reacted with water, obtained acetylene
Gas is 87.4% through gas chromatographic analysis content.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not limited to the substantial technological content model of the present invention
Enclose, substantial technological content of the invention is broadly to be defined in the right of application, any technology that other people complete
Entity or method, if with the right of application defined in it is identical, also or a kind of equivalent change, will
It is considered as being covered by among the right.
Claims (9)
- A kind of 1. method of coal base calcium carbide acetylene, it is characterised in that the method includes the steps：(1) microwave heating will be carried out containing the mixed-forming material of coal and calcium source, reaction obtains solid-state calcium carbide；The molding materials It is to obtain the mixture containing coal and calcium source of 30-1000 nanometers of granularity through forming processes；(2) the solid-state calcium carbide of generation is contacted in acetylene generator with water, acetylene gas is obtained through hydrolysis.
- 2. the method as described in claim 1, it is characterised in that the coal is less than 5 centimetres of coal dust for particle diameter；The calcium source choosing Consisting of quicklime or lime stone (calcite), 5 centimetres of powder is less than for particle diameter.
- 3. the method as described in claim 1, it is characterised in that coal dust and calcium source powder in the mixture containing coal and calcium source The molar ratio (in terms of carbon, calcium constituent) at end is 2-4:1.
- 4. the method as described in claim 1, it is characterised in that the forming processes be by the mixture containing coal and calcium source or It is compressing after mixing with binding agent.
- 5. method as claimed in claim 4, it is characterised in that the addition of binding agent is 2-25%；The binding agent is selected from Following one or more：Tar, kerosene, diesel oil, sugar, flour, starch, water.
- 6. the method as described in claim 1, it is characterised in that the microwave heating temperature is 1400-2000 DEG C, reaction pressure For 0.03-1.1atm, reaction time 30-180min.
- 7. such as claim 1-6 any one of them methods, it is characterised in that the step (1) is obtaining the same of solid-state calcium carbide When obtain carbon monoxide content be more than 95% gas.
- 8. the method as described in claim 1, it is characterised in that solid-state calcium carbide described in step (2) is and straight without broken process It is connected in acetylene generator and reacts to obtain acetylene gas with water.
- 9. a kind of system that can be achieved such as claim 1-8 any one of them methods, it is characterised in that the system comprises powder Broken powder unit processed, material plastotype forming unit, calcium carbide generation unit, acetylene generation unit and carbon monoxide cogeneration unit.
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| CN108675911A (en) * | 2018-08-21 | 2018-10-19 | 中国科学院上海高等研究院 | A kind of carbide acetylene production technology for reducing carbide slag and generating |
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