CN100372820C - Process of co-producing acetylene and synthetic gas with petroleum coke and low ash coal - Google Patents
Process of co-producing acetylene and synthetic gas with petroleum coke and low ash coal Download PDFInfo
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- CN100372820C CN100372820C CNB2006101043955A CN200610104395A CN100372820C CN 100372820 C CN100372820 C CN 100372820C CN B2006101043955 A CNB2006101043955 A CN B2006101043955A CN 200610104395 A CN200610104395 A CN 200610104395A CN 100372820 C CN100372820 C CN 100372820C
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Abstract
The process of co-producing acetylene and synthetic gas includes the following steps: mixing and drying petroleum coke and lime powder and spraying to gasifying furnace together with oxygen for partial oxidation reaction to produce molten calcium carbide flowing to back reaction area of the gasifying furnace for further reaction to produce synthetic gas; exhausting the synthetic gas through the pellet filler layer in the upper part of the gasifying furnace, dedusting in the cyclonic separator and ceramic tube filter and recovering afterheat in the afterheat recovering system to generate high and medium pressure steam; chilling the reacted molten calcium carbide with the chilling agent of arene-rich wax oil in the chilling trough below the molten bath to form calcium carbide oil slurry; reducing pressure and temperature of calcium carbide oil slurry and reacting with water in the acetylene generator to produce acetylene and calcium hydroxide.
Description
Technical field
The invention relates to the method for producing acetylene and synthetic gas, belong to technical field of chemical engineering.
Background technology
Along with Chinese national economy is lasting, fast-developing, China's Petrochemical Enterprises for the raw materials requirement that satisfies transport fuel and ethene, chemical fibre, deepened the level of crude oil processing, with the raising light oil yield, by the end of the year 2004, the ability that heavy oil catalytically cracking equipment is had in China has exceeded hundred million tons/year, and the ability of delayed coking unit is above 3,700 ten thousand tons/year.The same year, refinery coke output reached 7,350,000 tons.
According to relevant department's prediction, the burnt output of China's oil will surpass 1,000 ten thousand tons very soon, and wherein many is sulfur-bearing, high sulfur petroleum coke.More and more stricter and oil price constantly rises violently along with environmental requirement, needs the outlet of its economical rationality of research badly.
At present, sulfur-bearing oil Jiao has the fuel as cement baking.Many considerations are as circulating fluidized bed (CFB) boiler oil.The useful refinery coke of Nanjing petroleum chemical enterprise is raw material, adopts the water coal slurry pressure gasification technology to produce synthetic gas, transforms its synthetic ammonia oil head gas making device but all fails to make full use of the low advantage of refinery coke ash, creates higher added value.
No matter it is domestic in recent years in the big moulded coal system oil project of building and planning to build or big moulded coal system methyl alcohol project, mostly introduce external advanced person's dry powder charging fluidized-bed gasification, slag tap, pure oxygen pressurized gasification technology.This technology is relatively more tolerant to the requirement of coal, and to high-sulfur bituminous coal, the hard coal of ash-rich, the brown coal of especially high moisture content, ash-rich can be used.But the gasification furnace structure more complicated, the initial cost expense is higher, and the patent royalties that the foreign trader asks for are quite high.
According to one's analysis, by introducing the gasification technology present situation, if do not improve, then be difficult to give full play to the low advantage of refinery coke ash, with the cost of reduction synthetic gas and the burden of environmental protection, more be difficult to make full use of the high reaction temperature heat energy of pure oxygen gasification refinery coke, to produce high value added product.
China's polyvinyl chloride production capacity had reached 9,720,000 tons/year in 2005, and output is 6,490,000 tons/year, wherein with about about 62% of carbide acetylene production.Estimate that " 11 " five initial stages also can increase.The electric heating process calcium carbide, seriously polluted, current consumption is high, reaches 8,770,000 tons by calcium carbide output in 2005, estimates that annual power consumption is about 31,600,000,000 kilowatts, is about 1.45% of national generating capacity in 2004.Therefore, country classifies the calcium carbide industry as country restriction development class enterprise.Count for survival, the calcium carbide industry should be carried out the energy saving and pollution alleviation technological transformation.
Summary of the invention
According to above-mentioned, for more economical benefit utilize high sulfur petroleum coke, reduce the acetylene cost and alleviate environmental pollution.In order to reduce the methanol production cost, to make the ethene of methanol conversion generation more competitive, we are according to theory, the optimum combination modern technique both domestic and external of recycling economy, carrying out integrated innovation, proposing one is raw material in conjunction with China's national situation, with high sulfur petroleum coke or high-sulfur, low ash coal, lime is the secondary material of circulation, the pure oxygen gasification technology of co-producing acetylene and synthetic gas.
The technical process general introduction.
Refinery coke and lime separated pulverizing to≤1mm with after being dried to moisture content about 2%, are pressurizeed respectively through the lock hopper system and to deliver to separately hopper.
The petroleum coke powder of hopper and lime dry powder is respectively after metering and proportioning separately, delivers to that mixing tank mixes and further drying.Deliver to the spray gun of vapourizing furnace then with nitrogen or synthetic gas, enter the vapourizing furnace reaction chamber by spray gun, carry out partial oxidation reaction with oxygen.Spray gun is inclined in " air port " and has a down dip slightly, and charging tangentially shape is entered in the vapourizing furnace.Vapourizing furnace is established 4 spray guns altogether.
In addition, part refinery coke and lime are made pelletizing by proportioning, add in the stove from top of gasification furnace by the lock hopper system.And with " iron-smelting blast furnace " furnace charge form filling vapourizing furnace.Vapourizing furnace is the pressurized vessel of a liner highiy refractory brick, and the block method of refractory brick is similar to " iron-smelting blast furnace ".
Vapourizing furnace is divided into preheating zone, reduction zone, reaction zone and afterreaction district from top to bottom.
Spray into the charging of reaction in furnace chamber by spray gun, the partial oxidation of the element charcoal of pure oxygen wherein and refinery coke, theoretical combustion temperature will be up to more than 3000 ℃, but, and temperature of reaction is controlled at 2200 ℃～2500 ℃ because the element charcoal of lime in the charging and refinery coke generates the thermo-negative reaction effect of carbide of calcium.The fusion carbide of calcium that generates under this high temperature flow to the afterreaction district and continues reaction.The synthetic gas that generates passes through the pelletizing packing layer on vapourizing furnace top from bottom to top.Its high temperature sensible heat reacts and the generation heat of generation carbide of calcium in order to calcium oxide in the lime in the pelletizing that reaction zone is provided and the element charcoal in the refinery coke successively; Then be used for the preheating pelletizing to the carbide of calcium temperature of reaction in pyrogen district and preheating zone; For the CO2 in impurity in the reducting pellet and the synthetic gas provides heat, last synthetic gas is discharged from the vapourizing furnace upside simultaneously.After passing through cyclonic separator and the dedusting of vitrified pipe strainer successively, enter residual neat recovering system, produce high, middle pressure steam.
The dust that cyclonic separator and vitrified pipe strainer are told returns the pelletizing preparation system, recycling.
The fusion carbide of calcium that the vapourizing furnace reaction zone generates drops to the afterreaction district and continues reaction.
Finish reacted fusion carbide of calcium and flow to the Quench groove that is positioned under the molten bath, carry out cold shock at this with rich aromatic hydrocarbons wax oil and become the carbide of calcium slurry oil through " cinder notch " of afterreaction district molten bath central authorities.Slurry oil liquid level at the Quench groove will be kept corresponding height, with the heat of solidification that guarantees to be arranged on the recyclable fusion carbide of calcium of coil pipe in the groove and high temperature sensible heat thereof to produce middle pressure steam and to keep the slurry oil temperature under the initial boiling point temperature of rich aromatic hydrocarbons wax oil.The middle pressure steam that produces is delivered to heat recovery boiler through the steam groove.
The carbide of calcium slurry oil flow to carbide-feed generator behind the decompression desuperheat, react, generate acetylene and calcium hydroxide at this and the clear water that returns from subsider.Acetylene gas drains into Acetylene Gas Holder from the carbide-feed generator upside, and calcium hydroxide is sink to the producer bottom.
Oil in the carbide-feed generator and calcium hydroxide water slurry converge delivers to separator.At this isolated oil phase that does not contain calcium hydroxide, do the Quench agent with pumped back Quench groove, the calcium hydroxide aqueous slurry is delivered to subsider after cooling, the clear water of overflowing in subsider top, return carbide-feed generator with pump and reuse, bottom calcium hydroxide sediment send filter to filter, and filtrate is returned subsider, filter cake is sent the system of getting the raw materials ready back to after dehydration, drying, recycling.
Should illustrate that though the senior lime impurity that the refinery coke ash less than 0.8%, replenishes is very low, a small amount of filter cake discharging is unavoidable, this filter cake can be sold and make cement raw material.
The invention belongs to the gasification technology of dry powder charging, slag tap.But following characteristics are arranged:
1, refinery coke in the gasified raw material and the O in the lime
2: the ratio of C: CaO is configured by the generation requirement of synthetic gas and carbide of calcium, does not add water vapor.
2, the gasification, and combustion temperature is brought up to 2200 ℃～2500 ℃ with the transformation efficiency of raising refinery coke and the production rate of carbide of calcium.
3, the high temperature sensible heat of synthetic gas carries out the gradient recovery, optimizes and utilize.At first, generate temperature in order to preheating carbide of calcium raw material pelletizing to carbide of calcium then, and be impurity in the reduction and carbonization calcium raw material pelletizing and the CO in the synthetic gas in order to the heat of reaction that generates carbide of calcium to be provided in the vapourizing furnace
2For CO provides heat, at last in order to the feedwater of high, medium and low voltage steam and preboiler to take place.
4, the high temperature cabonization calcium solution is carried out cold shock with rich aromatic hydrocarbons wax oil, and reclaim the heat of solidification and the sensible heat thereof of carbide of calcium, middle pressure steam takes place.
5, the calcium hydroxide Ca (OH) of carbide-feed generator discharge
2Drying, dehydration are re-used as a secondary material recycling of circulation in process of production.
Advantage of the present invention:
(1) the partial oxidation C+1/2O of pure oxygen and elemental carbon
2→ CO, its theoretical flame temperature are higher than 3000 ℃.According to the ultimate analysis of refinery coke, its carbon is nearly 89.55%, with the refinery coke is being raw material when adopting the evaporating method of dry powder charging to produce synthetic gas, the input amount that must strengthen steam with the control gasification temperature in 1600 ℃～1700 ℃ scopes.
The present invention does not add steam, generates needs but press carbide of calcium, strengthens the CaO input amount, and gasification temperature is brought up to 2200 ℃～2500 ℃, equals carbide of calcium and generates temperature.Make this gasifying process can produce synthetic gas, can produce carbide of calcium again.Improve its superiority in economy greatly.Though 2200 ℃ gasification temperature exceeds 400～500 ℃ than the gasification temperature of dry powder charging, the fine coal oxygen enrichment blast furnace of USSR (Union of Soviet Socialist Republics) is operated in being lower than 2300 ℃ of theoretical flame temperature scopes.The hot method calcium carbide of the oxygen in Korea chemical plant vapourizing furnace is operated in 2500 ℃～3000 ℃ scopes.
(2), the evaporating method of the heat of high temperature of the high-temperature synthesis gas dry powder charging of reclaiming, introducing carries out Quench with high-temperature synthesis gas with the normal temperature synthetic gas earlier, then in order to generation high pressure steam.And present technique provides the pyroreaction heat with the high temperature sensible heat of high-temperature synthesis gas for carbide of calcium generates earlier, then in order to high pressure steam to take place.This has improved the economic benefit of heat of high temperature, has saved the power of Quench synthetic gas.
(3), the liquid slag of slag tap vapourizing furnace water Quench commonly used, be difficult to reclaim the heat of solidification and the high temperature sensible heat thereof of liquid slag.The liquid slag of vapourizing furnace of the present invention is that liquid carbide of calcium, amount are big, heat content is high, so the rich aromatic hydrocarbons wax oil of employing carries out Quench and establishes coil pipe at the chiller oil reservoir and reclaimed, middle pressure steam takes place.
(4), the calcium carbide of the hot method generation of electric furnace electric heating process or German CATO oxygen, regularly in stove, discharge, put to the calcium carbide dish, be dragged to cooling room with dolly and carry out naturally cooling, be broken into certain particle size after the cooling, deliver to carbide-feed generator generation acetylene then, the plant area area is big, investment height, severe operational environment, seriously polluted.And present technique at the vapourizing furnace bottom effusive carbide of calcium in molten bath (calcium carbide), becomes slurry oil, delivers to carbide-feed generator generation acetylene through pipeline delumper, reducing valve with rich aromatic hydrocarbons wax oil Quench, and facility compact is taken up an area of little, reduced investment, operating environment is greatly improved.
Description of drawings
Fig. 1 is the process flow sheet of co-producing acetylene and synthetic gas.
1 is loading hopper among the figure, the 2nd, and hybrid heater, the 3rd, spray gun, the 4th, vapourizing furnace, the 5th, cyclonic separator, the 6th, vitrified pipe strainer, the 7th, heat recovery boiler, the 8th, carbide-feed generator, the 9th, separator, the 10th, pump, the 11st, Quench groove, the 12nd, subsider, the 13rd, filter, the 14th, steam groove.
Embodiment
Below in conjunction with accompanying drawing, flow process of the present invention is further introduced.
Petroleum coke powder and lime powder pressurizeed respectively through the lock hopper system deliver to separately hopper 1.The petroleum coke powder of hopper and lime powder be respectively after metering and proportioning separately, delivers to that hybrid heater 2 mixes and further drying.Deliver to the spray gun 3 of vapourizing furnace 4 then with nitrogen carrier gas, enter the reaction chamber of vapourizing furnace 4 by spray gun 3, carry out partial oxidation reaction with oxygen.Spray gun is inclined in " air port " and has a down dip slightly, and charging tangentially shape is entered in the vapourizing furnace.Vapourizing furnace is established 4 spray guns altogether.
In addition, part refinery coke and lime are made pelletizing by proportioning, add in the stove from top of gasification furnace by the lock hopper system.And with " iron-smelting blast furnace " furnace charge form filling vapourizing furnace.Vapourizing furnace is the pressurized vessel of a liner highiy refractory brick, and the block method of refractory brick is similar to " iron-smelting blast furnace ".
Vapourizing furnace is divided into preheating zone, reduction zone, reaction zone and afterreaction district from top to bottom.
Spray into the charging of reaction in furnace chamber by spray gun 3, the partial oxidation of the element charcoal of pure oxygen wherein and refinery coke, theoretical combustion temperature will be up to more than 3000 ℃, but, and temperature of reaction is controlled at 2200 ℃～2300 ℃ because the element charcoal of lime in the charging and refinery coke generates the thermo-negative reaction effect of carbide of calcium.The fusion carbide of calcium that generates under this high temperature flow to the afterreaction district and continues reaction.The synthetic gas that generates passes through the pelletizing packing layer on vapourizing furnace top from bottom to top.Its high temperature sensible heat reacts and the generation heat of generation carbide of calcium in order to calcium oxide in the lime in the pelletizing that reaction zone is provided and the element charcoal in the refinery coke successively; Then be used for the preheating pelletizing to the carbide of calcium temperature of reaction in pyrogen district and preheating zone; For the CO2 in impurity in the reducting pellet and the synthetic gas provides heat, last synthetic gas is discharged from the vapourizing furnace upside simultaneously.After passing through cyclonic separator 5 and 6 dedustings of vitrified pipe strainer successively, enter heat recovery boiler 7, produce high, middle pressure steam.
The dust that cyclonic separator 5 and vitrified pipe strainer 6 are told returns the pelletizing preparation system, recycling.
The fusion carbide of calcium that the vapourizing furnace reaction zone generates drops to the afterreaction district and continues reaction.
Finish reacted fusion carbide of calcium and flow to the Quench groove 11 that is positioned under the fusion pool, carry out cold shock at this with rich aromatic hydrocarbons wax oil and become the carbide of calcium slurry oil through " cinder notch " of afterreaction district molten bath central authorities.Slurry oil liquid level at the Quench groove will be kept corresponding height, with the heat of solidification that guarantees to be arranged on the recyclable fusion carbide of calcium of coil pipe in the groove and high temperature sensible heat thereof to produce middle pressure steam and to keep the slurry oil temperature under the initial boiling point temperature of rich aromatic hydrocarbons wax oil.The middle pressure steam that produces is delivered to heat recovery boiler 7 through steam groove 14.
The carbide of calcium slurry oil flow to carbide-feed generator 8 behind the decompression desuperheat, react at this and the clear water that returns from subsider 12, generates acetylene and calcium hydroxide.Acetylene gas drains into Acetylene Gas Holder from the carbide-feed generator upside, and calcium hydroxide is sink to the producer bottom.
Oil in the carbide-feed generator and calcium hydroxide water slurry converge delivers to separator 9.At this isolated oil phase that does not contain calcium hydroxide, send Quench groove 11 back to pump 10 and do the Quench agent, the calcium hydroxide aqueous slurry is delivered to subsider 12 after cooling, the clear water that subsider 12 upsides are overflowed, return carbide-feed generator 8 with pump and reuse, bottom calcium hydroxide sediment send filter 13 to filter, and filtrate is returned subsider, filter cake is sent the system of getting the raw materials ready back to after dehydration, drying, recycling.
Embodiment
With per hour 37.5 tons (anhydrous ashless) refinery cokes is raw material, adopts this gasification process, can produce 7.2 tons/hour of acetylene, (CO+H
2) gas 91360NM
3/ hour, in order to be processed as methyl alcohol, can get 40.90 tons/hour of methyl alcohol.
37.5 the refinery coke of ton (anhydrous ashless) is divided into two portions and adds vapourizing furnace, 23.37 tons of wherein a part of refinery cokes are equipped with 5.17 tons in lime, behind combination drying with 33.870NM
3Oxygen is sent into the vapourizing furnace reaction chamber by spray gun together, carries out partial oxidation reaction under 2200 ℃～2500 ℃ of temperature and pressure 10～30 atmospheric pressure, and the fusion carbide of calcium of generation drops to vapourizing furnace afterreaction district.Another part refinery coke is equipped with 14.30 tons in lime for 14.13 tons and makes pelletizing in gasification furnace roof adding stove.Pelletizing reacts at reaction zone from top to bottom with from vapourizing furnace reaction chamber pyroreaction gas from bottom to top.The fusion carbide of calcium that generates drops to the afterreaction district, reaction gas reduce by vapourizing furnace reduction zone and preheating zone successively and heat exchange after, discharge from the vapourizing furnace upside, its tolerance is about 93.890N/M
3/ hour.
22.18 tons of fusion carbide of calcium of discharging from vapourizing furnace afterreaction district are the Quench groove carries out cold shock to 325 ℃ with the rich aromatic hydrocarbons wax oil of capacity below, the slurry oil that forms is again with after being water-cooled to 70～80 ℃, flow to carbide-feed generator, react at this and an amount of water, the acetylene of generation is about 7.2 tons; The calcium hydroxide aqueous slurry that generates is with after chill oil separates, the calcium hydroxide aqueous slurry is after sedimentation, clarification, filtration, and clear water returns carbide-feed generator, after filter cake drying, the dehydration, return the feed circuit recycling, return the recycling of Quench groove from the isolated chill oil of separator.
Claims (6)
1. the technology for preparing acetylene and synthetic gas, it is characterized in that, refinery coke is mixed and further drying through hybrid heater (2) with lime powder, enter the reaction chamber of vapourizing furnace (4) by spray gun (3) with oxygen, carry out partial oxidation reaction, the afterreaction district that the fusion carbide of calcium that generates flow to vapourizing furnace (4) continues reaction, the synthetic gas that generates passes through the pelletizing packing layer on vapourizing furnace (4) top from bottom to top, its high temperature sensible heat reacts and the generation heat of generation carbide of calcium in order to calcium oxide in the lime in the pelletizing that reaction zone is provided and the element charcoal in the refinery coke successively, then be used for the preheating pelletizing to the carbide of calcium temperature of reaction in pyrogen district and preheating zone, provide heat for the CO2 in impurity in the reducting pellet and the synthetic gas simultaneously, last synthetic gas is discharged from the vapourizing furnace upside, after passing through cyclonic separator (5) and vitrified pipe strainer (6) dedusting successively, enter residual neat recovering system (7), produce high, middle pressure steam;
The fusion carbide of calcium that the vapourizing furnace reaction zone generates drops to the afterreaction district and continues reaction;
Finish reacted fusion carbide of calcium and flow to the Quench groove (11) that is positioned under the molten bath through " cinder notch " of afterreaction district molten bath central authorities, doing the Quench agent at this with rich aromatic hydrocarbons wax oil carries out cold shock and becomes the carbide of calcium slurry oil, the carbide of calcium slurry oil is behind the decompression desuperheat, flow to carbide-feed generator (8), react, generate acetylene and calcium hydroxide at this and the clear water that returns from subsider (12), acetylene gas drains into Acetylene Gas Holder from the carbide-feed generator upside, and calcium hydroxide is sink to the carbide-feed generator bottom;
Refinery coke and lime are made pelletizing by proportioning simultaneously, add in the stove from top of gasification furnace by the lock hopper system, and with furnace charge form filling vapourizing furnace, vapourizing furnace is the pressurized vessel of a liner highiy refractory brick.
2. according to the preparation acetylene of claim 1 and the technology of synthetic gas, it is characterized in that the described dust of being told through cyclonic separator (5) and vitrified pipe strainer (6) returns the pelletizing preparation system, recycling.
3. according to the preparation acetylene of claim 1 and the technology of synthetic gas, it is characterized in that, the slurry oil liquid level of described Quench groove (11) will be kept corresponding height, with the heat of solidification that guarantees to be arranged on the recyclable fusion carbide of calcium of coil pipe in the groove and high temperature sensible heat thereof to produce middle pressure steam and to keep the slurry oil temperature under the initial boiling point temperature of rich aromatic hydrocarbons wax oil.
4. according to the preparation acetylene of claim 1 and the technology of synthetic gas, it is characterized in that described spray gun is inclined in " air port " and has a down dip slightly, and charging tangentially shape is entered in the vapourizing furnace, vapourizing furnace is established 4 spray guns altogether.
5. according to the preparation acetylene of claim 1 and the technology of synthetic gas, it is characterized in that described vapourizing furnace (4) is divided into preheating zone, reduction zone, reaction zone and afterreaction district from top to bottom.
6. according to the preparation acetylene of claim 1 and the technology of synthetic gas, it is characterized in that, oil in the described carbide-feed generator (8) and calcium hydroxide water slurry converge delivers to separator (9), at this isolated oil phase that does not contain calcium hydroxide, do the Quench agent with pumped back Quench groove, the calcium hydroxide aqueous slurry is delivered to subsider (12) after cooling, the clear water of overflowing in subsider top, returning carbide-feed generator (8) with pump reuses, bottom calcium hydroxide sediment send filter to filter (13), filtrate is returned subsider, and filter cake is through dehydration, send the system of getting the raw materials ready after the drying back to, recycling.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101043955A CN100372820C (en) | 2006-08-11 | 2006-08-11 | Process of co-producing acetylene and synthetic gas with petroleum coke and low ash coal |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101043955A CN100372820C (en) | 2006-08-11 | 2006-08-11 | Process of co-producing acetylene and synthetic gas with petroleum coke and low ash coal |
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| CN1887830A CN1887830A (en) | 2007-01-03 |
| CN100372820C true CN100372820C (en) | 2008-03-05 |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101525118B (en) * | 2008-03-07 | 2010-12-22 | 周开根 | Gasification process for producing synthesis gas from garbage and biomass raw materials |
| CN102153085B (en) * | 2010-12-03 | 2013-10-16 | 中国五环工程有限公司 | Method for preparing calcium carbide and synthesis gas through thermal oxidation reaction and calcium carbide reactor |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0068303A2 (en) * | 1981-06-24 | 1983-01-05 | Hoechst Aktiengesellschaft | Process for the manufacture of calcium carbide |
| WO1990015296A1 (en) * | 1989-06-10 | 1990-12-13 | September 27 Research Institute, Hamhung Branch, Academy Of Sciences | Calcium carbide production furnace by oxy-thermal process |
| CN1283586A (en) * | 1999-11-08 | 2001-02-14 | 许绍良 | Energy-saving low-pollution process for preparing raw material of calcium carbide furnace |
-
2006
- 2006-08-11 CN CNB2006101043955A patent/CN100372820C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0068303A2 (en) * | 1981-06-24 | 1983-01-05 | Hoechst Aktiengesellschaft | Process for the manufacture of calcium carbide |
| WO1990015296A1 (en) * | 1989-06-10 | 1990-12-13 | September 27 Research Institute, Hamhung Branch, Academy Of Sciences | Calcium carbide production furnace by oxy-thermal process |
| CN1283586A (en) * | 1999-11-08 | 2001-02-14 | 许绍良 | Energy-saving low-pollution process for preparing raw material of calcium carbide furnace |
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