CN101186291A - Composite carbon element material and preparation method thereof - Google Patents
Composite carbon element material and preparation method thereof Download PDFInfo
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- CN101186291A CN101186291A CNA2007101428026A CN200710142802A CN101186291A CN 101186291 A CN101186291 A CN 101186291A CN A2007101428026 A CNA2007101428026 A CN A2007101428026A CN 200710142802 A CN200710142802 A CN 200710142802A CN 101186291 A CN101186291 A CN 101186291A
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Abstract
The invention relates to a composite carbon material with unique properties and a preparation method thereof, in particular to a composite carbon material which can replace coke, one of the raw material of calcium carbide production and a preparation method thereof, which pertains to the technical field of calcium carbide industry with energy saving and environmental protection. The invention is characterized in that: slack coal, coke powder, asphalt and slight of additive are taken as raw materials to produce composite carbon material and the produced composite carbon material meets the requirements of calcium carbide production and can totally replace coke, thus being applied to the calcium carbide production. The iodine value containing in the composite carbon material is 488mg/g while in material that takes coke as raw material is only 216mg/g, which shows that the composite carbon material replacing coke can improve production efficiency. The slack coal and coke powder are taken as main raw materials, the asphalt is taken as binder, and then aluminium oxide is added as additive of main component, thereby improving the high temperature performance of carbon material. The prescription of the raw materials is 40-80 percent of slack coal, 10-30 percent of soft coal, 2-12 percent of asphalt, 2-5 percent of aluminum compound. The technique of producing carbon material is also invented and the technical key point of the technique is the added sintering process, which is significant technical breakthrough in briquette technology field. In order to guarantee the smooth operation of the technique during the industrial production, a baking furnace, a forming machine and a mixing device are modified according to the requirements.
Description
Technical field
The present invention relates to a kind of composite carbon element material and preparation method, especially relate to and a kind ofly can substitute one of calcium carbide raw materials for production--composite carbon element material and the preparation method of-----coke belong to calcium carbide industry energy-saving environmental technology field with special performance.
Technical background
The polyvinyl chloride resin market requirement of China is huge, has reached 4500Kt/a in the production capacity of domestic PVC production equipment in 2005, and wherein the polyvinyl chloride resin with carbide acetylene method production reaches 3200Kt/a, accounts for 73% of resin total amount.Therefore, the market demand of calcium carbide is very big.Along with the raising of country about the environmental protection standard of furnace of calcium carbide and internal combustion type furnace of calcium carbide, add all multifactor impacts such as electric power, electricity price, raw material in recent years, supply with the situation of anxiety at the raw material (especially coke) that calcium carbide manufacturing enterprise all can occur recent and at a specified future date.Yet, because a variety of causes, be used for producing the main raw material lump coal and the coke of calcium carbide, go into the stokehold and will sift out about 20% the powder that accounts for lump coal and total coke, the value of these powder is far below original lump coal or lump coke, thereby causes the calcium carbide production cost further to rise; If these powder are not used appropriately, also will cause problem of environmental pollution.Research and development utilize the preparation technology of the coal dust, coke powder and other solid waste (as refinery coke, waste Crumb rubber etc.) production composite carbon element material that produce in the calcium carbide production process, produce the qualified composite carbon element material of performance to substitute one of calcium carbide raw materials for production---block coke or lump coal, on the one hand, can solve useless admittedly problem of complex utilization such as the depleted coal dust of calcium carbide in producing, coke powder, enlarge the raw material sources that calcium carbide is produced; Can reduce the raw materials cost that calcium carbide is produced on the other hand greatly; Simultaneously, also help the production of solution calcium carbide problem of environmental pollution that causes and the productivity that improves calcium carbide production.
Summary of the invention
Based on above-mentioned cognition, we have developed with smalls, coke powder, pitch and a small amount of additive is the technology of raw material production composite carbon element material, and the composite carbon element material performance of producing sees Table 1.
The main quality index of table 1 composite carbon element material
| Quality index | Record empirical value |
| Average cold ultimate compression strength (kilogram /) | 57 |
| Average cold ultimate compression strength (kilogram /) | 36 |
| Ash content (%) | 13.62 |
| Volatile matter (%) | 1.87 |
| Moisture (%) | 2.73 |
| Fixed carbon (%) | 81.78 |
| Shatter strength (M 40，％) | 73.5 |
| Abrasive wear resistance (M 10，％) | 9.9 |
| Porosity (%) | 25.3 |
| Than resistance, U Ω M | 5627 |
| Iodine number, mg/g | 488 |
Compare the requirement (in detail see GB1996-80) of calcium carbide production to coke: ash content is less than 15%, shatter strength is greater than 65%, abrasive wear resistance is not more than 11% etc., as seen we have reached the calcium carbide production requirement in the quality of the composite carbon element material of Laboratory Production, can substitute coke in theory fully and be used for calcium carbide production.As for from characterize the composite carbon element material surface-area what, and then the iodine number that can react it and calcium based compound reactive behavior is seen, composite carbon element material is 488mg/g, and have only 216mg/g by the sample coke that company provides, this shows with the alternative coke of composite carbon element material to have the potential that improves furnace of calcium carbide production efficiency.In addition, the raw material of producing composite carbon element material is fully based on the resource and the utilization of waste material of this locality, so it is secure to produce the raw material of composite carbon element material.
Why carbon materials with above-mentioned quality index can obtain, fully based on following summary of the invention:
A, the choose reasonable of producing the raw material of carbon materials:
Based on following two principles: solid waste utilization and making rational use of resources, we select for use coke powder and fine coal as the main raw material of producing carbon materials, with pitch is binding agent, and adding a small amount of again is that the additive of main component is in order to improve the high-temperature behavior of carbon materials with the aluminum oxide.
B, invented suitable composition of raw materials: coke powder content: 40-80%; Bituminous coal content: 10-30%; Asphalt content: 2-12%; Aluminium porcelain enamelling content: 2-5%.
C, the technology of having invented suitable production carbon materials:
The production technique of the production composite carbon element material that we develop is seen Figure of description.
Description of drawings
Figure is a process flow sheet.As can be seen from the flow chart, the flow process before the granulating working procedure and traditional briquette production technology and it makes no odds.The key problem in technology of this technical process is to have increased the calcination operation.This procedure has been arranged, and the hot compressive strength of the composite carbon element material of producing can guarantee to meet the requirement of calcium carbide production to carbon materials, simultaneously, accomplishes that again ash content does not exceed standard, and this is a major technological breakthrough at the moulded coal sciemtifec and technical sphere.In order to guarantee this technical process smooth implementation in industrial production, we have also carried out necessary and transformation uniqueness to relevant device, as stoving oven, shaper with mix the equipment of pinching.
Specific embodiments
Finished composite carbon element material and substituted the commerical test of coke, and obtained success, following is specific embodiment.
1, material choice and burden process: material choice has the bigger cold ultimate compression strength except guaranteeing the moulded coal of producing, and also must satisfy following 2 requirements.For the carbon materials that the present invention is produced has higher hot compressive strength, must be to one of the moulded coal produced critical process by the present invention: calcination process.Because moulded coal calcination process disclosed by the invention is finished by stoving oven, and the required heat of stoving oven is obtained by the volatile matter that briquet discharges during high-temperature calcination under reducing atmosphere, so, when determining composition of raw materials, must guarantee that moulded coal has enough volatile matters, so that by these volatile matters of burning, make the temperature of stoving oven can reach the required temperature of calcining moulded coal: 1100 ℃, the volatile matter that requires moulded coal usually is greater than 13%; In addition, produce the specification of quality of stove to carbon materials according to calcium carbide, the fixed carbon of the carbon materials that obtains after the calcination of moulded coal process is greater than 80%, so, when determining composition of raw materials, also must consider the fixed carbon problem.Based on above-mentioned 2 considerations, the prescription that we select for use is: bituminous coal is 20%, and coke powder is 70%, and pitch is 8%, and aluminium porcelain enamelling is 2%.
2, the production technique of carbon materials:
A, compounding process: adopt the mixing procedure of heating.Because this production technique is to utilize pitch as briquette binder, and pitch only is higher than 110 ℃ and just has adhesive property, various raw materials could be mixed, so mixing procedure has to adopt the mixing procedure of heating, mixture temperature is 120 ℃.
B, molding procedure: the raw material that mixes is delivered to the rod shaper is carried out moulding, to obtain moulded coal.The shape of moulded coal is relevant with the purposes of carbon materials, and this example adopts ellipse; Forming pressure is 300-450KG/CM
2
C, calcination process: the moulded coal that moulding is obtained is delivered to stoving oven and is carried out calcination, to obtain to have the carbon materials of higher hot and cold ultimate compression strength.Calcining temperature is 1100 ℃, and calcination time is 5 hours.
D, screening operation: will sieve by the carbon materials that calcination process obtains, granularity reaches the carbon materials confession furnace of calcium carbide usefulness that calcium carbide is produced the stove requirement, and granularity does not reach requirement, is back to burden process, is reused for production.By above-mentioned production technique, giving up with the solid of the former metal and stone chemical inc in sky---coke powder is a main raw material, has prepared nearly 300 tons of composite carbon element materials.The quality index such as the following table 2 of carbon materials closed in this reply:
The main quality index of table 2 composite carbon element material
| Index | Analytical results |
| Shape | The pillow type |
| Sample maximal side (MM) | 25 |
| Fixed carbon (%) | 86 |
| Volatile matter (%) | 2.0 |
| Moisture (%) | 1.0 |
| Ash content (%) | 12.0 |
| Cold ultimate compression strength (KG/) | 49 |
| Hot compressive strength (KG/) | 28 |
| Abrasive wear resistance (M 10) | ＜11％ |
| Porosity (%) | 23.7 |
| Than resistance (U Ω M) | 4913 |
Can find out that from These parameters the quality of this batch composite carbon element material meets calcium carbide production basically to main raw material--the specification of quality of-coke.On the theoretical analysis angle, this batch composite carbon element material can substitute coke, is used for actual calcium carbide production.Just the intensity of sample and the level that the laboratory is obtained also have some gaps, and this may be regular not enough relevant with production unit.
Based on above-mentioned analysis, three and carbon element company limited, day former metal and stone chemical industry limited liability company and China Mining Univ. (Beijing) through holding a conference or consultation decision: on April 6th, 2007 began, to April 11, substitute the original coke that uses with this batch composite carbon, on the 20000KVA furnace of calcium carbide (No. 2 stoves) of the former metal and stone chemical industry in sky limited liability company, carry out commerical test.Whole test divides three phases to carry out:
1) composite carbon element material substitutes 20% of total carbon, and 80% remaining carbon is by coke (fixed carbon of the coke that is used to test is 81%, and volatilization is divided into 2.5%) and hard coal (the anthracitic ature of coal of test usefulness: fixed carbon 79%; Volatile matter 7%) supplies with.Concrete batching is: composite carbon: 140KG; Coke: 140KG; Hard coal: 420KG.
2) when finishing the fs (24 hours), find that furnace of calcium carbide is working properly, and calcium carbide output, quality and power consumption be when becoming better to some extent all, carry out the subordinate phase test: substitute 40% of total carbon with composite carbon element material, 60% remaining carbon is provided by hard coal.Concrete batching is: composite carbon: 280KG; Hard coal: 420KG, promptly all coke is all replaced by composite carbon.3) finish (24 hours) after the subordinate phase, find that furnace of calcium carbide is working properly, and calcium carbide output, quality and power consumption be when still becoming better, carry out the phase III test: substitute 50% of total carbon with composite carbon element material, 50% remaining carbon is provided by hard coal.Concrete batching is: composite carbon: 350KG; Hard coal: 350KG.Should be pointed out that conversion must have long transition period between implementation phase, could forward another kind of carbon amount to by the alternative ratio of a kind of carbon amount like this and substitute ratio.In this transition period, the discovery furnace of calcium carbide is produced steady running in the same old way.
After above-mentioned three phases test, when finding to carry out the phase III, furnace of calcium carbide calcium carbide output has increased 2-3%; Calcium carbide product hot sample gas forming amount in stokehold is 297L/KG, and 289L/KG has than usual increased the 8L gas forming amount, shows that the calcium carbide quality also obviously improves; The ton power consumption of producing calcium carbide is below 3270KWH, and nearly 70KWH has than usual descended; In addition, find that also the calcium carbide current that calcium carbide comes out of the stove in the process are relatively good, help shortening and come out of the stove the time, improve the output of furnace of calcium carbide.
The parameter index measurement result mean value that relates to environmental problem in the process of the test sees the following form 3.Numerical value is the mean value of the test data that can collect in the table.
Table 3 stack gas test result
As can be seen from Table 3, behind alternative coke of composite carbon element material and hard coal, flue-gas temperature has descended, and flue dust has reduced, so the utilization ratio of material carbon has improved.In addition, oxygen concentration also increases in the flue gas, and it is more thorough to show that the reaction of carbon reduction calcium oxide is carried out.The reduction of smoke moisture means that then the moisture that composite carbon is brought into lacks than coke and hard coal.In a word, carrying out calcium carbide production with composite carbon coke for replacing and hard coal, from this experiment, is fully feasible.
Claims (5)
1. the material choice of composite carbon element material:
With smalls, coke powder, pitch and a small amount of additive is the raw material production composite carbon element material, and the quality of the composite carbon element material of production has reached the calcium carbide production requirement, can substitute coke fully and be used for calcium carbide production.
2. composite carbon element material composition of raw materials: selecting for use coke powder and fine coal as main raw material, is binding agent with pitch, and the additive that adds aluminum oxide again and be main component is in order to improve the high-temperature behavior of carbon materials.It is characterized in that: coke powder accounts for 40-80%; Bituminous coal accounts for 10-30%; Pitch accounts for 2-12%; Aluminium porcelain enamelling accounts for 2-5%.
3. Du Te composite carbon element material production technique:
The main composition operation of this production technique:
A) burden process: prepare burden by given prescription.
B) compounding process: adopt the mixing procedure of heating, various raw materials could be mixed, so mixing procedure has to adopt the mixing procedure of heating, mixture temperature is 120 ℃.
C) molding procedure: the raw material that mixes is delivered to the rod shaper is carried out moulding, to obtain moulded coal.The shape of moulded coal is relevant with the purposes of carbon materials, and this example adopts ellipse; Forming pressure is 300-450KG/CM
2
D) calcination process: the moulded coal that moulding is obtained is delivered to stoving oven and is carried out calcination, to obtain to have the carbon materials of higher hot and cold ultimate compression strength.Calcining temperature is 1100 ℃, and calcination time is 5 hours.
The key of producing the satisfied composite carbon element material of quality is to develop suitable production technique.Briquette production technology based on commonly used in conjunction with the specification of quality of composite carbon element material, has increased moulded coal calcination operation, to guarantee composite carbon element material high hot compressive strength is arranged, and this is a moulded coal sciemtifec and technical sphere major technological breakthrough.The feature of calcination process is: moulded coal calcination operation is finished by stoving oven, and the required heat of stoving oven is obtained by the volatile matter that briquet discharges during high-temperature calcination under reducing atmosphere, must guarantee that moulded coal has enough volatile matters, make the temperature of stoving oven can reach the required temperature of calcining moulded coal: 1100 ℃, the volatile matter that requires moulded coal usually is greater than 13%.
4. the production unit of Zhuan Yong composite carbon element material:
These specific equipments are characterized as: the mixer that a) is used for mixing raw material has the mixture temperature controlled function, and temperature controlling range is 50-200C °.B) be used for moulded coal incinerating stoving oven and have heat energy that utilizes the intrinsic volatilization branch of moulded coal and the function of regulating calcining temperature automatically, the calcining temperature regulation range is: 850-1200C °.
5. the composite carbon element material of unique properties:
The alternative coke of this composite carbon element material is used for calcium carbide production; Alternative anthracite block coal or coke are used for producer gas generator gas making.Its main quality index is:
The main quality index of composite carbon element material
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| CNA2007101428026A CN101186291A (en) | 2007-07-27 | 2007-07-27 | Composite carbon element material and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102275920A (en) * | 2011-05-31 | 2011-12-14 | 宁夏兴平精细化工股份有限公司 | Method for synthesizing calcium carbide smelting raw material by extruding calcined coal powder and lime powder |
| CN102408104A (en) * | 2011-08-02 | 2012-04-11 | 杭州福康炊具有限公司 | Carbon material shaping method |
| CN104480302A (en) * | 2014-11-26 | 2015-04-01 | 北京神雾环境能源科技集团股份有限公司 | Agglomerating method of pellets containing superfine pulverized coal and superfine quicklime powder |
| CN112837842A (en) * | 2021-01-05 | 2021-05-25 | 商都中建金马冶金化工有限公司 | Electrode paste and preparation method thereof |
-
2007
- 2007-07-27 CN CNA2007101428026A patent/CN101186291A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102275920A (en) * | 2011-05-31 | 2011-12-14 | 宁夏兴平精细化工股份有限公司 | Method for synthesizing calcium carbide smelting raw material by extruding calcined coal powder and lime powder |
| CN102408104A (en) * | 2011-08-02 | 2012-04-11 | 杭州福康炊具有限公司 | Carbon material shaping method |
| CN104480302A (en) * | 2014-11-26 | 2015-04-01 | 北京神雾环境能源科技集团股份有限公司 | Agglomerating method of pellets containing superfine pulverized coal and superfine quicklime powder |
| CN112837842A (en) * | 2021-01-05 | 2021-05-25 | 商都中建金马冶金化工有限公司 | Electrode paste and preparation method thereof |
| CN112837842B (en) * | 2021-01-05 | 2022-12-13 | 商都中建金马冶金化工有限公司 | Electrode paste and preparation method thereof |
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Open date: 20080528 |