CN102220179A - Productive technology of high energy low sulphur coal - Google Patents

Productive technology of high energy low sulphur coal Download PDF

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Publication number
CN102220179A
CN102220179A CN2010101481725A CN201010148172A CN102220179A CN 102220179 A CN102220179 A CN 102220179A CN 2010101481725 A CN2010101481725 A CN 2010101481725A CN 201010148172 A CN201010148172 A CN 201010148172A CN 102220179 A CN102220179 A CN 102220179A
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China
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carbon black
coal
coarse carbon
sodium
high energy
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CN102220179B (en
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许文姬
李国声
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Southern China Renewable Resources (zhongshan) Co Ltd
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Southern China Renewable Resources (zhongshan) Co Ltd
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Priority to CN 201010148172 priority Critical patent/CN102220179B/en
Priority to PCT/CN2010/075545 priority patent/WO2011127700A1/en
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L9/00—Treating solid fuels to improve their combustion
    • C10L9/02—Treating solid fuels to improve their combustion by chemical means
    • C10L9/06—Treating solid fuels to improve their combustion by chemical means by oxidation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L5/00—Solid fuels
    • C10L5/02—Solid fuels such as briquettes consisting mainly of carbonaceous materials of mineral or non-mineral origin
    • C10L5/04—Raw material of mineral origin to be used; Pretreatment thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L5/00—Solid fuels
    • C10L5/02—Solid fuels such as briquettes consisting mainly of carbonaceous materials of mineral or non-mineral origin
    • C10L5/06—Methods of shaping, e.g. pelletizing or briquetting
    • C10L5/10—Methods of shaping, e.g. pelletizing or briquetting with the aid of binders, e.g. pretreated binders
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L5/00—Solid fuels
    • C10L5/02—Solid fuels such as briquettes consisting mainly of carbonaceous materials of mineral or non-mineral origin
    • C10L5/34—Other details of the shaped fuels, e.g. briquettes
    • C10L5/36—Shape
    • C10L5/361—Briquettes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L5/00—Solid fuels
    • C10L5/40—Solid fuels essentially based on materials of non-mineral origin
    • C10L5/48—Solid fuels essentially based on materials of non-mineral origin on industrial residues and waste materials
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L9/00—Treating solid fuels to improve their combustion
    • C10L9/10—Treating solid fuels to improve their combustion by using additives

Abstract

The invention discloses a productive technology of high energy low sulphur coal, which comprises the following steps of: carrying out artificial aging on crude carbon black to ensure that the internal surface area of the crude carbon black is increased by more than 4 times; carrying out vapor treatment on the crude carbon black subjected to the artificial aging; carrying out sealing treatment on voids of the crude carbon black by using a sealant; using the processed crude carbon black as a main material, and adding compatible materials into the main material, wherein the weight percent of the main material is 45% to 60%; and preparing finished coal from the material. After the novel high energy coal prepared by the productive technology is synthesized, the advantages, such as high fixed carbon content, low ash content and few volatile matters of the carbon black are fully reflected, and the advantages and social economy benefits of the crude carbon black as the solid fuels are achieved. Meanwhile, the problem that the carbon black with low value is difficult to dispose is completely solved.

Description

The production technique of high energy low sulphur coal
Technical field
The present invention discloses a kind of production technique of coal, particularly a kind of production technique of high energy low sulphur coal.
Background technology
For a long time, coal industry is subjected to the great attention of country always, particularly to eco-environment restoration and improvement, adjusts coal resources tax etc., and country strengthens regulatory efforts to the exploitation of special coal simultaneously.Coal price rises, and coal is shortage still.Along with the application in people's life of organic chemistry product is more and more, the generation of organic waste is also more and more.At present, known can produce the cinder coarse carbon black in plastic waste, the damaged tire oil refining process, because impurity is more in the cinder coarse carbon black (carbon black) of its generation, economic worth is low, cause the producer disorderly bury, disorderly abandon or huddle long-pending, phenomenon, havoc soil and atmospheric environment such as can't handle.And according to the existing thinking notion of existing society, chemical circles generally believes that carbon black is a kind of fixed carbon height, burning-point height, burns slowly, ratio of carbon-hydrogen approximate 1 to 0.In the burning of reality, carbon black can not mix with airborne oxygen is full and uniform, combustion conditions can not reach desired level, thermosteresis significantly increases, in use gap is very big for theoretical calorific value and actual calorific value, its calorific value can't be compared with coal, therefore it is believed that so far to use coarse carbon black (carbon black).
Summary of the invention
The shortcoming of not having economic worth at the above-mentioned coarse carbon black of mentioning of the prior art as solid fuel, the invention provides the method for a kind of employing coarse carbon black (carbon black) as high energy, doctor negative fat coal, coarse carbon black (carbon black) had especially solved the conversion direction difficult problem of low value coarse carbon black (carbon black) to high-value product not as thinking that solid fuel is used since this method had changed always.
The technical scheme that the present invention solves its technical problem employing is: a kind of production technique of high energy low sulphur coal, this technology comprises the steps:
A, coarse carbon black is carried out preaging;
B, be to carry out steam treatment, 25 minutes-35 minutes treatment time under the condition of 2.8MPa-3.2MPa with the coarse carbon black after the preaging at pressure;
C, the coarse carbon black that will handle add the compatibility material therein as major ingredient, form coal-based material, and wherein major ingredient shared weight percent in coal-based material is 45%-60%;
D, coal-based material is made readymade coal.
The technical scheme that the present invention solves its technical problem employing further comprises:
Also include step B1 between described step B and the step C, step B1 is in the coarse carbon black after steam treatment, adds sodium-chlor.
Among the described step B1, with the sodium-chlor dissolving, form sodium chloride solution earlier, sodium chloride solution is adopted Sprayable to be sprayed on the coarse carbon black surface again, the straying quatity of sodium-chlor is that the weight ratio of sodium-chlor and coarse carbon black is 2: 100-4: 100.
Described sodium chloride solution is with in per minute 8000-12000 rpm the high speed rotating atomizer spray regime adding coarse carbon black.
Preaging is to adopt ozone oxidation or warm air oxidation in the described steps A.
The compatibility material is raw coal, ferrocene, six methynes, four ammoniums, sodium hydroxide, unslaked lime and cakingagent among the described step C, wherein the shared weight percent of raw coal is 30%-35%, the shared weight percent of ferrocene is 0.2%-0.4%, the shared weight percent of six methynes, four ammoniums is 0.4%-0.6%, the shared weight percent of sodium hydroxide is 1.3%-1.7%, the shared weight percent of unslaked lime is 4%-6%, and remaining uses the cakingagent polishing.
Described ferrocene utilizes diesel oil to dissolve earlier, and the weight ratio of ferrocene and diesel oil is 1: 2-1: 1, add with per minute 8000-12000 rpm of high speed rotating atomizer spray regime then.
Adopt rare Summoning oxide compound as catalyzer among the described step C.
Described rare Summoning oxide compound adopts V 2O 5
Described V 2O 5Add-on be the 0.1%-0.3% of gross weight.
The invention has the beneficial effects as follows: after the novel high-energy coal of making by technology of the present invention is synthetic, demonstrated fully sooty fixed carbon height, ash content is little, fugitive constituent is little favourable condition, achieved coarse carbon black as solid-fuelled advantage and economic results in society.Result through check is: ash content 6.58%, volatile matter 8-11% (ratio on synthetics is decided), 1 grade of characteristic of char residue, full sulphur 0.2-0.5%, fixed carbon 95%, thermal value 7850kcal/kg, above-mentioned check data shows that the value of this synthetic coal is high, quality good.Meanwhile, solve the low value sooty fully and be difficult to disposal concerns.
The present invention will be further described below in conjunction with the drawings and specific embodiments.
Description of drawings
Fig. 1 is technological process of production figure of the present invention.
Embodiment
Present embodiment is the preferred embodiment for the present invention, and other all its principles are identical with present embodiment or proximate with basic structure, all within protection domain of the present invention.
The coarse carbon black (or also can be called carbon black) that the present invention adopts plastic waste, damaged tire (factory's particle of polyethylene, polypropylene, polystyrene) to produce is made the high-energy coal for raw materials for production, and concrete processing step can adopt following several embodiment to be specifically described:
Embodiment one:
A, coarse carbon black is carried out preaging, make the internal surface area of coarse carbon black increase more than 4 times, to increase the oxygen functional group in the coarse carbon black, because most coarse carbon blacks (the particularly coarse carbon black of thermal process generation) are smooth atresias, the outside crystallization of coarse carbon black particle is more orderly, and the relatively poor characteristics of the preface of particle inside, in the present embodiment, coarse carbon black is changed the coarse carbon black specific volume by preaging means such as ozone oxidation or hot gas oxidations, during preaging, adopt the ready-made a whole set of oxidizing carbon black through ozone equipment in market, coarse carbon black is carried out preaging, the internal surface area of coarse carbon black is increased more than 4 times, make total hydrogen-oxygen amount increase in the coarse carbon black, improve ratio of carbon-hydrogen, this step is an emphasis of the present invention.
B, the coarse carbon black after the preaging is carried out steam treatment in special equipment, steam treatment is to carry out (because pressure limits its treatment temp and is about 200 ℃-250 ℃) under the condition of 2.8MPa at pressure, treatment time is 25 minutes, steam treatment impels carbon black to expand, and helps increasing the embedding of oxidizer.
C, in the coarse carbon black that steam treatment is crossed, add sodium-chlor,, under identical pressure ratio, adsorption hole is formed sealing because sodium-chlor itself can oxygen consumption, and can play the loss effect of blocking-up coarse carbon black hole insert.In the burning of coarse carbon black, sodium only plays the physical reaction that the extranuclear electron transition causes, and can oxygen consumption, simultaneously, in certain burning heats up, because the coarse carbon black insert desorbs, make coarse carbon black between a very short time with competent air and oxidizer catalytic combustion, change the carbon black characteristics slowly of burning with this, especially improve the condition of coarse carbon black own, improve the Actual combustion value, and the intensification condition.In the present embodiment, sodium-chlor dissolving back is earlier adding, sodium-chlor solvent first-selection is a water, sodium-chlor dissolving back forms sodium chloride solution, sodium chloride solution changes the high speed rotating atomizer by the high speed rotating atomizer with per minute 8000 and adds in the coarse carbon black with spray regime, after the adding, the weight ratio of sodium-chlor and coarse carbon black is 2: 100, in sodium chloride solution, solvent can spray some more for a long time, in sodium chloride solution, solvent can spray more after a little while less, and the weight ratio that keeps sodium-chlor and coarse carbon black is to get final product at 2: 100.
D, the coarse carbon black that will handle add the compatibility material therein as major ingredient, form coal-based material, and wherein the shared weight percent of major ingredient is 45%; In this process, adopt a kind of rare ferrous metal through oxidation and transform (in the present embodiment, catalyzer adopts V for polyvalent Summoning oxide compound increases the reactive behavior of coal as catalyzer 2O 5, V 2O 5Add-on be coal-based material gross weight 0.1%), in the present embodiment, adopt six methynes, four ammoniums to make the burning-point that ignitor reduces the coal of the present invention's production, the add-on of six methynes, four ammoniums be total coal-based material weight percent 0.4%, other compatibility materials are raw coal, ferrocene, sodium hydroxide, unslaked lime, cakingagent etc., wherein, the weight percent of the shared total coal-based material of raw coal is 35%, the weight percent of the shared total coal-based material of ferrocene is 0.2%, the shared weight percent of the total coal-based material of sodium hydroxide is 1.3%, the weight percent of the shared total coal-based material of unslaked lime is 4%, and remaining uses the cakingagent polishing.In the present embodiment, ferrocene utilizes diesel oil to dissolve earlier, and the weight ratio of ferrocene and diesel oil is 1: 2, changes high speed rotating atomizer spray regime with per minute 8000 then and adds.
E, the material use shaper is made readymade coal.
The novel high-energy coal of producing through the foregoing description, result through check is: ash content 6.58%, volatile matter 8%, 1 grade of characteristic of char residue, full sulphur 0.5%, fixed carbon 95%, thermal value 8300kcal/kg, above-mentioned check data shows and should not only reach high-quality coal standard by synthetic coal, and the approximate heavy oil calorific value of its combustion heat value, is worth the good of high, quality.
Embodiment two:
A, coarse carbon black is carried out preaging, make the internal surface area of coarse carbon black increase more than 4 times, to increase the oxygen functional group in the coarse carbon black, because most coarse carbon blacks (the particularly coarse carbon black of thermal process generation) are smooth atresias, the outside crystallization of coarse carbon black particle is more orderly, and the relatively poor characteristics of the preface of particle inside, in the present embodiment, coarse carbon black is changed the coarse carbon black specific volume by preaging means such as ozone oxidation or hot gas oxidations, during preaging, adopt the ready-made a whole set of oxidizing carbon black through ozone equipment in market, coarse carbon black is carried out preaging, the internal surface area of coarse carbon black is increased more than 4 times, make total hydrogen-oxygen amount increase in the coarse carbon black, improve ratio of carbon-hydrogen, this step is an emphasis of the present invention.
B, the coarse carbon black after the preaging is carried out steam treatment in special equipment, steam treatment is to carry out (because pressure limits its treatment temp and is about 200 ℃-250 ℃) under the condition of 2.9MPa at pressure, treatment time is 25 minutes, steam treatment impels carbon black to expand, and helps increasing the embedding of oxidizer.
C, in the coarse carbon black that steam treatment is crossed, add sodium-chlor,, under identical pressure ratio, adsorption hole is formed sealing because sodium-chlor itself can oxygen consumption, and can play the loss effect of blocking-up coarse carbon black hole insert.In the burning of coarse carbon black, sodium only plays the physical reaction that the extranuclear electron transition causes, and can oxygen consumption, simultaneously, in certain burning heats up, because the coarse carbon black insert desorbs, make coarse carbon black between a very short time with competent air and oxidizer catalytic combustion, change the carbon black characteristics slowly of burning with this, especially improve the condition of coarse carbon black own, improve the Actual combustion value, and the intensification condition.In the present embodiment, sodium-chlor dissolving back is earlier adding, sodium-chlor solvent first-selection is a water, sodium-chlor dissolving back forms sodium chloride solution, sodium chloride solution changes the high speed rotating atomizer by the high speed rotating atomizer with per minute 9000 and adds in the coarse carbon black with spray regime, after the adding, the weight ratio of sodium-chlor and coarse carbon black is 2.4: 100, in sodium chloride solution, solvent can spray some more for a long time, in sodium chloride solution, solvent can spray more after a little while less, and the weight ratio that keeps sodium-chlor and coarse carbon black is to get final product at 2.4: 100.
D, the coarse carbon black that will handle add the compatibility material therein as major ingredient, form coal-based material, and wherein the shared weight percent of major ingredient is 48%; In this process, adopt a kind of rare ferrous metal through oxidation and transform (in the present embodiment, catalyzer adopts V for polyvalent Summoning oxide compound increases the reactive behavior of coal as catalyzer 2O 5, V 2O 5Add-on be coal-based material gross weight 0.14%), in the present embodiment, adopt six methynes, four ammoniums to make the burning-point that ignitor reduces the coal of the present invention's production, the add-on of six methynes, four ammoniums be total coal-based material weight percent 0.44%, other compatibility materials are raw coal, ferrocene, sodium hydroxide, unslaked lime, cakingagent etc., wherein, the weight percent of the shared total coal-based material of raw coal is 31%, the weight percent of the shared total coal-based material of ferrocene is 0.24%, the shared weight percent of the total coal-based material of sodium hydroxide is 1.38%, the weight percent of the shared total coal-based material of unslaked lime is 4.4%, and remaining uses the cakingagent polishing.In the present embodiment, ferrocene utilizes diesel oil to dissolve earlier, and the weight ratio of ferrocene and diesel oil is 1.2: 2, changes high speed rotating atomizer spray regime with per minute 9000 then and adds.
E, the material use shaper is made readymade coal.
The novel high-energy coal of producing through the foregoing description, result through check is: ash content 6.58%, volatile matter 8.5%, 1 grade of characteristic of char residue, full sulphur 0.4%, fixed carbon 95%, thermal value 8200kcal/kg (, above-mentioned check data shows and should not only reach high-quality coal standard by synthetic coal, and the approximate heavy oil calorific value of its combustion heat value, is worth the good of high, quality.
Embodiment three:
A, coarse carbon black is carried out preaging, make the internal surface area of coarse carbon black increase more than 4 times, to increase the oxygen functional group in the coarse carbon black, because most coarse carbon blacks (the particularly coarse carbon black of thermal process generation) are smooth atresias, the outside crystallization of coarse carbon black particle is more orderly, and the relatively poor characteristics of the preface of particle inside, in the present embodiment, coarse carbon black is changed the coarse carbon black specific volume by preaging means such as ozone oxidation or hot gas oxidations, during preaging, adopt the ready-made a whole set of oxidizing carbon black through ozone equipment in market, coarse carbon black is carried out preaging, the internal surface area of coarse carbon black is increased more than 4 times, make total hydrogen-oxygen amount increase in the coarse carbon black, improve ratio of carbon-hydrogen, this step is an emphasis of the present invention.
B, the coarse carbon black after the preaging is carried out steam treatment in special equipment, steam treatment is to carry out (because pressure limits its treatment temp and is about 200 ℃-250 ℃) under the condition of 3MPa at pressure, treatment time is 30 minutes, steam treatment impels carbon black to expand, and helps increasing the embedding of oxidizer.
C, in the coarse carbon black that steam treatment is crossed, add sodium-chlor,, under identical pressure ratio, adsorption hole is formed sealing because sodium-chlor itself can oxygen consumption, and can play the loss effect of blocking-up coarse carbon black hole insert.In the burning of coarse carbon black, sodium only plays the physical reaction that the extranuclear electron transition causes, and can oxygen consumption, simultaneously, in certain burning heats up, because the coarse carbon black insert desorbs, make coarse carbon black between a very short time with competent air and oxidizer catalytic combustion, change the carbon black characteristics slowly of burning with this, especially improve the condition of coarse carbon black own, improve the Actual combustion value, and the intensification condition.In the present embodiment, sodium-chlor dissolving back is earlier adding, sodium-chlor solvent first-selection is a water, sodium-chlor dissolving back forms sodium chloride solution, sodium chloride solution changes the high speed rotating atomizer by the high speed rotating atomizer with per minute 10000 and adds in the coarse carbon black with spray regime, after the adding, the weight ratio of sodium-chlor and coarse carbon black is 2.8: 100, in sodium chloride solution, solvent can spray some more for a long time, in sodium chloride solution, solvent can spray more after a little while less, and the weight ratio that keeps sodium-chlor and coarse carbon black is to get final product at 2.8: 100.
D, the coarse carbon black that will handle add the compatibility material therein as major ingredient, form coal-based material, and wherein the shared weight percent of major ingredient is 51%; In this process, adopt a kind of rare ferrous metal through oxidation and transform (in the present embodiment, catalyzer adopts V for polyvalent Summoning oxide compound increases the reactive behavior of coal as catalyzer 2O 5, V 2O 5Add-on be coal-based material gross weight 0.18%), in the present embodiment, adopt six methynes, four ammoniums to make the burning-point that ignitor reduces the coal of the present invention's production, the add-on of six methynes, four ammoniums be total coal-based material weight percent 0.48%, other compatibility materials are raw coal, ferrocene, sodium hydroxide, unslaked lime, cakingagent etc., wherein, the weight percent of the shared total coal-based material of raw coal is 32%, the weight percent of the shared total coal-based material of ferrocene is 0.28%, the shared weight percent of the total coal-based material of sodium hydroxide is 1.46%, the weight percent of the shared total coal-based material of unslaked lime is 4.8%, and remaining uses the cakingagent polishing.In the present embodiment, ferrocene utilizes diesel oil to dissolve earlier, and the weight ratio of ferrocene and diesel oil is 1.4: 2, changes high speed rotating atomizer spray regime with per minute 10000 then and adds.
E, the material use shaper is made readymade coal.
The novel high-energy coal of producing through the foregoing description, result through check is: ash content 6.58%, volatile matter 9%, 1 grade of characteristic of char residue, full sulphur 0.4%, fixed carbon 95%, thermal value 8100kcal/kg (look material and cooperate ratio), above-mentioned check data shows and should not only reach high-quality coal standard by synthetic coal, and the approximate heavy oil calorific value of its combustion heat value, is worth the good of high, quality.
Embodiment four:
A, coarse carbon black is carried out preaging, make the internal surface area of coarse carbon black increase more than 4 times, to increase the oxygen functional group in the coarse carbon black, because most coarse carbon blacks (the particularly coarse carbon black of thermal process generation) are smooth atresias, the outside crystallization of coarse carbon black particle is more orderly, and the relatively poor characteristics of the preface of particle inside, in the present embodiment, coarse carbon black is changed the coarse carbon black specific volume by preaging means such as ozone oxidation or hot gas oxidations, during preaging, adopt the ready-made a whole set of oxidizing carbon black through ozone equipment in market, coarse carbon black is carried out preaging, the internal surface area of coarse carbon black is increased more than 4 times, make total hydrogen-oxygen amount increase in the coarse carbon black, improve ratio of carbon-hydrogen, this step is an emphasis of the present invention.
B, the coarse carbon black after the preaging is carried out steam treatment in special equipment, steam treatment is to carry out (because pressure limits its treatment temp and is about 200 ℃-250 ℃) under the condition of 3MPa at pressure, treatment time is 30 minutes, steam treatment impels carbon black to expand, and helps increasing the embedding of oxidizer.
C, in the coarse carbon black that steam treatment is crossed, add sodium-chlor,, under identical pressure ratio, adsorption hole is formed sealing because sodium-chlor itself can oxygen consumption, and can play the loss effect of blocking-up coarse carbon black hole insert.In the burning of coarse carbon black, sodium only plays the physical reaction that the extranuclear electron transition causes, and can oxygen consumption, simultaneously, in certain burning heats up, because the coarse carbon black insert desorbs, make coarse carbon black between a very short time with competent air and oxidizer catalytic combustion, change the carbon black characteristics slowly of burning with this, especially improve the condition of coarse carbon black own, improve the Actual combustion value, and the intensification condition.In the present embodiment, sodium-chlor dissolving back is earlier adding, sodium-chlor solvent first-selection is a water, sodium-chlor dissolving back forms sodium chloride solution, sodium chloride solution changes the high speed rotating atomizer by the high speed rotating atomizer with per minute 10000 and adds in the coarse carbon black with spray regime, after the adding, the weight ratio of sodium-chlor and coarse carbon black is 3: 100, in sodium chloride solution, solvent can spray some more for a long time, in sodium chloride solution, solvent can spray more after a little while less, and the weight ratio that keeps sodium-chlor and coarse carbon black is to get final product at 3: 100.
D, the coarse carbon black that will handle add the compatibility material therein as major ingredient, form coal-based material, and wherein the shared weight percent of major ingredient is 50%; In this process, adopt a kind of rare ferrous metal through oxidation and transform (in the present embodiment, catalyzer adopts V for polyvalent Summoning oxide compound increases the reactive behavior of coal as catalyzer 2O 5, V 2O 5Add-on be coal-based material gross weight 0.2%), in the present embodiment, adopt six methynes, four ammoniums to make the burning-point that ignitor reduces the coal of the present invention's production, the add-on of six methynes, four ammoniums be total coal-based material weight percent 0.5%, other compatibility materials are raw coal, ferrocene, sodium hydroxide, unslaked lime, cakingagent etc., wherein, the weight percent of the shared total coal-based material of raw coal is 33%, the weight percent of the shared total coal-based material of ferrocene is 0.3%, the shared weight percent of the total coal-based material of sodium hydroxide is 1.5%, the weight percent of the shared total coal-based material of unslaked lime is 5%, and remaining uses the cakingagent polishing.In the present embodiment, ferrocene utilizes diesel oil to dissolve earlier, and the weight ratio of ferrocene and diesel oil is 1: 2, changes high speed rotating atomizer spray regime with per minute 10000 then and adds.
E, the material use shaper is made readymade coal.
The novel high-energy coal of producing through the foregoing description, result through check is: ash content 6.58%, volatile matter 9.5%, 1 grade of characteristic of char residue, full sulphur 3.5%, fixed carbon 95%, thermal value 8000kcal/kg (look material and cooperate ratio), above-mentioned check data shows and should not only reach high-quality coal standard by synthetic coal, and the approximate heavy oil calorific value of its combustion heat value, is worth the good of high, quality.
Embodiment five:
A, coarse carbon black is carried out preaging, make the internal surface area of coarse carbon black increase more than 4 times, to increase the oxygen functional group in the coarse carbon black, because most coarse carbon blacks (the particularly coarse carbon black of thermal process generation) are smooth atresias, the outside crystallization of coarse carbon black particle is more orderly, and the relatively poor characteristics of the preface of particle inside, in the present embodiment, coarse carbon black is changed the coarse carbon black specific volume by preaging means such as ozone oxidation or hot gas oxidations, during preaging, adopt the ready-made a whole set of oxidizing carbon black through ozone equipment in market, coarse carbon black is carried out preaging, the internal surface area of coarse carbon black is increased more than 4 times, make total hydrogen-oxygen amount increase in the coarse carbon black, improve ratio of carbon-hydrogen, this step is an emphasis of the present invention.
B, the coarse carbon black after the preaging is carried out steam treatment in special equipment, steam treatment is to carry out (because pressure limits its treatment temp and is about 200 ℃-250 ℃) under the condition of 3MPa at pressure, treatment time is 30 minutes, steam treatment impels carbon black to expand, and helps increasing the embedding of oxidizer.
C, in the coarse carbon black that steam treatment is crossed, add sodium-chlor,, under identical pressure ratio, adsorption hole is formed sealing because sodium-chlor itself can oxygen consumption, and can play the loss effect of blocking-up coarse carbon black hole insert.In the burning of coarse carbon black, sodium only plays the physical reaction that the extranuclear electron transition causes, and can oxygen consumption, simultaneously, in certain burning heats up, because the coarse carbon black insert desorbs, make coarse carbon black between a very short time with competent air and oxidizer catalytic combustion, change the carbon black characteristics slowly of burning with this, especially improve the condition of coarse carbon black own, improve the Actual combustion value, and the intensification condition.In the present embodiment, sodium-chlor dissolving back is earlier adding, sodium-chlor solvent first-selection is a water, sodium-chlor dissolving back forms sodium chloride solution, sodium chloride solution changes the high speed rotating atomizer by the high speed rotating atomizer with per minute 10000 and adds in the coarse carbon black with spray regime, after the adding, the weight ratio of sodium-chlor and coarse carbon black is 3.2: 100, in sodium chloride solution, solvent can spray some more for a long time, in sodium chloride solution, solvent can spray more after a little while less, and the weight ratio that keeps sodium-chlor and coarse carbon black is to get final product at 3.2: 100.
D, the coarse carbon black that will handle add the compatibility material therein as major ingredient, form coal-based material, and wherein the shared weight percent of major ingredient is 54%; In this process, adopt a kind of rare ferrous metal through oxidation and transform (in the present embodiment, catalyzer adopts V for polyvalent Summoning oxide compound increases the reactive behavior of coal as catalyzer 2O 5, V 2O 5Add-on be coal-based material gross weight 0.22%), in the present embodiment, adopt six methynes, four ammoniums to make the burning-point that ignitor reduces the coal of the present invention's production, the add-on of six methynes, four ammoniums be total coal-based material weight percent 0.52%, other compatibility materials are raw coal, ferrocene, sodium hydroxide, unslaked lime, cakingagent etc., wherein, the weight percent of the shared total coal-based material of raw coal is 33%, the weight percent of the shared total coal-based material of ferrocene is 0.32%, the shared weight percent of the total coal-based material of sodium hydroxide is 1.54%, the weight percent of the shared total coal-based material of unslaked lime is 5.2%, and remaining uses the cakingagent polishing.In the present embodiment, ferrocene utilizes diesel oil to dissolve earlier, and the weight ratio of ferrocene and diesel oil is 1.6: 2, changes high speed rotating atomizer spray regime with per minute 10000 then and adds.
E, the material use shaper is made readymade coal.
The novel high-energy coal of producing through the foregoing description, result through check is: ash content 6.58%, volatile matter 10%, 1 grade of characteristic of char residue, full sulphur 0.3%, fixed carbon 95%, thermal value 8000kcal/kg, above-mentioned check data shows and should not only reach high-quality coal standard by synthetic coal, and the approximate heavy oil calorific value of its combustion heat value, is worth the good of high, quality.
Embodiment six:
A, coarse carbon black is carried out preaging, make the internal surface area of coarse carbon black increase more than 4 times, to increase the oxygen functional group in the coarse carbon black, because most coarse carbon blacks (the particularly coarse carbon black of thermal process generation) are smooth atresias, the outside crystallization of coarse carbon black particle is more orderly, and the relatively poor characteristics of the preface of particle inside, in the present embodiment, coarse carbon black is changed the coarse carbon black specific volume by preaging means such as ozone oxidation or hot gas oxidations, during preaging, adopt the ready-made a whole set of oxidizing carbon black through ozone equipment in market, coarse carbon black is carried out preaging, the internal surface area of coarse carbon black is increased more than 4 times, make total hydrogen-oxygen amount increase in the coarse carbon black, improve ratio of carbon-hydrogen, this step is an emphasis of the present invention.
B, the coarse carbon black after the preaging is carried out steam treatment in special equipment, steam treatment is to carry out (because pressure limits its treatment temp and is about 200 ℃-250 ℃) under the condition of 3.1MPa at pressure, treatment time is 35 minutes, steam treatment impels carbon black to expand, and helps increasing the embedding of oxidizer.
C, in the coarse carbon black that steam treatment is crossed, add sodium-chlor,, under identical pressure ratio, adsorption hole is formed sealing because sodium-chlor itself can oxygen consumption, and can play the loss effect of blocking-up coarse carbon black hole insert.In the burning of coarse carbon black, sodium only plays the physical reaction that the extranuclear electron transition causes, and can oxygen consumption, simultaneously, in certain burning heats up, because the coarse carbon black insert desorbs, make coarse carbon black between a very short time with competent air and oxidizer catalytic combustion, change the carbon black characteristics slowly of burning with this, especially improve the condition of coarse carbon black own, improve the Actual combustion value, and the intensification condition.In the present embodiment, sodium-chlor dissolving back is earlier adding, sodium-chlor solvent first-selection is a water, sodium-chlor dissolving back forms sodium chloride solution, sodium chloride solution changes the high speed rotating atomizer by the high speed rotating atomizer with per minute 11000 and adds in the coarse carbon black with spray regime, after the adding, the weight ratio of sodium-chlor and coarse carbon black is 3.6: 100, in sodium chloride solution, solvent can spray some more for a long time, in sodium chloride solution, solvent can spray more after a little while less, and the weight ratio that keeps sodium-chlor and coarse carbon black is to get final product at 3.6: 100.
D, the coarse carbon black that will handle add the compatibility material therein as major ingredient, form coal-based material, and wherein the shared weight percent of major ingredient is 57%; In this process, adopt a kind of rare ferrous metal through oxidation and transform (in the present embodiment, catalyzer adopts V for polyvalent Summoning oxide compound increases the reactive behavior of coal as catalyzer 2O 5, V 2O 5Add-on be coal-based material gross weight 0.26%), in the present embodiment, adopt six methynes, four ammoniums to make the burning-point that ignitor reduces the coal of the present invention's production, the add-on of six methynes, four ammoniums be total coal-based material weight percent 0.56%, other compatibility materials are raw coal, ferrocene, sodium hydroxide, unslaked lime, cakingagent etc., wherein, the weight percent of the shared total coal-based material of raw coal is 34%, the weight percent of the shared total coal-based material of ferrocene is 0.36%, the shared weight percent of the total coal-based material of sodium hydroxide is 1.62%, the weight percent of the shared total coal-based material of unslaked lime is 5.6%, and remaining uses the cakingagent polishing.In the present embodiment, ferrocene utilizes diesel oil to dissolve earlier, and the weight ratio of ferrocene and diesel oil is 1.8: 2, changes high speed rotating atomizer spray regime with per minute 11000 then and adds.
E, the material use shaper is made readymade coal.
The novel high-energy coal of producing through the foregoing description, result through check is: ash content 6.58%, volatile matter 10.5%, 1 grade of characteristic of char residue, full sulphur 0.45%, fixed carbon 95%, thermal value 7900kcal/kg, above-mentioned check data shows and should not only reach high-quality coal standard by synthetic coal, and the approximate heavy oil calorific value of its combustion heat value, is worth the good of high, quality.
Embodiment seven:
A, coarse carbon black is carried out preaging, make the internal surface area of coarse carbon black increase more than 4 times, to increase the oxygen functional group in the coarse carbon black, because most coarse carbon blacks (the particularly coarse carbon black of thermal process generation) are smooth atresias, the outside crystallization of coarse carbon black particle is more orderly, and the relatively poor characteristics of the preface of particle inside, in the present embodiment, coarse carbon black is changed the coarse carbon black specific volume by preaging means such as ozone oxidation or hot gas oxidations, during preaging, adopt the ready-made a whole set of oxidizing carbon black through ozone equipment in market, coarse carbon black is carried out preaging, the internal surface area of coarse carbon black is increased more than 4 times, make total hydrogen-oxygen amount increase in the coarse carbon black, improve ratio of carbon-hydrogen, this step is an emphasis of the present invention.
B, the coarse carbon black after the preaging is carried out steam treatment in special equipment, steam treatment is to carry out (because pressure limits its treatment temp and is about 200 ℃-250 ℃) under the condition of 3.2MPa at pressure, treatment time is 35 minutes, steam treatment impels carbon black to expand, and helps increasing the embedding of oxidizer.
C, in the coarse carbon black that steam treatment is crossed, add sodium-chlor,, under identical pressure ratio, adsorption hole is formed sealing because sodium-chlor itself can oxygen consumption, and can play the loss effect of blocking-up coarse carbon black hole insert.In the burning of coarse carbon black, sodium only plays the physical reaction that the extranuclear electron transition causes, and can oxygen consumption, simultaneously, in certain burning heats up, because the coarse carbon black insert desorbs, make coarse carbon black between a very short time with competent air and oxidizer catalytic combustion, change the carbon black characteristics slowly of burning with this, especially improve the condition of coarse carbon black own, improve the Actual combustion value, and the intensification condition.In the present embodiment, sodium-chlor dissolving back is earlier adding, sodium-chlor solvent first-selection is a water, sodium-chlor dissolving back forms sodium chloride solution, sodium chloride solution changes the high speed rotating atomizer by the high speed rotating atomizer with per minute 12000 and adds in the coarse carbon black with spray regime, after the adding, the weight ratio of sodium-chlor and coarse carbon black is 4: 100, in sodium chloride solution, solvent can spray some more for a long time, in sodium chloride solution, solvent can spray more after a little while less, and the weight ratio that keeps sodium-chlor and coarse carbon black is to get final product at 4: 100.
D, the coarse carbon black that will handle add the compatibility material therein as major ingredient, form coal-based material, and wherein the shared weight percent of major ingredient is 60%; In this process, adopt a kind of rare ferrous metal through oxidation and transform (in the present embodiment, catalyzer adopts V for polyvalent Summoning oxide compound increases the reactive behavior of coal as catalyzer 2O 5, V 2O 5Add-on be coal-based material gross weight 0.3%), in the present embodiment, adopt six methynes, four ammoniums to make the burning-point that ignitor reduces the coal of the present invention's production, the add-on of six methynes, four ammoniums be total coal-based material weight percent 0.6%, other compatibility materials are raw coal, ferrocene, sodium hydroxide, unslaked lime, cakingagent etc., wherein, the weight percent of the shared total coal-based material of raw coal is 35%, the weight percent of the shared total coal-based material of ferrocene is 0.4%, the shared weight percent of the total coal-based material of sodium hydroxide is 1.7%, the weight percent of the shared total coal-based material of unslaked lime is 6%, and remaining uses the cakingagent polishing.In the present embodiment, ferrocene utilizes diesel oil to dissolve earlier, and the weight ratio of ferrocene and diesel oil is 1: 1, changes high speed rotating atomizer spray regime with per minute 12000 then and adds.
E, the material use shaper is made readymade coal.
The novel high-energy coal of producing through the foregoing description, result through check is: ash content 6.58%, volatile matter 11%, 1 grade of characteristic of char residue, full sulphur 0.2%, fixed carbon 95%, thermal value 7850kcal/kg, above-mentioned check data shows and should not only reach high-quality coal standard by synthetic coal, and the approximate heavy oil calorific value of its combustion heat value, is worth the good of high, quality.
The present invention changes the carbon black specific volume to coarse carbon black (carbon black) by preaging means such as ozone oxidation hot gas oxidations, revise its burning feature, raw coal and a spot of catalyzer with certain score, sulphur-fixing agent, ignitor, after cakingagent cooperates, cause high-quality high energy coal, after this novel high-energy coal is synthetic, result through check is: ash content 6.58%, volatile matter 8-11% (ratio on synthetics is decided), 1 grade of characteristic of char residue, full sulphur 0.2-0.5%, fixed carbon 95%, thermal value 7850-8300kcal/kg (look material and cooperate ratio), above-mentioned check data shows and should not only reach high-quality coal standard by synthetic coal, and the approximate heavy oil calorific value of its combustion heat value, is worth high, quality good.Meanwhile, changed carbon black and do not thought, also solved the low value sooty fully and be difficult to handling problems, innovated a kind of high-quality solid energy of Sustainable development as solid-fuelled.Confirm that through producing in batches it has considerable economic value, may reach the improved seeds in the coal.

Claims (10)

1. the production technique of a high energy low sulphur coal, it is characterized in that: described technology comprises the steps:
A, coarse carbon black is carried out preaging;
B, be to carry out steam treatment, 25 minutes-35 minutes treatment time under the condition of 2.8MPa-3.2MPa with the coarse carbon black after the preaging at pressure;
C, the coarse carbon black that will handle add the compatibility material therein as major ingredient, form coal-based material, and wherein major ingredient shared weight percent in coal-based material is 45%-60%;
D, coal-based material is made readymade coal.
2. the production technique of high energy low sulphur coal according to claim 1 is characterized in that: also include step B1 between described step B and the step C, step B1 is in the coarse carbon black after steam treatment, adds sodium-chlor.
3. the production technique of high energy low sulphur coal according to claim 2, it is characterized in that: among the described step B1, earlier sodium-chlor is dissolved, form sodium chloride solution, sodium chloride solution is adopted Sprayable to be sprayed on the coarse carbon black surface, the straying quatity of sodium-chlor is that the weight ratio of sodium-chlor and coarse carbon black is 2: 100-4: 100 again.
4. the production technique of high energy low sulphur coal according to claim 3 is characterized in that: described sodium chloride solution is with in per minute 8000-12000 rpm the high speed rotating atomizer spray regime adding coarse carbon black.
5. the production technique of high energy low sulphur coal according to claim 1 is characterized in that: preaging is to adopt ozone oxidation or warm air oxidation in the described steps A.
6. the production technique of high energy low sulphur coal according to claim 1, it is characterized in that: the compatibility material is raw coal, ferrocene, six methynes, four ammoniums, sodium hydroxide, unslaked lime and cakingagent among the described step C, wherein the shared weight percent of raw coal is 30%-35%, the shared weight percent of ferrocene is 0.2%-0.4%, the shared weight percent of six methynes, four ammoniums is 0.4%-0.6%, the shared weight percent of sodium hydroxide is 1.3%-1.7%, the shared weight percent of unslaked lime is 4%-6%, and remaining uses the cakingagent polishing.
7. the production technique of high energy low sulphur coal according to claim 6, it is characterized in that: described ferrocene utilizes diesel oil to dissolve earlier, the weight ratio of ferrocene and diesel oil is 1: 2-1: 1, add with per minute 8000-12000 rpm of high speed rotating atomizer spray regime then.
8. the production technique of high energy low sulphur coal according to claim 1 is characterized in that: adopt rare Summoning oxide compound as catalyzer among the described step C.
9. the production technique of high energy low sulphur coal according to claim 8 is characterized in that: described rare Summoning oxide compound adopts V 2O 5
10. the production technique of high energy low sulphur coal according to claim 9 is characterized in that: described V 2O 5Add-on be the 0.1%-0.3% of gross weight.
CN 201010148172 2010-04-16 2010-04-16 Productive technology of high energy low sulphur coal Expired - Fee Related CN102220179B (en)

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