CN106433839A - High-temperature binder for forming of long flame coal and quick lime mixed pellets and application of high-temperature binder - Google Patents
High-temperature binder for forming of long flame coal and quick lime mixed pellets and application of high-temperature binder Download PDFInfo
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- CN106433839A CN106433839A CN201611053150.4A CN201611053150A CN106433839A CN 106433839 A CN106433839 A CN 106433839A CN 201611053150 A CN201611053150 A CN 201611053150A CN 106433839 A CN106433839 A CN 106433839A
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- Prior art keywords
- coal
- temperature
- pelletizing
- quick lime
- binding
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Classifications
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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
- 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
- C10L5/14—Methods of shaping, e.g. pelletizing or briquetting with the aid of binders, e.g. pretreated binders with organic binders
- C10L5/143—Methods of shaping, e.g. pelletizing or briquetting with the aid of binders, e.g. pretreated binders with organic binders with lignin-containing products
Abstract
The invention discloses a high-temperature binder for forming of long flame coal and quick lime mixed pellets as well as a preparation method and an application of the high-temperature binder. The preparation method of the high-temperature binder comprises steps as follows: (1) binding coal is crushed; (2) a CS2/NMP mixed solvent is added to the crushed binding coal granules for extraction and centrifugal separation, and an extracting solution is obtained; (3) lignin and concentrated sulfuric acid are added to the extracting solution and stirred uniformly, and a mixture is obtained; (4) the mixture is subjected to a reaction; (5) a reaction product is distilled, residues are washed and dried, and the binder is obtained. Alcohol micromolecules containing 2-3 aromatic rings are extracted from the binding coal by adding the CS2/NMP organic solvent and are subjected to a crosslinking reaction with lignin, the high-temperature binder with a moderate molecular weight is formed, can substantially improve the strength of pellets of long flame coal without any binding property and quick lime after pyrolysis and can meet the requirement of smelting in a calcium carbide furnace.
Description
Technical field
The present invention relates to high-temperature agglomerant of being molded with quick lime mixing pelletizing of jet coal and preparation method thereof, the present invention
Improve jet coal and the application in quick lime mixing pelletizing elevated temperature strength further to described high-temperature agglomerant, belong to long flame
The preparation field of coal and quick lime mixing pelletizing.
Background technology
Jet coal is a kind of minimum bituminous coal of degree of metamorphism, is the minimus bituminous coal that degree of coalification is only above brown coal, from
No adhesion has to weak caking property.The caking property of coal refers to, when bituminous coal heats under conditions of completely cutting off air, organic in coal
Matter macromolecular is thermally decomposed, and forms the mixture of gas, liquid, solid three-phase coexistence, referred to as gel, gel bond itself or outer
Come the ability of inert substance, the referred to as caking property of coal.For the strong coal of caking property, in gel, liquid product is many and mobility
Suitably, can preferably be filled with solid particle gap has certain viscosity again, now, gel poor air permeability, the gas in gel
State product can not freely separate out, and swelling therefore, raises with temperature, and the liquid product in gel produces further
Decompose.A part of thermal decomposition product is in that gaseous state continues to separate out；Another part is then combined together with solid granulates, thermal polycondensation and solidify,
Generate the semicoke of high intensity.For no adhesion or weak caking coal, the liquid product in gel seldom, far can not fill
Full solid granulates gap even can not infiltrate solid granulates surface, then gaseous products freely separate out, each self-dispersing of solid particle, raw
Half char strength becoming is very poor.
For the non-cohesive jet coal of milli, its shaping pelletizing with quick lime after being pyrolyzed, intensity
Very poor.How to maintain the elevated temperature strength that it is later with the pyrolysis of quick lime mixing pelletizing, pertinent literature does not have research.
Quick lime meet water after can occur fierceness reaction, generate calcium hydroxide, therefore the binding agent adding water in need
It is not suitable for the shaping of jet coal and quick lime, and for the organic binder bond that need not add water, its resistance to temperature is too low,
It is unable to reach 700 DEG C～900 DEG C of high temperature, and the cost of binding agent is too high.Non-cohesive jet coal and quick lime in the least
Mixing pelletizing, after pyrolysis, the compression strength of pelletizing very poor it would be highly desirable to improve.
Content of the invention
In order to solve the pressure resistance mixing existing for pelletizing after pelletizing is pyrolyzed of non-cohesive jet coal and quick lime
The problems such as spend very poor, the invention provides a kind of combined high temperature binding agent, applies this combined high temperature binding agent can effectively carry
High jet coal and the elevated temperature strength of quick lime pelletizing.
According to an aspect of the present invention, the invention provides a kind of high temperature that is molded with quick lime mixing pelletizing of jet coal
Binding agent, the preparation method of this high-temperature agglomerant includes：(1) binding coal is pulverized；(2) the binding coal particle to after pulverize
Middle addition CS2/ NMP mixed solvent is extracted, and centrifugation is extracted liquid；(3) lignin and dense sulphur are added in extract
Acid, is uniformly mixing to obtain mixture；(4) mixture is reacted；(5) product distillation, the washing of gained residue, baking
Dry, obtain final product.
In some preferred embodiments, the pulverizing described in step (1) is that binding coal is crushed to granularity≤75 μm.
CS described in step (2)2/ NMP mixed solvent is by CS2(carbon disulfide) and NMP (1-METHYLPYRROLIDONE) group
Become；
In some preferred embodiments, according to volume basis, CS2Ratio with NMP is 1:2～3.
In some preferred embodiments, binding coal particle and CS in step (2)2The weight ratio of/NMP mixed solvent
Example is 1:30～40.
In some preferred embodiments, according to weight ratio meter, binding coal, lignin and the concentrated sulfuric acid in step (3)
Additional proportion be binding coal：Lignin：The concentrated sulfuric acid=1：0.2～0.4：0.005～0.01 mass ratio adds.
In some preferred embodiments, granularity≤75 μm of heretofore described lignin.
In some preferred embodiments, in step (4) by mixture temperature be 100～200 DEG C, pressure be 0.1
Under conditions of～0.3MPa；The described reaction time is 3～5 hours.
In some preferred embodiments, after in step (5) drying residue, moisture controls below 5%.
Heretofore described binding coal refers to that caking index is more than the 50 or thickness of colloidal matter layer Y coals being more than 10.
According to a further aspect in the invention, the invention provides the described high-temperature agglomerant of application improves jet coal and raw stone
The method of ash mixing pelletizing elevated temperature strength, including：(1) after jet coal, quick lime and high-temperature agglomerant being pulverized respectively according to
1:0.9～1.2:0.05～0.15 mass ratio mixes and obtains mixed material；(2) mixed material is compressing, obtain
To pelletizing；(3) pelletizing is pyrolyzed, is obtained pelletizing after the pyrolysis of high intensity.
The caking index of heretofore described jet coal is 0.
In some preferred embodiments, by jet coal, quick lime and high-temperature agglomerant in the step (1) of said method
It is crushed to granularity and be less than less than 150 microns.
In some preferred embodiments, the temperature of pyrolysis described in the step (3) of said method is 700～900 DEG C,
The time of described pyrolysis is 1～2 hour.
Also include in said method pelletizing to be sent directly in furnace of calcium carbide and carrying out smelting and obtain calcium carbide product after pyrolysis.
The present invention passes through to add CS2/ NMP organic solvent is by the small molecule of the alcohols containing 2～3 aromatic rings in binding coal
Extract, itself and lignin are carried out cross-linking reaction, form the moderate high-temperature agglomerant of molecular weight, this binding agent can be significantly
Improve the intensity after the non-cohesive jet coal of milli is pyrolyzed with quick lime pelletizing so as to meet the requirement smelted into furnace of calcium carbide.
The main beneficial effect of the present invention includes：
(1) present invention is with binding coal as raw material, by adding CS2/ NMP organic solvent will contain 2 in binding coal
The alcohols small-molecule substance of～3 aromatic rings extracts, and itself and lignin are carried out cross-linking reaction, forms the moderate height of molecular weight
Warm binding agent, this binding agent mainly generates gel liquid phase in pyrolytic process, can be filled between solid granulates, and with
The raising of pyrolysis temperature, thermal polycondensation reaction occurs such that it is able to strong after jet coal and the pyrolysis of quick lime pelletizing are greatly improved
Degree.
(2) binding coal and lignin are all very universal chemical industry products, and wide material sources are with low cost.
Specific embodiment
To further describe the present invention with reference to specific embodiment, advantages of the present invention and feature will be with description and
Apparent.It should be understood that described embodiment is only exemplary, any restriction is not constituted to the scope of the present invention.This area
Technical staff should be understood that lower without departing from the spirit and scope of the present invention can to the details of technical solution of the present invention and
Form is modified or is replaced, but these modifications or replacement each fall within protection scope of the present invention.
Embodiment 1
Add CS in caking property coal dust (caking index is more than 50)2/ NMP mixed solvent (CS2Volume ratio with NMP is 1:
2) extracted, wherein, caking property coal dust and CS2The part by weight of/NMP mixed solvent is 1:30；Extracted after centrifugation
Take liquid, in extract, then add lignin and the concentrated sulfuric acid, the addition of lignin is the 0.2 of binding coal weight portion, dense
The addition of sulfuric acid is the 0.005 of caking coal weight portion, is sufficiently mixed uniformly, then in 100 DEG C of temperature, anti-under pressure 0.1MPa
Answer 3 hours, residue is obtained by distillation, residue is carried out with washing and drying process and obtains high-temperature agglomerant.
Jet coal (caking index is 0), quick lime, high-temperature agglomerant are crushed to granularity and are less than less than 150 microns；By powder
Jet coal after broken, quick lime, high-temperature agglomerant are according to 1:0.9:0.05 part by weight carries out mixed processing, obtains mixture
Material, mixed material is carried out forming processes with high-pressure ball press, obtains the no more than oval pelletizing of 5cm, the pressure resistance of pelletizing
Degree is not less than 500N/, carries out pyrolysis processing, 2 hours time of staying, obtain heat in the pyrolysis oven this pelletizing being put into 700 DEG C
Pelletizing after solution, after pyrolysis, the compression strength of pelletizing is not less than 700N/, and heat endurance is not less than 90%, and this pelletizing is loaded
Carry out in furnace of calcium carbide smelting the calcium carbide obtaining that gas forming amount is not less than 290L/kg.
Embodiment 2
Add CS in caking property coal dust (caking index is more than 50, granularity≤75 μm)2/ NMP mixed solvent (CS2With NMP
Volume ratio be 1:3) extracted, wherein, caking property coal dust and CS2The part by weight of/NMP mixed solvent is 1:40；Centrifugation
It is extracted liquid after separating, in extract, then add lignin and the concentrated sulfuric acid, the addition of high temperature coal-tar is caking property
The 0.3 of coal weight portion, the addition of the concentrated sulfuric acid is the 0.007 of caking coal weight portion, is sufficiently mixed uniformly, then in temperature 150
DEG C, react 4 hours under pressure 0.2MPa, residue is obtained by distillation, residue is carried out with washing and drying process and obtains high temperature
Binding agent.
Jet coal (caking index is 0), quick lime, high-temperature agglomerant are crushed to granularity and are less than less than 150 microns；By powder
Jet coal after broken, quick lime, high-temperature agglomerant are according to 1:1.1:0.1 part by weight carries out mixed processing, obtains mixture
Material, mixed material is carried out forming processes with high-pressure ball press, obtains the no more than oval pelletizing of 5cm, the pressure resistance of pelletizing
Degree is not less than 500N/, carries out pyrolysis processing, 1.5 hours time of staying, obtain in the pyrolysis oven this pelletizing being put into 800 DEG C
Pelletizing after pyrolysis, after pyrolysis, the compression strength of pelletizing is not less than 800N/, and heat endurance is not less than 90%, and this pelletizing is filled
Enter and carry out in furnace of calcium carbide smelting the calcium carbide obtaining that gas forming amount is not less than 290L/kg.
Embodiment 3
Add CS in caking property coal dust (caking index is more than 50)2/ NMP mixed solvent (CS2Volume ratio with NMP is 1:
2.5) extracted, wherein, caking property coal dust and CS2The part by weight of/NMP mixed solvent is 1:35；Obtain after centrifugation
Extract, then adds lignin and the concentrated sulfuric acid, the addition of high temperature coal-tar is binding coal weight portion in extract
0.4, the addition of the concentrated sulfuric acid is the 0.01 of caking coal weight portion, is sufficiently mixed uniformly, then in 200 DEG C of temperature, pressure
React 5 hours under 0.3MPa, residue is obtained by distillation, residue is carried out with washing and drying process and obtains high-temperature agglomerant.
Jet coal (caking index is 0), quick lime and high-temperature agglomerant are pulverized；By pulverize after jet coal, quick lime,
High-temperature agglomerant is according to 1:1.2:0.15 part by weight carries out mixed processing, obtains mixed material, by mixed material high pressure
Ball press carries out forming processes, obtains the no more than oval pelletizing of 5cm, and the compression strength of pelletizing is not less than 500N/, should
Pelletizing is put in 900 DEG C of pyrolysis oven and is carried out pyrolysis processing, 1 hour time of staying, the pelletizing after being pyrolyzed, pelletizing after pyrolysis
Compression strength be not less than 900N/, heat endurance is not less than 90%, this pelletizing is loaded and carries out smelting in furnace of calcium carbide and sent out
Tolerance is not less than the calcium carbide of 290L/kg.
Comparative example 1
Jet coal (caking index is 0), calcium lime powder are broken to granularity and are less than less than 150 microns；By the long flame after pulverizing
Coal, quick lime are according to 1:1 part by weight is mixed, to be mixed uniformly after, pressure ball test, ball are carried out by high-pressure ball press
The compression strength of group is not less than 500N/, then puts into pelletizing in pyrolysis oven, sets pyrolysis final temperature as 900 DEG C, the time of staying
For 1 hour, after pyrolysis, the compression strength of pelletizing was less than 200N/, and heat endurance is less than 40%, and its intensity cannot meet into calcium carbide
The requirement of stove.
Comparative example 2
Jet coal (caking index is 0), calcium lime powder are broken to granularity and are less than less than 150 microns；By the long flame after pulverizing
Coal, quick lime and the concentrated sulfuric acid are according to 1:1：0.01 part by weight is mixed, to be mixed uniformly after, entered by high-pressure ball press
Row pressure ball is tested, and the compression strength of pelletizing is not less than 500N/, then puts into pelletizing in pyrolysis oven, sets be pyrolyzed final temperature as
900 DEG C, the time of staying is 1 hour, and after pyrolysis, the compression strength of pelletizing is less than 200N/, and heat endurance is less than 40%, its intensity
The requirement into furnace of calcium carbide cannot be met.
Claims (9)
1. the high-temperature agglomerant that jet coal is molded with quick lime mixing pelletizing is it is characterised in that its preparation method includes：(1)
Binding coal is pulverized；(2) add CS in the binding coal particle to after pulverize2/ NMP mixed solvent is extracted, centrifugation point
From being extracted liquid；(3) add lignin and the concentrated sulfuric acid in extract, be uniformly mixing to obtain mixture；(4) mixture is entered
Row reaction；(5) product distillation, the washing of gained residue, drying, obtain final product.
2. according to the high-temperature agglomerant described in claim 1 it is characterised in that described binding coal refers to that caking index is more than
The 50 or thickness of colloidal matter layer Y coals being more than 10；Described pulverizing is that binding coal is crushed to granularity≤75 μm.
3. according to the high-temperature agglomerant described in claim 1 it is characterised in that described CS2/ NMP mixed solvent is by CS2And NMP
Composition, according to volume basis, CS2Ratio with NMP is 1:2～3；Binding coal particle and CS2The weight ratio of/NMP mixed solvent
Example is 1:30～40.
4. according to the high-temperature agglomerant described in claim 1 it is characterised in that in step (3) lignin and the concentrated sulfuric acid addition
Amount is according to binding coal：Lignin：The concentrated sulfuric acid=1：0.2～0.4：0.005～0.01 mass ratio adds.
5. according to the high-temperature agglomerant described in claim 1 or 4 it is characterised in that granularity≤75 μm of described lignin.
6. according to the high-temperature agglomerant described in claim 1 it is characterised in that in step (4) by mixture temperature be 100～
200 DEG C, pressure be to be reacted under conditions of 0.1～0.3MPa, described reaction time is 3～5 hours；Will in step (5)
After residue is dried, moisture controls below 5%.
7. utilize the method that high-temperature agglomerant described in claim 1～6 improves jet coal and quick lime mixing pelletizing elevated temperature strength,
It is characterized in that, including：(1) according to 1 after jet coal, quick lime and high-temperature agglomerant being pulverized respectively:0.9～1.2:0.05
～0.15 mass ratio mixes and obtains mixed material；(2) mixed material is compressing, obtain pelletizing；(3) by pelletizing
It is pyrolyzed, obtained pelletizing after the pyrolysis of high intensity.
8. in accordance with the method for claim 7 it is characterised in that the caking index of described jet coal is 0；In step (1)
Jet coal, quick lime and high-temperature agglomerant are crushed to granularity and are less than less than 150 microns.
9. in accordance with the method for claim 7 it is characterised in that the temperature of pyrolysis described in step (3) is 700～900 DEG C,
The time of described pyrolysis is 1～2 hour.
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| CN201611053150.4A CN106433839A (en) | 2016-11-24 | 2016-11-24 | High-temperature binder for forming of long flame coal and quick lime mixed pellets and application of high-temperature binder |
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| CN201611053150.4A CN106433839A (en) | 2016-11-24 | 2016-11-24 | High-temperature binder for forming of long flame coal and quick lime mixed pellets and application of high-temperature binder |
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| CN106938847A (en) * | 2017-03-30 | 2017-07-11 | 神雾环保技术股份有限公司 | The system and method that a kind of utilization carbide slag prepares calcium carbide smelting palletizing with lignite |
| CN109734095A (en) * | 2019-03-13 | 2019-05-10 | 北京双零矿山装备技术有限公司 | A method of with coal dust and calcium lime powder preparation production calcium carbide pelletizing |
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| CN106938847A (en) * | 2017-03-30 | 2017-07-11 | 神雾环保技术股份有限公司 | The system and method that a kind of utilization carbide slag prepares calcium carbide smelting palletizing with lignite |
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