CN106590796A - High temperature binder and method of improving strength of long flame coal and quicklime mixture pellets - Google Patents
High temperature binder and method of improving strength of long flame coal and quicklime mixture pellets Download PDFInfo
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- CN106590796A CN106590796A CN201611053168.4A CN201611053168A CN106590796A CN 106590796 A CN106590796 A CN 106590796A CN 201611053168 A CN201611053168 A CN 201611053168A CN 106590796 A CN106590796 A CN 106590796A
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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
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Abstract
The invention discloses a high temperature binder and a method of improving strength of long flame coal and quicklime mixture pellets. A method of preparing the high temperature binder includes the steps of: (1) crushing binding coal to obtain binding coal powder; (2) adding a CS2/NMP mixed solvent to the binding coal powder to perform extraction; (3) adding humic acid and concentrated sulfuric acid to the extract and uniformly mixing the component to obtain a mixture; (4) performing a reaction to the mixture, and distilling the mixture to obtain a residue after the reaction is finished; (5) washing and drying the residue to obtain the binder. The invention also discloses a method of improving strength of long flame coal and quicklime mixture pellets by means of the high temperature binder after pyrolysis. The method includes the steps of crushing the long flame coal, the quicklime and the high temperature binder, mixing and shaping the components into pellets, and performing pyrolysis to obtain pyrolyzed pellets. The high temperature binder effectively improves the strength of the long flame coal and quicklime mixture pellets after pyrolysis.
Description
Technical field
The present invention relates to a kind of preparation method of high-temperature agglomerant, is further related to a kind of raising using the high-temperature agglomerant and is grown
Flame coal and the method for intensity after the pyrolysis of quick lime mixing pelletizing, belong to binding agent field.
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 to weak caking property has.The caking property of coal refers to that bituminous coal is organic in coal when heating under conditions of completely cutting off air
Matter macromolecular is thermally decomposed, and forms the mixture of gas, liquid, solid three-phase coexistence, referred to as gel.Gel bond itself or it is outer
Come the ability of inert substance, the referred to as caking property of coal.The coal strong for caking property, liquid product is more in gel 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 be separated out freely, therefore swelling occur.As temperature is raised, the liquid product in gel produces further
Decompose, a part of thermal decomposition product continues to separate out in gaseous state；Another part then combines 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, or even solid granulates surface can not be infiltrated, then gaseous products are freely separated out, each self-dispersing of solid particle,
Half char strength for generating is very poor.
At present, for the non-cohesive jet coal of milli, its shaping pelletizing with quick lime after being pyrolyzed, pelletizing
Compression strength it is very poor.How to maintain it to be pyrolyzed later elevated temperature strength with quick lime mixing pelletizing, do not there is report on pertinent literature
Road.Due to quick lime meet water after can occur fierceness reaction, generate calcium hydroxide, therefore the binding agent for adding water in need not
Suitable for the shaping of jet coal and quick lime, and for the organic binder bond that need not be added water, its resistance to temperature is too low, nothing
Method reaches 700 DEG C～900 DEG C of high temperature, and the cost of binding agent is too high.It would therefore be highly desirable to develop a kind of new combined high temperature
Binding agent, to effectively improve the intensity after jet coal is pyrolyzed with quick lime pelletizing.
The content of the invention
First technical problem to be solved by this invention is to provide a kind of preparation method of high-temperature agglomerant.
Second technical problem to be solved by this invention is to provide a kind of using high-temperature agglomerant raising jet coal
With the method for intensity after the pyrolysis of quick lime mixing pelletizing.
To solve above-mentioned technical problem, the technical solution used in the present invention is：
The present invention discloses first a kind of preparation method of high-temperature agglomerant, comprises the following steps：(1) by caking property coal dust
It is broken, obtain caking property coal dust；(2) CS is added in caking property coal dust2/ NMP mixed solvents are extracted, and are then centrifuged for separating,
Obtain extract；(3) humic acid and the concentrated sulfuric acid are added in extract, is well mixed, obtain mixture；(4) mixture is entered
Row reaction, distills to the mixture after the completion of reaction, evaporates CS2/ NMP mixed solvents, obtain residue；(5) to residual
Stay thing to be washed, dried, obtain high-temperature agglomerant.
Wherein, step (1) binding coal is coal of the caking index more than 50 or thickness of colloidal matter layer Y more than 10.
Granularity≤75 μm of the caking property coal dust.
According to volume basis, step (2) CS2In/NMP mixed solvents, CS2(carbon disulfide) and NMP (N- methyl pyrroles
Pyrrolidone) mixed proportion be 1：1-2.The binding coal and CS2The part by weight of/NMP mixed solvents is 1：5-10.
Step (2) can add CS in caking property coal dust in batches2/ NMP mixed solvents are extracted repeatedly, extract
In extract be mainly the phenol containing aliphatic structure and containing 2～3 aromatic rings, alcohol, the material of ethers structure.Institute of the present invention
State CS2It is with NMP commercially available.
The addition of step (3) humic acid and the concentrated sulfuric acid is：According to mass ratio meter, binding coal：Humic acid：Dense sulphur
Acid=1：0.3-0.5：0.005-0.01.Wherein, granularity≤75 μm of the humic acid.
The condition that step (4) mixture is reacted includes：Temperature is 150-200 DEG C, and pressure is 0.1-0.3MPa
Under, react 3-5 hours.
Step (5) washing is to be washed with water, can carry out cyclic washing.
The drying is drying to moisture≤5% (mass percent).
Humic acid is animals and plants remains, mainly plant remains through microorganism decomposition and conversion and it is geochemical
A series of type organic matter that processes are caused and accumulated, its basic structure is aromatic ring and alicyclic ring, there is carboxyl, hydroxyl on ring
The functional groups such as base, quinonyl, methoxyl group.The phenol containing 2～3 aromatic rings, alcohol in carboxyl functional group and extract in humic acid
There is chemical reaction in class material, form macro molecules under the catalytic action of the concentrated sulfuric acid, and the macromolecular molecular weight is moderate, plus
Gel can be formed in thermal process such that it is able to effectively improve jet coal with the intensity after the pyrolysis of quick lime mixing pelletizing.
The present invention further discloses the high-temperature agglomerant prepared using the preparation method improves jet coal and life
The method of intensity, comprises the following steps after the pyrolysis of lime mixing pelletizing：(1) jet coal, quick lime and high-temperature agglomerant are distinguished
Crush, be then well mixed, obtain mixed material；(2) mixed material is molded, is obtained pelletizing；(3) pelletizing is carried out into heat
Solution, pelletizing after being pyrolyzed is obtained final product.
Wherein, step (1) is described crushes to be crushed to granularity≤150 micron；According to mass ratio meter, jet coal：Quick lime：
High-temperature agglomerant=1：0.9-1.2：0.05-0.15.
The caking index of jet coal of the present invention is 0.
Step (2) pelletizing is the oval pelletizing of diameter≤5cm.
The temperature of step (3) pyrolysis is 700-900 DEG C, and the time of pyrolysis is 1-2 hours.
The present invention can adopt all kinds of mixing equipments in this area, such as batch mixer, for jet coal, quick lime and high temperature to be glued
Knot agent is well mixed.Described shaping can be molded using high-voltage double-roller forming machine, and the pyrolysis is carried out in pyrolysis oven.
The present invention is by jet coal, quick lime and adds pelletizing prepared by the high-temperature agglomerant and is pyrolyzed, and obtains high-strength
Pelletizing after the pyrolysis of degree, the compression strength of pelletizing is not less than 750-950N/ after pyrolysis, and heat endurance is not less than 90%.The heat
Pelletizing after solution can be sent directly in furnace of calcium carbide to be smelted, so as to obtain the high-quality calcium carbide that gas forming amount is not less than 290L/kg.
However, without high-temperature agglomerant of the present invention, being only pyrolyzed the pelletizing that jet coal and quick lime are mixed with, it is pyrolyzed
Afterwards less than 200N/, heat endurance is less than 40% to the compression strength of pelletizing, and its intensity cannot meet the requirement into furnace of calcium carbide.
Technical solution of the present invention compared with prior art, has the advantages that：
The present invention with binding coal as raw material, by add CS2/ NMP organic solvents will contain 2～3 in binding coal
The phenol of aromatic ring, alcohol micromolecular are extracted, and itself and humic acid are carried out into cross-linked esterification reaction, form the moderate high temperature of molecular weight
Binding agent, the binding agent mainly generates gel liquid phase in pyrolytic process, can be filled between solid granulates, and with
, there is thermal polycondensation reaction such that it is able to greatly improve intensity after the pyrolysis of jet coal and quick lime pelletizing in the raising of pyrolysis temperature,
It is set to meet the requirement smelted into furnace of calcium carbide.The wide material sources of binding coal of the present invention and humic acid, it is with low cost.
Specific embodiment
Further describe the present invention with reference to specific embodiment, advantages of the present invention and feature will be with description and
It is apparent.It should be understood that the embodiment is only exemplary, any restriction is not constituted to the scope of the present invention.This area
Technical staff should be understood that without departing from the spirit and scope of the 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
CS is added in caking property coal dust (granularity≤75 μm)2/ NMP mixed solvent (CS2It is 1 with the volume ratio of NMP：1) enter
Row extraction, wherein caking property coal dust are 1 with the part by weight of mixed solvent：5；Extract is obtained after centrifugation, then to extraction
Take and add in liquid humic acid (granularity≤75 μm of humic acid) and the catalyst concentrated sulfuric acid, the addition of humic acid is binding coal weight
0.3 times of amount part, the addition of catalyst is 0.005 times of binding coal weight portion, is sufficiently mixed uniformly, then in temperature
150 DEG C, react 3 hours under pressure 0.1MPa, CS (is evaporated by distillation2/ NMP mixed solvents) residue is obtained, to residual
Thing is washed (wash with water) drying and processing (making moisture control below 5%), obtains high-temperature agglomerant.
By jet coal (caking index is 0), quick lime and the high-temperature agglomerant (be crushed to 150 microns of granularity respectively with
Under), according to 1:0.9:0.05 ratio (mass ratio) carries out mixed processing, obtains mixed material；By mixed material high pressure pressure
Ball machine carries out forming processes, obtains the oval pelletizing that diameter is not more than 5cm, and the compression strength of pelletizing is not less than 500N/.Will
The pelletizing is put in 700 DEG C of pyrolysis oven carries out pyrolysis processing, 2 hours time of staying, the pelletizing after being pyrolyzed, ball after pyrolysis
The compression strength of group is not less than 750N/, and heat endurance is not less than 90%, obtains smelting is carried out in pelletizing loading furnace of calcium carbide
Gas forming amount is not less than the calcium carbide of 290L/kg.
Embodiment 2
CS is added in caking property coal dust (granularity≤75 μm)2/ NMP mixed solvent (CS2It is 1 with the volume ratio of NMP：2) enter
Row extraction, wherein caking property coal dust are 1 with the part by weight of mixed solvent：10；Extract is obtained after centrifugation, then to extraction
Take and add in liquid humic acid (granularity≤75 μm of humic acid) and the catalyst concentrated sulfuric acid, the addition of humic acid is binding coal weight
0.4 times of amount part, the addition of the catalyst concentrated sulfuric acid is 0.007 times of binding coal weight portion, is sufficiently mixed uniform, Ran Hou
150 DEG C of temperature, reacts 4 hours under pressure 0.2MPa, and (CS is evaporated by distillation2/ NMP mixed solvents) residue is obtained, it is right
Residue is washed (wash with water) drying and processing (making moisture control below 5%), obtains high-temperature agglomerant.
Jet coal (caking index is 0), quick lime and the high-temperature agglomerant (being crushed to granularity≤150 micron respectively) are pressed
According to 1:1.1:0.1 ratio (mass ratio) carries out mixed processing, obtains mixed material, and mixed material is carried out with high-pressure ball press
Forming processes, obtain the oval pelletizing that diameter is not more than 5cm, and the compression strength of pelletizing is not less than 500N/, the pelletizing is put
Enter and carry out in 800 DEG C of pyrolysis oven pyrolysis processing, 1.5 hours time of staying, the pelletizing after being pyrolyzed, pelletizing is anti-after pyrolysis
Compressive Strength is not less than 850N/, and heat endurance is not less than 90%, and by smelting is carried out in pelletizing loading furnace of calcium carbide gas forming amount is obtained
It is not less than the calcium carbide of 290L/kg.
Embodiment 3
CS is added in caking property coal dust (granularity≤75 μm)2/ NMP mixed solvent (CS2It is 1 with the volume ratio of NMP：1.5)
Extracted, wherein caking property coal dust and the part by weight of mixed solvent are 1：8；Extract, Ran Houxiang are obtained after centrifugation
Humic acid (granularity≤75 μm of humic acid) and the catalyst concentrated sulfuric acid are added in extract, the addition of humic acid is binding coal
0.5 times of weight portion, the addition of the catalyst concentrated sulfuric acid is 0.01 times of binding coal weight portion, is sufficiently mixed uniformly, then
In 200 DEG C of temperature, react 5 hours under pressure 0.3MPa, CS (is evaporated by distillation2/ NMP mixed solvents) residue is obtained,
Drying and processing (making moisture control below 5%) is washed (wash with water) to residue, high-temperature agglomerant is obtained.
By jet coal, quick lime and the high-temperature agglomerant (being crushed to respectively below 150 microns of granularity) according to 1:1.2:
0.15 ratio (mass ratio) carries out mixed processing, obtains mixed material, and mixed material is carried out at shaping with high-pressure ball press
Reason, obtains the oval pelletizing that diameter is not more than 5cm, and the compression strength of pelletizing is not less than 500N/, the pelletizing is put into into 900
DEG C pyrolysis oven in carry out pyrolysis processing, 1 hour time of staying, the pelletizing after being pyrolyzed, the compression strength of pelletizing after pyrolysis
950N/ is not less than, heat endurance is not less than 90%, the pelletizing to be loaded carry out smelting in furnace of calcium carbide and obtain gas forming amount and is not less than
The calcium carbide of 290L/kg.
Comparative example 1
By the jet coal handled well, quick lime (being crushed to granularity≤150 micron respectively) according to 1:1 ratio (mass ratio)
Mixed, it is to be mixed it is uniform after, pressure ball test is carried out by high-pressure ball press, the compression strength of pelletizing is not less than 500N/,
Then pelletizing is put in pyrolysis oven, sets pyrolysis final temperature as 900 DEG C, the time of staying is 1 hour, the pressure resistance of pelletizing after pyrolysis
Less than 200N/, heat endurance is less than 40% to degree, and its intensity cannot meet the requirement into furnace of calcium carbide.
Comparative example 2
By the jet coal handled well, quick lime (being crushed to granularity≤150 micron respectively), the concentrated sulfuric acid according to 1:1:0.01
Ratio (mass ratio) is mixed, it is to be mixed it is uniform after, pressure ball test is carried out by high-pressure ball press, the compression strength of pelletizing is not
Less than 500N/, then pelletizing is put in pyrolysis oven, sets pyrolysis final temperature as 900 DEG C, the time of staying is 1 hour, after pyrolysis
Less than 200N/, heat endurance is less than 40% to the compression strength of pelletizing, and its intensity cannot meet the requirement into furnace of calcium carbide.
Claims (10)
1. a kind of preparation method of high-temperature agglomerant, it is characterised in that comprise the following steps：(1) binding coal is crushed, is obtained
Caking property coal dust；(2) CS is added in caking property coal dust2/ NMP mixed solvents are extracted, and are then centrifuged for separating, and are extracted
Liquid；(3) humic acid and the concentrated sulfuric acid are added in extract, is well mixed and is obtained mixture；(4) mixture is reacted, it is right
Mixture after the completion of reaction is distilled, and evaporates CS2/ NMP mixed solvents, obtain residue；(5) residue is washed
Wash, dry, obtain high-temperature agglomerant.
2. according to the preparation method described in claim 1, it is characterised in that：Step (1) binding coal is that caking index is big
In the 50 or thickness of colloidal matter layer Y coals more than 10.
3. according to the preparation method described in claim 1, it is characterised in that：According to volume basis, step (2) CS2/ NMP is mixed
In bonding solvent, CS2It is 1 with the mixed proportion of NMP：1-2；The binding coal and CS2The part by weight of/NMP mixed solvents is 1：
5-10。
4. according to the preparation method described in claim 1, it is characterised in that：Granularity≤75 μ of step (1) the caking property coal dust
m。
5. according to the preparation method described in claim 1, it is characterised in that the addition of step (3) humic acid and the concentrated sulfuric acid
Measure and be：According to mass ratio meter, binding coal：Humic acid：The concentrated sulfuric acid=1：0.3-0.5：0.005-0.01.
6. according to the preparation method described in claim 1 or 5, it is characterised in that：Granularity≤75 μ of step (3) humic acid
m。
7. according to the preparation method described in claim 1, it is characterised in that the condition of step (4) reaction includes：Temperature is
150-200 DEG C, pressure is under 0.1-0.3MPa, to react 3-5 hours.
8. according to the preparation method described in claim 1, it is characterised in that：Step (5) washing is to be washed with water；Institute
Drying is stated to dry to moisture≤5%.
9. the high-temperature agglomerant for being prepared using preparation method described in claim 1 to 8 any one improves jet coal and life
The method of intensity after the pyrolysis of lime mixing pelletizing, it is characterised in that comprise the following steps：(1) by jet coal, quick lime and high temperature
Binding agent is crushed respectively, is then well mixed, and obtains mixed material；(2) mixed material is molded, is obtained pelletizing；(3) will
Pelletizing is pyrolyzed, pelletizing after being pyrolyzed, and is obtained final product.
10. in accordance with the method for claim 9, it is characterised in that step (1) is according to mass ratio meter, jet coal：Quick lime：
High-temperature agglomerant=1：0.9-1.2：0.05-0.15.
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| CN201611053168.4A CN106590796A (en) | 2016-11-24 | 2016-11-24 | High temperature binder and method of improving strength of long flame coal and quicklime mixture pellets |
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Cited By (1)
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| CN113056542A (en) * | 2018-10-29 | 2021-06-29 | 泰克煤业有限公司 | Method for coal fines agglomeration |
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Application publication date: 20170426 |