CN107189800A - A kind of coking process and products thereof and application - Google Patents
A kind of coking process and products thereof and application Download PDFInfo
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- CN107189800A CN107189800A CN201710532940.9A CN201710532940A CN107189800A CN 107189800 A CN107189800 A CN 107189800A CN 201710532940 A CN201710532940 A CN 201710532940A CN 107189800 A CN107189800 A CN 107189800A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
- C10B57/04—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
- C10B57/045—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition containing mineral oils, bitumen, tar or the like or mixtures thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/08—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form in the form of briquettes, lumps and the like
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- Oil, Petroleum & Natural Gas (AREA)
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Abstract
The present invention relates to a kind of coking process and products thereof and application, including：According to mass ratio it is 30~95 by mill coal and coal liquifaction residue:5~70 mixing, coking obtains coke；The coal liquifaction residue includes the residue that coal direct liquefaction liquefaction is produced.The mill coal that low ash content, low-sulfur divide in the present invention produces melting, not only increases coke quality, and reduce production cost with being mixed with good adhesion, the dregs of fat of meltbility with rear coking；The species of coal for coking is expanded, the independent purpose that production high grade coke is provided using mill coal is realized, there is good social benefit to saving the precious coking coal resource of China；Realize the harmless treatment of the dangerous waste-oil refining slag produced to coal direct liquefaction technique.
Description
Technical field
The present invention relates to coking production technical field, and in particular to a kind of coking process and products thereof and application.
Background technology
According to the degree of coalification of coal from low to high, coal can be divided into lignite, bituminous coal to anthracite.Traditionally, will
It can be united with certain caking property, under the conditions of cell-type coking by coke oven with coking, for producing the feed coal of certain mass coke
Referred to as coking coal.According to the coal phenols standard of China, bottle coal, rich coal, gas rich coal, 1/3 coking coal, coking coal, lean coal in bituminous coal
Coking coal is belonged to poor enzyme, and the jet coal, non caking coal and meager coal in lignite, anthracite and bituminous coal belong to non-coking
Coal.
Because the caking property of various coking coals is different with coking capacity, the effect played in the production process of coke is different,
In order to rationally be used using coal resource, saving high-quality caking coal, it is necessary to which each coal is arranged in pairs or groups in accordance with the appropriate ratio, this process
Referred to as coal blending.In coal blending process, coking coal is essential coal, belongs to basic coking coal.
In recent years, the development of TAMPING COKING PROCESS expands the usage amount of mill coal, but coking coal in coal blending still
Occupy great ratio, using coking coal as main coking raw material, be equipped with the technology that a certain amount of mill coal produces coke, still
It is the main Coal Blending Technology of coke production.To find out its cause, being because in the high temperature forming process of coke, coking coal can melt to be formed
Substantial amounts of gel, gel can continue cracking, polycondensation at high temperature, ultimately form coke.Single mill coal is can not
Enough produce gel, although can also volatilize the substantial amounts of gaseous products of precipitation at high temperature, but will not produce molten condition,
Therefore coke can not be formed.
In the past, also had and be incorporated a small amount of pitch to improve the coal-blending coking technology of coke quality, but its Coal Gasification of Main Coal Species remains unchanged
It is coking coal, the supplying of pitch also improves the quality of coke just to be lifted, it is impossible in the forming process of the high-temperature fusion of coke
Middle performance leading role.
After being coordinated according to a certain percentage using coke powder, anthracite, coking coal etc. plus the binding agent such as pitch, after heating kneading into
Type, then coking, although also can larger amount of utilization mill coal, but need to use the special type of furnace, the size of capacity is general
All over very little, its technical characterstic also determines that the technology is unable to large-scale use on conventional coke oven.Separately most importantly, due to the skill
In art after the use ratio increase of mill coal, the form of coke differs markedly from traditional coke, hence it is evident that do not melt
Melt together, more bonded together by cementation, so the wearability of this coke is low.
Understand above, in the production of large-scale coking industry metaplasia, especially in traditional coke oven cell-type process of coking,
Coking coal is indispensable as the primary raw material of coke.Its reason is to produce gel after coking coal can be melted at high temperature
State, gel is the essential intermediate state to form coke, mill coal because lacking gel produces process,
Coke can not be formed alone.In coke making and coal blending, although can be incorporated part mill coal to adjust coke index, but its is basic
Effect is to dilute gel state, and amount of allocating is excessive, and the intensity, resistance to of the quality of coke, especially coke will be influenceed strongly
Mill property great can be deteriorated.
In the last few years, with the excessive development of China's coke industry, coking coal resource increasingly depleted, so, develop coking skill
Art, especially develops the technology of the good coke of non-coking coal production intensity height, wearability, the money to alleviating China's coking coal
Source shortage situation, with good social benefit.The surging economic pressures of the insufficient price of coking coal can be alleviated in addition, to carrying
The economic benefit of high coke production enterprise has great benefit.
The content of the invention
For coking raw material essential in the prior art --- coking coal shortage of resources, the quality and quality of coke
The problem of being difficult to balance, it is an object of the invention to develop one kind using mill coal and coal direct liquefaction dangerous waste product ---
Oil refining slag is mixed with coking, the method for producing satisfactory coke.Shortage of resources situation to alleviating China's coking coal, with good
Social benefit.
For up to above-mentioned purpose, the present invention is adopted the following technical scheme that：
On the one hand, the invention provides a kind of coking process, methods described includes：Mill coal is pressed with coal liquifaction residue
It is 30~95 according to mass ratio:5~70 mixing, such as 30:70、40:50、50:50、60:45、70:30、70:20 or 95:5 etc., refining
Jiao, obtains coke；The coal liquifaction residue includes the residue that coal direct liquefaction liquefaction is produced.
The softening point of coal liquifaction residue of the present invention more than 80 DEG C, such as 80 DEG C, 90 DEG C, 110 DEG C, 150 DEG C, 151
DEG C, 153 DEG C, 155 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C or 200 DEG C etc., now the light component content in residue is low and residual
Slag hardness is moderate, is conducive to coke to generate, preferably more than 150 DEG C.
Preferably, the mass percent in the coal liquifaction residue shared by ash content be less than 30%, such as 1%, 5%,
10%th, 13%, 14%, 15%, 16%, 17%, 18%, 19% or 20% etc., the ash content of produced coke can be effectively reduced, it is excellent
Select less than 20%.
Preferably, the mass percent in the coal liquifaction residue shared by sulphur content is less than 4.0%, such as 1.20%,
1.35%th, 1.50%, 1.60%, 1.70%, 1.80%, 1.90%, 2.00% or 2.20% etc., it can effectively reduce and be produced
The sulphur content of coke, preferably less than 2.0%.
Preferably, the mass percent in the coal liquifaction residue shared by volatile matter be less than 60%, such as 1%, 2%,
5%th, 10%, 20%, 30%, 40%, 50% or 60% etc., can preferably it be melted with mill coal, preferably less than 40%.
Mill coal of the present invention preferably includes any in anthracite, jet coal, lean coal, meager coal, lignite or bottle coal
It is a kind of or at least two combination, wherein typical but non-limiting be combined as：The combination of anthracite and lean coal, anthracite, length
Any one in the combination of the combination of flame coal and meager coal, lignite and bottle coal, preferably jet coal, bottle coal or anthracite or at least two
The combination planted.
Preferably, in the mill coal fineness be below 3mm mill coal accounting more than 80%, such as 80%,
82%th, 85%, 90%, 95%, 98%, 99% or 100% etc., fineness increase is conducive to generating the quality of coke.It is preferred that 90%
More than.
Mass percent shared by non-coking moisture in coal of the present invention is preferably 6~20%, such as 6%, 8%,
10%th, 12%, 15%, 16%, 18% or 20% etc., the moisture in the range of this can ensure to make ratio of briquetting firm by ramming, and reduction is coaling
When flue dust yield.It is preferred that 6~12%.
The mass ratio of mill coal of the present invention and the coal liquifaction residue is preferably 60~85:15~40, further
Improve coke quality.
The temperature at charge of coke center is preferably 650 DEG C~1150 DEG C during coking of the present invention, it is ensured that coke is ripe.For example
650 DEG C, 800 DEG C, 900 DEG C, 1000 DEG C, 1100 DEG C or 1150 DEG C etc., preferably 800~950 DEG C.
Coking of the present invention is carried out preferably in cell-type coke oven.
Preferably, the mode that the mill coal is added in the cell-type coke oven with coal liquifaction residue is each independently selected from
Top fills and/or made firm by ramming side dress.
As currently preferred technical scheme, methods described includes：
The residue that mill coal and DCL/Direct coal liquefaction liquefaction are produced is 30~95 according to mass ratio:5~70 mixing, top dress
And/or make side firm by ramming and be fitted into coking in cell-type coke oven, the temperature at charge of coke center is 650 DEG C~1150 DEG C, obtains coke；
The mill coal is including any one in anthracite, jet coal, lean coal, meager coal, lignite or bottle coal or at least
Two kinds of combination, the mass percent shared by moisture is 6~20%, and fineness is below 3mm mill coal accounting more than 80%；
The softening point of the coal liquifaction residue is more than 80 DEG C, ash content, sulphur content, the mass percent difference shared by volatile matter
For less than 30%, less than 4.0%, less than 60%.
Second aspect, the invention provides the coke that coking process is prepared is stated as described in the first purpose.
The third aspect, is used the invention provides the coke as described in the second purpose in smelter coke, Foundry Coke, chemical industry gasification
Application during burnt, calcium carbide production is burnt.
Compared with prior art, the present invention at least has the advantages that：
(1) mill coal generally has the advantages that low ash content, low-sulfur point, good caking property, meltbility that the dregs of fat have.
The two is mixed with rear coking, produces synergy, not only increases coke quality, and reduce production cost；
(2) present invention expands the species of coal for coking, realizes independent provided using mill coal and produces high grade coke
Purpose, has good social benefit to saving the precious coking coal resource of China；
(3) present invention realizes the harmless treatment of the dangerous waste-oil refining slag produced to coal direct liquefaction technique, in height
Under temperature, many phenyl ring materials in the dregs of fat can be cracked fully, polycondensation, with the co-melting graphited coke of generation of coal, the liquid volatilized
State, gaseous products can be reclaimed by the change Product Collection System of coke-oven plant.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is used only for help and understands the present invention, is not construed as the concrete restriction to the present invention.
The Shenfu coalfield having a common boundary positioned at China Inner Mongol, Shaanxi is one of China and the especially big coalfield in the world, is that China has been visited
Bright maximum coalfield, the coal trade mark is jet coal and dross coal, substantially belongs to special low ash, the coal of special low-sulfur, generally referred to as
For shenfu coal.
The characteristics of shenfu coal：Special low ash, special low-phosphorous, special low-sulfur, golf calorific value, high volatile.Leading indicator is：Ash content 4
~10%, sulfur-bearing 0.3~0.8%, phosphorous 0.002~0.3%, moisture 5~11%, volatile matter 36.5~41%, caloric value
6000 (low level) -7200 kilocalories/kg.Shenfu coal is good coal for gasification, chemical industry coal and steam coal, can make activity
Charcoal, water-coal-slurry etc., are widely used in chemical industry and metallurgy, are the ideals of high energy-consuming industry (product such as calcium carbide, carborundum, ferroalloy)
Raw material, while being also the desirable feedstock of steel industry blast furnace blowing.
Low-sulfur, low grey feature due to shenfu coal, in conventional coking production, before the quality of coke is not influenceed excessively
Put, a small amount of shenfu coal can be incorporated, ash content, sulphur content index to improve coke.Table 1 is that Shenfu coalfield producing coal is referred mainly to
Mark.
Table 1
| Coal | Ash content | Sulphur content | Volatile matter | Caking index | Y value |
| Shenfu coal | 4.0~5.0 | 0.3~0.5 | 36.5~41.0 | 0 | 0 |
As shown in Table 1, shenfu coal has the advantages that low ash content, low-sulfur point, and volatile matter is higher, the production of being conducive to product
Go out, but do not bond, also without gel (Y=0), independent coking can not be used.
Erdos coal liquifaction company of Shenhua positioned at Ordos, inner Mongolia possesses coal liquifaction device the biggest in the world ---
Erdos Direct coal liquefaction device, this is also coal direct liquefaction device the biggest in the world at present.Institute in the embodiment of the present invention
It is dangerous waste --- dregs of fat after its oil refining, under index such as table 2：
Table 2
| Title | Ash content % | Sulphur content % | Volatile matter % | Fixed carbon % | Caking index | Caloric value (kilocalorie) |
| The dregs of fat | 12.0-16.0 | 1.4-1.8 | 38 | 48 | 92 | 7000 |
The dregs of fat are the residues after coal direct liquefaction, and itself is the carbocyclic ring and heterocyclic compound of height polycondensation, by height boiling
Polycondensation product and the ash composition of residual of the aromatic compound and stability extreme difference of point.
Coke is produced based on shenfu coal completely now, according to the index request of required coke, shenfu coal and the dregs of fat
Mix in proportion, be then crushed to regulation fineness requirement, make into briquette firm by ramming on side coal car and load coke oven progress coking.
Embodiment 1
A kind of coking process, step is as follows：
1) it is 80 according to mass ratio by shenfu coal and the dregs of fat:20 mixing coal blendings, coal blending accuracy reaches 92%, enters pulverizer
Carry out broken until fineness accounts for 80wt% in below 3mm；
Wherein, moisture content of coal is coordinated：It is 12% by weight percentage；
2) it is briquette density up to more than 1.0 to make firm by ramming, and side is fitted into cell-type coke oven, coke oven precise control of temperature, it is ensured that charge of coke
900 DEG C of central temperature, coke is ripe；
The index of gained coke product is as shown in table 3.AdAsh content is represented, Std represents sulphur content, and M40 represents that coke is anti-crushing strong
Degree, M25 represents crushing strength, and M10 represents the wear-resisting intensity of coke, and Fc.ad represents application layer fixed carbon.
Table 3
| Analysis project | Ad | Std | M40 | M25 | M10 | Fc.ad |
| Index | 12.3 | 0.94 | 78 | 88 | 8 | 86.5 |
From table 3, the characteristics of coke has low grey high fixed carbon, intensity is good, disclosure satisfy that the burnt requirement of calcium carbide.
Embodiment 2
A kind of coking process, step is as follows：
1) it is 10 according to mass ratio by anthracite, jet coal, bottle coal and the dregs of fat:10:10:70 mixing coal blendings, coal blending is accurate
Degree reaches 92%, enters pulverizer and carries out broken until fineness accounts for 90wt% in below 3mm；
Wherein, moisture content of coal is coordinated：It is 20% by weight percentage；
2) it is briquette density up to more than 1.0 to make firm by ramming, and side is fitted into cell-type coke oven, coke oven precise control of temperature, it is ensured that charge of coke
1150 DEG C of central temperature, coke is ripe；
The index of gained coke product is as shown in table 4.
Table 4
| Analysis project | Ad | Std | M40 | M25 | M10 | Fc.ad |
| Index | 10.4 | 1.21 | 75 | 85 | 10.09 | 88.02 |
From table 4, the characteristics of coke has low grey high fixed carbon, intensity is good, disclosure satisfy that the requirement of Foundry Coke.
Embodiment 3
A kind of coking process, step is as follows：
1) it is 50 according to mass ratio by lean coal, meager coal and the dregs of fat:45:5 mixing coal blendings, coal blending accuracy reaches 92%, entered
Pulverizer carries out broken until fineness accounts for 95wt% in below 3mm；
Wherein, moisture content of coal is coordinated：It is 6% by weight percentage；
2) it is briquette density up to more than 1.0 to make firm by ramming, and side is fitted into cell-type coke oven, coke oven precise control of temperature, it is ensured that charge of coke
More than 650 DEG C of central temperature, coke is ripe；
The index of gained coke product is as shown in table 5.
Table 5
| Analysis project | Ad | Std | M40 | M25 | M10 | Fc.ad |
| Index | 8.8 | 0.98 | 75 | 84 | 9.7 | 90.87 |
From table 3, the characteristics of coke has low grey high fixed carbon, intensity is good, disclosure satisfy that chemical industry gasification is burnt and wants
Ask.
Comparative example 1
With differing only in for embodiment 1：Shenfu coal is 97 according to mass ratio with the dregs of fat:3 mixing coal blendings.
Comparative example 2
With differing only in for embodiment 1：Shenfu coal is 20 according to mass ratio with the dregs of fat:80 mixing coal blendings.
Comparative example 3
With differing only in for embodiment 1：The dregs of fat are replaced with into coking coal.
Table 6
| Analysis project | Ad | Std | M40 | M25 | M10 | Fc.ad |
| Comparative example 1 | 8.2 | 0.65 | 30 | 35 | 40 | 91 |
| Comparative example 2 | 18.9 | 1.97 | 82 | 92 | 8 | 78.2 |
| Comparative example 3 | 11.5 | 0.76 | 50 | 58 | 26 | 87.6 |
The table of comparisons 6 can be seen that with table 3, wherein the dregs of fat content of comparative example 1 is less than the minimum value of the present invention, as a result coke
Crushing strength and wear-resisting intensity are remarkably decreased compared to the coke of embodiment 1, and the dregs of fat content of comparative example 2 is more than the present invention most
Big value, as a result the ash content of product is obvious compared with embodiment 1 increases, and does not meet low grey use standard, it is difficult to meet calcium carbide Jiao's
It is required that, illustrate that the proportion of the invention by rationally controlling the dregs of fat and mill coal obtains the coke of good combination property.It is right
The crushing strength of ratio 3 is equally remarkably decreased compared to the coke of embodiment 1.And coke quality is an overall target, there is short
The coke of plate index is substandard product.By control as can be seen that the present invention selects specific coal liquifaction residue, i.e. coal
The residue that direct liquefaction liquefaction is produced, makes itself and mill coal and certain proportion mixed coking, is deposited between raw material type and ratio
In conspiracy relation, being omitted or substituted wherein any one all can cause the combination property of coke product not up to standard, and the present invention is not only
Relieve dependence of the current coal-coking process to coking coal, moreover it is possible to obtain the qualified coke product of overall target.
Applicant states that the present invention illustrates detailed process equipment and the technological process of the present invention by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological process, that is, do not mean that the present invention has to rely on above-mentioned detailed
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within the present invention's
Within the scope of protection domain and disclosure.
Claims (10)
1. a kind of coking process, it is characterised in that methods described includes：It is according to mass ratio with coal liquifaction residue by mill coal
30~95:5~70 mixing, coking obtains coke；
The coal liquifaction residue includes the residue that coal direct liquefaction liquefaction is produced.
2. coking process as claimed in claim 1, it is characterised in that the softening point of the coal liquifaction residue more than 80 DEG C,
It is preferred that more than 150 DEG C；
Preferably, the mass percent in the coal liquifaction residue shared by ash content is less than 30%, preferably less than 20%；
Preferably, the mass percent in the coal liquifaction residue shared by sulphur content is less than 4.0%, preferably less than 2.0%；
Preferably, the mass percent in the coal liquifaction residue shared by volatile matter is less than 60%, preferably less than 40%.
3. coking process as claimed in claim 1 or 2, it is characterised in that the mill coal include anthracite, jet coal,
In lean coal, meager coal, lignite or bottle coal any one or at least two combination, preferably in jet coal, bottle coal or anthracite
Any one or at least two combination；
Preferably, fineness is below 3mm mill coal accounting more than 80%, preferably more than 90% in the mill coal.
4. the coking process as described in any one of claims 1 to 3, it is characterised in that shared by the non-coking moisture in coal
Mass percent is 6~20%, preferably 6~12%.
5. the coking process as described in any one of Claims 1 to 4, it is characterised in that the mill coal and the coal liquifaction
The mass ratio of residue is 60~85:15~40.
6. the coking process as described in any one of Claims 1 to 5, it is characterised in that the temperature at charge of coke center during the coking
For 650 DEG C~1150 DEG C, preferably 800~950 DEG C.
7. the coking process as described in any one of claim 1~6, it is characterised in that the coking is carried out in cell-type coke oven；
Preferably, the mode that the mill coal is added in the cell-type coke oven with coal liquifaction residue is each independently selected from top dress
And/or make side dress firm by ramming.
8. the coking process as described in any one of claim 1~6, it is characterised in that methods described includes：
The residue that mill coal and DCL/Direct coal liquefaction liquefaction are produced is 30~95 according to mass ratio:5~70 mixing, top dress and/
Or make side firm by ramming and be fitted into coking in cell-type coke oven, the temperature at charge of coke center is 650 DEG C~1150 DEG C, obtains coke；
The mill coal includes any one or at least two in anthracite, jet coal, lean coal, meager coal, lignite or bottle coal
Combination, mass percent shared by moisture is 6~20%, and fineness is below 3mm mill coal accounting more than 80%；
The coal liquifaction residue softening point is more than 80 DEG C, and ash content, sulphur content, the mass percent shared by volatile matter are respectively 30%
Below, less than 4.0%, less than 60%.
9. the coke that the coking process as described in any one of claim 1~8 is prepared.
10. coke as claimed in claim 9 answering in smelter coke, Foundry Coke, chemical industry gasification use burnt, calcium carbide production burnt
With.
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| CN107828436A (en) * | 2017-11-14 | 2018-03-23 | 太原理工大学 | A kind of method that civilian clean coke is produced using coal directly-liquefied residue |
| CN108359482A (en) * | 2018-02-01 | 2018-08-03 | 国家能源投资集团有限责任公司 | In the method for directly liquefying coal into oil residue used coking |
| CN108977210A (en) * | 2018-08-01 | 2018-12-11 | 国家能源投资集团有限责任公司 | A kind of preparation method of semi-coke |
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