CN102432306B - Method for intensively producing refractory material binder by coal tar pitch needle coke - Google Patents
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Abstract
The invention discloses a method for intensively producing a refractory material binder by coal tar pitch needle coke, comprising: separating, settling, purifying, oxidizing and modifying the QI1 residue which is not utilized in the prior art, coal tar, byproduct oils of a delay coking tower, a conditioning agent and a nickel, vanadium and cobalt depriving agent, to obtain the refractory material binder with high softening point, high slagging resistance, high oxidizability and high thermal shock resistance, mixing the refractory material binder with the activators: white carbon black, ammonium humate, polyvinyl alcohol, carboxymethyl cellulose, etc., and dry-pressing and forming the mixture to obtain the refractory material for a steel furnace with the performance batter than that of the phenolic resins. The refractory material binder is dissolved in the solution of carbon black, xylene, coumarone, polyethylene glycol, etc., to obtain a liquid spray coating type binder for repairing the steel furnace, which has higher repairing intensity than the common medium temperature asphalt does. The refractory material binder can effectively prolong the service life of a converter, an electric furnace, a calciner, etc.
Description
Technical field
The present invention relates to the method for the intensive production fire bond of a kind of tar needle-shape coke, the technical field that belongs to the preparation of pyrocarbon material and use.
Background technology
Softening temperature is one of main performance index of Coal-tar Pitch, used for refractory material Coal-tar Pitch on electric furnace, converter steelmaking and the high-temperature calcination equipment, more require the softening temperature of coal-tar pitch up to 230～280 ℃, also require simultaneously coal-tar pitch to have higher slag resistance, oxidation-resistance, heat-shock resistance, otherwise will directly have influence on the work-ing life of converter, electric furnace, this is that general middle temperature, coal tar pitch institute are inaccessiable.Existing Coal-tar Pitch mostly by the oxidative polycondensation of mesophase pitch, utilizes special technique and equipment to produce, and to the needle coke production technology at an isolated quinoline insolubles (QI with impurity such as heavy metal, carbon residues
1) deep processing and utilization no longer.Its defective can make the production cost of tar needle-shape coke improve, and forms solid waste in production process.
Summary of the invention
The present invention aims to provide the method for the intensive production fire bond of a kind of tar needle-shape coke, and the method is more reasonable than single needle coke production, and cost is lower, and energy
Acquisition is than high softening-pointThe used for refractory material Coal-tar Pitch.
The present invention realizes by following technical proposal: the method for the intensive production fire bond of a kind of tar needle-shape coke is characterized in that comprising following each step:
A. get raw material by the prescription of following mass percent:
Coal-tar pitch 30～50%
Modified coal-tar 40～50%
Conditioning agent 5.5～19.5%
Nickel, vanadium, cobalt remove agent 1.0～10.5%;
B. the raw material with steps A is 50～200 ℃ in temperature, and speed is to separate under the condition of 10～50mm/min, obtains bottom isolate and top isolate;
C. the top isolate that the separation of B step is obtained gets the solvent oil product on upper strata through centrifugation, and middle level thing and lower floor's thing;
D. the bottom isolate that step B is obtained remains under 120～250 ℃, mass ratio by bottom Fen Li Wu ︰ mixture=1 ︰ 0.01～0.5, mixture is passed in the isolate of bottom, under 220～300 ℃ of temperature, react 3～8h, get softening temperature and reach 230～260 ℃ intermediates, wherein mixture is following volume ratio: air: oxygen: carbolic oil=0.5～1.2: 0.25～1.2: 0.1;
E. be that 250～400 ℃, sieve aperture are to carry out the heat screening under the condition of 50～1000um with the intermediates of step D in temperature, obtain the screen overflow of particle diameter＞50～1000um, further pulverize screen overflow and get fire bond, and the screen underflow of particle diameter＜50～1000um is directly as fire bond.
Modified coal-tar in the described steps A obtains through following method: the mass ratio of pressing Mei Jiao You ︰ by-product oil=30～50 ︰ 40～50, after the by-product oil of coal tar and needle coke delayed coking drums mixed, amount by 0.20～1L/min, in mixing oil, pass into technical grade hydrogen, and be that 350～460 ℃, pressure are that 0.1～5Mpa, oil gas speed ratio are 0.1～3.0h in temperature
-1, catalyzer is γ-Al
2O
3, ZSM-5 molecular sieve condition under, the reaction 3～15h, namely obtain modified coal-tar.
Conditioning agent in the described steps A is that aromatize degree BMCI is 30～75 conditioning agent, for a kind of in the following organism or by several composition the in the following organism: crude benzol, toluene, heavy benzol, kerosene, diesel oil, ethylene glycol, propylene glycol, aromatic solvent naphtha, washing oil, carbolineum, take off aromatic solvent naphtha, wherein, described aromatize degree BMCI is calculated by following formula:
BMCI=?48640/Tb,m+473.6d-456.8
In the formula, Tb, m are raw material boiling point mean value, and unit is K;
D is the density of raw material when 288.5K, and unit is kg/m
3
Conditioning agent preferred fragrance degree BMCI in the described steps A is 55～70 conditioning agent.
Coal-tar pitch in the described steps A is mid-temperature pitch, is the lighting coal tar of coal needle coke delay coking process by-product.
It is to obtain according to " preparation method of N-Methylimidazole ionic liquid " that nickel in the described steps A, vanadium, cobalt remove agent, the reference of the method is: Shanghai University Of Electric Power's journal, 2010(1), the 61-65 page or leaf, by Liu Kejia, " the synthetic and purification of the microwave method of alkyl imidazole ionic liquid " that Li Xiaohua, the people such as Wang Luochun deliver.
The separation of described step B is finished in conventional settlement separator, the centrifugation of described C step is finished at conventional three sections centrifuge separators, perhaps, the separation of B, C step is to finish in the tripping device that is combined into by settlement separate machine and three sections centrifuge separators.
The heat screening condition of described step e, preferred 250～300 ℃ of temperature, the preferred 300～600um of sieve aperture.
Described step e gained fire bond mixes with white carbon black, silicon carbide, white fused alumina by following mass ratio, that is: fire bond: white carbon black: silicon carbide: white fused alumina=1～5: 25～40: 30～50: 40～60, and be 1～5Mpa/m at pressure
2Lower, dry-pressing formed after, under 110～300 ℃, 300～550 ℃, 550～850 ℃, 850～1100 ℃, 1100～1500 ℃, 1500～2000 ℃, stage drying 3～15h makes the refractory materials that calcining furnace is used respectively.
Described step e gained fire bond and white carbon black, ammonium humate (HA-NH
4), tween (TWEEN-85), silane-KH570, polyvinyl alcohol (PVA-1799), carboxymethyl cellulose (CMC) promoting agent, mix by following mass ratio, that is: fire bond: white carbon black: ammonium humate (HA-NH
4): tween (TWEEN-85): silane-KH570: polyvinyl alcohol (PVA-1799): carboxymethyl cellulose (CMC) promoting agent=10～35:10～50: 5～20: 25～50: 25～50: 5～10: 5～15, and after dissolving mixes under 50～300 ℃ of temperature, make the refractory materials that steel melting furnace is used.
The middle level thing of described C step can be used as needle coke viscid bitumen raw material; Lower floor's thing can be used as the carbon fiber raw material.
Advantage of the present invention and effect: adopt such scheme, the QI that prior art is not utilized
1Residue, with coal tar, delayed coking drums by-product oil, conditioning agent and nickel, vanadium, cobalt remove agent together through separate, subsiding and purifying, oxidation modification, make the fire bond of high softening-point, wherein softening temperature reaches 210～260 ℃, heat-shock resistance R=2.0 * 104～2.6 * 104s, thermal expansivity a=1.0 * 10
-6～1.3 * 10
-6/ K, viscosity reaches 25200～149000/mPas
-1, not only softening temperature is high, and has higher slag resistance, oxidation-resistance, thermal shock resistance, mix with white carbon black, ammonium humate, polyvinyl alcohol, the agent of carboxymethyl cellulose isoreactivity, and after dry-pressing formed, namely making the steel melting furnace refractory materials, performance is better than resol; Behind the dissolving mixed dissolutions such as carbon black, dimethylbenzene, cumarone, polyoxyethylene glycol, make again steel melting furnace and study for a second time courses one has flunked with liquid spray type binding agent, it is high to study for a second time courses one has flunked the common mid-temperature pitch of strength ratio.Can effectively prolong the work-ing life of the equipment such as converter, electric furnace, calcining furnace.The present invention had both guaranteed the cleaner production of needle coke, had reduced again production cost, and the feed composition that has solved tar needle-shape coke intensive production carbon fiber, fire bond separates and processing and utilization.
Embodiment
Below in conjunction with embodiment the present invention is described further.
Embodiment 1
A. get raw material by the prescription of following mass percent:
Coal-tar pitch 50%
Modified coal-tar 40%
Conditioning agent 9.0%
Nickel, vanadium, cobalt remove agent 1.0%;
Wherein, modified coal-tar obtains through following method: the mass ratio of pressing Mei Jiao You ︰ by-product oil=30 ︰ 45, after the by-product oil of coal tar and needle coke delayed coking drums mixed, press the amount of 1L/min, in mixing oil, pass into technical grade hydrogen, and be that 460 ℃, pressure are that 0.1Mpa, oil gas speed ratio are 2.0h in temperature
-1, catalyzer is γ-Al
2O
3, ZSM-5 molecular sieve condition under, the reaction 15h, namely obtain modified coal-tar; Conditioning agent is that aromatize degree BMCI is 75 conditioning agent, is comprised of following organism: crude benzol, toluene, heavy benzol, diesel oil, ethylene glycol; Coal-tar pitch is mid-temperature pitch, is the lighting coal tar of coal needle coke delay coking process by-product; It is to obtain according to " preparation method of N-Methylimidazole ionic liquid " that nickel, vanadium, cobalt remove agent;
B. the raw material with steps A is 100 ℃ in temperature, and speed is to separate in conventional settlement separator under the condition of 50mm/min, obtains bottom isolate and top isolate;
C. step B is separated the top isolate that obtains and in conventional three sections centrifuge separators, carry out centrifugation, get the recycled solvent oil on upper strata, and middle level thing and lower floor's thing; The middle level thing can be used as needle coke viscid bitumen raw material; Lower floor's thing can be used as the carbon fiber raw material;
D. the bottom isolate that step B is obtained remains under 120 ℃, mass ratio by bottom Fen Li Wu ︰ mixture=1 ︰ 0.3, mixture is passed in the isolate of bottom, under 300 ℃ of temperature, react 3h, get softening temperature and reach 250 ℃ intermediates, wherein mixture is following volume ratio: air: oxygen: carbolic oil=1.2: 1.2: 0.1;
E. be that 300 ℃, sieve aperture are to carry out the heat screening under the condition of 50um with the intermediates of step D in temperature, obtain the screen overflow of particle diameter＞50um, further pulverize screen overflow and get fire bond, and the screen underflow of particle diameter＜50um is directly as fire bond.
Step e gained fire bond mixes with white carbon black, silicon carbide, white fused alumina by following mass ratio: 5: 25: 40: 60, and be 3Mpa/m at pressure
2Lower, dry-pressing formed after, under 110 ℃, 550 ℃, 650 ℃, 1100 ℃, 1300 ℃, 1500 ℃, stage drying 12h makes the calcining furnace refractory materials respectively.
Step e gained fire bond and white carbon black, ammonium humate (HA-NH
4), tween (TWEEN-85), silane-KH570, polyvinyl alcohol (PVA-1799), carboxymethyl cellulose (CMC) promoting agent, mix by following mass ratio: 35:40: 5: 25: 50: 8: 15, and after dissolving mixes under 300 ℃ of temperature, make the steel melting furnace refractory materials.
Embodiment 2
A. get raw material by the prescription of following mass percent:
Coal-tar pitch 30%
Modified coal-tar 45%
Conditioning agent 14.5%
Nickel, vanadium, cobalt remove agent 10.5%;
Wherein, modified coal-tar obtains through following method: the mass ratio of pressing Mei Jiao You ︰ by-product oil=50 ︰ 40, after the by-product oil of coal tar and needle coke delayed coking drums mixed, press the amount of 0.8L/min, in mixing oil, pass into technical grade hydrogen, and be that 400 ℃, pressure are that 5Mpa, oil gas speed ratio are 3.0h in temperature
-1, catalyzer is γ-Al
2O
3, ZSM-5 molecular sieve condition under, the reaction 12h, namely obtain modified coal-tar; Conditioning agent is that aromatize degree BMCI is 30 conditioning agent, is comprised of organism kerosene; Coal-tar pitch is mid-temperature pitch, is the lighting coal tar of coal needle coke delay coking process by-product; It is to obtain according to " preparation method of N-Methylimidazole ionic liquid " that nickel, vanadium, cobalt remove agent;
B. the raw material with steps A is 200 ℃ in temperature, speed be under the condition of 10mm/min separating by in settlement separate machine and the tripping device that three sections centrifuge separators are combined into, obtain bottom isolate and top isolate;
C. step B is separated in the tripping device that the top isolate obtain is combined into via settlement separate machine and three sections centrifuge separators and carry out centrifugation, get the recycled solvent oil on upper strata, and middle level thing and lower floor's thing; The middle level thing can be used as needle coke viscid bitumen raw material; Lower floor's thing can be used as the carbon fiber raw material;
D. the bottom isolate that step B is obtained remains under 250 ℃, mass ratio by bottom Fen Li Wu ︰ mixture=1 ︰ 0.01, mixture is passed in the isolate of bottom, under 220 ℃ of temperature, react 8h, get softening temperature and reach 230 ℃ intermediates, wherein mixture is following volume ratio: air: oxygen: carbolic oil=0.5: 0.25: 0.1;
E. be that 250 ℃, sieve aperture are to carry out the heat screening under the condition of 1000um with the intermediates of step D in temperature, obtain the screen overflow of particle diameter＞1000um, further pulverize screen overflow and get fire bond, and the screen underflow of particle diameter＜1000um is directly as fire bond.
Step e gained fire bond mixes with white carbon black, silicon carbide, white fused alumina by following mass ratio: 1:30: at pressure be 5Mpa/m at 50: 40
2Lower, dry-pressing formed after, under 300 ℃, 400 ℃, 850 ℃, 1000 ℃, 1500 ℃, 1800 ℃, stage drying 3h makes the calcining furnace refractory materials respectively.
Step e gained fire bond and white carbon black, ammonium humate (HA-NH
4), tween (TWEEN-85), silane-KH570, polyvinyl alcohol (PVA-1799), carboxymethyl cellulose (CMC) promoting agent, mix by following mass ratio: 10:10: 10: 50: 35: 10: 5, and after dissolving mixes under 200 ℃ of temperature, make the steel melting furnace refractory materials.
Embodiment 3
A. get raw material by the prescription of following mass percent:
Coal-tar pitch 35%
Modified coal-tar 40%
Conditioning agent 19.5%
Nickel, vanadium, cobalt remove agent 5.5%;
Wherein, modified coal-tar obtains through following method: the mass ratio of pressing Mei Jiao You ︰ by-product oil=40 ︰ 50, after the by-product oil of coal tar and needle coke delayed coking drums mixed, press the amount of 0.20L/min, in mixing oil, pass into technical grade hydrogen, and be that 350 ℃, pressure are that 3Mpa, oil gas speed ratio are 0.1h in temperature
-1, catalyzer is γ-Al
2O
3, ZSM-5 molecular sieve condition under, the reaction 3h, namely obtain modified coal-tar; Conditioning agent is that aromatize degree BMCI is 55 conditioning agent, is comprised of following organism: propylene glycol, aromatic solvent naphtha, washing oil, carbolineum, take off aromatic solvent naphtha; Coal-tar pitch is mid-temperature pitch, is the lighting coal tar of coal needle coke delay coking process by-product; It is to obtain according to " preparation method of N-Methylimidazole ionic liquid " that nickel, vanadium, cobalt remove agent;
B. the raw material with steps A is 50 ℃ in temperature, and speed is to separate in conventional settlement separator under the condition of 30mm/min, obtains bottom isolate and top isolate;
C. step B is separated the top isolate that obtains and in conventional three sections centrifuge separators, carry out centrifugation, get the recycled solvent oil on upper strata, and middle level thing and lower floor's thing; The middle level thing can be used as needle coke viscid bitumen raw material; Lower floor's thing can be used as the carbon fiber raw material;
D. the bottom isolate that step B is obtained remains under 200 ℃, mass ratio by bottom Fen Li Wu ︰ mixture=1 ︰ 0.5, mixture is passed in the isolate of bottom, under 280 ℃ of temperature, react 5h, get softening temperature and reach 260 ℃ intermediates, wherein mixture is following volume ratio: air: oxygen: carbolic oil=1.0: 1.0: 0.1;
E. be that 400 ℃, sieve aperture are to carry out the heat screening under the condition of 300um with the intermediates of step D in temperature, obtain the screen overflow of particle diameter＞300um, further pulverize screen overflow and get fire bond, and the screen underflow of particle diameter＜300um is directly as fire bond.
Step e gained fire bond mixes with white carbon black, silicon carbide, white fused alumina by following mass ratio: 3: 40: 30: 50, and be 1Mpa/m at pressure
2Lower, dry-pressing formed after, under 200 ℃, 300 ℃, 550 ℃, 850 ℃, 1100 ℃, 2000 ℃, stage drying 15h makes the calcining furnace refractory materials respectively.
Step e gained fire bond and white carbon black, ammonium humate (HA-NH
4), tween (TWEEN-85), silane-KH570, polyvinyl alcohol (PVA-1799), carboxymethyl cellulose (CMC) promoting agent, mix by following mass ratio: 25:50: 20: 35: 25: 5: 10, and after dissolving mixes under 50 ℃ of temperature, make the steel melting furnace refractory materials.
Embodiment 4
A. get raw material by the prescription of following mass percent:
Coal-tar pitch 30%
Modified coal-tar 50%
Conditioning agent 10.5%
Nickel, vanadium, cobalt remove agent 9.5%;
Wherein, modified coal-tar obtains through following method: the mass ratio of pressing Mei Jiao You ︰ by-product oil=50 ︰ 50, after the by-product oil of coal tar and needle coke delayed coking drums mixed, press the amount of 0.5L/min, in mixing oil, pass into technical grade hydrogen, and be that 360 ℃, pressure are that 4Mpa, oil gas speed ratio are 1h in temperature
-1, catalyzer is γ-Al
2O
3, ZSM-5 molecular sieve condition under, the reaction 8h, namely obtain modified coal-tar; Conditioning agent is that aromatize degree BMCI is 70 conditioning agent, is comprised of the organism aromatic solvent naphtha; Coal-tar pitch is mid-temperature pitch, is the lighting coal tar of coal needle coke delay coking process by-product; It is to obtain according to " preparation method of N-Methylimidazole ionic liquid " that nickel, vanadium, cobalt remove agent;
B. the raw material with steps A is 130 ℃ in temperature, speed be under the condition of 40mm/min separating by in settlement separate machine and the tripping device that three sections centrifuge separators are combined into, obtain bottom isolate and top isolate;
C. step B is separated in the tripping device that the top isolate obtain is combined into via settlement separate machine and three sections centrifuge separators and carry out centrifugation, get the recycled solvent oil on upper strata, and middle level thing and lower floor's thing; The middle level thing can be used as needle coke viscid bitumen raw material; Lower floor's thing can be used as the carbon fiber raw material;
D. the bottom isolate that step B is obtained remains under 160 ℃, mass ratio by bottom Fen Li Wu ︰ mixture=1 ︰ 0.4, mixture is passed in the isolate of bottom, under 290 ℃ of temperature, react 4h, get softening temperature and reach 240 ℃ intermediates, wherein mixture is following volume ratio: air: oxygen: carbolic oil=1.2: 0.25: 0.1;
E. be that 280 ℃, sieve aperture are to carry out the heat screening under the condition of 600um with the intermediates of step D in temperature, obtain the screen overflow of particle diameter＞600um, further pulverize screen overflow and get fire bond, and the screen underflow of particle diameter＜600um is directly as fire bond.
Step e gained fire bond mixes with white carbon black, silicon carbide, white fused alumina by following mass ratio: 2: 40: 35: 45, and be 4Mpa/m at pressure
2Lower, dry-pressing formed after, under 110 ℃, 450 ℃, 750 ℃, 900 ℃, 1500 ℃, 1900 ℃, stage drying 13h makes the calcining furnace refractory materials respectively.
Step e gained fire bond and white carbon black, ammonium humate (HA-NH
4), tween (TWEEN-85), silane-KH570, polyvinyl alcohol (PVA-1799), carboxymethyl cellulose (CMC) promoting agent, mix by following mass ratio: 20:50: 15: 40: 25: 9: 13, and after dissolving mixes under 220 ℃ of temperature, make the steel melting furnace refractory materials.
Claims (4)
1. the method for the intensive production fire bond of tar needle-shape coke is characterized in that comprising following each step:
A. get raw material by the prescription of following mass percent:
Coal-tar pitch 30～50%
Modified coal-tar 40～50%
Conditioning agent 5.5～19.5%
Nickel, vanadium, cobalt remove agent 1.0～10.5%;
Described coal-tar pitch is the lighting coal tar of coal needle coke delay coking process by-product;
Described modified coal-tar obtains through following method: the mass ratio of pressing Mei Jiao You ︰ by-product oil=30～50 ︰ 40～50, with coal tar with after by-product oil mixes mixing oil, amount by 0.20～1L/min, in mixing oil, pass into technical grade hydrogen, and be that 350～460 ℃, pressure are that 0.1～5Mpa, oil gas speed ratio are 0.1～3.0h in temperature
-1, catalyzer is γ-Al
2O
3, ZSM-5 molecular sieve condition under, the reaction 3～15h, namely get modified coal-tar;
Described conditioning agent is that aromatize degree BMCI is 30～75 conditioning agent, for a kind of in the following organism or by several composition the in the following organism: crude benzol, toluene, heavy benzol, kerosene, diesel oil, ethylene glycol, propylene glycol, aromatic solvent naphtha, washing oil, carbolineum, take off aromatic solvent naphtha, wherein, described aromatize degree BMCI is calculated by following formula:
BMCI=?48640/Tb,m+473.6d-456.8
In the formula, Tb, m are raw material boiling point mean value, and unit is K;
D is the density of raw material when 288.5K, and unit is kg/m
3
It is to obtain according to " preparation method of N-Methylimidazole ionic liquid " that described nickel, vanadium, cobalt remove agent;
B. the raw material with steps A is 50～200 ℃ in temperature, and speed is to separate under the condition of 10～50mm/min, obtains bottom isolate and top isolate;
C. the top isolate that the separation of B step is obtained gets the solvent oil product on upper strata through centrifugation, and middle level thing and lower floor's thing;
D. the bottom isolate that step B is obtained remains under 120～250 ℃, mass ratio by bottom Fen Li Wu ︰ mixture=1 ︰ 0.01～0.5, mixture is passed in the isolate of bottom, under 220～300 ℃ of temperature, react 3～8h, get softening temperature and reach 230～260 ℃ intermediates, wherein the volume ratio of mixture is: air: oxygen: carbolic oil=0.5～1.2: 0.25～1.2: 0.1;
E. be that 250～400 ℃, sieve aperture are to carry out the heat screening under the condition of 50～1000 μ m with the middle level thing of step D in temperature, obtain the screen overflow of particle diameter＞50～1000 μ m, further pulverize this screen overflow and get fire bond, and the screen underflow of particle diameter＜50～1000 μ m is directly as fire bond.
2. method according to claim 1, it is characterized in that: the conditioning agent in the described steps A is that aromatize degree BMCI is 55～70 conditioning agent.
3. method according to claim 1, it is characterized in that: the separation of described step B is finished in conventional settlement separator, the centrifugation of described C step is finished at conventional three sections centrifuge separators, perhaps, the separation of B, C step is to finish in the tripping device that is combined into by settlement separate machine and three sections centrifuge separators.
4. method according to claim 1 is characterized in that: the heat screening condition of described step e, and temperature is 250～300 ℃, sieve aperture is 300～600 μ m.
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| CN102766478B (en) * | 2012-07-23 | 2014-01-29 | 辽宁科技大学 | Method for producing low-Na+ high-QI (quinoline insoluble) mid-temperature pitch |
| EP3004070B1 (en) | 2013-05-28 | 2017-10-11 | Empire Technology Development LLC | Antioxidant humic acid derivatives and methods of preparation and use |
| EP3004069B1 (en) | 2013-05-28 | 2017-04-19 | Empire Technology Development LLC | Humic acid derivatives and methods of preparation and use |
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| CN104291841B (en) * | 2014-09-24 | 2016-02-10 | 中国京冶工程技术有限公司 | Environment-friendly type blast furnace iron outlet groove ramming mass and preparation method thereof |
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| CN101787298B (en) * | 2009-01-23 | 2014-05-28 | 北京石油化工学院 | Coal art pitch purification method |
| CN101508903B (en) * | 2009-03-20 | 2014-03-12 | 上海宝钢化工有限公司 | Process for continuously removing quinoline insoluble substances in coal tar pitch |
| CN102051191B (en) * | 2009-11-03 | 2013-07-24 | 上海宝钢化工有限公司 | Production method and system of coal-based needle coke |
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