CN115353902B - Additive for enhancing thermal state performance of coke and application method thereof - Google Patents
Additive for enhancing thermal state performance of coke and application method thereof Download PDFInfo
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- CN115353902B CN115353902B CN202210997051.0A CN202210997051A CN115353902B CN 115353902 B CN115353902 B CN 115353902B CN 202210997051 A CN202210997051 A CN 202210997051A CN 115353902 B CN115353902 B CN 115353902B
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- 239000000571 coke Substances 0.000 title claims abstract description 90
- 239000000654 additive Substances 0.000 title claims abstract description 57
- 230000000996 additive effect Effects 0.000 title claims abstract description 57
- 230000002708 enhancing effect Effects 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000003245 coal Substances 0.000 claims abstract description 144
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- UWTDFICHZKXYAC-UHFFFAOYSA-N boron;oxolane Chemical compound [B].C1CCOC1 UWTDFICHZKXYAC-UHFFFAOYSA-N 0.000 claims abstract description 21
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052796 boron Inorganic materials 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 230000035484 reaction time Effects 0.000 claims abstract description 6
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 239000000853 adhesive Substances 0.000 claims abstract description 4
- 230000001070 adhesive effect Effects 0.000 claims abstract description 4
- 238000004939 coking Methods 0.000 claims description 33
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical group C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 claims description 8
- 239000003077 lignite Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- -1 bicyclic aromatic compound Chemical class 0.000 claims description 6
- 238000000638 solvent extraction Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- 239000011802 pulverized particle Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 9
- 238000006197 hydroboration reaction Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000009257 reactivity Effects 0.000 description 16
- 239000007789 gas Substances 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000002802 bituminous coal Substances 0.000 description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005087 graphitization Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000011302 mesophase pitch Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000009798 Shen-Fu Substances 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 1
- 239000003830 anthracite Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- NNTOJPXOCKCMKR-UHFFFAOYSA-N boron;pyridine Chemical compound [B].C1=CC=NC=C1 NNTOJPXOCKCMKR-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 239000011294 coal tar pitch Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000003476 subbituminous coal Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- C10B57/06—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition containing additives
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Coke Industry (AREA)
Abstract
The invention relates to an additive for enhancing the thermal state performance of coke and a use method thereof, wherein the additive is prepared by mixing ashless coal and tetrahydrofuran borane and then reacting under the protection of inert gas; the mixing proportion of the ashless coal and the tetrahydrofuran borane is determined according to the mass percentage of boron in the mixture of 1-3 percent; the reaction temperature is 250-350 ℃, the reaction pressure is 0.5-1.2 Mpa, and the reaction time is 6-12 h; the adhesive capacity G of the additive is 85-95, and the basic fluidity MF is 5400-9500 ddpm. According to the invention, the ashless coal is used as a raw material, and boron element is introduced into the ashless coal through the hydroboration reaction of the ashless coal and the tetrahydrofuran borane, so that the bonding capacity of the ashless coal is improved, and the thermal performance of coke is improved; the additive has simple preparation method and low cost, and is suitable for mass production.
Description
Technical Field
The invention relates to the technical field of high-strength coke preparation, in particular to an additive for enhancing the thermal state performance of coke and a use method thereof.
Background
The traditional blast furnace has higher carbon emission, and the blast furnace hydrogen-rich smelting technology developed in recent years uses hydrogen, coke oven gas and the like as reducing agents to replace part of coke in the blast furnace, so that the situation of shortage of coal resources can be relieved by replacing part of metallurgical coke, and energy conservation and emission reduction can be realized. Because H is produced when hydrogen gas is used to reduce iron ore as compared with a carbon-based reducing agent 2 O instead of CO 2 Thus, it is more beneficial to reduce CO 2 And the emission is realized, so that the aim of carbon emission reduction is fulfilled.
When hydrogen is used as a reducing agent of the blast furnace, coke is lower than that of the traditional blast furnace, but the coke in the blast furnace has an irreplaceable effect, namely a framework effect of maintaining the ventilation property of a blast furnace material column and ensuring the smooth flow of reducing gas. In addition, since the heat absorption amount is increased by the participation of hydrogen in the reduction reaction to lower the temperature in the furnace and the rate of CO generation by the coke gasification reaction is reduced with the decrease of the temperature, the reactivity of the coke must be improved when hydrogen or coke oven gas (hydrogen-based reducing agent) is injected, and therefore, the study of high-strength high-reactivity coke plays an important supporting role in the study of the hydrogen reduction ironmaking technology. Compared with common coke, the high-reactivity coke has higher thermal reactivity, has the characteristics of low initial reaction temperature and high reaction rate, and the strength can meet the production requirement of a hydrogen-rich blast furnace.
At present, a great deal of research has been done on the preparation of high-reaction high-strength coke at home and abroad, and the high-strength high-reactivity coke researched and produced in japan is generally realized by adding catalysts (such as calcium-based, magnesium-based, iron-based catalysts and the like), wherein the adjustment of the coke strength is generally realized by adding a strong binder HPC.
The strong binder HPC is called as an ashless coal, and is prepared by the solvent extraction of bituminous coal, subbituminous coal, lignite and the like in an autoclave, and researches show that the strong binder HPC can improve the cohesiveness of the blended coal and improve the coke quality. But has limited improvement on coking coal quality and coke performance due to the characteristics of the chemical structure. According to the invention, the ashless coal and the tetrahydrofuran borane are used as raw materials, and boron element is introduced into the ashless coal through the hydroboration reaction, so that the bonding capacity of the ashless coal is improved, and meanwhile, the thermal state performance of coke is effectively improved due to the introduction of the boron element.
The Chinese patent publication No. CN1142245C discloses a preparation method of boron substituted carbon material, which comprises the steps of uniformly mixing coal tar without quinoline insoluble matters or coal tar pitch without quinoline insoluble matters with pyridine borane complex according to a certain proportion, reacting for 4-20 hours at the pressure of 0.4-2MPa and the temperature of 380-460 ℃ to obtain boron substituted mesophase pitch, carrying out hot melting by tetrahydrofuran, carrying out vacuum drying, oxidizing for 0.5-20 hours in air or oxygen at 160-300 ℃, grinding oxidized powder to the granularity d of less than or equal to 100 mu m, carrying out cold press molding at the pressure of 70-120MPa, and carrying out carbonization and graphitization to obtain the high-density high-strength carbon product. The method is easy to obtain sintering powder with good sintering performance, and the boron-substituted carbon material with higher mechanical strength can be obtained under lower pressure.
Compared with the prior art, the method adopts the raw material of ashless coal which is prepared from coal and has the property of coal and is essentially different from asphalt. The patent carries out the processes of hot melting, filtering, vacuum drying, oxidizing and the like on the obtained boron-substituted mesophase pitch to obtain boron-substituted mesophase powder, and then grinding, cold press molding, carbonizing and graphite to obtain the high-strength boron-substituted carbon material. The technological process and the final finished product are completely different from the invention. In addition, the boron is introduced into the ashless coal to better maintain the cohesiveness of the ashless coal and improve the thermal state performance of the coke, and if the oxidation process in the patent is adopted, the cohesiveness of the coal is destroyed. The additive is the boron-containing ashless coal, and is favorable for improving the quality of coke when being matched into coking coal due to strong cohesiveness, and meanwhile, the existence of boron element passivates the dissolution loss reaction of the coke, so that the thermal state performance of the coke is improved. The patent prepares a carbon material, and the purpose of adding boron is to improve the mechanical property, oxidation resistance and graphitization property of the carbon material.
Disclosure of Invention
The invention provides an additive for enhancing the thermal performance of coke and a use method thereof, wherein ashless coal is used as a raw material, boron element is introduced into the ashless coal through the hydroboration reaction of the ashless coal and tetrahydrofuran borane, so that the bonding capacity of the ashless coal is improved, and the thermal performance of the coke is improved; the additive has simple preparation method and low cost, and is suitable for mass production.
In order to achieve the above purpose, the invention is realized by adopting the following technical scheme:
an additive for enhancing the thermal state performance of coke is prepared by mixing ashless coal with tetrahydrofuran borane and reacting under the protection of inert gas; the mixing proportion of the ashless coal and the tetrahydrofuran borane is determined according to the mass percentage of boron in the mixture of 1-3 percent; the reaction temperature is 250-350 ℃, the reaction pressure is 0.5-1.2 Mpa, and the reaction time is 6-12 h; the adhesive capacity G of the additive is 85-95, and the basic fluidity MF is 5400-9500 ddpm.
Further, the ashless coal is prepared from low-rank coal with the volatile matter Vdaf more than 37% through solvent extraction.
Further, the low-rank coal is composed of one or more of brown coal, long flame coal, non-caking coal and weak caking coal.
Further, the granularity of the low-rank coal is less than 200 meshes, and the water content is less than 3%.
Further, the solvent is a coal derived bicyclic aromatic compound.
Further, the solvent is methylnaphthalene.
The application method of the additive for enhancing the thermal state performance of the coke comprises the steps of crushing the additive, mixing the crushed additive into coking coal for coking, wherein the crushed granularity of the additive is matched with the granularity of the coking coal.
Further, when the blended coal is adopted for coking, the additive is added according to 5-20% of the total weight of the blended coal.
Compared with the prior art, the invention has the beneficial effects that:
1) Adopting ashless coal to react with tetrahydrofuran borane, decomposing the tetrahydrofuran borane into borane after heating, and carrying out hydroboration reaction with aromatic hydrocarbon in the ashless coal, thereby introducing boron element into the ashless coal; not only improves the bonding capacity of the ashless coal, but also improves the thermal state performance of the coke well due to the introduction of boron;
2) The additive has simple preparation method and low cost, and is suitable for mass production.
Drawings
FIG. 1 is a block diagram of the preparation and use of an additive for enhancing the thermal properties of coke according to the present invention.
Detailed Description
The additive for enhancing the thermal performance of coke is prepared by mixing ashless coal and tetrahydrofuran borane and then reacting under the protection of inert gas; the mixing proportion of the ashless coal and the tetrahydrofuran borane is determined according to the mass percentage of boron in the mixture of 1-3 percent; the reaction temperature is 250-350 ℃, the reaction pressure is 0.5-1.2 Mpa, and the reaction time is 6-12 h; the adhesive capacity G of the additive is 85-95, and the basic fluidity MF is 5400-9500 ddpm.
Further, the ashless coal is prepared from low-rank coal with the volatile matter Vdaf more than 37% through solvent extraction.
Further, the low-rank coal is composed of one or more of brown coal, long flame coal, non-caking coal and weak caking coal.
Further, the granularity of the low-rank coal is less than 200 meshes, and the water content is less than 3%.
Further, the solvent is a coal derived bicyclic aromatic compound.
Further, the solvent is methylnaphthalene.
According to the application method of the additive for enhancing the thermal performance of the coke, the additive is crushed and then is mixed into coking coal for coking, and the crushed granularity of the additive is matched with the granularity of the coking coal.
Further, when the blended coal is adopted for coking, the additive is added according to 5-20% of the total weight of the blended coal.
The preparation and application flow chart of the additive for enhancing the thermal state property of coke (simply referred to as additive) is shown in figure 1.
The preparation method of the additive comprises mixing ashless coal with tetrahydrofuran borane, placing in a reaction vessel (such as autoclave), and placing in inert gas (such as N 2 Gas) under the protection of the gas, and reacting for a period of time under the condition of certain pressure and temperature; the ashless coal is prepared by solvent extraction of low-rank coal with higher volatile matters (Vdaf is more than 37%), and the low-rank coal is selected from one or more of brown coal, long flame coal, non-caking coal and weak caking coal.
The pressure range of the ashless coal in the reaction with tetrahydrofuran borane is 0.5-1.2 Mpa; preferably, the pressure ranges from 0.7 to 1.0Mpa.
The temperature range of the ashless coal when reacting with tetrahydrofuran borane is 250-350 ℃; preferably, the temperature is in the range of 280 to 300 ℃.
The reaction time of the ashless coal and the tetrahydrofuran borane is 6-12 h; preferably, the reaction time is 8.5 to 10 hours.
Further, the granularity of the low-rank coal is less than 200 meshes.
Further, the water content of the low-rank coal is less than 3%.
The solvent is a coal-derived bicyclic aromatic compound; preferably, the solvent is methylnaphthalene.
The bonding capacity G of the additive for enhancing the thermal state performance of the coke prepared by the invention is 85-95, and preferably, the bonding capacity G is 90-95; the basic fluidity MF is 5400-9500 ddpm, and the boron content in the additive is 1-3%.
The application method of the additive for enhancing the thermal state performance of coke comprises the steps of crushing the additive and then blending the crushed additive into coking coal for coking.
The thermal performance of the coke refers to the capability of the coke to react with carbon dioxide at high temperature and the capability of the coke to resist fragmentation and abrasion after the reaction, and the coke reactivity is evaluated by adopting the reaction between the coke and the carbon dioxide according to GB/T4000-2017 Experimental methods of coke reactivity and strength after the reaction, namely: a coke sample of a certain mass was weighed and placed in a reactor and reacted with carbon dioxide at 1100 ℃ for 2 hours, and the coke reactivity (Coke Reactivity Index, abbreviated CRI) was expressed as a percentage of the mass loss of coke. After the reaction, the coke was subjected to a type I drum test, and the post-reaction strength (Coke Strength After Reaction, abbreviated as CSR) was expressed as a percentage of the mass of the coke having a particle size of more than 10mm to the mass of the coke after the reaction.
The invention relates to the binding capacity, which is the capacity of a coal sample to bind anthracite in the coking process, and is expressed by G, and the binding capacity is evaluated according to GB/T5447-2014 Bituminous coal binding index determination method, and the sum of coke mass weight m1 multiplied by 30 of more than 1mm after a first rotary drum and coke mass weight m2 multiplied by 70 of more than 1mm after a second rotary drum is divided by the total weight of coke slag after coking treatment, and is expressed by 10.
The invention relates to a base fluidity, which is characterized in that a rotatable stirrer inserted into a coal sample is driven by a fixed moment, when the coal sample is heated to generate a colloid body under the condition of air isolation, different resistances are applied to the stirrer along with the change of the fluidity of the colloid body of the coal, and the resistances are expressed by MF. The invention measures the basic fluidity according to the measuring method of the maximum fluidity in GB/T25213-2010 "coal plasticity measuring-constant moment base plasticity meter method", and the unit ddpm is represented by the data when the stirring paddle rotates to the maximum speed.
In order to make the purposes, technical schemes and technical effects of the embodiments of the present invention more clear, the technical schemes in the embodiments of the present invention are clearly and completely described. The embodiments described below are some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art without the benefit of the teachings of this invention, are intended to be within the scope of the invention.
In the examples below, each of the starting reagent materials is commercially available, and the experimental methods without specifying the specific conditions are conventional methods and conventional conditions well known in the art or are conducted under conditions recommended by the instrument manufacturer.
In the following examples, the low rank coals used are specifically as follows: the long flame coal is black mountain long flame coal, the lignite is Hoolin Guo lignite, the non-sticky coal is Shenfu non-sticky coal, the weak sticky coal is Huang Ling weak sticky coal, and each coal type accords with the definition of coking coal classification in GB/T5751-2009 "China coal Classification".
In the following examples, the autoclave was purchased and the specification and model were GSH-100, and the manufacturer was Taixing Xinfa laboratory instrument.
[ example 1 ]
In the embodiment, according to the weight percentage of boron being 1%, the ashless coal and tetrahydrofuran borane are mixed together by 120g and then placed in an autoclave, nitrogen is introduced for protection, the initial pressure is 0.1MPa, the heating speed is 5 ℃/min, the final temperature is 280 ℃, the final pressure is 8.3MPa, and the temperature and pressure are maintained for reaction for 8.5 hours, so that the additive for enhancing the thermal performance of the coke is obtained.
In this example, ashless coal was prepared from lignite by extraction with a-methylnaphthalene, G of the ashless coal being 75 and MF being 13224ddpm. The G of the prepared additive for enhancing the thermal state performance of coke is 88, and the MF is 9231ddpm.
The prepared additive is added into conventional blended coal according to the total weight of the blended coal to carry out 2kg coking experiments, and the reactivity and the strength after reaction of the obtained high-strength coke are measured.
In the embodiment, the proportion of the blended coal is as follows by weight percent: 5% of Jiangchang gas coal, 20% of Dongshan 1/3 coking coal, 33% of dragon lake fat coal, 32% of peduncles coking coal and 10% of red sun lean coal.
The high strength coke prepared in this example was tested using GB/T4000-2017 method for Coke reactivity and post reaction Strength test, with a Coke reactivity CRI of 22.6% and a Coke post reaction Strength CSR of 63.3%.
[ example 2 ]
In the embodiment, according to the weight percentage of boron being 2%, the ashless coal and tetrahydrofuran borane are mixed together by 120g and then placed in an autoclave, nitrogen is introduced for protection, the initial pressure is 0.1MPa, the heating speed is 5 ℃/min, the final temperature is 280 ℃, the final pressure is 8.5MPa, and the temperature and pressure are maintained for reaction for 8.5 hours, so that the additive for enhancing the thermal performance of the coke is obtained.
In this example, ashless coal was prepared from long flame coal by extraction with a-methylnaphthalene, the ashless coal having a G of 85 and an MF of 12021ddpm. The G of the prepared additive for enhancing the thermal state property of coke is 90, and the MF is 8205ddpm.
The prepared additive is added into conventional blended coal according to the total weight of the blended coal to carry out 2kg coking experiments, and the reactivity and the strength after reaction of the obtained high-strength coke are measured.
In the embodiment, the proportion of the blended coal is as follows by weight percent: 5% of Jiangchang gas coal, 20% of Dongshan 1/3 coking coal, 33% of dragon lake fat coal, 32% of peduncles coking coal and 10% of red sun lean coal.
The high strength coke prepared in the examples was measured using GB/T4000-2017 method for Coke reactivity and post reaction Strength test, with a Coke reactivity CRI of 20.6% and a Coke post reaction Strength CSR of 65.3%.
[ example 3 ]
In the embodiment, according to the weight percentage of boron being 3%, the ashless coal and tetrahydrofuran borane are mixed together by 120g and then placed in an autoclave, nitrogen is introduced for protection, the initial pressure is 0.1MPa, the heating speed is 5 ℃/min, the final temperature is 300 ℃, the final pressure is 9.4MPa, and the temperature and pressure are maintained for reaction for 9 hours, so that the additive for enhancing the thermal state performance of coke is obtained.
In this example, ashless coal was prepared from non-caking coal by extraction with a-methylnaphthalene, the ashless coal having a G of 88 and an MF of 10247ddpm. The additive G for enhancing the thermal state performance of the coke is 94, and the MF is 7242ddpm.
The prepared additive is added into conventional blended coal according to 15 percent of the total weight of the blended coal to carry out 2kg coking experiments, and the reactivity and the strength after reaction of the obtained high-strength coke are measured.
In the embodiment, the proportion of the blended coal is as follows by weight percent: 5% of Jiangchang gas coal, 20% of Dongshan 1/3 coking coal, 33% of dragon lake fat coal, 32% of peduncles coking coal and 10% of red sun lean coal.
The high strength coke prepared in this example was found to have a coke reactivity CRI of 20.1% and a coke post-reaction strength CSR of 66.5% using GB/T4000-2017 method for Coke reactivity and post-reaction strength test.
[ comparative example ]
The difference between this comparative example and examples 1, 2 and 3 is that no additive for enhancing the thermal performance of coke was added to the blended coal. The same coal types and weight percentages as in examples 1, 2 and 3 are adopted, and the proportions thereof are as follows: 5% of Jiangchang gas coal, 20% of Dongshan 1/3 coking coal, 33% of dragon lake fat coal, 32% of peduncles coking coal and 10% of red sun lean coal.
Weighing each coal according to the proportion to obtain 2kg of mixture, uniformly mixing by a mixer, and then feeding into a 2kg test coke oven for coking to obtain coke.
The GB/T4000-2017 test method for coke reactivity and strength after reaction is adopted, and the CRI of the coke is measured to be 30.6 percent, and the CSR of the coke after reaction is measured to be 51.3 percent.
Conclusion: the embodiment adopts the ashless coal and the tetrahydrofuran borane to react to prepare the additive for enhancing the thermal performance of the coke, and the additive is crushed and then is mixed into the coking coal for coking.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (8)
1. An additive for enhancing the thermal state performance of coke is characterized in that the additive is prepared by mixing ashless coal and tetrahydrofuran borane and then reacting under the protection of inert gas; the mixing proportion of the ashless coal and the tetrahydrofuran borane is determined according to the mass percentage of boron in the mixture of 1-3 percent; the reaction temperature is 250-350 ℃, the reaction pressure is 0.5-1.2 Mpa, and the reaction time is 6-12 h; the adhesive capacity G of the additive is 85-95, and the basic fluidity MF is 5400-9500 ddpm.
2. An additive for enhancing the thermal properties of coke according to claim 1, wherein the ashless coal is produced from low rank coal having a volatile Vdaf > 37% by solvent extraction.
3. The additive for enhancing the thermal performance of coke according to claim 2, wherein the low-rank coal is composed of one or more of brown coal, long flame coal, non-caking coal and weakly caking coal.
4. An additive for enhancing the thermal properties of coke according to claim 2, wherein the particle size of the low-rank coal is less than 200 mesh and the water content is less than 3%.
5. An additive for enhancing the thermal properties of coke according to claim 2, wherein the solvent is a coal derived bicyclic aromatic compound.
6. An additive for enhancing the thermal properties of coke according to claim 5, wherein said solvent is methylnaphthalene.
7. The method of using the additive for enhancing thermal performance of coke according to any one of claims 1 to 6, wherein the additive is pulverized and then added into coking coal for coking, and the pulverized particle size of the additive is adapted to the particle size of the coking coal.
8. The method of claim 7, wherein the additive is added in an amount of 5% to 20% by weight based on the total weight of the blended coal when the blended coal is used for coking.
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