TW201406945A - Process and device for the production of metallurgical coke from petrol coal obtained in petroleum refineries by carbonisation in non-recovery or heat-recovery coke ovens - Google Patents
Process and device for the production of metallurgical coke from petrol coal obtained in petroleum refineries by carbonisation in non-recovery or heat-recovery coke ovens Download PDFInfo
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- 239000000571 coke Substances 0.000 title claims abstract description 192
- 239000003245 coal Substances 0.000 title claims abstract description 179
- 238000000034 method Methods 0.000 title claims abstract description 74
- 238000003763 carbonization Methods 0.000 title claims abstract description 35
- 238000011084 recovery Methods 0.000 title claims abstract description 31
- 239000003208 petroleum Substances 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 title abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 71
- 230000009257 reactivity Effects 0.000 claims abstract description 18
- 239000003502 gasoline Substances 0.000 claims description 127
- 239000000203 mixture Substances 0.000 claims description 63
- 239000007789 gas Substances 0.000 claims description 51
- 238000003860 storage Methods 0.000 claims description 33
- 239000000654 additive Substances 0.000 claims description 31
- 230000000996 additive effect Effects 0.000 claims description 27
- 238000002485 combustion reaction Methods 0.000 claims description 23
- 239000002737 fuel gas Substances 0.000 claims description 19
- 238000000926 separation method Methods 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 9
- 238000012545 processing Methods 0.000 claims description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000010298 pulverizing process Methods 0.000 claims description 7
- 238000009826 distribution Methods 0.000 claims description 5
- 238000005056 compaction Methods 0.000 claims description 4
- 239000003345 natural gas Substances 0.000 claims description 4
- 238000009423 ventilation Methods 0.000 claims description 4
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 238000005360 mashing Methods 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- 239000010426 asphalt Substances 0.000 claims description 2
- 229910010293 ceramic material Inorganic materials 0.000 claims description 2
- 239000002817 coal dust Substances 0.000 claims description 2
- 238000012840 feeding operation Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000012423 maintenance Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000011214 refractory ceramic Substances 0.000 claims description 2
- 239000004576 sand Substances 0.000 claims description 2
- 239000011232 storage material Substances 0.000 claims 1
- 125000004122 cyclic group Chemical group 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000011335 coal coke Substances 0.000 description 5
- 238000004939 coking Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 239000003039 volatile agent Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 238000010000 carbonizing Methods 0.000 description 2
- 238000010310 metallurgical process Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
Classifications
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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
- C10B15/00—Other coke ovens
- C10B15/02—Other coke ovens with floor heating
-
- 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
- C10B45/00—Other details
- C10B45/02—Devices for producing compact unified coal charges outside the oven
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Coke Industry (AREA)
Abstract
Description
本發明係關於一種藉由在非回收或熱回收煉焦爐中碳化自煉油廠獲得之汽油煤以製備冶金焦的方法,該方法係基於在煉油廠中獲得或製備的汽油煤,且該汽油煤自一開始便具有15wt.%至19wt.%之揮發物含量及至多2wt.%之灰分含量,且以壓實之形式饋送至該非回收或熱回收型煉焦爐以進行循環碳化,該煉焦爐配備有至少一個獨立加熱之燃燒器,由此將主要加熱空間或在該煉焦爐室下方之次要加熱空間或二者加熱至介於1000℃與1550℃之間的溫度,且在不到120小時之時間段內,該汽油煤中所含的揮發物含量完全脫氣,從而獲得CSR強度為至少44%且CRI反應性小於33%之冶金焦,且其適於用作冶金焦。本發明亦係關於一種煉焦爐,其係根據該非回收或熱回收類型設計,且配備有主要加熱空間,具備加熱該主要加熱空間之燃燒器。 The present invention relates to a method for preparing metallurgical coke by carbonizing gasoline coal obtained from a refinery in a non-recovered or heat recovery coke oven based on gasoline coal obtained or prepared in a refinery, and the gasoline coal From the beginning, having a volatile content of 15 wt.% to 19 wt.% and an ash content of up to 2 wt.%, and feeding it to the non-recovery or heat recovery coke oven in a compacted form for cyclic carbonization, the coke oven is equipped Having at least one independently heated burner thereby heating the primary heating space or the secondary heating space below the coke oven chamber or both to a temperature between 1000 ° C and 1550 ° C, and in less than 120 hours During the time period, the volatiles contained in the gasoline coal are completely degassed, thereby obtaining a metallurgical coke having a CSR strength of at least 44% and a CRI reactivity of less than 33%, and which is suitable for use as a metallurgical coke. The present invention also relates to a coke oven designed according to the non-recovery or heat recovery type and equipped with a main heating space having a burner for heating the main heating space.
在精煉廠中將礦物油及石油加工成石油產品時,除了獲得想要的產品外,亦獲得所謂的汽油焦,該汽油焦係由煉油廠之蒸餾製程、重組步驟、氫化製程及純化操作中之殘留物高溫沸騰而形成。此汽油焦典型地由超過88wt.%之碳及8wt.%至12wt.%含量之揮發性成分(volatile constituent,VOC)組成。此汽油焦僅具有極少經濟利益,因為就許多應用製程而言,其具有一些不想要的特性,諸如低CSR強度及高CRI反應性,且出於此原因,其無法容易地上市銷售。 When processing mineral oil and petroleum into petroleum products in a refinery, in addition to obtaining the desired products, so-called gasoline coke is obtained, which is processed by the distillation process, recombination step, hydrogenation process and purification operation of the refinery. The residue is formed by boiling at a high temperature. This gasoline coke is typically composed of more than 88 wt.% carbon and 8 wt.% to 12 wt.% volatile components (volatile Constituent, VOC) composition. This gasoline coke has only minimal economic benefit because it has some undesirable characteristics, such as low CSR strength and high CRI reactivity, for many applications, and for this reason it cannot be easily marketed.
汽油焦常用於諸如製造電極之冶金製程之適合應用。不可能在冶金工廠中使用汽油焦,例如在鼓風爐製程中作為還原劑以製造粗鐵,因為汽油焦之強度不足以用於鼓風爐中。此外,已知向硬煤混合物中混合數個汽油焦部分,然而,汽油焦之混合部分因由其產生之鼓風爐焦的等級低而侷限於不到10wt.%之量值。 Gasoline coke is commonly used in suitable applications such as metallurgical processes for making electrodes. It is not possible to use gasoline coke in a metallurgical plant, for example as a reducing agent in a blast furnace process to produce coarse iron, since the strength of the gasoline coke is insufficient for use in a blast furnace. Furthermore, it is known to mix several gasoline coke portions into a hard coal mixture, however, the mixed portion of the gasoline coke is limited to a value of less than 10 wt.% due to the low level of blast furnace coke produced therefrom.
汽油焦之另一問題為源自於石油加工之雜質,且當該焦已排出時,雜質仍積累於該焦中。常見於汽油焦中之雜質為例如釩、鎳、硫、矽、鐵或鈦。因此,汽油焦部分中之釩含量可為至多0.17wt.%、鎳含量為至多0.04wt.%且硫含量為至多5wt.%。該等雜質使得汽油焦無法容易地用於加熱目的,因為此將影響環境。汽油焦之另一特性為其火焰溫度低於鼓風爐焦或煤。就用作燃料及其處理而言,此為不想要的,且因此其無法用於許多後續製程。因此,有機會尋求提供汽油焦之可能的經濟應用。 Another problem with gasoline coke is that it is derived from impurities in petroleum processing, and when the coke has been discharged, impurities still accumulate in the coke. Common impurities in gasoline char are, for example, vanadium, nickel, sulfur, antimony, iron or titanium. Therefore, the vanadium content in the gasoline coke portion may be at most 0.17 wt.%, the nickel content is at most 0.04 wt.%, and the sulfur content is at most 5 wt.%. These impurities make gasoline coke unusable for heating purposes as this will affect the environment. Another characteristic of gasoline coke is that the flame temperature is lower than that of blast furnace coke or coal. This is undesirable for use as a fuel and its treatment, and therefore it cannot be used in many subsequent processes. Therefore, there is an opportunity to seek a possible economic application of providing gasoline coke.
此外,防止冶金焦以使得碳化製程適合於汽油焦特性之方式製造的根本原因除雜質及缺乏產品強度之外,還有波動部分的揮發性成分。波動部分的揮發性成分使得由於加熱特性因揮發性成分而難以預測,故在煉焦爐中的使用很難控制。通常,在精煉廠中製造的汽油焦之主要部分含有不到19wt.%之極低部分揮發性成分,因此,當用於非回收或熱回收煉焦爐中時,汽油焦不適合於維持自持性燃燒製程且由此無法維持碳化製程。事實上,若在此煉焦爐中僅使用汽油焦作為原料,則碳化製程將在若干碳化循環後結束,因為在碳化期間由揮發性成分燃燒產生且儲存於該爐之耐火材料中的熱不再足以使爐溫在後續批次期間保持在超過1000℃之所需高值。 In addition, the root cause of preventing metallurgical coke from being manufactured in such a manner that the carbonization process is suitable for gasoline coke characteristics, in addition to impurities and lack of product strength, is also a volatile component of the fluctuating portion. The volatile component of the fluctuating portion makes it difficult to predict the use in the coke oven because the heating characteristics are difficult to predict due to the volatile components. Typically, the major portion of gasoline coke produced in a refinery contains less than 19 wt.% of very low volatile components, so gasoline coke is not suitable for maintaining self-sustaining combustion when used in non-recovery or heat recovery coke ovens. The process and thus the carbonization process cannot be maintained. In fact, if only gasoline char is used as the raw material in the coke oven, the carbonization process will end after several carbonization cycles because the heat generated by the combustion of the volatile components during the carbonization and stored in the refractory of the furnace is no longer Sufficient to maintain the furnace temperature at a desired high value in excess of 1000 °C during subsequent batches.
利用煤碳化之另一難點在於在碳化中,汽油焦之特徵為極高膨脹壓力,且此係歸因於其中所含揮發性成分之低沸點。在碳化期間,該等特徵導致焦餅之體積明顯增加,事實上為「膨脹」。因此,不可能在習知煉焦爐中使汽油煤碳化,因為在碳化期間,煉焦爐室之壁將因汽油煤餅之體積增加而受到損壞。由所提及之汽油煤餅特性引起之汽油煤餅體積增加亦使得很難將利用硬煤混合物中之汽油焦部分製造的煤焦產品推出習知煉焦爐室。 Another difficulty in utilizing coal carbonization is that in carbonization, gasoline coke is characterized by extremely high expansion pressures, and this is due to the low boiling point of the volatile components contained therein. During carbonization, these features result in a significant increase in the volume of the coke cake, which is in fact "expanded." Therefore, it is impossible to carbonize gasoline coal in a conventional coke oven because the wall of the coke oven chamber will be damaged by the increase in the volume of the gasoline coal cake during carbonization. The increase in the volume of gasoline briquettes caused by the characteristics of the gasoline briquettes mentioned also makes it difficult to introduce coal char products made from the gasoline coke portion of the hard coal mixture into conventional coke oven chambers.
WO0010914A1中給出了用於加工且進一步使用汽油焦之一種可能性。該教示內容提供了一種方法,在該方法中,源自於煉油廠及由來自礦物油之汽油焦前驅材料獲得的汽油焦在適宜壓力及足夠高的溫度下經歷熱重組製程且持續一段足夠長的時間,由此獲得汽油焦,該汽油焦含有13wt.%至50wt.%之較低且精確可調之揮發物含量。該方法亦揭露一種使汽油焦去離子從而移除其中所含之金屬雜質的可能性。最後,該教示內容亦揭露一種例如藉由在流化床中添加脫硫劑將汽油焦中之硫雜質降低到較低且環境可接受之部分的可能性。該方法提供了一種提供具有經相當精確地計算之揮發性成分及雜質含量的汽油焦部分的可能性。具有15wt.%至25wt.%之揮發性部分的汽油焦部分因為特性類似於習知之乾蒸汽煤(dry steam coal)或肥煤(fat coal),亦稱為「汽油煤(petrol coal)」。 One possibility for processing and further use of gasoline coke is given in WO0010914A1. The teachings provide a method in which a gasoline coke derived from a refinery and a gasoline coke precursor material derived from mineral oil undergoes a thermal recombination process at a suitable pressure and a sufficiently high temperature for a length of time sufficient At that time, gasoline char is obtained, which contains a low and precisely adjustable volatile content of 13 wt.% to 50 wt.%. The method also discloses the possibility of deionizing gasoline char to remove metal impurities contained therein. Finally, the teachings also disclose the possibility of reducing the sulfur impurities in the gasoline char to a lower and environmentally acceptable portion, for example by adding a desulfurizing agent to the fluidized bed. The method provides the possibility of providing a gasoline char portion having a relatively accurately calculated volatile component and impurity content. The gasoline coke portion having a volatile portion of 15 wt.% to 25 wt.% is similar in characteristics to the conventional dry steam coal or fat coal, also referred to as "petrol coal".
具有可精確測定部分之揮發性成分及雜質之汽油煤的可用性提供了使用所獲得的汽油煤製造冶金焦之新可能。在石油加工過程中,製造出揮發物含量為15wt.%至19wt.%之特別高部分之汽油煤。截至目前,因為低能含量、低成本效益、在碳化期間之危險膨脹壓力、大量雜質及與此產品相關之高燃燒損失之問題無法藉由習知碳化製程解決,所以此產品尚未在工業規模上進行加工。然而,由該特定分數之汽油焦製造的冶金焦之實驗室測試已經確定,該冶金焦具有良好等級。與該等測試有關之實例 教示於Stukov等人之文章,「Increasing the Strength of Met-allurgical Petroleum Coke to the Coking Batch」,Coke and Chemistry.2009,第52卷,第8期,第349-352頁中。由於截至目前,由汽油煤製造冶金焦之技術可行性尚未進行安全處理,故需要獲得一種藉由汽油煤之碳化製造冶金焦之可實行的方法。 The availability of gasoline coal with precisely quantifiable portions of volatile components and impurities provides a new possibility to produce metallurgical coke using the obtained gasoline coal. In the petroleum processing process, a particularly high portion of gasoline coal having a volatile content of 15 wt.% to 19 wt.% is produced. As of now, the problem of low energy content, low cost efficiency, dangerous expansion pressure during carbonization, large amounts of impurities and high combustion losses associated with this product cannot be solved by conventional carbonization processes, so this product has not been carried out on an industrial scale. machining. However, laboratory testing of metallurgical coke made from this particular fraction of gasoline coke has determined that the metallurgical coke has a good rating. Examples related to such tests The teachings of Stukov et al., "Increasing the Strength of Met-allurgical Petroleum Coke to the Coking Batch", Coke and Chemistry. 2009, Vol. 52, No. 8, pp. 349-352. Since the technical feasibility of manufacturing metallurgical coke from gasoline coal has not been safely treated so far, it is necessary to obtain a practicable method for manufacturing metallurgical coke by carbonization of gasoline coal.
因此,一個目的係提供一種提供具有15wt.%至19wt.%部分之揮發性成分及增加部分之雜質之汽油煤的方法,該方法在工業規模上使用該汽油煤進行碳化並製造煤焦,該煤焦具有增加之強度及低反應性且適合用作冶金焦。 Accordingly, it is an object to provide a method of providing gasoline coal having a volatile component of 15 wt.% to 19 wt.% and an increased portion of impurities, which is carbonized on an industrial scale using the gasoline coal and produces coal char. Coal char has increased strength and low reactivity and is suitable for use as a metallurgical coke.
本發明藉由如下之方法來實現該目的,該方法提供具有15wt.%至19wt.%之已知揮發性成分含量及至多2wt.%之已知灰分部分之汽油煤,且隨後在正常狀況下,在非回收或熱回收型煉焦爐之加熱室中在介於1000℃與1550℃之間之溫度下,將呈壓實形式之該汽油煤在120小時內碳化成冶金焦,該爐配備有至少一個燃燒器,用於加熱在汽油煤餅上方在操作期間包含殘留氣體空間的主要加熱空間,或用於加熱在煉焦爐室下方之次要加熱空間,或二者。 The present invention achieves this object by providing a gasoline having a known volatile component content of 15 wt.% to 19 wt.% and a known ash fraction of up to 2 wt.%, and then under normal conditions. The carbonized coal in a compacted form is carbonized into metallurgical coke in a heating chamber of a non-recovery or heat recovery type coke oven at a temperature between 1000 ° C and 1550 ° C, and the furnace is equipped with At least one burner for heating a primary heating space containing a residual gas space above the gasoline coal cake during operation, or for heating a secondary heating space below the coke oven chamber, or both.
汽油焦之揮發物含量及灰分含量係藉由在碳化之前進行分析來測定,不管分析是在煉焦爐工廠還是汽油煤供應商之前提下進行。對於體現本發明之方法之具體實例,唯一重要的是,提供一種具有已知揮發性成分含量之汽油煤,所觀測之揮發性成分含量在最低15wt.%與最高19wt.%之間之範圍內。 The volatile content and ash content of the gasoline coke are determined by analysis prior to carbonization, regardless of whether the analysis is carried out prior to the coke oven plant or the gasoline coal supplier. For the specific example of the method embodying the present invention, it is only important to provide a gasoline coal having a known volatile component content, and the observed volatile component content is in the range of at least 15 wt.% and up to 19 wt.%. .
為了補償具有所提及特性之汽油煤因揮發性成分部分較低而引起的降低之能含量,主要加熱空間或次要加熱空間必須使用外部燃料氣加熱,因為僅僅想要此低能量汽油煤部分在非回收或熱回收型煉焦反應器中加工成冶金焦。另外,由於原料之低能含量不足以持久地將溫度維持 在高於1000℃之所需值且因此不足以補償該方法必然伴隨之高廢氣及輻射損失,故將產生極長且不經濟之碳化期。 In order to compensate for the reduced energy content of gasoline coal with the mentioned properties due to the lower fraction of volatile components, the main heating space or secondary heating space must be heated with external fuel gas, as only this low-energy gasoline coal portion is desired Processed into metallurgical coke in a non-recovery or heat recovery coking reactor. In addition, due to the low energy content of the raw materials, the temperature is maintained for a long time. At temperatures above 1000 ° C and therefore insufficient to compensate for the high exhaust gas and radiation losses that are necessarily associated with the process, an extremely long and uneconomical carbonization period will result.
然而,使用非回收或熱回收型煉焦爐允許將主要由汽油煤組成且具有所提及之特性的進料混合物碳化,因為此類煉焦爐在操作期間於汽油煤餅之上方提供殘留氣體空間,該氣體空間吸收汽油煤之逐漸升高的膨脹壓力。在本發明之框架內,已確定由此獲得的煤焦等級之特徵在於超過44%之CSR強度及不到33%之CRI反應性,因此,該等煤焦等級可用作例如冶金或鼓風爐製程中之冶金焦。若將該煤焦用於鼓風爐製程中,則所提及之煤焦值將對鼓風爐製程具有有利影響。 However, the use of a non-recycled or heat recovery type coke oven allows the carbonization of a feed mixture consisting essentially of gasoline coal and having the properties mentioned, since such coke ovens provide a residual gas space above the gasoline briquettes during operation, This gas space absorbs the gradually increasing expansion pressure of the gasoline coal. Within the framework of the present invention, it has been determined that the coal char grade thus obtained is characterized by a CSR strength of more than 44% and a CRI reactivity of less than 33%, and therefore, such coal char grades can be used, for example, in metallurgical or blast furnace processes. Metallurgical coke in the middle. If the coal char is used in a blast furnace process, the coal char values mentioned will have a beneficial effect on the blast furnace process.
本發明特別主張一種由在石油加工工業中獲得的汽油煤製造冶金焦之方法,其中 The invention particularly claims a method for producing metallurgical coke from gasoline coal obtained in the petroleum processing industry, wherein
.對來自石化製程之汽油焦進行揮發物含量及灰分含量分析,由此可依照具有已知揮發性成分含量及灰分含量之批料對其進行揀選,及 . Analysis of the volatile matter content and ash content of the gasoline coke from the petrochemical process, whereby the batch can be sorted according to the batch having the known volatile component content and the ash content, and
.揀選出揮發物含量為15wt.%至19wt.%且灰分含量不到2wt.%之汽油煤批料(稱為無水無灰分汽油煤批料)且饋送至儲煤倉或儲煤容器中。 . A gasoline coal batch having a volatile content of 15 wt.% to 19 wt.% and an ash content of less than 2 wt.% (referred to as an anhydrous ashless gasoline coal batch) is sorted and fed into a coal storage bin or a coal storage vessel.
.來自儲煤倉或儲煤容器之此汽油煤部分首先藉由加料機饋送至壓實機中壓緊,且隨後饋送至具有非回收或熱回收型尺寸之煉焦爐中進行循環碳化,且該方法之特徵在於 . This portion of the gasoline coal from the coal storage bin or coal storage vessel is first fed into the compactor by means of a feeder and then fed to a coke oven having a non-recovered or heat recovery type for cyclic carbonization, and the method Characterized by
.該煉焦爐配備有至少一個獨立加熱之燃燒器用於加熱在汽油煤餅上方之主要加熱空間或用於加熱在煉焦爐室下方之次要加熱空間或二者,該燃燒器用於在熱燃料氣之幫助下在不到120小時之時間段內將煉焦爐室中之汽油煤加熱至介於1000℃與1550℃之間的溫度,由此獲得具有CSR強度值為至少44%且CRI反應性值不到33%之冶金焦。 . The coke oven is equipped with at least one independently heated burner for heating a primary heating space above the gasoline coal cake or for heating a secondary heating space below the coke oven chamber, the burner being used in hot fuel gas With the help of heating the gasoline coal in the coke oven chamber to a temperature between 1000 ° C and 1550 ° C in less than 120 hours, thereby obtaining a CSR strength value of at least 44% and a CRI reactivity value is not To 33% metallurgical coke.
熟習碳化技術之技術人員已知配備有主要及次要加熱空間 之非回收或熱回收型煉焦爐。此類構造詳細描述於例如Walter Buss等人之文章,「Thyssen Still Otto/PACTI Non-recovery coke making system」,Iron and Steel Engineer,Association of Iron and Steel Engineers,Pittsburgh,USA,第76卷,第1期,1999年1月,第33-38頁中。由適合碳化具有高膨脹壓力之煤之煉焦爐組成的煉焦爐組之實例提供於WO2011107198A1中。當加熱時,汽油煤餅達到估算之900℃至1100℃之溫度。 Those skilled in the art of carbonization are known to be equipped with primary and secondary heating spaces. Non-recovery or heat recovery coke ovens. Such a construction is described in detail in, for example, the article by Walter Buss et al., "Thyssen Still Otto/PACTI Non-recovery coke making system", Iron and Steel Engineer, Association of Iron and Steel Engineers, Pittsburgh, USA, Vol. 76, No. 1. Period, January 1999, pp. 33-38. An example of a coke oven group consisting of a coke oven suitable for carbonizing coal having a high expansion pressure is provided in WO2011107198A1. When heated, the gasoline briquettes reach an estimated temperature of 900 ° C to 1100 ° C.
藉助於在壓實之汽油煤餅上方加熱來加熱汽油煤,由此製造出具有想要等級之煤焦,在該汽油煤中揮發性成分之部分係來自呈粗煉焦氣形式之批料。在此情況下,首先藉由至少偶爾地添加空氣,在主要加熱空間中燃燒一部分脫氣之成分以亞化學計量之方式產生熱。隨後,藉助於煉焦爐室之側部氣道排出部分燃燒之廢氣混合物,且藉由在次要加熱空間中進一步燃燒來完全燃燒。由於汽油煤中含有揮發性部分,由此該汽油煤亦自下方加熱,以致除側門區域外,汽油煤餅自所有側進行加熱且獲得均勻碳化品質。 The gasoline coal is heated by heating over the compacted gasoline coal cake, thereby producing a coal char of the desired grade in which the volatile components are derived from the batch in the form of a crude coke. In this case, heat is first produced in a substoichiometric manner by first burning a portion of the degassed component in the primary heating space by at least occasionally adding air. Subsequently, the partially combusted exhaust gas mixture is discharged by means of the side air passages of the coke oven chamber, and is completely combusted by further combustion in the secondary heating space. Since the gasoline coal contains a volatile portion, the gasoline coal is also heated from below, so that the gasoline briquettes are heated from all sides except the side door region and a uniform carbonization quality is obtained.
所得煤焦之等級可如所述測定,獲得至少44%之CSR強度值及不到33%之CRI反應性值。前提條件為使用揮發物含量為15wt.%至19wt.%且灰分部分不到2wt.%之汽油煤批料,稱為無水無灰分汽油煤批料。 The grade of coal char obtained can be determined as described to obtain a CSR strength value of at least 44% and a CRI reactivity value of less than 33%. The precondition is to use a gasoline coal batch having a volatile content of 15 wt.% to 19 wt.% and an ash fraction of less than 2 wt.%, which is referred to as an anhydrous ashless gasoline coal batch.
亦可能使用揮發性成分含量經更精確地測定之汽油煤。在本發明一個具體實例中,汽油煤之揮發物含量為16wt.%至18wt.%。因此,可更容易地控制該方法。 It is also possible to use gasoline coal whose volatile component content is more accurately determined. In a specific embodiment of the invention, the volatile content of the gasoline coal is from 16 wt.% to 18 wt.%. Therefore, the method can be controlled more easily.
一般而言,對於本發明之具體實例,汽油煤餅可自所有側進行加熱,由此達到想要的溫度。在本發明之一個有利的具體實例中,煉焦爐之加熱方式使得燃燒器火焰水平地埋在汽油煤批料上方之氣體空間中,所謂的主要加熱空間。在一個有利的具體實例中,藉助於燃燒器裝有熱氣體或燃燒氣體且經由開口延伸至汽油煤上方之氣體空間中的至少一個燃燒 管係位於在煉焦爐室門上方之壁中,由此該氣體空間經熱氣體加熱。在批料上方燃燒管之水平佈置確保,在汽油煤餅上方之內流氣體流入主要加熱空間中且因此,減少煤表面與燃燒空氣之間的直接接觸且由此減少不想要的煤或煤焦燒除。同時,設定自埋入之燃燒管至批料上部邊緣之垂直距離超過100mm,使得上部汽油煤層不燃燒。 In general, for a specific embodiment of the invention, the gasoline briquettes can be heated from all sides to thereby achieve the desired temperature. In an advantageous embodiment of the invention, the coke oven is heated in such a way that the burner flame is horizontally buried in the gas space above the gasoline coal batch, the so-called main heating space. In an advantageous embodiment, at least one of the gas spaces above the gasoline coal is extended via the opening by means of a burner containing hot gas or combustion gases and via an opening. The piping is located in the wall above the door of the coke oven chamber whereby the gas space is heated by hot gases. The horizontal arrangement of the combustion tubes above the batch ensures that the inflowing gas above the gasoline briquettes flows into the main heating space and, therefore, reduces the direct contact between the coal surface and the combustion air and thereby reduces unwanted coal or coal char Burn out. At the same time, the vertical distance from the buried combustion tube to the upper edge of the batch is set to exceed 100 mm, so that the upper gasoline coal seam does not burn.
在本發明之框架內,例如亦可能藉助於佈置在汽油煤下方之次要加熱空間中的其他燃燒器來加熱汽油煤。在另一具體實例中,主張在次要加熱空間之側前部開口上單獨或同時佈置至少一個燃燒器,因此,此加熱空間之溫度亦增加,使批料自下方之加熱增加。最後,亦可能使用煉焦爐室之頂部開口進行加熱。如例如US4045299A中所揭露之壁加熱型煉焦爐為可行的,即使尚未在本發明中進行測試。 Within the framework of the invention, it is also possible, for example, to heat the gasoline coal by means of other burners arranged in the secondary heating space below the gasoline coal. In another embodiment, it is claimed that at least one burner is disposed separately or simultaneously on the side front opening of the secondary heating space, and therefore, the temperature of the heating space is also increased to increase the heating of the batch from below. Finally, it is also possible to use the top opening of the coke oven chamber for heating. A wall-heated coke oven as disclosed, for example, in US Pat. No. 4,045,299 A is feasible, even if it has not been tested in the present invention.
該加熱可例如在煉焦爐室之通風及壓力控制之幫助下設定,由此在煉焦爐室中設定0.01至20毫巴(mbar)之壓力。此可藉由相應控制燃燒器及通風活板(venting flap)來實現。在本發明之一個較佳具體實例中,在通風及壓力控制之幫助下設定加熱,由此在煉焦爐室中設定0.1至10毫巴之壓力。 This heating can be set, for example, with the aid of ventilation and pressure control of the coke oven chamber, whereby a pressure of 0.01 to 20 mbar is set in the coke oven chamber. This can be achieved by correspondingly controlling the burner and the venting flap. In a preferred embodiment of the invention, the heating is set with the aid of ventilation and pressure control, whereby a pressure of 0.1 to 10 mbar is set in the coke oven chamber.
煉焦爐室可例如藉由天然氣或燃料氣加熱。然而,煉焦爐室亦可藉由液化氣、煉焦爐氣、鼓風爐氣或轉爐氣作為燃料氣進行加熱。對於體現本發明之方法的具體實例,亦可能使用任何部分之來自天然氣、液化氣、煉焦爐氣、鼓風爐氣或轉爐氣之群的至少兩種氣體之混合物進行加熱。適合燃料氣之選擇取決於各種因素,諸如可用性。 The coke oven chamber can be heated, for example, by natural gas or fuel gas. However, the coke oven chamber can also be heated by using liquefied gas, coke oven gas, blast furnace gas or converter gas as fuel gas. For specific embodiments embodying the process of the invention, it is also possible to use any portion of the mixture of at least two gases from the group of natural gas, liquefied gas, coke oven gas, blast furnace gas or converter gas for heating. The choice of fuel gas depends on various factors such as availability.
為了使煤焦產品具有想要的CSR強度及CRI反應性,且為了確保在脫氣成分之加熱能力之幫助下獲得想要的熱能力,所提供之汽油煤中揮發性成分含量之調整極為重要。在本發明之一個具體實例中,在粉碎之前,將汽油煤混合物與作為添加劑之硬煤混合,由此將揮發物含量設 定在19wt.%與25wt.%之間,稱為乾式進料混合物。在另一具體實例中,在粉碎之前,將汽油煤混合物與作為添加劑之瀝青混合,由此將揮發物含量設定在19wt.%與25wt.%之間,稱為乾式進料混合物。在另一具體實例中,在粉碎之前,將汽油煤混合物與作為添加劑之油等級(oil grade)混合,由此將揮發物含量設定在19wt.%與25wt.%之間,稱為乾式進料混合物。由此獲得的煤焦產品具有超過44%之CSR強度及不到33%之CRI反應性。 In order to achieve the desired CSR strength and CRI reactivity of the coal char product, and in order to ensure the desired heat capacity with the help of the heating ability of the degassing component, the adjustment of the volatile component content of the supplied gasoline coal is extremely important. . In a specific embodiment of the present invention, the gasoline coal mixture is mixed with the hard coal as an additive prior to pulverization, thereby setting the volatile content. Set between 19 wt.% and 25 wt.%, referred to as a dry feed mixture. In another embodiment, the gasoline coal mixture is mixed with the bitumen as an additive prior to comminution, thereby setting the volatiles content between 19 wt.% and 25 wt.%, referred to as the dry feed mixture. In another embodiment, the gasoline coal mixture is mixed with the oil grade as an additive prior to comminution, thereby setting the volatile content between 19 wt.% and 25 wt.%, referred to as dry feed. mixture. The coal char product thus obtained has a CSR strength of more than 44% and a CRI reactivity of less than 33%.
此外,所用汽油煤因獲得該煤之製程步驟而具有不到2wt.%之灰分部分。通常,此灰分部分剛好足以保護汽油煤不致在碳化期間被燃燒過度燒除。然而,為確保該製程具有適當成本效益,常需要採取額外措施來防止汽油焦經歷不想要的燒除。為此,若將汽油煤與對汽油煤之燃燒具有抑制性影響之添加劑混合,則亦可選擇略微較高之揮發性成分含量。 In addition, the gasoline coal used has less than 2 wt.% of the ash portion due to the process steps for obtaining the coal. Typically, this ash portion is just sufficient to protect the gasoline coal from being burned out excessively during carbonization. However, to ensure that the process is cost effective, additional measures are often required to prevent the gasoline coke from experiencing unwanted burnouts. For this reason, if gasoline coal is mixed with an additive having an inhibitory effect on the combustion of gasoline coal, a slightly higher volatile component content may be selected.
若將汽油煤與對汽油煤之燒除行為具有影響之添加劑混合,則甚至能選擇更高的灰分部分。該灰分部分之目的在於避免汽油煤發生不想要的燃燒。在本發明一個具體實例中,將汽油煤混合物與作為添加劑之灰分混合,由此將灰分部分設定在2wt.%與12wt.%之間,較佳為2wt.%至6wt.%,稱為總乾燥混合物,且將此混合物粉碎並篩分,從而獲得粒度分佈d為0.5<d<3mm之部分,且將經篩分之混合物饋送至儲煤倉或儲煤容器以進一步碳化。為將灰分以使所達到的CSR強度及CRI反應性不會以不利方式改變之方式分佈於產品中,粉碎及篩分為必需的。 If the gasoline coal is mixed with additives that have an effect on the burning behavior of the gasoline coal, even a higher ash portion can be selected. The purpose of this ash portion is to avoid undesired burning of gasoline coal. In a specific embodiment of the invention, the gasoline coal mixture is mixed with the ash as an additive, whereby the ash portion is set between 2 wt.% and 12 wt.%, preferably 2 wt.% to 6 wt.%, referred to as total The mixture was dried, and the mixture was pulverized and sieved to obtain a portion having a particle size distribution d of 0.5 < d < 3 mm, and the sieved mixture was fed to a coal storage tank or a coal storage container for further carbonization. In order to distribute the ash in the product so that the CSR strength and CRI reactivity achieved are not changed in an unfavorable manner, pulverization and sieving are necessary.
在另一具體實例中,將汽油煤混合物與作為添加劑之含灰分之煤混合,由此將灰分部分設定在2wt.%與12wt.%之間,較佳為2wt.%至6wt.%,稱為總乾燥混合物,且將此混合物粉碎並篩分,從而獲得粒度分佈d為0.5<d<3mm之部分,且將經篩分之混合物饋送至儲煤倉或儲煤容器以進一步碳化。在添加劑混合之前或之後,甚至可在粉碎裝置中將汽油煤混合物完全或部分粉碎,從而獲得平均粒度小於3mm之殘餘物部分。亦可 對部分分數之總混合物進行該粉碎操作。其中部分分數為70至95重量分數較佳,部分分數為80至90重量分數尤佳。 In another embodiment, the gasoline coal mixture is mixed with the ash-containing coal as an additive, thereby setting the ash portion between 2 wt.% and 12 wt.%, preferably 2 wt.% to 6 wt.%, The mixture was total dried, and the mixture was pulverized and sieved to obtain a portion having a particle size distribution d of 0.5 < d < 3 mm, and the sieved mixture was fed to a coal storage tank or a coal storage container for further carbonization. The gasoline coal mixture may be completely or partially comminuted in the pulverizing apparatus before or after the additive is mixed, thereby obtaining a residue portion having an average particle size of less than 3 mm. Can also This comminution operation is carried out on a total mixture of partial fractions. Some of the scores are preferably 70 to 95 weight fractions, and some fractions are preferably 80 to 90 weight fractions.
在本發明之框架內,亦可能藉由添加水來改變所製造之汽油煤之水含量。添加水可改善汽油煤餅之穩定性。在本發明之一個具體實例中,藉由添加液態水將進料混合物之總水含量設定在7wt.%至11.5wt.%,且將此混合物饋送至儲煤倉或儲煤容器中以進一步碳化。水可直接添加,且亦可藉由噴霧或浸沒來添加。 Within the framework of the present invention, it is also possible to vary the water content of the produced gasoline coal by adding water. Adding water improves the stability of the gasoline briquettes. In a specific embodiment of the present invention, the total water content of the feed mixture is set at 7 wt.% to 11.5 wt.% by adding liquid water, and the mixture is fed to a coal storage tank or a coal storage container for further carbonization. . Water can be added directly and can also be added by spraying or immersion.
在本發明之框架內且在使用前,可藉助於任一類型之壓實機將進料混合物壓實,由此進料混合物之密度為0.8t/m3至1.225t/m3。一般而言,壓實操作可藉由擠壓、搗碎、錘擊或振動步驟進行,該等步驟亦可組合進行。在使用前,較佳藉助於搗碎裝置壓實進料混合物,由此進料混合物之密度為1.0t/m3至1.150t/m3。 Within the framework of the invention and prior to use, the feed mixture can be compacted by means of either type of compactor, whereby the density of the feed mixture is from 0.8 t/m 3 to 1.225 t/m 3 . In general, the compacting operation can be carried out by extrusion, mashing, hammering or vibrating steps, which can also be combined. Prior to use, the feed mixture is preferably compacted by means of a mashing device whereby the density of the feed mixture is from 1.0 t/m 3 to 1.150 t/m 3 .
為了影響碳化操作,可在加熱前,將對燃燒呈惰性之分離層施加於爐餅之表面。此分離層係例如由煤焦構成。在另一具體實例中,該對燃燒呈惰性之分離層係由煤構成。最後,該對燃燒呈惰性之分離層亦可由灰分或砂粒構成。最後,該對燃燒呈惰性之分離層可由含碳煤屑(carbonaceous breeze)(例如,粒度小於25mm之煤屑或煤焦屑)構成。 In order to affect the carbonization operation, a separation layer inert to combustion may be applied to the surface of the furnace cake before heating. This separation layer is composed, for example, of coal char. In another embodiment, the separation layer that is inert to combustion is comprised of coal. Finally, the separation layer which is inert to combustion may also consist of ash or sand. Finally, the separation layer that is inert to combustion may be composed of carbonaceous breeze (eg, coal dust or coal coke having a particle size of less than 25 mm).
在本發明之一個具體實例中,分離層之厚度為0.2cm至25cm。分離層可視需要施加。因此,可例如藉助於煤壓實機將分離層施加於壓實之煤塊,該煤壓實機配備有進料口,該進料口佈置於搗錘(stamp)之上或之間。為此,需要一種煤壓實裝置,該裝置包括至少一個搗錘且在批料上方配備有進料裝置。用於壓緊之配備有搗碎、錘擊、振動及擠壓裝置的煤壓實機為目前先進技術且描述於例如WO2010102714A2中。 In a specific embodiment of the invention, the separation layer has a thickness of from 0.2 cm to 25 cm. The separation layer can be applied as needed. Thus, the separation layer can be applied to the compacted coal mass, for example by means of a coal compactor, which is equipped with a feed port which is arranged on or between the stamps. To this end, there is a need for a coal compaction apparatus that includes at least one tamper and is equipped with a feed device above the batch. Coal compactors equipped with crushing, hammering, vibrating and squeezing devices for compaction are presently advanced and are described, for example, in WO2010102714A2.
在另一具體實例中,添加劑儲存於儲煤倉中之特定軸中,在壓實之煤塊之加料操作期間,添加劑自該軸饋送至煤壓實機之指定開口。 添加劑可藉助於螺旋輸送機饋送至煤壓實機之指定開口。因此,添加劑亦可藉助於滑動系統、鏈式輸送系統、重力裝置或滑槽饋送至煤壓實機之指定開口。分離層亦可在稍後傾倒於批料之表面上且不在壓實機內。 In another embodiment, the additive is stored in a particular shaft in the coal storage bin, and the additive is fed from the shaft to a designated opening of the coal compactor during the feeding operation of the compacted coal mass. The additive can be fed to a designated opening of the coal compactor by means of a screw conveyor. Thus, the additive can also be fed to a designated opening of the coal compactor by means of a sliding system, a chain conveyor system, a gravity device or a chute. The separation layer can also be poured on the surface of the batch later and not in the compactor.
在本發明之另一具體實例中,在四個連續混合倉中,將進料混合物與添加劑混合,粉碎及粉碎儲料之混合係在該等混合倉中進行。粉碎及混合亦可分若干階段進行。進料混合物亦可預加熱。因此,可例如在加料至煉焦爐之前,藉由在可加熱容器中預加熱,將進料混合物之溫度設定在120℃至250℃。 In another embodiment of the invention, in four continuous mixing chambers, the feed mixture is mixed with an additive, and the mixing of the comminuted and comminuted stock is carried out in the mixing chambers. The comminution and mixing can also be carried out in several stages. The feed mixture can also be preheated. Thus, the temperature of the feed mixture can be set between 120 ° C and 250 ° C, for example, by preheating in a heatable vessel prior to feeding to the coke oven.
必要時,自汽油煤獲得的冶金焦可用於其他應用。其尤其可用作鼓風爐焦。然而,其亦可用於非鐵冶金工業中以製造金屬或製備電極。 Metallurgical coke obtained from gasoline coal can be used for other applications where necessary. It is especially useful as a blast furnace coke. However, it can also be used in non-ferrous metallurgical industries to make metals or to prepare electrodes.
亦主張執行體現本發明之方法所藉助之裝置。特別主張一種由在石油加工工業中獲得的汽油煤製備煤焦之煉焦爐,該煉焦爐.屬於非回收或熱回收煉焦爐組類型,其具有2至6m之煉焦爐室寬度及10至20m之煉焦爐室長度,由此在高度為2m時,該煉焦爐室容積為40至240m3,且.該煉焦爐具有磚石砌築之拱形結構,在填充狀況下,其與位於下方之煉焦爐室一起可形成位於煤餅上方之氣體空間,用作主要加熱空間,且.該煉焦爐配備有側部煙道及位於煤下方之次要加熱空間,且.該煉焦爐室配備有儲煤倉或儲煤容器及加料機,該加料機可自儲煤倉或儲煤容器給煉焦爐室加料,且該煉焦爐之特徵在於.該煉焦爐室在外部燃燒器之幫助下加熱,該等外部燃燒器加熱主要加熱空間,且該等燃燒器經由沿著煉焦爐室前部且可調支線伸入燃燒器中之集氣幹線而被供給燃料氣及含氧氣體。 It is also claimed to carry out the means by which the method of the invention is carried out. In particular, a coke oven for preparing coal char from gasoline coal obtained in the petroleum processing industry is proposed. Is a non-recovery or heat recovery type coking ovens, having a width of 2 to 6m of the coke oven chamber and 10 to 20m length of the coke oven chamber, whereby the height is 2m, the coke oven chamber volume of 40 to 240m 3, And The coke oven has a masonry arch structure, and in the filling condition, together with the coke oven chamber located below, a gas space above the coal cake can be formed to serve as a main heating space, and The coke oven is equipped with a side flue and a secondary heating space below the coal, and The coke oven chamber is equipped with a coal storage bin or a coal storage container and a feeding machine, and the feeding device can feed the coking furnace chamber from the coal storage bin or the coal storage container, and the coke oven is characterized by: The coke oven chamber is heated with the aid of an external burner that heats the main heating space, and the burners extend into the gas gathering mains in the burner via an adjustable branch line along the front of the coke oven chamber. Fuel gas and oxygen-containing gas are supplied.
必要時,外部燃燒器可佈置在煉焦爐室上,以促進主要加熱 空間之加熱。每一煉焦爐室可佈置一個或若干個外部燃燒器。然而,在一個較佳具體實例中,該(該等)燃燒器位於煉焦爐室之至少一側之煉焦爐室門上方包圍該煉焦爐室門之壁中,且使用位於包圍該煉焦爐室門之壁中之開口加熱主要加熱空間。燃燒管之孔口段經由此開口導入氣體空間中。 If necessary, an external burner can be placed on the coke oven chamber to promote primary heating Heating of the space. One or several external burners may be arranged in each coke oven chamber. However, in a preferred embodiment, the (these) burners are located in the wall of the coke oven chamber door above the coke oven chamber door on at least one side of the coke oven chamber, and are used to surround the coke oven chamber door The opening in the wall heats the main heating space. The orifice section of the combustion tube is introduced into the gas space via this opening.
為此,該(該等)燃燒器位於煉焦爐室之至少一側之煉焦爐室門上方包圍該煉焦爐室門之壁中,且使用位於包圍該煉焦爐室門之壁中之開口加熱主要加熱空間,在一個有利的具體實例中,設定自燃燒管口至汽油煤批料上部邊緣之垂直距離超過100mm。燃燒器在煉焦爐室頂部上之佈置節省了空間。 To this end, the (these) burners are located in the wall of the coke oven chamber door above the coke oven chamber door on at least one side of the coke oven chamber and are heated primarily by openings located in the wall surrounding the coke oven chamber door The heating space, in an advantageous embodiment, sets the vertical distance from the combustion nozzle to the upper edge of the gasoline coal batch to exceed 100 mm. The arrangement of the burner on the top of the coke oven chamber saves space.
在本發明之一個具體實例中,該燃燒管口或該等燃燒管口係由耐熱鋼製成。在另一具體實例中,該(該等)燃燒管口係由耐火陶瓷材料製成。若已安裝多個燃燒器,則此可見於一個或若干個燃燒器上。 In a specific embodiment of the invention, the combustion nozzle or the combustion nozzles are made of heat resistant steel. In another embodiment, the (s) combustion nozzle is made of a refractory ceramic material. If multiple burners are installed, this can be seen on one or several burners.
在本發明之一個較佳具體實例中,體現本發明之煉焦爐與另外的多個煉焦爐一起集合成煉焦爐組,且集氣幹線係沿著該煉焦爐組之煉焦爐室前部架設。熟習煉焦技術之技術人員已知將非回收或熱回收型煉焦爐集合成煉焦爐組。 In a preferred embodiment of the present invention, the coke oven embodying the present invention is combined with a plurality of other coke ovens to form a coke oven group, and the gas collection trunk line is erected along the front portion of the coke oven chamber of the coke oven group. Those skilled in the art of coking are known to assemble non-recovery or heat recovery coke ovens into a coke oven group.
次要加熱空間亦可藉助於一個或若干個外部燃燒器來加熱,該等外部燃燒器經由沿煉焦爐室前部、可調支線延伸至燃燒器中之集氣幹線而被供給燃料氣及含氧氣體。在本發明之一個具體實例中,該(該等)燃燒器係設計為通風燃燒器。對於該具體實例,集氣幹線可例如位於煉焦爐室之頂部上。集氣幹線亦可安裝在煉焦爐維修機之平臺下方或沿著支柱。最後,集氣幹線可視需要佈置以確保燃燒器之供應。 The secondary heating space may also be heated by means of one or several external burners that are supplied with fuel gas via a gas gathering main line extending into the burner along the adjustable branch line at the front of the coke oven chamber. Oxygen gas. In one embodiment of the invention, the (these) burners are designed as ventilated burners. For this particular example, the gas collection mains can be located, for example, on top of the coke oven chamber. The gas collection mains can also be installed under the platform of the coke oven maintenance machine or along the pillars. Finally, the gas collection trunks can be arranged as needed to ensure the supply of burners.
支線可例如藉助於活栓、閘閥、噴嘴、擋板或孔板進行控制。在本發明之一個具體實例中,煉焦爐組配備有壓力控制站,在該壓力控制站中,燃料氣之壓力降低至所需值,由此將燃料氣自壓力控制站經由集氣 幹線饋送至燃燒器且以對燃燒器而言合適的壓力直接供應。 The branch line can be controlled, for example, by means of a stopcock, a gate valve, a nozzle, a baffle or an orifice plate. In a specific embodiment of the invention, the coke oven group is equipped with a pressure control station in which the pressure of the fuel gas is reduced to a desired value, thereby passing the fuel gas from the pressure control station through the gas gathering The mains are fed to the burner and supplied directly at a suitable pressure for the burner.
亦主張一種壓實機,其用於壓緊煤且適於在製備壓實塊時將分離層施加至壓實之煤塊上。可用於此裝置總成之適合的壓實機描述於WO201D102714A2中。此機器由用作側面之六個搗錘組成,以藉由擠壓裝置製備壓實塊。在本發明之一個具體實例中,搗錘係以液力操作。適合的壓實機亦可由振動裝置形成。對於體現本發明之壓實機總成,WO2010102714A2中壓實機之振動裝置的上部搗錘或上部板具備傾卸裝置,藉助於該傾卸裝置,可將添加劑饋送至壓實塊之表面上,由此在壓實期間,由傾卸裝置饋送之另一添加劑層出現在壓實之進料混合物之表面上。 A compactor is also claimed which is used to compact coal and is adapted to apply a separation layer to the compacted coal mass when preparing the compacted mass. Suitable compactors that can be used in this device assembly are described in WO201D102714A2. This machine consists of six tampers used as sides to prepare a compacted block by means of a squeezing device. In one embodiment of the invention, the tamper is operated hydraulically. A suitable compactor can also be formed by a vibrating device. For the compactor assembly embodying the invention, the upper ram or upper plate of the vibrating device of the compactor of WO2010102714A2 is provided with a tipping device by means of which the additive can be fed onto the surface of the compacting block, Thereby another additive layer fed by the tipping device appears on the surface of the compacted feed mixture during compaction.
亦主張一種煉焦爐組,其由體現本發明之煉焦爐組成且配備有該壓實機。 A coke oven group is also claimed which consists of a coke oven embodying the invention and is equipped with the compactor.
體現本發明之方法主要在煉焦爐組中執行,該煉焦爐組由體現本發明之煉焦爐室連同額外的先前技術裝置組成。其包括例如1至10個等級之儲倉,在該等儲倉中,儲存有不同的汽油煤進料混合物。其亦包括例如1至4個粉碎裝置、1至4個篩分裝置或1至4個混合倉,汽油煤、添加劑或整個進料混合物在其中儲存、篩分及混合。煉焦爐組亦可配備有壓實機。 The method embodying the invention is primarily carried out in a coke oven group consisting of a coke oven chamber embodying the invention along with additional prior art devices. It includes, for example, 1 to 10 levels of storage bins in which different gasoline coal feed mixtures are stored. It also includes, for example, 1 to 4 comminuting devices, 1 to 4 sieving devices or 1 to 4 mixing bins in which gasoline coal, additives or the entire feed mixture is stored, sieved and mixed. The coke oven group can also be equipped with a compactor.
本發明的優勢在於為汽油煤提供了一種可能的經濟應用,該汽油煤係在煉油廠中及礦物油加工工業中獲得且具有揮發物含量為15wt.%至19wt.%之汽油焦部分,其藉由製造CSR強度超過44%且CRI反應性不到33%之煤焦,使得此煤焦可用於鼓風爐製程中或冶金製程中以製造金屬,與碳化之汽油焦形成對比。 The invention has the advantage of providing a possible economic application for gasoline coal, which is obtained in a refinery and a mineral oil processing industry and has a gasoline coke portion having a volatile content of 15 wt.% to 19 wt.%. By making coal char with a CSR strength of more than 44% and a CRI reactivity of less than 33%, the char can be used in a blast furnace process or in a metallurgical process to produce metal in contrast to carbonized gasoline coke.
在下文中,描述了針對汽油焦之分析方法,該等方法用於提供用作體現本發明之方法之進料汽油煤的汽油煤。 In the following, analytical methods for gasoline coke are described, which are used to provide gasoline coal for use as feed gasoline coal embodying the method of the present invention.
1. 揮發物含量. 汽油焦之揮發物含量係例如根據DIM 51720測定。量測在煤加熱後7分鐘內仍處於真空下之殘餘物部分。快速測定煤中揮發物含量之方法提供於US6074205A中。 1. Volatile content. The volatile content of gasoline char is determined, for example, according to DIM 51720. The portion of the residue that was still under vacuum within 7 minutes after heating of the coal was measured. A method for the rapid determination of volatiles in coal is provided in US 6074205A.
2. 灰分含量. 灰分含量係例如根據DIN 51719測定。量測爐中在燃燒煤後仍為815℃之殘餘物部分。快速測定煤中灰分含量之方法提供於DE3120064A1中。 2. Ash content. The ash content is determined, for example, according to DIN 51719. The residue in the measuring furnace was still 815 ° C after burning coal. A method for the rapid determination of ash content in coal is provided in DE 31 2006 4 A1.
3. 煤焦強度. 煤焦強度係藉由所謂的CSR測試來測定。CSR為「反應後煤焦強度(Coke Strength after Reaction)」之英文縮寫。量測殘餘物之重量百分比,該殘餘物係由200g煤焦樣品,在1巴二氧化碳(CO2)下加熱至1100℃後維持2小時且隨後在滾筒中以每分鐘(min-1)600轉處理30分鐘後獲得。現今,此測試方法為一般認可的,經標準化且描述於例如EP07387B0B2中。 3. Coal coke strength. Coal coke strength is determined by a so-called CSR test. CSR is the abbreviation of "Coke Strength after Reaction". The weight percentage of the residue was measured and the residue was heated from 200 bar of carbon dioxide (CO 2 ) to 1100 ° C for 2 hours and then to 600 minutes per minute (min -1 ) in a drum. Obtained after 30 minutes of treatment. Today, this test method is generally accepted, standardized and described, for example, in EP07387B0B2.
4. 煤焦反應性. 煤焦反應性係藉由所謂的CRI測試來測定。CRI為「煤焦反應性指數(Coke Reactivity index)」之英文縮寫且描述煤焦之化學反應性。量測殘餘物之重量百分比,該殘餘物係由200g煤焦樣品在1巴二氧化碳(CO2)下加熱至1100℃後維持2小時而獲得。所獲得的值稱為CRI反應性。得到的值越小,該反應性越低。此方法可容易且迅速地進行且特徵值CRI與煤焦在鼓風爐製程中之行為良好相關。現今,此測試方法為一般認可的,根據ISO 18894標準化且描述於例如EP1142978A1中。 4. Coal coke reactivity. Coal coke reactivity is determined by a so-called CRI test. CRI is the abbreviation of "Coke Reactivity Index" and describes the chemical reactivity of coal char. The weight percentage of the residue was measured, which was obtained by heating 200 g of the char sample to 1100 ° C under 1 bar of carbon dioxide (CO 2 ) for 2 hours. The value obtained is called CRI reactivity. The smaller the value obtained, the lower the reactivity. This method can be performed easily and quickly and the characteristic value CRI is well correlated with the behavior of coal char in the blast furnace process. Today, this test method is generally accepted, standardized according to ISO 18894 and described, for example, in EP 1 142 978 A1.
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