WO2016101327A1 - 一种高硫石油焦的煅烧方法及专用罐式煅烧炉和罐壁砖 - Google Patents

一种高硫石油焦的煅烧方法及专用罐式煅烧炉和罐壁砖 Download PDF

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WO2016101327A1
WO2016101327A1 PCT/CN2015/000226 CN2015000226W WO2016101327A1 WO 2016101327 A1 WO2016101327 A1 WO 2016101327A1 CN 2015000226 W CN2015000226 W CN 2015000226W WO 2016101327 A1 WO2016101327 A1 WO 2016101327A1
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petroleum coke
brick
tank
calcination
sulfur
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PCT/CN2015/000226
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English (en)
French (fr)
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王征宇
赵满生
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中碳能源(山东)有限公司
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Publication of WO2016101327A1 publication Critical patent/WO2016101327A1/zh

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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D1/00—Casings; Linings; Walls; Roofs
    • F27D1/04—Casings; Linings; Walls; Roofs characterised by the form, e.g. shape of the bricks or blocks used
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay

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  • the invention relates to a calcination method of high sulfur petroleum coke and a special tank calciner and tank wall brick, belonging to the technical field of refractory material preparation.
  • the calcined coke products produced by the tank calciner have a raw material cost factor of more than 95%, and the tonnage cost of the medium sulfur petroleum coke is more than 200 yuan higher than the high sulfur petroleum coke.
  • the sulfur in petroleum coke is divided into organic sulfur and inorganic sulfur, most of which is organic sulfur bonded to carbon in coke to SC, and some may be sulfate and pyrite sulfur (but the total sulfur in these sulfur insufficiency) 0.02%).
  • the sulfur content in petroleum coke mainly depends on the nature of crude oil and its sulfur content. With the increase of imported crude oil, the sulfur content in petroleum coke has an increasing trend. Desulfurization of petroleum coke involves the desorption of sulfur in the coke pores and on the surface of the coke, and the separation and removal of sulfur on the carbon skeleton. Therefore, the desulfurization of petroleum coke is a complicated process.
  • Calcination desulfurization generally refers to the process in which petroleum coke is heated to a specified temperature and maintained at this temperature for a certain period of time, and part of sulfur is precipitated in the form of SO 2 while removing moisture and volatile matter. This process is considered to be the most The future of petroleum coke desulfurization process.
  • the tank calciner is the key equipment for calcining carbon raw materials.
  • the raw petroleum coke When calcining petroleum coke, the raw petroleum coke is fed into the tank through the feeding mechanism of the top of the tank furnace, and is indirectly heated by the fire passages on both sides. The moisture and a part of the volatile matter in the raw material are discharged through the pre-tropical zone and then the temperature is 1250. Calcination of the high temperature zone of °C-1350 °C, petroleum coke releases a large amount of volatiles, resulting in volume shrinkage, density, strength, conductivity is improved; finally, after cooling the cooling jacket, the qualified calcined coke is discharged.
  • the maximum temperature of the fire in the domestic common calciner is 1380 °C.
  • the desulfurization rate of the calcined coke is less than 20%.
  • the crude oil imported by each refinery increases, the sulfur content increases.
  • the service life of the calciner is reduced from about 10 years to about 3 years due to sulfur corrosion damage.
  • the return on investment is low, and the pressure on equipment corrosion and environmental protection is increased.
  • the existing pot-type bricks of the tank-type calciner use silica bricks which are resistant to sulfur permeation and extremely poor corrosion performance.
  • Siliceous The refractory material is a typical acidic refractory material.
  • the silica brick used in conventional calcination has a sulfur content of 2.0% or less. According to the experience of domestic carbon plants, the normal service life of the calciner should be 8-10 years. However, in the high-sulfur calcination atmosphere of high temperature 1400 ⁇ 1600 ° C, the contact surface of silica brick and petroleum coke will be seriously eroded and then peeled off. The service life of the furnace is only about 3 years.
  • Silicon bricks do not have the refractory conditions for high temperature desulfurization and calcination:
  • the present invention provides a method for calcining high sulfur petroleum coke, which achieves the following objects: high desulfurization rate, low production cost, and long service life of the furnace body.
  • the invention also provides a tank type calcining furnace, which realizes the following object: the tank type calcining furnace has high anti-penetration and anti-erosion ability under high sulfur and high temperature conditions, has long service life, high desulfurization rate of calcined high sulfur petroleum coke, and production low cost.
  • the invention also provides a tank wall brick and a preparation method thereof, the tank wall brick has good anti-sulfur corrosion and anti-penetration performance, no exfoliation phenomenon in high-temperature high-sulfur calcination, long service life, low production cost, preparation
  • the method is simple, environmentally friendly and non-polluting.
  • a method for calcining high-sulfur petroleum coke which comprises placing high-sulfur petroleum coke in a tank calciner and calcining in a furnace
  • the temperature of the strip material is 1350-1550 ° C, and the high sulfur petroleum coke is calcined at a high temperature.
  • the temperature of the can calciner fire channel is 1400-1600 °C.
  • the high sulfur petroleum coke desulfurization rate reaches 42-72%.
  • the temperature of the can calciner fire channel is 1400-1500 ° C, and the high sulfur petroleum coke desulfurization rate reaches 42-67%.
  • a can calciner comprising an outer wall, a fire channel and a calcination tank.
  • Each of the tank calcining furnaces is composed of four calcining tanks, each of which is composed of a total number of tanks composed of 4 ⁇ furnace groups; the calcining tank has a fire passage outside the tank wall and an inner side with oil a contact surface of the coke; the calcination tank is surrounded by a shaped tank wall brick with a mother groove, and the shaped tank wall brick is made of a brick material resistant to high temperature and sulfur corrosion.
  • the thickness of the shaped tank wall brick is 90 mm, and the refractory mud used for the brick wall of the shaped tank wall is a high temperature resistant and sulfur resistant material similar to the material of the brick body.
  • a tank wall brick which is any one of zirconium corundum mullite brick, silicon carbide corundum mullite brick, and chrome corundum brick.
  • the zirconium corundum mullite brick by weight percentage, comprises the following components: zirconium corundum and/or zircon powder 30 to 45%, zircon aggregate 15 to 25%, mullite aggregate 10 ⁇ 20%, special grade alumina aggregate 15 ⁇ 25%, ⁇ alumina powder 3 ⁇ 8%, silicon powder 1 ⁇ 3%, Guangxi white clay 2 ⁇ 5%; additionally contains 6% chemical binder.
  • the silicon carbide corundum mullite brick has a raw material composition including the following components in a weight percentage: 40 to 60% of mullite aggregate, 15 to 30% of mullite and/or corundum powder, and 15 to 25 of silicon carbide powder. %, silicon micropowder 2 to 5%, Guangxi white clay 3 to 8%; additionally contains 0.8% boron carbide.
  • the chrome corundum brick is composed of the following components in terms of weight percentage: 50-70% of fused corundum aggregate, 5-15% of platy corundum powder, -8-18% of chromium oxide, monoclinic zirconia powder 3 to 8%, activated alumina fine powder 3 to 8%, other 10%; additionally contains chemical binder 4 to 10%.
  • a method for preparing a tank wall brick comprises the following steps: crushing, sieving, pulverizing, compounding, kneading, forming, drying and firing; the firing process: the dried brick is pushed into the high temperature tunnel via the electric trailer In the kiln, the maximum firing temperature is controlled at 1600 ° C ⁇ 1800 ° C.
  • the present invention adopts the above technical solutions, and has the following advantages compared with the prior art:
  • the method for calcining high-sulfur petroleum coke used in the invention has high desulfurization rate of petroleum coke, reaching 42-72%, high desulfurization rate, and the prior art desulfurization rate is less than 20%;
  • the calcination method of high sulfur petroleum coke used in the invention greatly reduces the production cost, and the cost per ton of high sulfur petroleum coke is higher than that of sulfur
  • the cost per ton of petroleum coke is lower than 200 yuan, while the raw material cost factor of calcined coke products accounts for more than 95%, so the cost is greatly reduced;
  • the furnace body has a long service life, high return on investment: high sulfur petroleum coke tank furnace calcination, can extend the life of the tank calciner, from the original 3 years to 8-10 years, the service life is extended 5-7 years ;
  • tank-type calciner tank wall bricks Through the innovative application of tank-type calciner tank wall bricks, the penetration and erosion ability of the tank-type calciner tank wall brick and petroleum coke contact surface can be reduced, and the rapid flaking phenomenon of the tank wall brick refractory material in the calcination process can be effectively prevented;
  • the calcination temperature of the industrialized tank calciner is 1400-1600 °C, so that the desulfurization rate of petroleum coke is 42-72%, and the desulfurization rate is high, which is the first in the world;
  • High-temperature desulfurization calcination has the elimination of moisture and volatile matter in the raw material high-sulfur petroleum coke, improves the density and mechanical strength of the raw material; improves the electrical conductivity of the raw material; improves the chemical stability and oxidation resistance of the raw material, and reduces the sulfur content of the product.
  • Figure 1 is a schematic view of the structure of a tank calciner:
  • 3 is an SEM scanning electron micrograph of the residual brick erosion surface of the silicon brick after the calciner is produced and used;
  • Figure 6 is a flow chart showing the preparation of the tank wall brick of the present invention.
  • the sulfur in petroleum coke is divided into organic sulfur and inorganic sulfur, most of which is organic sulfur bonded to carbon in coke to SC, and some may be sulfate and pyrite sulfur (but this part of sulfur is relatively small, in The total sulfur content in petroleum coke is less than 0.02%).
  • the sulfur content in petroleum coke mainly depends on the nature of crude oil and its sulfur content. With the increase of imported crude oil, the sulfur content in petroleum coke has an increasing trend. Desulfurization of petroleum coke involves the desorption of sulfur in the coke pores and on the surface of the coke, and the separation and removal of sulfur on the carbon skeleton. Therefore, the desulfurization of petroleum coke is a complicated process.
  • Calcination desulfurization generally refers to the process in which petroleum coke is heated to a specified temperature and maintained at this temperature for a certain period of time, and part of sulfur is precipitated in the form of SO 2 while removing moisture and volatile matter. This process is considered to be the most The future of petroleum coke desulfurization process.
  • the high-sulfur petroleum coke is placed in a calcination tank of an industrial tank-type calciner, and the temperature of the calciner is 1400-1600 ° C, and the high-sulfur petroleum coke is calcined by an industrialized tank calciner by using a heat source generated by the petroleum coke itself.
  • the temperature of the calcined strip in the calcined tank is 1350-1550 ° C, and the sulfur is desulfurized.
  • the calcination temperature of the fire tube of the tank calciner is 1400-1600 °C, that is, the temperature of the high-sulfur petroleum coke in the furnace tank is 1350-1550 °C, the desulfurization rate reaches 42-72%, and the desulfurization rate is high, compared with the existing In the technology, the desulfurization rate is increased by 2 to 4 times when the temperature of the fire is 1380 °C.
  • the temperature of the fire tube of the tank calciner is 1400-1500 ° C, and the desulfurization rate of petroleum coke reaches 42-67%.
  • the service life of the tank calciner is long, and the quality requirements of the brick wall of the calciner Reasonable, the production cost is optimal.
  • the tank calciner comprises: a furnace body and a metal skeleton, and a cooling water jacket attached to the furnace body, a feeding device and the like; wherein the furnace body comprises a calcination tank (2), a fire channel (3) and an outer wall (1) three parts;
  • Each of the tank calciners consists of four calcination tanks, each consisting of a total number of tanks consisting of 4 ⁇ furnace groups, such as 28 tanks, 32 tanks, 48 tank calciners, and the like.
  • the calcination tank (2) is the most important component of the furnace body.
  • the calcination tank (2) is arranged in double in the longitudinal and transverse directions, together with four fire passages on both sides of it, one furnace can have 8-12 sets, calcination tank
  • the horizontal section of (2) is the flat length of the curved ends Shape, the tank wall is built vertically.
  • Masonry tank wall brick is a special-shaped refractory brick different from the conventional tank type calciner tank wall, which is made of a new formula and different chemical components.
  • the new refractory brick is any one of zirconium corundum mullite brick, silicon carbide corundum mullite brick and chrome corundum brick.
  • the thickness of the special-shaped tank wall brick is increased by 10 mm
  • the thickness of the conventional silicon brick is 80 mm
  • the thickness of the special-shaped tank wall brick is 90 mm
  • the refractory mud used for the brick wall of the shaped tank wall is High temperature resistant, sulfur resistant material similar to brick body material. After the furnace body passes through the oven, the refractory mud has good bonding strength and ensures the sealing property of the furnace body.
  • the shaped tank wall brick used has the functions of high temperature resistance and sulfur corrosion resistance, the outer side of the tank wall brick is the fire passage (3), and the inner side is the contact surface with the petroleum coke.
  • the high-temperature desulfurization calciner has the advantages of excluding water and volatiles in the raw materials; increasing the density and mechanical strength of the raw materials; improving the electrical conductivity of the raw materials; improving the chemical stability and oxidation resistance of the raw materials, and reducing the sulfur content in the products;
  • a chrome corundum brick process recipe is as follows:
  • a method for preparing a tank wall brick comprises the following steps:
  • the various raw material large particle materials required are broken into small particles by a jaw crusher and a roll crusher.
  • crushed raw materials are sieved into the raw materials conforming to the specifications through the sieving machine, and then enter the respective storage bins, and the unqualified sieve materials are re-crushed.
  • the sieved 0.5-1 mm particle size material is used to prepare a 200-300 mesh powder by entering a Raymond mill.
  • the various granules are accurately weighed according to the raw material ratio by the automatic batching system, and then sent to the mixer, and the binder and water are added to the mixer in proportion.
  • the materials of different compositions and particle sizes are mixed and squeezed to achieve uniform distribution and sufficient wetting, and then enter the mud tank in the form of mud.
  • the mixed mud material is sent into a vibration molding machine brick blank mold for vibration molding.
  • the press-formed brick is dried in a waste heat drying kiln using hot flue gas in a tunnel kiln to remove moisture from the brick.
  • firing the dried bricks are pushed into the high temperature tunnel kiln via electric trailers, and the different bricks are respectively heated according to the corresponding The system completes its firing process, and the maximum temperature of firing is controlled at 1600 ° C ⁇ 1800 ° C.
  • the finished refractory bricks are sent to the finished product warehouse picking area for inspection. Some bricks that need to be trimmed are trimmed with brick grinders, trimmed scraps and non-conforming products are used as ingredients.
  • the siliceous refractory is a typical acidic refractory.
  • Conventional calcination uses silica bricks, the sulfur content is controlled at 2.0%, and at high temperature 1400-1600 °C, high sulfur calcination atmosphere, the contact surface between silica brick and petroleum coke will be seriously eroded and then peeled off.
  • the service life of the furnace is only 3 years. Left and right time.
  • the surface of the silica brick after the furnace is used for SEM scanning electron microscopy analysis, as shown in Figures 2, 3 and 4. It can be clearly seen from Figure 2 that the silica brick used in the calciner has a very small surface glass phase. The particles are prominent and there is a phenomenon of gas substance formation.
  • chrome corundum brick, silicon carbide brick and zircon brick developed by the invention are not observed to have penetration and erosion after being calcined at 1520 ° C in a high sulfur atmosphere, which proves that the above three bricks have strong sulfur attack resistance.
  • the silica brick In the high sulfur atmosphere, the silica brick is calcined at a temperature of 1520 ° C, and the erosion depth is about 11 mm, and there is a serious peeling phenomenon on the contact surface with petroleum coke.
  • High-sulfur petroleum coke drum furnace calcination can extend the service life of tank calciner for 5-7 years.

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Abstract

本发明公开了一种高硫石油焦的煅烧方法，所述煅烧方法为将高硫石油焦置于罐式煅烧炉内，煅烧温度为1350-1550℃，对高硫石油焦进行高温煅烧，高硫石油焦脱硫率达到42-72％。一种高硫石油焦用罐式煅烧炉，包括炉体、火道和煅烧罐，所述煅烧罐的罐壁外侧是火道，内侧为与石油焦的接触面，所述煅烧罐四周由带子母槽的异形罐壁砖砌筑而成，所述异形罐壁砖采用耐高温和耐硫侵蚀的砖体材料制成。本发明还公开了一种罐壁砖及其制备方法，该罐壁砖具有良好的抗硫腐蚀、抗渗透的性能，在高温高硫煅烧中无剥落现象产生，使用寿命长，生产成本低，制备方法工艺简单，环保无污染。

Description

一种高硫石油焦的煅烧方法及专用罐式煅烧炉和罐壁砖 技术领域
本发明涉及一种高硫石油焦的煅烧方法及专用罐式煅烧炉和罐壁砖，属于耐火材料制备技术领域。
背景技术
在目前国内外煅烧焦产品微利或亏损年代，要想通过同品质、低成本的产品竞争优势占领国内外市场，只有采用高硫石油焦生产。利用罐式煅烧炉生产的煅烧焦产品，其原料成本因素占比高达95％以上，而中硫石油焦的吨成本比高硫石油焦的吨成本比高出200元以上。
目前，在国内外石油焦市场存在的普遍问题是：硫含量增加，对罐式煅烧炉的罐壁砖侵蚀严重，煅烧炉使用寿命从10年左右缩短为3年左右，同时对设备腐蚀和环保的压力加大，产品质量受到影响。
石油焦中的硫分为有机硫和无机硫，其中大部分硫为与焦中碳键合为S-C的有机硫，有些可能为硫酸盐和黄铁矿硫(但这些硫不足焦中总硫量的0.02％)。石油焦中的硫含量主要取决于原油的性质及其硫含量，随着进口原油的增加，石油焦中的硫含量有增加的趋势。石油焦脱硫涉及焦孔隙中、焦表面上硫的脱附，连结在碳骨架上硫的分离与脱除，因此，石油焦的脱硫是一个复杂的过程。
煅烧脱硫：一般指石油焦被加热到指定温度并在该温度下保持一定的时间，在去除水分、挥发分的同时，部分硫分以SO2形式析出的过程，这一过程被认为是最有前途的石油焦脱硫过程。
罐式煅烧炉是煅烧炭素原料的关键设备。在煅烧石油焦时，生石油焦经罐式炉炉顶的加料机构加入料罐，受到两侧火道的间接加热，原料中的水分和一部分挥发分经预热带被排出再经过温度为1250℃-1350℃的高温带的煅烧，石油焦释放出大量的挥发分，产生体积收缩，密度、强度、导电率得到提高；最后，经过冷却水套冷却后排出合格的煅后焦。国内普通煅烧炉的火道最高温度为1380℃，此温度条件下，煅烧焦的脱硫率小于20％，随着国内外石油焦市场供应存在的突出问题：各炼油厂进口原油增多，硫含量越来越高，普通煅烧炉很难满足生产需求，煅烧炉的使用寿命因硫的浸蚀破坏由10年左右时间减至3年左右，投资回报率低下，对设备腐蚀和环保的压力加大。
但是，现有的罐式煅烧炉的罐体砌砖使用的是抗硫渗透、侵蚀性能极差的硅砖。硅质 耐火材料为典型的酸性耐火材料。常规煅烧使用的硅砖，硫含量控制在2.0％以下，按照国内各碳素厂使用经验，煅烧炉正常使用寿命应在8-10年。但在高温1400～1600℃、高硫煅烧气氛下，硅砖与石油焦接触面会受到严重的侵蚀现象并进而剥落，炉体使用寿命仅有3年左右时间。
硅砖不具备高温脱硫煅烧用耐火材料条件的原因：
硅质耐火材料可能的反应方程-C-S-SiO2，具体如下表所示。
编号 反应方程式 G-T 反应开始温度/K
1 1.5S2(g)+SiO2(s)＝SiS2(s)+SO2(g) 283400-6.7T 42298
2 S2(g)+SiO2(s)＝SiS(g)+SO2(g) 568830-173.7T 3274
3 0.5S2(g)+2C(s)+SiO2(s)＝SiS(g)+2CO(g) 314300-272.24T 1154.5
4 S2(g)+2C+SiO2(s)＝SiS2(g)+2CO(g) 416260-250.92T 1658
5 SiO2(s)+C(s)＝SiO(g)+CO(g) 635130-306.43T 2073
从上述方程式可以看出，硅砖在高温含硫气氛中与硫发生化学反应，并通过在高温高硫石油焦模拟试验条件下多次试验，也证明其抗渗透、抗侵蚀能力较差，这是目前国内通用硅砖煅烧炉在使用高硫石油焦情况下，煅烧炉使用寿命大大缩短的重要原因。
由此可以得出的结论是：目前国内外石油焦煅烧生产在用的罐式煅烧炉罐壁砖为硅砖，而硅砖在1400-1600℃温度条件下，对气态硫组分的抗渗透、抗侵蚀效果极差，无法解决其使用中的剥落问题。
因此，在高温条件下，抗硫渗透、侵蚀的罐壁砖耐火材料的选择，已是目前炭素专业科研机构研究的课题，也是各碳素厂需要使用高含硫石油焦原料在罐式煅烧炉中组织生产、降低生产成本的技术发展的主要方向。
发明内容
为解决上述技术问题，本发明提供一种高硫石油焦的煅烧方法，实现以下发明目的：脱硫率高，生产成本低，炉体使用寿命长。
本发明还提供一种罐式煅烧炉，实现以下发明目的：罐式煅烧炉在高硫高温条件下抗渗透、抗侵蚀能力强，使用寿命长，煅烧的高硫石油焦的脱硫率高，生产成本低。
本发明还提供一种罐壁砖及其制备方法，该罐壁砖具有良好的抗硫腐蚀、抗渗透的性能，在高温高硫煅烧中无剥落现象产生，使用寿命长，生产成本低，制备方法工艺简单，环保无污染。
为实现上述发明目的，本发明采用的技术方案为：
一种高硫石油焦的煅烧方法，所述煅烧方法为将高硫石油焦置于罐式煅烧炉内，炉罐内煅烧 带物料温度为1350-1550℃，对高硫石油焦进行高温煅烧。
以下是对上述技术方案的进一步改进：
所述罐式煅烧炉火道的温度为1400-1600℃。
高硫石油焦脱硫率达到42-72％。
所述罐式煅烧炉火道的温度为1400-1500℃，高硫石油焦脱硫率达到42-67％。
一种罐式煅烧炉，所述罐式煅烧炉包括外墙、火道和煅烧罐。
所述罐式煅烧炉每组由四个煅烧罐组成，每台罐式煅烧炉由4×炉组数组成的总罐数构成；所述煅烧罐的罐壁外侧是火道，内侧为与石油焦的接触面；所述煅烧罐四周由带子母槽的异形罐壁砖砌筑而成，所述异形罐壁砖采用耐高温和耐硫侵蚀的砖体材料制成。
所述异形罐壁砖的厚度90mm，异形罐壁砖砌筑时所用耐火泥为与砖体主体材料相近似的耐高温、耐硫侵蚀材料。
一种罐壁砖，所述罐壁砖为锆刚玉莫来石砖、碳化硅刚玉莫来石砖、铬刚玉砖中的任一种。
所述锆刚玉莫来石砖，以重量百分比计，其原料组成包括以下成分：锆刚玉和/或锆英石粉30～45％，锆英石骨料15～25％，莫来石骨料10～20％，特级矾土骨料15～25％，α氧化铝微粉3～8％，硅微粉1～3％，广西白泥2～5％；另外含有6％的化学结合剂。
所述碳化硅刚玉莫来石砖，以重量百分比计，其原料组成包括以下成分：莫来石骨料40～60％，莫来石和/或刚玉粉15～30％，碳化硅粉15～25％，硅微粉2～5％，广西白泥3～8％；另外含有0.8％的碳化硼。
所述铬刚玉砖，以重量百分比计，其原料组成包括以下成分：电熔致密刚玉骨料50～70％，板状刚玉粉5～15％，氧化铬8～18％，单斜氧化锆粉3～8％，活性氧化铝微粉3～8％，其他10％；另外含有化学结合剂4～10％。
一种罐壁砖的制备方法，包括以下步骤：原料破碎、筛分、粉碎、配料、混炼、成型、干燥和烧成；所述烧成工序：干燥后的砖坯经由电拖车推入高温隧道窑内，烧成最高温度控制在1600℃～1800℃。
有益效果：
本发明采用以上技术方案，与现有技术相比，具有以下优点：
1、本发明采用的高硫石油焦的煅烧方法，石油焦脱硫率高，达到42-72％，脱硫率高，而现有技术脱硫率小于20％；
2、本发明采用的高硫石油焦的煅烧方法，生产成本大大降低，高硫石油焦的吨成本比中硫 石油焦的吨成本低200元以上，而煅烧焦产品，其原料成本因素占比高达95％以上，因此成本大大降低；
3、炉体使用寿命长，投资回报率高：高硫石油焦罐式炉煅烧，可延长罐式煅烧炉使用寿命，从原来的3年延长到8-10年，使用寿命延长5-7年；
4、通过罐式煅烧炉罐壁砖的创新应用，降低罐式煅烧炉罐壁砖与石油焦接触面的渗透、侵蚀能力，有效阻止罐壁砖耐火材料在煅烧过程中快速剥落现象；
5、利用石油焦自身产生的热源，通过工业化罐式煅烧炉火道温度1400-1600℃高温煅烧，使石油焦脱硫率达到42～72％，脱硫率高，为全球首创；
6、高温脱硫煅烧具有排除原料高硫石油焦中的水分和挥发分，提高原料的密度和机械强度；提高原料的导电性能；提高原料的化学稳定性和抗氧化性能，降低产品的硫含量。
附图说明：
图1为罐式煅烧炉的结构示意图：
1-外墙；2-煅烧罐；3-火道；
图2为煅烧炉生产使用后的硅砖表面的SEM扫描电镜图；
图3为煅烧炉生产使用后的硅砖的残砖侵蚀面的SEM扫描电镜图；
图4为煅烧炉生产使用后的硅砖的残砖表面气泡富集情况的SEM扫描电镜图；
图5为煅烧炉生产使用后的硅砖的残砖中的SiO2纤维的SEM扫描电镜图；
图6为本发明罐壁砖的制备流程图。
具体实施方式
以下对本发明的优选实施例进行说明，应当理解，此处所描述的优选实施例仅用于说明和解释本发明，并不用于限定本发明。
实施例1：
石油焦中的硫分为有机硫和无机硫，其中大部分硫为与焦中碳键合为S-C的有机硫，有些可能为硫酸盐和黄铁矿硫(但这部分硫含量比较少，在石油焦中总硫量小于0.02％)。
石油焦中的硫含量主要取决于原油的性质及其硫含量，随着进口原油的增加，石油焦中的硫含量有增加的趋势。石油焦脱硫涉及焦孔隙中、焦表面上硫的脱附，连结在碳骨架上硫的分离与脱除，因此，石油焦的脱硫是一个复杂的过程。
煅烧脱硫：一般指石油焦被加热到指定温度并在该温度下保持一定的时间，在去除水分、挥发分的同时，部分硫分以SO2形式析出的过程，这一过程被认为是最有前途的石油焦脱硫过程。
一种高硫石油焦的煅烧方法：
将高硫石油焦置于工业化罐式煅烧炉煅烧罐内，煅烧炉火道的温度为1400-1600℃，利用石油焦自身产生的热源，通过工业化罐式煅烧炉对高硫石油焦进行高温煅烧，锻烧罐内煅烧带物料温度为1350-1550℃，对高硫石油焦进行脱硫，试验结果如下表：
表1、煅烧温度与脱硫率试验结果
Figure PCTCN2015000226-appb-000001
由上表可以看出：
1、罐式煅烧炉火道的煅烧温度为1400-1600℃，即高硫石油焦在炉罐内的温度在1350-1550℃时，脱硫率达到42-72％，脱硫率高，比现有技术中火道温度为1380℃时脱硫率提高了2～4倍。
2、所述罐式煅烧炉火道的温度为1400～1500℃，石油焦脱硫率达到42-67％的基础上，罐式煅烧炉的使用寿命较长，对煅烧炉罐壁砖的质量要求合理，生产成本最优。
实施例2：
如图1所示，一种高硫石油焦的煅烧中使用的罐式煅烧炉：
罐式煅烧炉包括：炉体和金属骨架以及附属在炉体上的冷却水套、加排料装置等几部分组成；其中，炉体包括煅烧罐(2)、火道(3)和外墙(1)三部分；
罐式煅烧炉每组由四个煅烧罐组成，每台煅烧炉由4×炉组数组成的总罐数构成，如28罐、32罐、48罐煅烧炉等。
煅烧罐(2)是炉体最重要的组成部分，煅烧罐(2)按纵横方向成双排列，连同它两侧的四条火道构成一组，一台炉可有8-12组，煅烧罐(2)的水平截面为两端是弧形的扁长 形，罐壁垂直砌筑。
煅烧罐(2)砌筑用罐壁砖为带子母槽的不同于常规罐式煅烧炉罐壁用硅砖的异形耐火砖，该新型耐火砖采用新的配方组成及不同的化学组分，该新型耐火砖为锆刚玉莫来石砖、碳化硅刚玉莫来石砖和铬刚玉砖中的任一种。
所述异形罐壁砖同常规罐式煅烧炉用硅砖相比，厚度增加10mm，常规用的硅砖厚度80mm，异形罐壁砖的厚度为90mm，异形罐壁砖砌筑时所用耐火泥为与砖体主体材料相近似的耐高温、耐硫侵蚀材料。以使炉体经过烘炉后，耐火泥具有良好的粘结强度，确保炉体的密封性。
使用的异形罐壁砖，具有耐高温、耐硫侵蚀作用，罐壁砖外侧为火道(3)，内侧为与石油焦的接触面。
该罐式煅烧炉具有以下有益效果：
1、高温脱硫煅烧炉具有排除原料中的水分和挥发分；提高原料的密度和机械强度；提高原料的导电性能；提高原料的化学稳定性和抗氧化性能，降低产品中的硫含量；
2、降低罐式煅烧炉罐壁砖与石油焦接触面的渗透、侵蚀能力，有效阻止了耐火材料在生产过程中快速剥落现象；
3、实现工业化罐式煅烧炉火道温度1400-1600℃高温煅烧，使石油焦脱硫率达到42-72％；
4、延长罐式煅烧炉的使用寿命，可延长罐式煅烧炉使用寿命5-7年。
实施例3
1、一种锆刚玉莫来石砖工艺配方如下表：
表2、锆刚玉莫来石砖工艺配方
Figure PCTCN2015000226-appb-000002
2、一种碳化硅刚玉莫来石砖工艺配方如下表：
表3、碳化硅刚玉莫来石砖工艺配方
Figure PCTCN2015000226-appb-000003
3、一种铬刚玉砖工艺配方如下表：
表4、铬刚玉砖工艺配方
Figure PCTCN2015000226-appb-000004
实施例4：
一种罐壁砖的制备方法，包括以下步骤：
a、原料破碎：
所需的各种原料大颗粒物料经颚式破碎机和对辊破碎机破碎成小颗粒。
b、筛分：
将破碎好的原料经筛分机筛分成符合规格的原料，进入各自的贮料仓，不合格的筛上料重新进行破碎处理。
c、粉碎：
经筛分后的0.5-1mm粒径的原料，进入雷蒙磨粉机制备成200～300目粉料。
d、配料：
经筛分及磨粉后的各种粒度料分别经自动配料系统按原料配料比准确称量后送入混炼机，同时将结合剂和水按比例加入混炼机。
e、混炼：
在强制混炼机中，将不同组分和粒度的物料同适量的结合剂经混合和挤压作用达到分布均匀和充分润湿，然后以泥料的形式进入到泥料罐中。
f、成型：
将混合好的泥料送入振动成型机砖坯模具中振动成型。
g、干燥：
将压制成型的砖坯在余热干燥窑中利用隧道窑内的热烟气进行干燥，排除砖坯中的水分。
h、烧成：干燥后的砖坯经由电拖车推入高温隧道窑内，不同砖坯分别按相应的升温 制度完成其烧成过程，烧成的最高温度控制在1600℃～1800℃。
i、检验：
出窑后的耐火砖成品，经过自然冷却后，送至成品库拣选区进行检验，对部分需要修整的砖坯用磨砖机进行修整，修整的边角料和不合格品做回配料使用。
实施例4
罐壁砖的侵蚀试验：
表5、试验用材及实验设备表
Figure PCTCN2015000226-appb-000005
表6、检测仪器及试验条件
Figure PCTCN2015000226-appb-000006
试验方法：
本试验选用山东某(砖厂)集团有限公司25m3高温梭式炉作为试验窑炉，在25m3高温梭式炉窑车台面上分别用试验砖砌筑长方形匣钵，并将试验用石油焦置于匣钵内装满，用相配套的高温火泥将匣钵密封，进行试验。
实验结果对比：
由图2-图4可以看出，硅质耐火材料为典型的酸性耐火材料。常规煅烧使用硅砖，硫含量控制在2.0％，在高温1400-1600℃、高硫煅烧气氛下，硅砖与石油焦接触面会受到严重的侵蚀现象并进而剥落，炉体使用寿命仅有3年左右时间。为准确判断硫对硅砖的侵蚀原因，对煅 烧炉使用后的硅砖表面进行SEM扫面电镜分析，如图2、3、4所示，从图2可清晰的看出，在煅烧炉内使用后的硅砖，其表面玻璃相极少，颗粒突出，有气体物质生成现象。
本发明研发的铬刚玉砖、碳化硅砖、锆质砖在高硫气氛中、1520℃下煅烧后观察不到有渗透、侵蚀现象，充分证明上述三种砖抗硫侵蚀能力极强。
而硅砖在高硫气氛中、煅烧1520℃温度下，侵蚀深度约11mm，且与石油焦接触面有严重的剥落现象。
山东淄博某碳素厂煅烧炉罐壁硅砖使用高硫石油焦生产，两年后的硅砖浸蚀结果：煅烧炉报废，不得不重新修建。
罐壁砖具有以下效果：
1、通过罐式煅烧炉罐壁耐火砖的创新应用，降低罐式煅烧炉罐壁砖与石油焦接触面的渗透、侵蚀能力，有效阻止罐壁砖耐火材料在生产过程中快速剥落现象；
2、利用石油焦自身产生的热源，通过工业化罐式煅烧炉1400-1600℃高温煅烧，使石油焦脱硫率达到42-72％，为全球首创；
3、高硫石油焦罐式炉煅烧，可延长罐式煅烧炉使用寿命5-7年。
最后应说明的是：以上所述仅为本发明的优选实施例而已，并不用于限制本发明，尽管参照前述实施例对本发明进行了详细的说明，对于本领域的技术人员来说，其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (12)

  1. 一种高硫石油焦的煅烧方法，其特征在于：所述煅烧方法为将高硫石油焦置于罐式煅烧炉内，炉罐内煅烧带物料温度为1350-1550℃，对高硫石油焦进行高温煅烧。
  2. 根据权利要求1所述的一种高硫石油焦的煅烧方法，其特征在于：所述罐式煅烧炉火道的温度为1400-1600℃。
  3. 根据权利要求1、2所述的一种高硫石油焦的煅烧方法，其特征在于：高硫石油焦脱硫率达到42-72％。
  4. 根据权利要求2所述的一种高硫石油焦的煅烧方法，其特征在于：所述罐式煅烧炉火道的温度为1400-1500℃，高硫石油焦脱硫率达到42-67％。
  5. 根据权利要求1所述的罐式煅烧炉，其特征在于：所述罐式煅烧炉包括外墙、火道和煅烧罐。
  6. 根据权利要求5所述的罐式煅烧炉，其特征在于：所述罐式煅烧炉每组由四个煅烧罐组成，每台罐式煅烧炉由4×炉组数组成的总罐数构成；所述煅烧罐的罐壁外侧是火道，内侧为与石油焦的接触面；所述煅烧罐四周由带子母槽的异形罐壁砖砌筑而成，所述异形罐壁砖采用耐高温和耐硫侵蚀的砖体材料制成。
  7. 根据权利要求5所述的罐式煅烧炉，其特征在于：所述异形罐壁砖的厚度90mm，异形罐壁砖砌筑时所用耐火泥为与砖体主体材料相近似的耐高温、耐硫侵蚀材料。
  8. 根据权利要求5所述的一种罐壁砖，其特征在于：所述罐壁砖为锆刚玉莫来石砖、碳化硅刚玉莫来石砖、铬刚玉砖中的任一种。
  9. 根据权利要求5所述的一种罐壁砖，其特征在于：所述锆刚玉莫来石砖，以重量百分比计，其原料组成包括以下成分：锆刚玉和/或锆英石粉30～45％，锆英石骨料15～25％，莫来石骨料10～20％，特级矾土骨料15～25％，α氧化铝微粉3～8％，硅微粉1～3％，广西白泥2～5％；另外含有6％的化学结合剂。
  10. 根据权利要求8所述的一种罐壁砖，其特征在于：所述碳化硅刚玉莫来石砖，以重量百分比计，其原料组成包括以下成分：莫来石骨料40～60％，莫来石和/或刚玉粉15～30％，碳化硅粉15～25％，硅微粉2～5％，广西白泥3～8％；另外含有0.8％的碳化硼。
  11. 根据权利要求8所述的一种罐壁砖，其特征在于：所述铬刚玉砖，以重量百分比计，其原料组成包括以下成分：电熔致密刚玉骨料50～70％，板状刚玉粉5～15％，氧化铬8～18％，单斜氧化锆粉3～8％，活性氧化铝微粉3～8％，其它10％；另外含有化学结合剂4～10％。
  12. 根据权利要求8所述的一种罐壁砖的制备方法，其特征在于：包括以下步骤：原料破碎、 筛分、粉碎、配料、混炼、成型、干燥和烧成；所述烧成工序：干燥后的砖坯经由电拖车推入高温隧道窑内，烧成最高温度控制在1600℃～1800℃。
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