CN105062612A - Method for desulfurization of petroleum coke - Google Patents
Method for desulfurization of petroleum coke Download PDFInfo
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- CN105062612A CN105062612A CN201510451291.0A CN201510451291A CN105062612A CN 105062612 A CN105062612 A CN 105062612A CN 201510451291 A CN201510451291 A CN 201510451291A CN 105062612 A CN105062612 A CN 105062612A
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- 239000002006 petroleum coke Substances 0.000 title claims abstract description 63
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 42
- 230000023556 desulfurization Effects 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 239000002245 particle Substances 0.000 claims abstract description 26
- 239000002131 composite material Substances 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 9
- 230000003009 desulfurizing effect Effects 0.000 claims abstract description 9
- 239000000571 coke Substances 0.000 claims description 13
- 238000002791 soaking Methods 0.000 claims 1
- 238000010792 warming Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 6
- 229910052961 molybdenite Inorganic materials 0.000 abstract description 5
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052982 molybdenum disulfide Inorganic materials 0.000 abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 description 53
- 239000011593 sulfur Substances 0.000 description 53
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 40
- 238000010438 heat treatment Methods 0.000 description 28
- 239000000843 powder Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000001354 calcination Methods 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 229910052573 porcelain Inorganic materials 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 101100069231 Caenorhabditis elegans gkow-1 gene Proteins 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Divinylene sulfide Natural products C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000002309 gasification Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 235000019738 Limestone Nutrition 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005272 metallurgy Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000005504 petroleum refining Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- MBXOOYPCIDHXGH-UHFFFAOYSA-N 3-butylpentane-2,4-dione Chemical compound CCCCC(C(C)=O)C(C)=O MBXOOYPCIDHXGH-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DFKNJGBWZHYIFN-UHFFFAOYSA-N OO.Cl.[N+](=O)(O)[O-] Chemical compound OO.Cl.[N+](=O)(O)[O-] DFKNJGBWZHYIFN-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- WVMYSOZCZHQCSG-UHFFFAOYSA-N bis(sulfanylidene)zirconium Chemical compound S=[Zr]=S WVMYSOZCZHQCSG-UHFFFAOYSA-N 0.000 description 1
- 239000011329 calcined coke Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- MMXSKTNPRXHINM-UHFFFAOYSA-N cerium(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[Ce+3].[Ce+3] MMXSKTNPRXHINM-UHFFFAOYSA-N 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- -1 thiophene aromatic hydrocarbons Chemical class 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种石油焦脱硫的方法。在氨气气氛下将石油焦与微量催化剂进行混合加热至700-900℃摄氏度之间，并保温，从而达到脱硫目的，石油焦颗粒和复合催化剂的质量比为（10000-100）：1，然后再通入氨气，同时升温至700-900℃并保温30-120min脱硫；所述的复合催化剂是采用粒度小于或等于0.1？mm的NiS，MoS2和CoS，NiS，MoS2和CoS质量比为1：（0.3-0.5）：（0.1-0.2）。本发明在不耗费较多热能，不影响石油焦性能的情况下，通过添加微量催化剂的手段，使得氨气气氛脱硫的效果进一步提高。The invention discloses a method for desulfurizing petroleum coke. In an ammonia atmosphere, mix petroleum coke and a small amount of catalyst and heat it to 700-900 degrees Celsius, and keep it warm to achieve the purpose of desulfurization. The mass ratio of petroleum coke particles to composite catalyst is (10000-100): 1, and then Ammonia gas is then introduced, and at the same time, the temperature is raised to 700-900° C. and kept for 30-120 minutes for desulfurization; the composite catalyst with a particle size of less than or equal to 0.1? mm of NiS, MoS2 and CoS, the mass ratio of NiS, MoS2 and CoS is 1 :(0.3-0.5):( 0.1-0.2 ). The present invention further improves the desulfurization effect of the ammonia atmosphere by adding a small amount of catalyst without consuming much heat energy and without affecting the performance of petroleum coke.
Description
技术领域 technical field
本发明涉及一种石油焦脱硫的方法，应用于冶金、材料、化工及环保技术领域。 The invention relates to a method for desulfurizing petroleum coke, which is applied in the technical fields of metallurgy, material, chemical industry and environmental protection.
背景技术 Background technique
石油焦是石油炼化行业的主要副产品，一般由延迟焦化工艺制得。石油焦因具有灰分低，固定碳含量高等特点，被广泛应用于冶金、材料和化工等领域。同时，因石油焦中硫含量不同，石油焦被分为高硫（>4%）、中硫（2-4%）和低硫焦（<2%）。但随着国际原油的劣化和酸化，作为石油炼化的副产品的石油焦的品质也在逐渐降低，尤其是石油焦中的硫含量在不断提高。石油焦中的硫分含量过高会极大的影响产品的质量。与此同时，随着石油焦中的硫分增加，以石油焦为原料的下级工业企业也相应的承担着越来越艰巨的控制硫排放的环保压力。 Petroleum coke is the main by-product of the petroleum refining industry and is generally produced by the delayed coking process. Because of its low ash content and high fixed carbon content, petroleum coke is widely used in metallurgy, materials and chemical industries. At the same time, due to the different sulfur content in petroleum coke, petroleum coke is divided into high sulfur (>4%), medium sulfur (2-4%) and low sulfur coke (<2%). However, with the deterioration and acidification of international crude oil, the quality of petroleum coke, a by-product of petroleum refining, is gradually decreasing, especially the sulfur content in petroleum coke is constantly increasing. Excessive sulfur content in petroleum coke will greatly affect the quality of the product. At the same time, as the sulfur content in petroleum coke increases, the lower-level industrial enterprises that use petroleum coke as raw materials are also correspondingly bearing more and more difficult environmental protection pressures to control sulfur emissions.
以石油焦作为原料制备炭阳极为例。石油焦中的硫主要是以噻吩类芳香烃物质存在，在正常的煅烧温度下无法从石油焦中脱除。在阳极制备过程中，为了有效的脱除硫分，只能以提高石油焦的煅烧温度来解决硫含量过高的问题。因此，在有限的降低高硫焦中硫含量的同时，高温煅烧不仅使煅烧的经济成本提高，在一定程度上也降低的煅后焦的实收率，提高了企业的阳极制造成本，影响了经济效益。 Take petroleum coke as a raw material to prepare carbon anode as an example. The sulfur in petroleum coke mainly exists as thiophene aromatic hydrocarbons, which cannot be removed from petroleum coke at normal calcination temperature. In the anode preparation process, in order to effectively remove sulfur, the problem of excessive sulfur content can only be solved by increasing the calcination temperature of petroleum coke. Therefore, while reducing the sulfur content in high-sulfur coke to a limited extent, high-temperature calcination not only increases the economic cost of calcination, but also reduces the actual yield of calcined coke to a certain extent, which increases the anode manufacturing cost of the enterprise and affects the economic benefits.
此外，高硫石油焦因为其硫含量高的特性，只能简单的作为燃料来使用。在以石油焦为原料的炭素行业飞快发展和生石油焦硫含量越来越高的行业背景下，优质低硫石油焦的产能缺口越来越大。因此，如何环保、高效的利用劣质高硫石油焦成为了当今炭素行业迫切需要解决的问题。 In addition, high-sulfur petroleum coke can only be used simply as a fuel because of its high sulfur content. Under the background of the rapid development of the carbon industry using petroleum coke as raw material and the increasing sulfur content of raw petroleum coke, the production capacity gap of high-quality low-sulfur petroleum coke is getting bigger and bigger. Therefore, how to use low-quality high-sulfur petroleum coke in an environmentally friendly and efficient manner has become an urgent problem for the carbon industry today.
公开专利申请CN104611087A是利用氨气煅烧法脱除石油焦中的硫，并未涉及到催化剂的添加和使用。 The published patent application CN104611087A uses the ammonia gas calcination method to remove sulfur in petroleum coke, and does not involve the addition and use of catalysts.
公开专利申请CN103555389A提到了一种石油焦的脱硫同时避免焦化的方法。但采用方法为固体燃料颗粒、石英砂石和石灰石，在高速流化床内燃烧。虽然控制温度为850～900℃，但操作过程需要加入石英砂石和石灰石。 Published patent application CN103555389A mentions a method for desulfurizing petroleum coke while avoiding coking. However, the method used is solid fuel particles, quartz sand and limestone, which are burned in a high-speed fluidized bed. Although the temperature is controlled at 850-900°C, quartz sandstone and limestone need to be added during the operation.
专利CN101020854A提到了一种石油焦气化制氢脱硫耦合方案。但采用方法为将石油焦和碳酸钠或碳酸钾混合加入反应器，并通入水蒸气气化。并在气化反应后对石油焦进行酸洗，水洗和干燥。 Patent CN101020854A mentions a petroleum coke gasification hydrogen production desulfurization coupled scheme. However, the method used is to mix petroleum coke and sodium carbonate or potassium carbonate into the reactor, and feed water vapor for gasification. And after the gasification reaction, the petroleum coke is pickled, washed with water and dried.
专利CN101804977A提到了一种酸法脱除石油焦中的硫分技术。方法为在常压、0-60℃下将石油焦细颗粒置于混合酸脱硫剂中一定时间，然后再将石油焦分离出并洗涤。 Patent CN101804977A mentions a technology for removing sulfur from petroleum coke by acid method. The method is to put the petroleum coke fine particles in the mixed acid desulfurizer under normal pressure and 0-60 DEG C for a certain period of time, and then separate and wash the petroleum coke.
专利CN101144044A是采用在石油焦中加入硫化锆、硫化铈和硫化钇中的一种脱硫剂进行煅烧，并且煅烧温度采用在1270-1500℃下进行。 Patent CN101144044A adopts adding a desulfurizer of zirconium sulfide, cerium sulfide and yttrium sulfide to petroleum coke for calcination, and the calcination temperature is carried out at 1270-1500°C.
专利CN104129774A提供了一种脱硫技术。方法是在石油焦破碎的前提下按照一定的混合比加入混合稀土和硝酸-盐酸-双氧水脱硫剂，然后再混合均匀并进行搅拌。再通过分离，1300-1350℃煅烧，最终得到低硫含量的石油焦产品。 Patent CN104129774A provides a desulfurization technology. The method is to add mixed rare earth and nitric acid-hydrochloric acid-hydrogen peroxide desulfurizer according to a certain mixing ratio under the premise of crushing petroleum coke, and then mix and stir evenly. After separation and calcination at 1300-1350°C, petroleum coke products with low sulfur content are finally obtained.
发明内容 Contents of the invention
本发明的目的是针对氨气火法脱除石油焦中硫的方法，提出了一种更加有效的促进脱硫效率的方法，脱硫率可以超过80%。 The object of the present invention is to propose a more effective method for promoting desulfurization efficiency for the ammonia fire method for removing sulfur in petroleum coke, and the desulfurization rate can exceed 80%.
具体过程如下：先将石油焦破碎成1mm及以下并与0.1mm粒级及以下的复合催化剂混合，石油焦颗粒和复合催化剂的质量比为（10000-100）：1，然后再通入氨气，同时升温至700-900℃并保温30-120min脱硫；所述的复合催化剂是采用粒度小于或等于0.1mm的NiS，MoS2和CoS，NiS，MoS2和CoS质量比为1：（0.3-0.5）：（0.1-0.2）。 The specific process is as follows: first crush the petroleum coke into 1mm and below and mix it with the composite catalyst with a particle size of 0.1mm and below. The mass ratio of petroleum coke particles and composite catalyst is (10000-100): 1, and then inject ammonia gas , while raising the temperature to 700-900°C and keeping it warm for 30-120min for desulfurization; the composite catalyst uses NiS, MoS 2 and CoS with a particle size less than or equal to 0.1mm, and the mass ratio of NiS, MoS 2 and CoS is 1: (0.3- 0.5): (0.1-0.2).
进一步的，其中复合催化剂是粒度小于或等于0.075mm。 Further, wherein the composite catalyst has a particle size less than or equal to 0.075mm.
进一步的，其中石油焦颗粒与复合催化剂混合的比例为（5000-1000）：1。 Further, the mixing ratio of the petroleum coke particles and the composite catalyst is (5000-1000):1.
进一步的，其中石油焦的粒度小于或等于0.5mm。 Further, the particle size of petroleum coke is less than or equal to 0.5mm.
进一步的，其中所述的脱硫温度为750-850℃，保温时间为30-60min。 Further, the desulfurization temperature is 750-850°C, and the holding time is 30-60min.
进一步的，其中氨气压力大于等于0.101MPa。 Further, wherein the ammonia pressure is greater than or equal to 0.101MPa.
进一步的，镍、钼和钴元素的硫化物可以促进氨气与石油焦中硫分反应的原理本质是在这种变价金属及其化合物存在的条件下，硫分更加容易从噻吩等有机化合物中脱离，与氨气产生的活性氢原子反应生成H2S而脱除于石油焦。但对于石油焦脱硫中，单一元素的催化效果并不好，相反，在约600℃以上氨气气氛下混合镍、钼和钴元素的硫化物经我们研究发现最终会形成一种可以表达为CoMo1.5NixSx+4（x>1）的复杂多孔大表面积物质，该物质会对氨气气氛下的石油焦脱硫呈现1+1>2的效果。为了在氨气气氛下煅烧脱硫过程中最大程度的转化成这种催化剂达以到最优的脱硫效果，我们在一系列的实验基础上确定了1：（0.3-0.5）：（0.1-0.2）这一配比。 Furthermore, the principle that the sulfides of nickel, molybdenum and cobalt elements can promote the reaction of sulfur in ammonia gas and petroleum coke is that in the presence of such variable-valence metals and their compounds, sulfur is more easily released from organic compounds such as thiophene. Detachment, reacting with active hydrogen atoms generated by ammonia gas to generate H 2 S, which is removed from petroleum coke. However, for the desulfurization of petroleum coke, the catalytic effect of a single element is not good. On the contrary, the sulfide of nickel, molybdenum and cobalt elements mixed in an ammonia atmosphere above about 600 ° C will eventually form a kind of sulfide that can be expressed as CoMo 1.5 Ni x S x+4 (x>1) is a complex porous material with a large surface area, which will show a 1+1>2 effect on the desulfurization of petroleum coke in an ammonia atmosphere. In order to maximize the conversion into this catalyst in the process of calcination and desulfurization under ammonia atmosphere to achieve the best desulfurization effect, we determined 1: (0.3-0.5): (0.1-0.2) based on a series of experiments This ratio.
本发明的突出特点： Outstanding features of the present invention:
1本发明可以在较低的温度下与单纯氨气脱硫相比进一步的大幅度减少高硫焦中的硫含量，使得石油焦中的硫可以集中处理，即减轻炭素生产后续工段的环保压力，又可以将脱除的硫制作含硫化学品。 1. Compared with pure ammonia gas desulfurization, the present invention can further greatly reduce the sulfur content in high-sulfur coke at a lower temperature, so that the sulfur in petroleum coke can be treated in a concentrated manner, that is, the environmental protection pressure of the subsequent section of carbon production can be reduced. The removed sulfur can also be used to make sulfur-containing chemicals.
2本发明可以有效的提高高硫石油焦的利用率。进一步拓展了炭素行业的原料使用范围。 2. The present invention can effectively improve the utilization rate of high-sulfur petroleum coke. Further expand the range of raw materials used in the carbon industry.
3本发明中使用的金属硫化物催化剂添加量少，价格便宜。 3 The metal sulfide catalyst used in the present invention has a small amount of addition and is cheap.
4本发明实施工艺简单方便，在原料正常煅烧过程中就可以将硫脱除。 4. The implementation process of the present invention is simple and convenient, and the sulfur can be removed during the normal calcination process of raw materials.
5本发明脱硫后的石油焦微观结构与原焦基本相同，这类金属催化剂的添加未对焦的表面结构造成破坏。 5. The microstructure of the petroleum coke after desulfurization in the present invention is basically the same as that of the original coke, and the addition of this type of metal catalyst does not cause damage to the surface structure of the coke.
具体实施方式 Detailed ways
下面结合具体实施例作进一步说明，但本发明并不因此而受到任何限制。 Further description will be made below in conjunction with specific examples, but the present invention is not limited thereto.
实施例1 Example 1
取国内某高硫石油焦15g，测得其硫含量为6.5wt%，将其破碎至1mm以下，与小于0.075mm粒度的MoS2粉0.0003g、小于0.075mm粒度的CoS粉0.0002g和小于0.075mm粒度的NiS粉0.001g充分混合，然后平铺在一个2×3cm的平底方形瓷舟中。再将样品置于气氛炉中进行加热脱硫。加热脱硫处理实验条件：气氛炉以7℃/Min升温速率升温至800℃，在800℃保温2小时。在加热开始时就通入氨气（反应炉内氨气压力保持1个大气压）。最后取出样品进行称量，减去混入的金属催化剂的质量后得到石油焦的实际质量再测硫，发现硫含量已经降至1.23wt%，脱硫率为81.08%。与对比例1，2，3中单一硫化物的催化相比复合催化剂的促进脱硫效果更好。另外如表1所示，在与实施例1相同的条件下改变CoS、MoS2和NiS的配比通过实验并XRD检测后得出结论，在NiS，MoS2和CoS质量比为1：（0.3-0.5）：（0.1-0.2）的范围内较易形成CoMo1.5NixSx+4的化合物，并达到较高的脱硫效果。在质量比超出范围后，由于在相同质量下的催化剂其中主要作用的化合物形成较少，效果反而受到影响。 Take 15g of a domestic high-sulfur petroleum coke, the measured sulfur content is 6.5wt%, crush it to less than 1mm, and mix with 0.0003g of MoS2 powder with a particle size of less than 0.075mm, 0.0002g of CoS powder with a particle size of less than 0.075mm and 0.001 g of NiS powder with a particle size of mm was thoroughly mixed, and then spread in a flat-bottomed square porcelain boat of 2 × 3 cm. The samples were then placed in an atmosphere furnace for heating and desulfurization. Experimental conditions for heating desulfurization treatment: the temperature of the atmosphere furnace is raised to 800°C at a heating rate of 7°C/Min, and the temperature is kept at 800°C for 2 hours. Just feed ammonia gas (the ammonia gas pressure in the reaction furnace keeps 1 atmospheric pressure) when heating starts. Finally, the sample was taken out for weighing, and the actual mass of the petroleum coke was obtained after subtracting the mass of the mixed metal catalyst. Then the sulfur was measured, and it was found that the sulfur content had dropped to 1.23wt%, and the desulfurization rate was 81.08%. Compared with the catalysis of single sulfide in Comparative Examples 1, 2, and 3, the desulfurization promotion effect of the composite catalyst is better. In addition, as shown in Table 1, under the same conditions as in Example 1, the ratio of CoS, MoS 2 and NiS was changed. After the experiment and XRD detection, it was concluded that the mass ratio of NiS, MoS 2 and CoS was 1: (0.3 -0.5): In the range of (0.1-0.2), it is easier to form CoMo 1.5 Ni x S x+4 compounds and achieve a higher desulfurization effect. After the mass ratio exceeds the range, the effect will be affected instead due to the formation of less active compounds in the catalyst under the same mass.
表格
对比例1 Comparative example 1
取国内某高硫石油焦15g，测得其硫含量为6.5wt%，将其破碎至1mm以下，与小于0.075mm粒度的NiS粉0.0015g充分混合，然后平铺在一个2×3cm的平底方形瓷舟中。再将样品置于气氛炉中进行加热脱硫。加热脱硫处理实验条件：气氛炉以7℃/Min升温速率升温至800℃，在800℃保温2小时。在加热开始时就通入氨气（反应炉内氨气压力保持1个大气压）。最后取出样品进行称量，减去混入的金属催化剂的质量后得到石油焦的实际质量再测硫，发现脱硫率为69.70%。 Take 15g of a domestic high-sulfur petroleum coke whose sulfur content is measured to be 6.5wt%, crush it to less than 1mm, fully mix it with 0.0015g of NiS powder with a particle size of less than 0.075mm, and spread it on a flat-bottomed square of 2×3cm In the porcelain boat. The samples were then placed in an atmosphere furnace for heating and desulfurization. Experimental conditions for heating desulfurization treatment: the temperature of the atmosphere furnace is raised to 800°C at a heating rate of 7°C/Min, and the temperature is kept at 800°C for 2 hours. Just feed ammonia gas (the ammonia gas pressure in the reaction furnace keeps 1 atmospheric pressure) when heating starts. Finally, the sample was taken out for weighing, and the actual mass of the petroleum coke was obtained after subtracting the mass of the mixed metal catalyst, and then the sulfur was measured, and the desulfurization rate was found to be 69.70%.
对比例2 Comparative example 2
取国内某高硫石油焦15g，测得其硫含量为6.5wt%，将其破碎至1mm以下，与小于0.075mm粒度的CoS粉0.0015g充分混合，然后平铺在一个2×3cm的平底方形瓷舟中。再将样品置于气氛炉中进行加热脱硫。加热脱硫处理实验条件：气氛炉以7℃/Min升温速率升温至800℃，在800℃保温2小时。在加热开始时就通入氨气（反应炉内氨气压力保持1个大气压）。最后取出样品进行称量，减去混入的金属催化剂的质量后得到石油焦的实际质量再测硫，发现脱硫率为70.1%。 Take 15g of a domestic high-sulfur petroleum coke, the measured sulfur content is 6.5wt%, crush it to less than 1mm, fully mix it with 0.0015g of CoS powder with a particle size of less than 0.075mm, and spread it on a flat-bottomed square of 2×3cm In the porcelain boat. The samples were then placed in an atmosphere furnace for heating and desulfurization. Experimental conditions for heating desulfurization treatment: the temperature of the atmosphere furnace is raised to 800°C at a heating rate of 7°C/Min, and the temperature is kept at 800°C for 2 hours. Just feed ammonia gas (the ammonia gas pressure in the reaction furnace keeps 1 atmospheric pressure) when heating starts. Finally, the sample was taken out for weighing, and the actual mass of the petroleum coke was obtained after subtracting the mass of the mixed metal catalyst, and then the sulfur was measured, and the desulfurization rate was found to be 70.1%.
对比例3 Comparative example 3
取国内某高硫石油焦15g，测得其硫含量为6.5wt%，将其破碎至1mm以下，与小于0.075mm粒度的MoS2粉0.0015g充分混合，然后平铺在一个2×3cm的平底方形瓷舟中。再将样品置于气氛炉中进行加热脱硫。加热脱硫处理实验条件：气氛炉以7℃/Min升温速率升温至800℃，在800℃保温2小时。在加热开始时就通入氨气（反应炉内氨气压力保持1个大气压）。最后取出样品进行称量，减去混入的金属催化剂的质量后得到石油焦的实际质量再测硫，发现脱硫率为69.8%。 Take 15g of a domestic high-sulfur petroleum coke, whose sulfur content is measured to be 6.5wt%, crush it to less than 1mm, fully mix it with 0.0015g of MoS 2 powder with a particle size of less than 0.075mm, and spread it on a flat bottom of 2×3cm In a square porcelain boat. The samples were then placed in an atmosphere furnace for heating and desulfurization. Experimental conditions for heating desulfurization treatment: the temperature of the atmosphere furnace is raised to 800°C at a heating rate of 7°C/Min, and the temperature is kept at 800°C for 2 hours. Just feed ammonia gas (the ammonia gas pressure in the reaction furnace keeps 1 atmospheric pressure) when heating starts. Finally, the sample was taken out for weighing, and the actual mass of the petroleum coke was obtained after subtracting the mass of the mixed metal catalyst, and then the sulfur was measured, and the desulfurization rate was found to be 69.8%.
实施例2 Example 2
取国内某高硫石油焦15g，测得其硫含量为6.5wt%，将其破碎至1mm以下，与小于0.1mm粒度的MoS2粉0.0003g、小于0.1mm粒度的CoS粉0.0002g和小于0.1mm粒度的NiS粉0.001g充分混合，然后平铺在一个2×3cm的平底方形瓷舟中。再将样品置于气氛炉中进行加热脱硫。加热脱硫处理实验条件：气氛炉以7℃/Min升温速率升温至800℃，在800℃保温2小时。在加热开始时就通入氨气（反应炉内氨气压力保持1个大气压）。最后取出样品进行称量，减去混入的金属催化剂的质量后得到石油焦的实际质量再测硫，发现脱硫率为80.52%。 Take 15g of a domestic high-sulfur petroleum coke, the measured sulfur content is 6.5wt%, crush it to less than 1mm, and mix it with 0.0003g of MoS 2 powder with a particle size of less than 0.1mm, 0.0002g of CoS powder with a particle size of less than 0.1mm and less than 0.1 0.001 g of NiS powder with a particle size of mm was thoroughly mixed, and then spread in a flat-bottomed square porcelain boat of 2 × 3 cm. The samples were then placed in an atmosphere furnace for heating and desulfurization. Experimental conditions for heating desulfurization treatment: the temperature of the atmosphere furnace is raised to 800°C at a heating rate of 7°C/Min, and the temperature is kept at 800°C for 2 hours. Just feed ammonia gas (the ammonia gas pressure in the reaction furnace keeps 1 atmospheric pressure) when heating starts. Finally, the sample was taken out for weighing, and the actual mass of the petroleum coke was obtained after subtracting the mass of the mixed metal catalyst, and then the sulfur was measured, and the desulfurization rate was found to be 80.52%.
实施例3 Example 3
取国内某高硫石油焦15g，测得其硫含量为6.5wt%，将其破碎至1mm以下，与小于0.1mm粒度的MoS2粉0.003g、小于0.1mm粒度的CoS粉0.002g和小于0.1mm粒度的NiS粉0.01g充分混合，然后平铺在一个2×3cm的平底方形瓷舟中。再将样品置于气氛炉中进行加热脱硫。加热脱硫处理实验条件：气氛炉以7℃/Min升温速率升温至800℃，在800℃保温2小时。在加热开始时就通入氨气（反应炉内氨气压力保持1个大气压）。最后取出样品进行称量，减去混入的金属催化剂的质量后得到石油焦的实际质量再测硫，发现脱硫率为82.50%。 Take 15g of a domestic high-sulfur petroleum coke, the measured sulfur content is 6.5wt%, crush it to less than 1mm, and mix with 0.003g of MoS2 powder with a particle size of less than 0.1mm, 0.002g of CoS powder with a particle size of less than 0.1mm and less than 0.1 0.01 g of NiS powder with a particle size of mm was thoroughly mixed, and then spread in a flat-bottomed square porcelain boat of 2 × 3 cm. The samples were then placed in an atmosphere furnace for heating and desulfurization. Experimental conditions for heating desulfurization treatment: the temperature of the atmosphere furnace is raised to 800°C at a heating rate of 7°C/Min, and the temperature is kept at 800°C for 2 hours. Just feed ammonia gas (the ammonia gas pressure in the reaction furnace keeps 1 atmospheric pressure) when heating starts. Finally, the sample was taken out for weighing, and the actual mass of the petroleum coke was obtained after subtracting the mass of the mixed metal catalyst, and then the sulfur was measured, and the desulfurization rate was found to be 82.50%.
实施例4 Example 4
取国内某高硫石油焦15g，测得其硫含量为6.5wt%，将其破碎至1mm以下，与小于0.1mm粒度的MoS2粉0.03g、小于0.1mm粒度的CoS粉0.02g和小于0.1mm粒度的NiS粉0.1g充分混合，然后平铺在一个2×3cm的平底方形瓷舟中。再将样品置于气氛炉中进行加热脱硫。加热脱硫处理实验条件：气氛炉以7℃/Min升温速率升温至800℃，在800℃保温2小时。在加热开始时就通入氨气（反应炉内氨气压力保持1个大气压）。最后取出样品进行称量，减去混入的金属催化剂的质量后得到石油焦的实际质量再测硫，发现脱硫率为84.71%。 Take 15g of a domestic high-sulfur petroleum coke, the measured sulfur content is 6.5wt%, crush it to less than 1mm, and mix it with 0.03g of MoS2 powder with a particle size of less than 0.1mm, 0.02g of CoS powder with a particle size of less than 0.1mm and less than 0.1 0.1 g of NiS powder with a particle size of mm was mixed thoroughly, and then spread in a flat-bottomed square porcelain boat of 2 × 3 cm. The samples were then placed in an atmosphere furnace for heating and desulfurization. Experimental conditions for heating desulfurization treatment: the temperature of the atmosphere furnace is raised to 800°C at a heating rate of 7°C/Min, and the temperature is kept at 800°C for 2 hours. Just feed ammonia gas (the ammonia gas pressure in the reaction furnace keeps 1 atmospheric pressure) when heating starts. Finally, the sample was taken out for weighing, and the actual mass of the petroleum coke was obtained after subtracting the mass of the mixed metal catalyst, and then the sulfur was measured, and the desulfurization rate was found to be 84.71%.
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