CN1319631C - Agent with three effect, sulphur transfers, denitrification and combustion supporting as well as its preparing method - Google Patents

Agent with three effect, sulphur transfers, denitrification and combustion supporting as well as its preparing method Download PDF

Info

Publication number
CN1319631C
CN1319631C CN 02153284 CN02153284A CN1319631C CN 1319631 C CN1319631 C CN 1319631C CN 02153284 CN02153284 CN 02153284 CN 02153284 A CN02153284 A CN 02153284A CN 1319631 C CN1319631 C CN 1319631C
Authority
CN
Grant status
Grant
Patent type
Prior art keywords
combustion
sulfur
magnesium
way
according
Prior art date
Application number
CN 02153284
Other languages
Chinese (zh)
Other versions
CN1480246A (en )
Inventor
刘振义
李小纬
陈华
刘有成
Original Assignee
北京三聚环保新材料有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Grant date

Links

Abstract

本发明涉及用于石油炼制催化裂化装置中的一种助剂及其制备方法。 The present invention relates to an aid apparatus in FCC petroleum refining process for its preparation. 本发明的三效剂包括吸附剂、作为氧化催化剂的二氧化铈和五氧化二钒、作为结构助剂的氟氧化铈,氧化催化剂和结构助剂分散在吸附剂中,吸附剂是具有通式为MgAl Triple Action present invention include adsorbents, ceria and vanadium pentoxide as an oxidation catalyst, a cerium oxyfluoride structure aids, dispersing aids and structure of the oxidation catalyst in the adsorbent, the adsorbent having the general formula is MgAl

Description

硫转移脱氮助燃三效剂及其制备方法和用途 Nitrogen and sulfur transfer agent and the three-way combustion preparation and use

技术领域 FIELD

本发明涉及石油炼制催化裂化中的一种助剂及其制备方法和用途。 The present invention relates to an adjuvant and preparation and use in catalytic cracking of petroleum refining. 具体说,该助剂用于催化裂化再生烟气中硫氧化物的转移、一氧化碳的助燃以及氮氧化物的还原。 In particular, the adjuvants used in the FCC regenerator flue gas transferring sulfur oxides, carbon monoxide combustion and the reduction of nitrogen oxides.

背景技术 Background technique

流化催化裂化(FCC)是炼油工业中最重要的一种二次加工手段,是轻质油品的重要来源,但是其向大气排放的再生烟气中含有大量的有害气体,如NOX、SOX和CO等。 Fluid catalytic cracking (FCC) is the most important oil refining industry to a secondary processing means, the oil is an important source of light, but the regeneration flue gas emission into the atmosphere contains large amounts of harmful gases, such as NOX, SOX and CO. 其中的SOX是大气中的SOX主要来源之一,约占整个人类生活中向大气排放的SOX总量的3%至4%。 SOX SOX which is one of the main sources of the atmosphere, accounting for about 3-4% of the total of the entire human life SOX emissions to the atmosphere. 催化裂化是我国重油二次加工的重要手段之一,目前催化裂化总加工能力占原油加工能力的三分之一以上,随着催化裂化原料的重质化和劣质化,原料中的硫、氮等杂质含量不断增加,有许多炼厂发生了再生系统设备腐蚀开裂的现象,严重威胁安全生产。 FCC is an important means of secondary processing of heavy oil, the current FCC more than a third of the total processing capacity of crude oil processing capacity, with the heavy catalytic cracking and poor quality of raw materials, raw sulfur, nitrogen and other impurities increasing, there are many refineries happened regeneration system equipment corrosion cracking phenomenon, a serious threat to safety in production. 目前普遍认为,在富氧再生的操作条件下,硫、氧在催化剂再生过程中生成的NOX、SOX等酸性气体,透过设备的隔热耐磨衬里到达设备金属内壁,并与烟气中水蒸气作用,在器壁冷凝生成酸性溶液,从而造成设备的腐蚀。 It is generally believed, at the operating conditions of the oxygen-rich regeneration, sulfur, oxygen generated in the catalyst regeneration process of NOX, SOX and other acidic gases, arrives at the device through the inner metal wall insulation resistant lining device, the flue gas and water vapor action, is condensed in the wall to produce acidic solution, thereby causing corrosion of apparatus. 为解决上述问题,人们在降低再生烟气中的NOX和SOX等酸性气体含量方面进行了大量的工作。 To solve the above problems, a lot of people in reducing the acid gas content of the regeneration of the working aspect of NOX and SOX in the flue gas and the like. 对于再生器烟气中的硫氧化物普遍采用硫转移剂进行氧化吸附的方法,吸附硫氧化物的硫转移剂随再生的裂化催化剂进入提升管反应器,该硫转移剂在提升管反应器的还原环境下得到再生,再生后的硫转移剂随裂化催化剂进入再生器循环使用。 Regenerator flue gas for sulfur oxides commonly used method for oxidizing sulfur transfer reagent is adsorbed, adsorbing sulfur transfer reagent with sulfur oxides regenerated cracking catalyst into the riser reactor, the sulfur transfer agent in the riser reactor regenerated reducing atmosphere, the sulfur transfer agent is regenerated cracking catalyst with recycled into the regenerator. 对硫转移剂的研究可分为固体硫转移剂和液体硫转移剂两类。 Study sulfur transfer agent can be divided into solid sulfur transfer agent and a liquid sulfur transfer reagent types. 从国内外硫转移剂的研究和发展看,几乎所有商用硫转移剂都载入了钒,这是因为钒对硫的氧化还原具有独特的催化作用。 From the research and development of domestic and sulfur transfer agent to see, almost all commercial sulfur transfer agent are loaded vanadium, vanadium because of the oxidation of sulfur has a unique catalytic reduction. 但钒对FCC催化剂(或称催化裂化催化剂,以下简称为裂化催化剂)有毒性作用,而液体硫转移剂因具有高度的分散性,会加强这种毒性作用。 However Vanadium on FCC catalyst (or catalytic cracking catalyst, the cracking catalyst is hereinafter referred to as) toxic effects, due to the liquid sulfur transfer agent has high dispersibility, this will enhance toxicity. 因此,固体硫转移剂应是发展的主要方向。 Thus, the solid sulfur transfer reagent should be the main direction of development. 80年代以前,对于硫转移剂的选择,是以金属氧化物为出发点的,最初采用Al2O3、MgO或其混合物作为硫转移剂,但性能不理想。 80 years ago, the choice of sulfur transfer agent is a metal oxide as the starting point, the initial use of Al2O3, MgO or mixtures thereof as a sulfur transfer agent, but the performance is not satisfactory. Al2(SO4)3在高温下具有热不稳定性,而MgO虽具有很好的脱硫性能,其硫酸盐MgSO4热稳定性也好,但再生效果不好。 Al2 (SO4) 3 having a thermally at a high temperature stability, although MgO having good desulfurization performance, thermal stability thereof sulfate MgSO4 good, but not regeneration. 80年代中期,由于发现尖晶石独特的吸硫与解吸性能,对硫转移剂的研究主要转为尖晶石或类尖晶石(主要是富MgO的固溶体尖晶石)系列。 The mid-1980s, due to the discovery of unique spinel sulfur absorption and desorption properties, research on sulfur transfer agent into the main spinel or spinel (mainly MgO-rich spinel solid solution) series. 近年来硫转移剂研究方向是如何使尖晶石具有更好的脱硫性能和再生性能,美国专利USP5,108,979提出了在形成尖晶石或类尖晶石结构时同时生成二氧化铈以及五氧化二钒的硫转移剂,但是该文献未提供脱硫性能和再生性能的参数,按其实施例所得到的硫转移剂的成本也较高。 In recent years, research on how the sulfur transfer agent is a spinel having a better desulfurization performance and reproduction performance, U.S. Patent No. USP5,108,979 proposes generated simultaneously when forming the spinel or spinel structure and ceria pentoxide vanadium sulfur transfer agents, but this document does not provide reproduction performance parameters and performance of desulfurization, the sulfur transfer reagent obtained in Example embodiments of its higher cost. 也有文献提到某些硫转移剂具有降氮和助燃的作用,但是未给出这些硫转移剂的具体的化学式或结构式。 Document also refers to certain sulfur transfer agent having a combustion reducing nitrogen and role, but these are not given a specific chemical formula or formula sulfur transfer agent.

发明内容 SUMMARY

本发明的目的是,提供一种能高效降低催化裂化再生烟气中硫氧化物、氮氧化物和一氧化碳含量的硫转移脱氮助燃三效剂及其一种成本较低的制备方法和用途。 Object of the present invention is to provide a highly efficient reduction of sulfur oxides in the FCC regenerator flue gas, sulfur, nitrogen oxides and carbon monoxide content of combustion of nitrogen and three transfer agent, and a cost-effective preparation and use less.

本发明提供的硫转移脱氮助燃三效剂包括吸附剂和氧化催化剂,氧化催化剂分散在吸附剂中,氧化催化剂包括五氧化二钒和含稀土铈的化合物二氧化铈;其特征在于:还具有分散在吸附剂中的结构助剂含稀土铈的化合物氟氧化铈;吸附剂是具有通式为AB2-xB′xO4·yAO的类尖晶石复合氧化物。 Nitrogen and sulfur transfer provided by the combustion of the present invention comprises an adsorbent and a three-way oxidation catalyst, an oxidation catalyst is dispersed in the adsorbent, the oxidation catalyst comprising vanadium pentoxide ceria rare earth-containing compound and cerium; characterized in that: further comprising structure aid dispersed in the adsorbent containing cerium rare earth cerium oxyfluoride compound; adsorbent having the formula AB2-xB'xO4 · yAO a spinel composite oxide. 式中的A为碱土金属元素Mg,B为IIIA族金属元素Al,B′为过渡金属元素Fe,x为0.01~0.5、优选0.05~0.4、进一步优选0.05~0.20,y为0.2~1.2、优选0.4~1.2、进一步优选0.8~1.0。 Where A is an alkaline earth metal element Mg, B is a Group IIIA metals Al, B 'is a transition metal element Fe, x is from 0.01 to 0.5, preferably 0.05 to 0.4, more preferably 0.05 ~ 0.20, y is from 0.2 to 1.2, preferably 0.4 to 1.2, more preferably 0.8 to 1.0.

上述吸附剂的成分为MgAl1.99Fe0.01O4·MgO、MgAl1.95Fe0.05O4·MgO、MgAl1.90Fe0.10O4·MgO、MgAl1.85Fe0.15O4·MgO、MgAl1.80Fe0.20O4·MgO、MgAl1.60Fe0.40O4·MgO、MgAl1.80Fe0.20O4·0.4MgO、MgAl1.80Fe0.20O4·0.6MgO、MgAl1.80Fe0.20O4·0.8MgO、MgAl1.80Fe0.20O4·1.0MgO或MgAl1.80Fe0.20O4·1.2MgO。 Component of the adsorbent is MgAl1.99Fe0.01O4 · MgO, MgAl1.95Fe0.05O4 · MgO, MgAl1.90Fe0.10O4 · MgO, MgAl1.85Fe0.15O4 · MgO, MgAl1.80Fe0.20O4 · MgO, MgAl1.60Fe0. 40O4 · MgO, MgAl1.80Fe0.20O4 · 0.4MgO, MgAl1.80Fe0.20O4 · 0.6MgO, MgAl1.80Fe0.20O4 · 0.8MgO, MgAl1.80Fe0.20O4 · 1.0MgO or MgAl1.80Fe0.20O4 · 1.2MgO.

上述三效剂中的含稀土铈的化合物占三效剂的重量百分比为20%至35%,氧化催化剂中的五氧化二钒占三效剂的重量百分比为2%至4%,其余为吸附剂。 The compound of Cerium-containing three-way three-way agents accounted agent weight percentage of 20-35%, the vanadium pentoxide oxidation catalyst weight percentage of the three-way agent 2-4%, the remainder being adsorbed agents.

上述三效剂中的含稀土铈的化合物所用的原料为氟碳铈矿粉。 The compound of Cerium-containing three-way agents used bastnaesite ore raw materials. 氧化催化剂中的五氧化二钒所用的原料为偏钒酸铵。 Vanadium pentoxide oxidation catalyst raw materials used for the ammonium metavanadate.

本发明提供的制备硫转移脱氮助燃三效剂的方法,所述的硫转移脱氮助燃三效剂包括吸附剂和分散在吸附剂中的氧化催化剂和结构助剂,氧化催化剂包括五氧化二钒和含稀土铈的化合物二氧化铈;结构助剂是含稀土铈的化合物氟氧化铈;吸附剂是具有通式为AB2-xB′xO4·yAO的类尖晶石复合氧化物,式中:A为碱土金属元素Mg,B为IIIA族金属元素Al,B′为过渡金属元素Fe,x为0.01~0.5,y为0.2~1.2;该方法具有以下步骤:①将氟碳铈矿粉与水搅拌混合得到氟碳铈矿粉的悬浮液待用;将偏钒酸铵与水及有机酸混合得到偏钒酸铵的有机酸水溶液待用;将氧化铝的水合物与水及单质子酸搅拌得到氢氧化铝胶待用;将轻质氧化镁与水、单质子酸搅拌得到镁盐浆料待用;将轻质氧化镁与水搅拌得到氢氧化镁浆料待用;将三价铁盐溶于水中得到三价铁的水溶液待用;其中 Preparation of sulfur present invention provides a method for the denitrification of combustion three-way transfer agent, the combustion of nitrogen and sulfur transfer agent include three-way catalysts and adsorbents and oxidation auxiliary structures, the oxidation catalyst is dispersed in the adsorbent comprises pentoxide vanadium compound and ceria rare earth-containing cerium; structure aid is a fluorine-containing compound ceria rare earth cerium; adsorbent having the formula AB2-xB'xO4 · yAO a spinel composite oxide, wherein: an alkaline earth metal element A is Mg, B is a group IIIA metals Al, B 'is a transition metal element Fe, x is 0.01 ~ 0.5, y is from 0.2 to 1.2; the method having the following: ① From the bastnaesite ore with water bastnasite ore stirred and mixed to obtain a suspension stand; ammonium metavanadate was mixed with water and an organic acid to obtain an aqueous solution of an organic acid ammonium metavanadate stand; alumina hydrate with water and stirred monoprotic acid aluminum hydroxide gel obtained stand; the water with light magnesium oxide, magnesium monoprotic acid slurry was stirred stand; the light magnesia stirred with water to give magnesium hydroxide slurry stand; the ferric dissolved in water to obtain an aqueous solution of trivalent iron stand; wherein 碳铈矿粉的用量按成品中含稀土铈的化合物占成品总重量的20%至35%而定,偏钒酸铵的用量按成品中五氧化二钒占成品总重量的2%至4%而定,氧化铝的水合物、轻质氧化镁以及三价铁盐的用量按所需的AB2-xB′xO4·yAO的化学成分以及成品中吸附剂占成品总重量的61%至78%而定;②将步骤①所得的氢氧化铝胶、镁盐浆料、氢氧化镁浆料、氟碳铈矿粉的悬浮液、偏钒酸铵有机酸溶液以及三价铁盐溶液混合得到混合液;③将混合液进行干燥,得到半成品;④将半成品在400~800℃下焙烧1~2小时得到成品。 The amount of slag by the carbon cerium-containing compound in the finished product of Cerium accounts 20 to 35% of the total weight of the finished product depends, ammonium metavanadate, vanadium pentoxide in an amount representing a finished 2-4% of the total weight of the finished may be, hydrate, light magnesium oxide and the amount of trivalent iron in the desired alumina AB2-xB'xO4 · yAO chemical composition of the final product and account for the adsorbent from 61 to 78% of the total weight of the finished product set; ② the step ① obtained aluminum hydroxide gel, magnesium slurry, magnesium hydroxide slurry, a suspension bastnaesite ore mixed iron salt solution, an organic acid ammonium metavanadate solution to obtain a mixture of trivalent and ; ③ the mixture was dried, to give semi-finished products; ④ semi-finished product to be finished in 400 ~ 800 ℃ baked 1 to 2 hours.

上述步骤①中的氟碳铈矿粉中、化学式为(Ce,La)(CO3)F的氟碳铈矿的含量≥93%(重量),氟碳铈矿粉中的稀土氧化物含量≥70%(重量),稀土氧化物中的稀土含量Ce>>La、Ce≥45%(重量)。 In the above step ① bastnaesite ore, the chemical formula (Ce, La) (CO3) F Bastnasite content of ≥93% (by weight), rare earth oxide content of bastnasite ore ≥70 % (by weight), rare earth oxide rare earth content of Ce >> La, Ce≥45% (by weight). 步骤①中与偏钒酸铵混合的有机酸为草酸,草酸的量以偏钒酸铵在水中全部溶解为下限。 ① Step of ammonium metavanadate with a mixed organic acid is oxalic acid, oxalic acid in an amount of ammonium metavanadate was completely dissolved in water at a lower limit.

上述步骤①中由拟薄水铝石与单质子酸反应、制得胶液酸值为2~6(体系中每克氧化铝Al2O3对应的单质子酸的毫摩尔数)、固含量为15%至25%(重量)的氢氧化铝胶,其中的拟薄水铝石的成胶率≥95%、拟薄水铝石中Al2O3·H2O的含量≥70%(重量),其中的单质子酸为硝酸或醋酸。 ① above step by quasi boehmite react with the acid monoprotic, to obtain an acid value of from 2 to 6 glue (alumina millimoles per gram of the system corresponding to Al2O3 molar monoprotic acid), a solids content of 15% to 25% (by weight) of aluminum hydroxide gel, wherein the pseudo-boehmite gel-forming rate ≥95%, pseudoboehmite, boehmite Al2O3 · H2O content of ≥70% (by weight), wherein the monoprotic acid nitric acid or acetic acid. 拟薄水铝石与单质子酸混合时的搅拌速度为每分钟300至600转。 Stirring speed of boehmite and quasi single protonic acid is 300 to 600 revolutions per minute. 单质子酸优选为硝酸,胶液酸值为3~5。 Monoprotic acid is preferably nitric acid, an acid value of from 3 to 5 glue.

上述步骤①中的制备镁盐浆料以及制备氢氧化镁浆料的轻质氧化镁的比表面积≥100m2/g、MgO含量≥95%(重量),制备镁盐浆料的单质子酸为醋酸或/和硝酸,醋酸或/和硝酸所用的量依其与MgO充分反应的摩尔比而定,镁盐浆料以及氢氧化镁浆料的固含量为10%~14%(重量)。 Preparation of the magnesium salt slurry and a specific surface area of ​​light magnesia magnesium hydroxide slurry prepared in the above step ① in ≥100m2 / g, MgO content of ≥95% (by weight), monoprotic acid slurry was prepared magnesium acetate and / or nitric acid, acetic acid or amount / nitric acid and used according to their fully reacted with a molar ratio of MgO may be, and slurry solids content of magnesium is magnesium hydroxide slurry (by weight) of 10% to 14%. 制备镁盐浆料时,先将轻质氧化镁与水搅拌均匀后、再加入冰醋酸或/和硝酸与氧化镁反应完全制得醋酸镁或/和硝酸镁,冰醋酸或/和硝酸与氧化镁反应时的搅拌速度为每分钟300至600转。 Preparing the magnesium slurry after the first light magnesium oxide with water Stir, then glacial acetic acid and / or nitric acid with a magnesium oxide or magnesium acetate completely made / and magnesium nitrate, acetic acid and / or nitric oxide stirring rate during the reaction of magnesium is 300 to 600 revolutions per minute. 步骤①中的三价铁盐为硝酸铁。 ① Step of ferric salt is ferric nitrate.

上述步骤②中混合时的搅拌速度为每分钟300至600转。 The above steps ② stirring rate during mixing is 300 to 600 revolutions per minute.

上述步骤③中的干燥为喷雾干燥,塔顶温度为300至350℃,压力为3.0至5.0Mpa,蒸发量为50至150Kg/h,半成品的粒径分布在80~120μm的部分的含量≥80%(重量)。 ③ Step of drying the spray-dried, a top temperature of 300 to 350 deg.] C, a pressure of 3.0 to 5.0Mpa, the evaporation amount of 50 to 150Kg / h, the particle size distribution of the content of the semi-finished part of 80 ~ 120μm ≥80 %(weight).

上述步骤③中的干燥也可为烘箱干燥,温度为100至150℃。 The above drying step may also be in ③ oven drying temperature of 100 to 150 ℃.

上述步骤④中焙烧过程采用缓慢升温的方法,焙烧温度优选为400~500℃,焙烧时间优选为80至100分钟。 In the above step ④ the method slowly warmed during firing, the firing temperature is preferably 400 ~ 500 ℃, calcination time is preferably from 80 to 100 minutes.

本发明的硫转移脱氮助燃三效剂用于石油炼制中催化裂化工艺中时,进入再生器中的积有焦碳的待生裂化催化剂中含有一定数量的硫、氮的氧化物,待生裂化催化剂与来自再生器底部的空气接触形成流化床层进行再生反应,其中所含的硫则与空气中的氧气反应生成二氧化硫,其中的碳与氧气反应生成一氧化碳;在本发明的三效剂中的五氧化二钒和二氧化铈的催化作用下,二氧化硫与氧气反应生成三氧化硫。 Nitrogen and sulfur transfer of the present invention is used in combustion Triple Action catalytic cracking process of petroleum refining, the product enters the regenerator spent cracking catalyst with an oxide containing a certain amount of coke sulfur, nitrogen, be Health cracking catalyst is formed in contact with air from the bottom of the regenerator for regeneration of the fluidized bed reactor, the sulfur contained therein reacts with oxygen in the air to form sulfur dioxide, wherein the reaction of carbon with oxygen to produce carbon monoxide; triple effect of the present invention under the catalysis of agent vanadium pentoxide and of cerium dioxide, sulfur dioxide is reacted with oxygen to form sulfur trioxide. 对于二氧化铈来说不仅催化了二氧化硫的氧化,而且催化了一氧化碳的氧化;在催化过程中,二氧化铈将二氧化硫和一氧化碳氧化成三氧化硫和二氧化碳,自身被还原成三氧化二铈,从而实现了降硫和助燃。 Ceria is not only for the catalytic oxidation of sulfur dioxide, and the catalytic oxidation of carbon monoxide; during catalysis, ceria oxidation of sulfur dioxide to sulfur trioxide and carbon monoxide and carbon dioxide, is itself reduced to cerium oxide, thereby to achieve a sulfur reduction and combustion. 此时的三氧化二铈因具有还原性而被氧化。 At this time, because of Cerium (III) oxide having reducibility to be oxidized. 大部分三氧化二铈在被氧气氧化成二氧化铈的同时,一部分三氧化二铈使一氧化氮还原成氮气,自身被氧化成二氧化铈,从而实现了降氮。 Most of Cerium (III) oxide is oxidized to oxygen at the same ceria, so that a portion of Cerium (III) oxide reduction of nitric oxide to nitrogen is oxidized to cerium oxide itself, in order to achieve reduction of nitrogen. 氮气和二氧化碳作为再生烟气的一部分排出,所生成的三氧化硫被本发明三效剂中的吸附剂吸附,并与其中的氧化镁反应生成硫酸镁,从而使本发明的三效剂对再生烟气中的二氧化硫进行了有效的催化氧化和吸附。 As nitrogen and carbon dioxide regeneration flue gas discharging part, the generated sulfur trioxide is adsorbed by the adsorbent of the present invention, the three-way and wherein the reaction of magnesium oxide with magnesium sulfate generated, so that the three-way regeneration agent of the invention the sulfur dioxide gas was effective catalytic oxidation and adsorption. 当本发明的三效剂随再生的裂化催化剂进入提升管反应器后,三效剂中的硫酸镁与氢气反应,生成氧化镁和硫化氢,硫化氢则随反应油气进入下道工序,氧化镁的生成则使本发明的三效剂中的吸附剂得到再生,再生后的三效剂随裂化催化剂进入再生器循环使用。 When the three-way agents of the invention with the regenerated cracking catalyst into the riser reactor, the three-way over magnesium agent is reacted with hydrogen to produce magnesium oxide and hydrogen sulfide, the reaction with hydrocarbon into the next process, magnesium oxide generating the three-way adsorbent of the present invention is regenerated, the regenerated cracking catalyst with Triple Action recycled into the regenerator. 有关反应式如下:(1)(2)(3)吸附了硫氧化物的三效剂进入反应器后,发生下述反应释放出H2S,自身也得到再生。 For reaction is as follows: (1) (2) (3) three-way agent adsorbed sulfur oxide into the reactor, the following reaction occurs releasing H2S, itself regenerated.

(4)(5)在汽提段,因水蒸气的参与,还存在下述反应:(6)三效剂中的二氧化铈可以被二氧化硫和一氧化碳还原为三氧化二铈:(7)(8)三价铈氧化物可以被一氧化氮或氧气氧化为四价铈:(9)(10)本发明具有积极的效果:(1)本发明所选用的富MgO类尖晶石结构的吸附剂具有很好的脱硫性能,也可有效再生。 (4) (5) in the stripping section due to the participation of water vapor, there is the following reaction: (6) three-way ceria agent may be reduced to carbon monoxide, sulfur dioxide and Cerium (III) oxide: (7) ( 8) trivalent cerium oxide or nitric oxide may be oxidized by oxygen to tetravalent cerium: (9) (10) has a positive effect of the present invention: adsorption chosen (1) of the present invention, MgO-rich spinel structure desulfurization agent has good performance, it can be effectively reproduced. 因为MgO可与V2O5相互作用,生成(MgO)3V2O8,所以具有很强的捕钒能力,从而抑制钒对裂化催化剂的毒性作用。 Since MgO and V2O5 can interact to produce (MgO) 3V2O8, vanadium traps and therefore have a strong ability to inhibit the toxic effect of vanadium on the cracking catalyst. (2)本发明选用氟碳铈矿粉作为提供铈化合物催化剂的原料,因类尖晶石的结构与氟氧化铈以及二氧化铈同时生成,从而提高了类尖晶石中MgO的容量,可使MgO含量过剩400%而不游离出来,从而大大提高了产品硫转移的活性。 (2) selection of the present invention is provided as bastnaesite ore raw material cerium compound catalyst, due to structural and fluoro ceria and ceria-based spinel generated simultaneously, thereby increasing the capacity of MgO spinel, may 400% content of MgO and not liberated excessive, thereby greatly improving the sulfur transfer of active product. 选用氟碳铈矿粉为原料也降低了产品的生产成本。 Selection Bastnaesite slag as raw material also reduces production costs. (3)本发明的三效剂的吸附剂中引入了过渡元素铁,使尖晶石结构发生晶格畸变,大幅度提高了产品脱硫性能。 (3) Adsorbent agonist of the present invention introduces a transition element iron, so that the spinel structure of lattice distortion, the product greatly improved desulfurization performance. (4)根据有关试验,使用本发明的三效剂可以使第一再生器烟气中的SOX脱除率≥60%,使第二再生器烟气中的SOX脱除率≥80%,第二再生器的烟气中SOX的含量平均为≤5mg/m3,第二再生烟气中NOX的脱除率≥90%,对一氧化碳的助燃效果明显,不需再使用铂助燃剂。 (4) According to the test, the present invention can make the three-way agents SOX removal rate ≥60% of the first regenerator flue gas in the SOX removal efficiency of the second regenerator flue gas ≥80%, of two regenerator flue gas content of SOX average ≤5mg / m3, a second regeneration flue gas NOX removal rate of ≥90%, the effect of carbon monoxide combustion obvious, do not need to use platinum accelerant. (5)使用本发明的三效剂后,再生烟气的酸露点温度降低,二再由122℃下降到≤60℃,同时二再烟气凝液的pH值显著提高,由2提高到5.4左右;由于再生烟气中腐蚀性物质含量减少,消除了产生硝酸盐应力腐蚀开裂的环境,具有抑制再生器裂纹的作用。 (5) After a three-agonist according to the present invention, the regeneration flue gas acid dew point temperature is lowered, two deg.] C and then decreased from 122 to ≤60 deg.] C, while the pH value of two and then the flue gas condensate is significantly increased by 2 raised to 5.4 left; the regenerative flue gas to reduce the content of corrosive substances, eliminating the generation of stress corrosion cracking environment nitrate, can inhibit cracking regenerator. (6)使用本发明的三效剂对催化裂化产品分布和产品的主要质量指标无明显的影响,且污染排放量显著下降。 (6) use of three agents of the invention effect no significant effect on the major product distribution and quality indicators cracking products, and significantly reduced pollution emissions.

附图说明 BRIEF DESCRIPTION

图1为本发明的三效剂吸附SOX前的X射线衍射图。 X-ray diffraction diagram before the SOX Triple Action 1 of the present invention FIG adsorption. 其中的Ge1表示二氧化铈和氟氧化铈的共晶物,P表示氧化镁,S表示尖晶石。 Wherein the ceria and Ge1 represents fluorine cerium oxide eutectic, P represents magnesium oxide, S represents spinel.

图2为本发明的三效剂吸附SOX后的X射线衍射图。 X-ray diffraction after the three-way SOX agent of the present invention FIG. 2 adsorption. 其中的Ce2表示二氧化铈,S表示尖晶石。 Wherein Ce2 represents ceria, S represents spinel.

具体实施方式 detailed description

三效剂的制备方法举下列实施例说明之,但不仅限于这些实施例。 Preparation of Triple Action The following examples illustrate the embodiments cited, but is not limited to these examples.

(实施例1)于搅拌器中依次加入99.84克水,3.73克冰醋酸以及18.28克拟薄水铝石,以每分钟400转的速度高速搅拌30分钟,得铝胶A。 (Example 1) were added to the blender 99.84 g of water, 3.73 g of glacial acetic acid and 18.28 g quasi boehmite, high speed stirring at 400 revolutions per minute for 30 minutes to give Alhydrogel A. 于搅拌器中依次加入26.88克水和6.17克轻质氧化镁,搅拌均匀后(约5分钟),缓慢加入18.37克冰醋酸,以每分钟400转的速度高速搅拌30分钟,得镁浆M1。 Agitator successively added 26.88 g of water and 6.17 g of light magnesia, stir (about 5 minutes), was slowly added 18.37 g of glacial acetic acid was stirred at a speed of 400 revolutions per minute high speed for 30 minutes to obtain slurry of magnesium M1. 于搅拌器中依次加入45.26克水和6.17克轻质氧化镁,搅拌均匀,得镁浆M2。 Agitator successively added 45.26 g of water and 6.17 g of light magnesia, uniformly stirred to obtain a magnesium slurry M2. 将0.615克Fe(NO3)3·9H2O与12克氟碳铈矿粉分别制成50%的水溶液。 The 0.615 g Fe (NO3) 3 · 9H2O and 12 g bastnaesite ore were made 50% aqueous. 将1.029克偏钒酸铵放入约9倍重的水中,放入草酸直至偏钒酸铵全部溶解而制成10%的草酸水溶液。 The 1.029 g of ammonium metavanadate placed about 9-fold weight of water, into the oxalic acid is completely dissolved until the ammonium metavanadate to prepare a 10% aqueous solution of oxalic acid. 将上述铝胶A、镁浆M1、镁浆M2、硝酸铁与氟碳铈矿的水溶液、偏钒酸铵的草酸溶液依次加入搅拌器中混合,以每分钟400转的速度高速搅拌30分钟。 The above-mentioned alumina gel A, magnesium pulp M1, magnesium slurry M2, an aqueous solution of ferric nitrate and bastnaesite, ammonium metavanadate were sequentially added oxalic acid solution mixed with a stirrer, a high speed stirring at 400 revolutions per minute for 30 minutes. 将所得浆料于120℃干燥,然后于500℃焙烧80分钟,即得三效剂成品。 The resulting slurry was dried at 120 deg.] C, and then calcined at 500 ℃ 80 minutes to obtain the finished three agonists. 焙烧后所制得的三效剂中的吸附剂的成分为MgAl1.99Fe0.01O4·MgO,作为氧化催化剂的CeO2和V2O5分散在吸附剂中,作为结构助剂的CeFO也分散在吸附剂中。 Adsorbent agonist obtained in the composition after firing is prepared MgAl1.99Fe0.01O4 · MgO, V2O5 and CeO2 as the oxidation catalyst is dispersed in the adsorbent, as a structural aid CeFO be dispersed in the adsorbent.

(实施例2)于搅拌器中依次加入97.22克水,3.63克冰醋酸以及17.80克拟薄水铝石,以每分钟350转的速度高速搅拌30分钟,得铝胶A。 (Example 2) were added to the blender 97.22 g of water, 3.63 g of glacial acetic acid and 17.80 g quasi boehmite agitated at 350 revolutions per minute for a high speed for 30 minutes to give Alhydrogel A. 于搅拌器中依次加入26.71克水和6.13克轻质氧化镁,搅拌均匀后(约5分钟),缓慢加入18.26克冰醋酸,以每分钟350转的速度高速搅拌30分钟,得镁浆M1。 Agitator successively added 26.71 g of water and 6.13 g of light magnesia, stir (about 5 minutes), 18.26 g of glacial acetic acid was slowly added, with stirring at 350 revolutions per minute high speed for 30 minutes to obtain slurry of magnesium M1. 于搅拌器中依次加入44.97克水和6.13克轻质氧化镁,搅拌均匀,得镁浆M2。 Agitator successively added 44.97 g of water and 6.13 g of light magnesia, uniformly stirred to obtain a magnesium slurry M2. 将3.073克Fe(NO3)3·9H2O与12克氟碳铈矿粉分别制成50%的水溶液。 The 3.073 g Fe (NO3) 3 · 9H2O and 12 g bastnaesite ore were made 50% aqueous. 将1.029克偏钒酸铵放入约9倍重的水中,放入草酸直至偏钒酸铵全部溶解而制成10%的草酸水溶液。 The 1.029 g of ammonium metavanadate placed about 9-fold weight of water, into the oxalic acid is completely dissolved until the ammonium metavanadate to prepare a 10% aqueous solution of oxalic acid. 将上述铝胶A、镁浆M1、镁浆M2、硝酸铁与氟碳铈矿的水溶液、偏钒酸铵的草酸溶液依次加入搅拌器中混合,以每分钟350转的速度高速搅拌30分钟。 The above-mentioned alumina gel A, magnesium pulp M1, magnesium slurry M2, an aqueous solution of ferric nitrate and bastnaesite, oxalic acid solution of ammonium metavanadate were sequentially added in a stirrer, and stirred at a high speed of 350 revolutions per minute for 30 minutes. 将所得浆料于120℃干燥,然后于500℃焙烧80分钟,即得三效剂成品。 The resulting slurry was dried at 120 deg.] C, and then calcined at 500 ℃ 80 minutes to obtain the finished three agonists. 焙烧后所制得的三效剂中的吸附剂的成分为MgAl1.95Fe0.05O4·MgO,作为氧化催化剂的CeO2和V2O5分散在吸附剂中,作为结构助剂的CeFO也分散在吸附剂中。 Adsorbent agonist obtained in the composition after firing is prepared MgAl1.95Fe0.05O4 · MgO, V2O5 and CeO2 as the oxidation catalyst is dispersed in the adsorbent, as a structural aid CeFO be dispersed in the adsorbent.

(实施例3)于搅拌器中依次加入93.99克水,3.51克冰醋酸以及17.21克拟薄水铝石,以每分钟350转的速度高速搅拌30分钟,得铝胶A。 (Example 3) were successively added in a stirrer 93.99 g of water, 3.51 g of glacial acetic acid and 17.21 g quasi boehmite, high speed stirring at 350 revolutions per minute for 30 minutes to give Alhydrogel A. 于搅拌器中依次加入26.51克水和6.09克轻质氧化镁,搅拌均匀后(约5分钟),缓慢加入18.12克冰醋酸,以每分钟350转的速度高速搅拌30分钟,得镁浆M1。 Agitator successively added 26.51 g of water and 6.09 g of light magnesia, stir (about 5 minutes), 18.12 g of glacial acetic acid was slowly added, with stirring at 350 revolutions per minute high speed for 30 minutes to obtain slurry of magnesium M1. 于搅拌器中依次加入44.62克水和6.09克轻质氧化镁,搅拌均匀,得镁浆M2。 Agitator successively added 44.62 g of water and 6.09 g of light magnesia, uniformly stirred to obtain a magnesium slurry M2. 将6.097克Fe(NO3)3·9H2O与12克氟碳铈矿粉分别制成50%的水溶液。 The 6.097 g Fe (NO3) 3 · 9H2O and 12 g bastnaesite ore were made 50% aqueous. 将1.029克偏钒酸铵放入约9倍重的水中,放入草酸直至偏钒酸铵全部溶解而制成10%的草酸水溶液。 The 1.029 g of ammonium metavanadate placed about 9-fold weight of water, into the oxalic acid is completely dissolved until the ammonium metavanadate to prepare a 10% aqueous solution of oxalic acid. 将上述铝胶A、镁浆M1、镁浆M2、硝酸铁与氟碳铈矿的水溶液、偏钒酸铵的草酸溶液依次加入搅拌器中混合,以每分钟350转的速度高速搅拌30分钟。 The above-mentioned alumina gel A, magnesium pulp M1, magnesium slurry M2, an aqueous solution of ferric nitrate and bastnaesite, oxalic acid solution of ammonium metavanadate were sequentially added in a stirrer, and stirred at a high speed of 350 revolutions per minute for 30 minutes. 将所得浆料子120℃干燥,然后于500℃焙烧80分钟,即得三效剂成品。 The resulting slurry was dried sub 120 deg.] C, and then calcined at 500 ℃ 80 minutes to obtain the finished three agonists. 焙烧后所制得的三效剂中的吸附剂的成分为MgAl1.90Fe0.10O4·MgO,作为氧化催化剂的CeO2和V2O5分散在吸附剂中,作为结构助剂的CeFO也分散在吸附剂中。 Adsorbent agonist obtained in the composition after firing is prepared MgAl1.90Fe0.10O4 · MgO, V2O5 and CeO2 as the oxidation catalyst is dispersed in the adsorbent, as a structural aid CeFO be dispersed in the adsorbent.

(实施例4)于搅拌器中依次加入90.81克水,3.39克冰醋酸以及16.62克拟薄水铝石,以每分钟350转的速度高速搅拌30分钟,得铝胶A。 (Example 4) were added sequentially to a blender 90.81 g of water, 3.39 g of glacial acetic acid and 16.62 g quasi boehmite, high speed stirring at 350 revolutions per minute for 30 minutes to give Alhydrogel A. 于搅拌器中依次加入26.30克水和6.04克轻质氧化镁,搅拌均匀后(约5分钟),缓慢加入17.98克冰醋酸,以每分钟350转的速度高速搅拌30分钟,得镁浆M1。 Agitator successively added 26.30 g of water and 6.04 g of light magnesia, stir (about 5 minutes), 17.98 g of glacial acetic acid was slowly added, with stirring at 350 revolutions per minute high speed for 30 minutes to obtain slurry of magnesium M1. 于搅拌器中依次加入44.28克水和6.04克轻质氧化镁,搅拌均匀,得镁浆M2。 Agitator successively added 44.28 g of water and 6.04 g of light magnesia, uniformly stirred to obtain a magnesium slurry M2. 将9.075克Fe(NO3)3·9H2O与12克氟碳铈矿粉分别制成50%的水溶液。 The 9.075 g Fe (NO3) 3 · 9H2O and 12 g bastnaesite ore were made 50% aqueous. 将1.029克偏钒酸铵放入约9倍重的水中,放入草酸直至偏钒酸铵全部溶解而制成10%的草酸水溶液。 The 1.029 g of ammonium metavanadate placed about 9-fold weight of water, into the oxalic acid is completely dissolved until the ammonium metavanadate to prepare a 10% aqueous solution of oxalic acid. 将上述铝胶A、镁浆M1、镁浆M2、硝酸铁与氟碳铈矿的水溶液、偏钒酸铵的草酸溶液依次加入搅拌器中混合,以每分钟350转的速度高速搅拌30分钟。 The above-mentioned alumina gel A, magnesium pulp M1, magnesium slurry M2, an aqueous solution of ferric nitrate and bastnaesite, oxalic acid solution of ammonium metavanadate were sequentially added in a stirrer, and stirred at a high speed of 350 revolutions per minute for 30 minutes. 将所得浆料于120℃干燥,然后于500℃焙烧80分钟,即得三效剂成品。 The resulting slurry was dried at 120 deg.] C, and then calcined at 500 ℃ 80 minutes to obtain the finished three agonists. 焙烧后所制得的三效剂中的吸附剂的成分为MgAl1.85Fe0.15O4·MgO,作为氧化催化剂的CeO2和V2O5分散在吸附剂中,作为结构助剂的CeFO也分散在吸附剂中。 Adsorbent agonist obtained in the composition after firing is prepared MgAl1.85Fe0.15O4 · MgO, V2O5 and CeO2 as the oxidation catalyst is dispersed in the adsorbent, as a structural aid CeFO be dispersed in the adsorbent.

(实施例5)于搅拌器中依次加入87.68克水,3.27克冰醋酸以及16.05克拟薄水铝石,以每分钟350转的速度高速搅拌30分钟,得铝胶A。 (Example 5) were added to the blender 87.68 g of water, 3.27 g of glacial acetic acid and 16.05 g quasi boehmite, high speed stirring at 350 revolutions per minute for 30 minutes to give Alhydrogel A. 于搅拌器中依次加入26.10克水和5.99克轻质氧化镁,搅拌均匀后(约5分钟),缓慢加入17.84克冰醋酸,以每分钟350转的速度高速搅拌30分钟,得镁浆M1。 Agitator successively added 26.10 g of water and 5.99 g of light magnesia, stir (about 5 minutes), 17.84 g of glacial acetic acid was slowly added, with stirring at 350 revolutions per minute high speed for 30 minutes to obtain slurry of magnesium M1. 于搅拌器中依次加入43.94克水和5.99克轻质氧化镁,搅拌均匀,得镁浆M2。 Agitator successively added 43.94 g of water and 5.99 g of light magnesia, uniformly stirred to obtain a magnesium slurry M2. 将12.008克Fe(NO3)3·9H2O与12克氟碳铈矿粉分别制成50%的水溶液。 The 12.008 g Fe (NO3) 3 · 9H2O and 12 g bastnaesite ore were made 50% aqueous. 将1.029克偏钒酸铵放入约9倍重的水中,放入草酸直至偏钒酸铵全部溶解而制成10%的草酸水溶液。 The 1.029 g of ammonium metavanadate placed about 9-fold weight of water, into the oxalic acid is completely dissolved until the ammonium metavanadate to prepare a 10% aqueous solution of oxalic acid. 将上述铝胶A、镁浆M1、镁浆M2、硝酸铁与氟碳铈矿的水溶液、偏钒酸铵的草酸溶液依次加入搅拌器中混合,以每分钟350转的速度高速搅拌30分钟。 The above-mentioned alumina gel A, magnesium pulp M1, magnesium slurry M2, an aqueous solution of ferric nitrate and bastnaesite, oxalic acid solution of ammonium metavanadate were sequentially added in a stirrer, and stirred at a high speed of 350 revolutions per minute for 30 minutes. 将所得浆料于120℃干燥,然后于500℃焙烧80分钟,即得三效剂成品。 The resulting slurry was dried at 120 deg.] C, and then calcined at 500 ℃ 80 minutes to obtain the finished three agonists. 焙烧后所制得的三效剂中的吸附剂的成分为MgAl1.80Fe0.20O4·MgO,作为氧化催化剂的CeO2和V2O5分散在吸附剂中,作为结构助剂的CeFO也分散在吸附剂中。 Adsorbent agonist obtained in the composition after firing is prepared MgAl1.80Fe0.20O4 · MgO, V2O5 and CeO2 as the oxidation catalyst is dispersed in the adsorbent, as a structural aid CeFO be dispersed in the adsorbent.

(实施例6)于搅拌器中依次加入75.62克水,2.82克冰醋酸以及13.84克拟薄水铝石,以每分钟350转的速度高速搅拌30分钟,得铝胶A。 (Example 6) were added to the blender 75.62 g of water, 2.82 g of glacial acetic acid and 13.84 g quasi boehmite, high speed stirring at 350 revolutions per minute for 30 minutes to give Alhydrogel A. 于搅拌器中依次加入25.32克水和5.81克轻质氧化镁,搅拌均匀后(约5分钟),缓慢加入17.31克冰醋酸,以每分钟350转的速度高速搅拌30分钟,得镁浆M1。 Agitator successively added 25.32 g of water and 5.81 g of light magnesia, stir (about 5 minutes), 17.31 g of glacial acetic acid was slowly added, with stirring at 350 revolutions per minute high speed for 30 minutes to obtain slurry of magnesium M1. 于搅拌器中依次加入42.63克水和5.81克轻质氧化镁,搅拌均匀,得镁浆M2。 Agitator successively added 42.63 g of water and 5.81 g of light magnesia, uniformly stirred to obtain a magnesium slurry M2. 将23.301克Fe(NO3)3·9H2O与12克氟碳铈矿粉分别制成50%的水溶液。 The 23.301 g Fe (NO3) 3 · 9H2O and 12 g bastnaesite ore were made 50% aqueous. 将1.029克偏钒酸铵放入约9倍重的水中,放入草酸直至偏钒酸铵全部溶解而制成10%的草酸水溶液。 The 1.029 g of ammonium metavanadate placed about 9-fold weight of water, into the oxalic acid is completely dissolved until the ammonium metavanadate to prepare a 10% aqueous solution of oxalic acid. 将上述铝胶A、镁浆M1、镁浆M2、硝酸铁与氟碳铈矿的水溶液、偏钒酸铵的草酸溶液依次加入搅拌器中混合,以每分钟350转的速度高速搅拌30分钟。 The above-mentioned alumina gel A, magnesium pulp M1, magnesium slurry M2, an aqueous solution of ferric nitrate and bastnaesite, oxalic acid solution of ammonium metavanadate were sequentially added in a stirrer, and stirred at a high speed of 350 revolutions per minute for 30 minutes. 将所得浆料于120℃干燥,然后于500℃焙烧80分钟,即得三效剂成品。 The resulting slurry was dried at 120 deg.] C, and then calcined at 500 ℃ 80 minutes to obtain the finished three agonists. 焙烧后所制得的三效剂中的吸附剂的成分为MgAl1.60Fe0.40O4·MgO,作为氧化催化剂的CeO2和V2O5分散在吸附剂中,作为结构助剂的CeFO也分散在吸附剂中。 Adsorbent agonist obtained in the composition after firing is prepared MgAl1.60Fe0.40O4 · MgO, V2O5 and CeO2 as the oxidation catalyst is dispersed in the adsorbent, as a structural aid CeFO be dispersed in the adsorbent.

(实施例7)于搅拌器中依次加入84.41克水,4.54克冰醋酸以及22.24克拟薄水铝石,以每分钟350转的速度高速搅拌30分钟,得铝胶A。 (Example 7) were successively added in a stirrer 84.41 g of water, 4.54 g of glacial acetic acid and 22.24 g quasi boehmite, high speed stirring at 350 revolutions per minute for 30 minutes to give Alhydrogel A. 于搅拌器中依次加入25.31克水和5.81克轻质氧化镁,搅拌均匀后(约5分钟),缓慢加入17.30克冰醋酸,以每分钟500转的速度高速搅拌30分钟,得镁浆M1。 Agitator successively added 25.31 g of water and 5.81 g of light magnesia, stir (about 5 minutes), was slowly added 17.30 g of glacial acetic acid, the high-speed stirring rate of 500 revolutions per minute for 30 minutes to obtain slurry of magnesium M1. 于搅拌器中依次加入42.61克水和5.81克轻质氧化镁,搅拌均匀,得镁浆M2。 Agitator successively added 42.61 g of water and 5.81 g of light magnesia, uniformly stirred to obtain a magnesium slurry M2. 将13.447克Fe(NO3)3·9H2O与15克氟碳铈矿粉分别制成50%的水溶液。 The 13.447 g Fe (NO3) 3 · 9H2O and 15 g bastnaesite ore were made 50% aqueous. 将1.607克偏钒酸铵放入约9倍重的水中,放入草酸直至偏钒酸铵全部溶解而制成10%的草酸水溶液。 The 1.607 g of ammonium metavanadate placed about 9-fold weight of water, into the oxalic acid is completely dissolved until the ammonium metavanadate to prepare a 10% aqueous solution of oxalic acid. 将上述铝胶A、镁浆M1、镁浆M2、硝酸铁与氟碳铈矿的水溶液、偏钒酸铵的草酸溶液依次加入搅拌器中混合,以每分钟500转的速度高速搅拌30分钟。 The above-mentioned alumina gel A, magnesium pulp M1, magnesium slurry M2, an aqueous solution of ferric nitrate and bastnaesite, oxalic acid solution of ammonium metavanadate were sequentially added in a stirrer, and stirred at high speed revolutions per minute 500 30 minutes. 将所得浆料于120℃干燥,然后于500℃焙烧80分钟,即得三效剂成品。 The resulting slurry was dried at 120 deg.] C, and then calcined at 500 ℃ 80 minutes to obtain the finished three agonists. 焙烧后所制得的三效剂中的吸附剂的成分为MgAl1.8Fe0.2O4·0.4MgO,作为氧化催化剂的CeO2和V2O5分散在吸附剂中,作为结构助剂的CeFO也分散在吸附剂中。 Adsorbent agonist obtained in the composition after firing is prepared MgAl1.8Fe0.2O4 · 0.4MgO, V2O5 and CeO2 as the oxidation catalyst is dispersed in the adsorbent, as a structural aid CeFO be dispersed in the adsorbent .

(实施例8)于搅拌器中依次加入80.59克水,4.33克冰醋酸以及21.23克拟薄水铝石,以每分钟350转的速度高速搅拌30分钟,得铝胶A。 (Example 8) were added to the blender 80.59 g of water, 4.33 g glacial acetic acid 21.23 g of pseudoboehmite and boehmite, high-speed stirring at a speed of 350 revolutions per minute for 30 minutes to give Alhydrogel A. 于搅拌器中依次加入27.62克水和6.34克轻质氧化镁,搅拌均匀后(约5分钟),缓慢加入18.88克冰醋酸,以每分钟350转的速度高速搅拌30分钟,得镁浆M1。 Agitator successively added 27.62 g of water and 6.34 g of light magnesia, stir (about 5 minutes), 18.88 g of glacial acetic acid was slowly added, with stirring at 350 revolutions per minute high speed for 30 minutes to obtain slurry of magnesium M1. 于搅拌器中依次加入46.49克水和6.34克轻质氧化镁,搅拌均匀,得镁浆M2。 Agitator successively added 46.49 g of water and 6.34 g of light magnesia, uniformly stirred to obtain a magnesium slurry M2. 将12.950克Fe(NO3)3·9H2O与15克氟碳铈矿粉分别制成50%的水溶液。 The 12.950 g Fe (NO3) 3 · 9H2O and 15 g bastnaesite ore were made 50% aqueous. 将1.607克偏钒酸铵放入约9倍重的水中,放入草酸直至偏钒酸铵全部溶解而制成10%的草酸水溶液。 The 1.607 g of ammonium metavanadate placed about 9-fold weight of water, into the oxalic acid is completely dissolved until the ammonium metavanadate to prepare a 10% aqueous solution of oxalic acid. 将上述铝胶A、镁浆M1、镁浆M2、硝酸铁与氟碳铈矿的水溶液、偏钒酸铵的草酸溶液依次加入搅拌器中混合,以每分钟350转的速度高速搅拌30分钟。 The above-mentioned alumina gel A, magnesium pulp M1, magnesium slurry M2, an aqueous solution of ferric nitrate and bastnaesite, oxalic acid solution of ammonium metavanadate were sequentially added in a stirrer, and stirred at a high speed of 350 revolutions per minute for 30 minutes. 将所得浆料于120℃干燥,然后于500℃焙烧80分钟,即得三效剂成品。 The resulting slurry was dried at 120 deg.] C, and then calcined at 500 ℃ 80 minutes to obtain the finished three agonists. 焙烧后所制得的三效剂中的吸附剂的成分为MgAl1.8Fe0.2O4·0.6MgO,作为氧化催化剂的CeO2和V2O5分散在吸附剂中,作为结构助剂的CeFO也分散在吸附剂中。 Adsorbent agonist obtained in the composition after firing is prepared MgAl1.8Fe0.2O4 · 0.6MgO, V2O5 and CeO2 as the oxidation catalyst is dispersed in the adsorbent, as a structural aid CeFO be dispersed in the adsorbent .

(实施例9)于搅拌器中依次加入77.10克水,4.14克冰醋酸以及20.31克拟薄水铝石,以每分钟350转的速度高速搅拌30分钟,得铝胶A。 (Example 9) were added to the blender 77.10 g of water, 4.14 g of glacial acetic acid and 20.31 g quasi boehmite agitated at 350 revolutions per minute for a high speed for 30 minutes to give Alhydrogel A. 于搅拌器中依次加入29.72克水和6.82克轻质氧化镁,搅拌均匀后(约5分钟),缓慢加入20.32克冰醋酸,以每分钟350转的速度高速搅拌30分钟,得镁浆M1。 Agitator successively added 29.72 g of water and 6.82 g of light magnesia, stir (about 5 minutes), 20.32 g of glacial acetic acid was slowly added, with stirring at 350 revolutions per minute high speed for 30 minutes to obtain slurry of magnesium M1. 于搅拌器中依次加入50.04克水和6.82克轻质氧化镁,搅拌均匀,得镁浆M2。 Agitator successively added 50.04 g of water and 6.82 g of light magnesia, uniformly stirred to obtain a magnesium slurry M2. 将12.489克Fe(NO3)3·9H2O与15克氟碳铈矿粉分别制成50%的水溶液。 The 12.489 g Fe (NO3) 3 · 9H2O and 15 g bastnaesite ore were made 50% aqueous. 将1.607克偏钒酸铵放入约9倍重的水中,放入草酸直至偏钒酸铵全部溶解而制成10%的草酸水溶液。 The 1.607 g of ammonium metavanadate placed about 9-fold weight of water, into the oxalic acid is completely dissolved until the ammonium metavanadate to prepare a 10% aqueous solution of oxalic acid. 将上述铝胶A、镁浆M1、镁浆M2、硝酸铁与氟碳铈矿的水溶液、偏钒酸铵的草酸溶液依次加入搅拌器中混合,以每分钟350转的速度高速搅拌30分钟。 The above-mentioned alumina gel A, magnesium pulp M1, magnesium slurry M2, an aqueous solution of ferric nitrate and bastnaesite, oxalic acid solution of ammonium metavanadate were sequentially added in a stirrer, and stirred at a high speed of 350 revolutions per minute for 30 minutes. 将所得浆料于120℃干燥,然后于500℃焙烧80分钟,即得三效剂成品。 The resulting slurry was dried at 120 deg.] C, and then calcined at 500 ℃ 80 minutes to obtain the finished three agonists. 焙烧后所制得的三效剂中的吸附剂的成分为MgAl1.8Fe0.2O4·0.8MgO,作为氧化催化剂的CeO2和V2O5分散在吸附剂中,作为结构助剂的CeFO也分散在吸附剂中。 Adsorbent agonist obtained in the composition after firing is prepared MgAl1.8Fe0.2O4 · 0.8MgO, V2O5 and CeO2 as the oxidation catalyst is dispersed in the adsorbent, as a structural aid CeFO be dispersed in the adsorbent .

(实施例10)于搅拌器中依次加入73.90克水,3.97克冰醋酸以及19.47克拟薄水铝石,以每分钟350转的速度高速搅拌30分钟,得铝胶A。 (Example 10) were added to the blender 73.90 g of water, 3.97 g of glacial acetic acid and 19.47 g quasi boehmite, high speed stirring at 350 revolutions per minute for 30 minutes to give Alhydrogel A. 于搅拌器中依次加入31.65克水和7.27克轻质氧化镁,搅拌均匀后(约5分钟),缓慢加入21.64克冰醋酸,以每分钟350转的速度高速搅拌30分钟,得镁浆M1。 Agitator successively added 31.65 g of water and 7.27 g of light magnesia, stir (about 5 minutes), 21.64 g of glacial acetic acid was slowly added, with stirring at 350 revolutions per minute high speed for 30 minutes to obtain slurry of magnesium M1. 于搅拌器中依次加入53.29克水和7.27克轻质氧化镁,搅拌均匀,得镁浆M2。 Agitator successively added 53.29 g of water and 7.27 g of light magnesia, uniformly stirred to obtain a magnesium slurry M2. 将12.059克Fe(NO3)3·9H2O与15克氟碳铈矿粉分别制成50%的水溶液。 The 12.059 g Fe (NO3) 3 · 9H2O and 15 g bastnaesite ore were made 50% aqueous. 将1.607克偏钒酸铵放入约9倍重的水中,放入草酸直至偏钒酸铵全部溶解而制成10%的草酸水溶液。 The 1.607 g of ammonium metavanadate placed about 9-fold weight of water, into the oxalic acid is completely dissolved until the ammonium metavanadate to prepare a 10% aqueous solution of oxalic acid. 将上述铝胶A、镁浆M1、镁浆M2、硝酸铁与氟碳铈矿的水溶液、偏钒酸铵的草酸溶液依次加入搅拌器中混合,以每分钟350转的速度高速搅拌30分钟。 The above-mentioned alumina gel A, magnesium pulp M1, magnesium slurry M2, an aqueous solution of ferric nitrate and bastnaesite, oxalic acid solution of ammonium metavanadate were sequentially added in a stirrer, and stirred at a high speed of 350 revolutions per minute for 30 minutes. 将所得浆料于120℃干燥,然后于500℃焙烧80分钟,即得三效剂成品。 The resulting slurry was dried at 120 deg.] C, and then calcined at 500 ℃ 80 minutes to obtain the finished three agonists. 焙烧后所制得的三效剂中的吸附剂的成分为MgAl1.8Fe0.2O4·MgO,作为氧化催化剂的CeO2和V2O5分散在吸附剂中,作为结构助剂的CeFO也分散在吸附剂中。 Adsorbent agonist obtained in the composition after firing is prepared MgAl1.8Fe0.2O4 · MgO, V2O5 and CeO2 as the oxidation catalyst is dispersed in the adsorbent, as a structural aid CeFO be dispersed in the adsorbent.

(实施例11)于搅拌器中依次加入70.95克水,3.81克冰醋酸以及18.69克拟薄水铝石,以每分钟350转的速度高速搅拌30分钟,得铝胶A。 (Example 11) were added to the blender 70.95 g of water, 3.81 g of glacial acetic acid and 18.69 g quasi boehmite, high speed stirring at 350 revolutions per minute for 30 minutes to give Alhydrogel A. 于搅拌器中依次加入33.43克水和7.68克轻质氧化镁,搅拌均匀后(约5分钟),缓慢加入22.85克冰醋酸,以每分钟350转的速度高速搅拌30分钟,得镁浆M1。 Agitator successively added 33.43 g of water and 7.68 g of light magnesia, stir (about 5 minutes), 22.85 g of glacial acetic acid was slowly added, with stirring at 350 revolutions per minute high speed for 30 minutes to obtain slurry of magnesium M1. 于搅拌器中依次加入56.28克水和7.68克轻质氧化镁,搅拌均匀,得镁浆M2。 Agitator successively added 56.28 g of water and 7.68 g of light magnesia, uniformly stirred to obtain a magnesium slurry M2. 将11.658克Fe(NO3)3·9H2O与15克氟碳铈矿粉分别制成50%的水溶液。 The 11.658 g Fe (NO3) 3 · 9H2O and 15 g bastnaesite ore were made 50% aqueous. 将1.607克偏钒酸铵放入约9倍重的水中,放入草酸直至偏钒酸铵全部溶解而制成10%的草酸水溶液。 The 1.607 g of ammonium metavanadate placed about 9-fold weight of water, into the oxalic acid is completely dissolved until the ammonium metavanadate to prepare a 10% aqueous solution of oxalic acid. 将上述铝胶A、镁浆M1、镁浆M2、硝酸铁与氟碳铈矿的水溶液、偏钒酸铵的草酸溶液依次加入搅拌器中混合,以每分钟350转的速度高速搅拌30分钟。 The above-mentioned alumina gel A, magnesium pulp M1, magnesium slurry M2, an aqueous solution of ferric nitrate and bastnaesite, oxalic acid solution of ammonium metavanadate were sequentially added in a stirrer, and stirred at a high speed of 350 revolutions per minute for 30 minutes. 将所得浆料于120℃干燥,然后于500℃焙烧80分钟,即得三效剂成品。 The resulting slurry was dried at 120 deg.] C, and then calcined at 500 ℃ 80 minutes to obtain the finished three agonists. 焙烧后所制得的三效剂中的吸附剂的成分为MgAl1.8Fe0.2O4·1.2MgO,作为氧化催化剂的CeO2和V2O5分散在吸附剂中,作为结构助剂的CeFO也分散在吸附剂中。 Adsorbent agonist obtained in the composition after firing is prepared MgAl1.8Fe0.2O4 · 1.2MgO, V2O5 and CeO2 as the oxidation catalyst is dispersed in the adsorbent, as a structural aid CeFO be dispersed in the adsorbent .

实施例1至实施例11为实验室制备三效剂方法,为普通干燥。 Example 1-3 The procedure of Example 11 was prepared agonist laboratory embodiment, ordinary drying. 其中所采用的氟碳铈矿粉中、化学式为(Ce,La)(CO3)F的氟碳铈矿的含量≥93%(重量),氟碳铈矿粉中的稀土氧化物含量≥70%(重量),稀土氧化物中的稀土配分Ce>>La、Ce≥45%(重量)。 Wherein bastnaesite ore employed, the chemical formula (Ce, La) (CO3) F Bastnasite content of ≥93% (by weight), rare earth oxide content of bastnasite ore ≥70% (by weight), rare earth oxide REE Ce >> La, Ce≥45% (by weight). 由拟薄水铝石与单质子酸反应、制得的氢氧化铝胶液的酸值(体系中每克氧化铝Al2O3对应的单质子酸的毫摩尔数)为3~5、固含量为15%至25%,所用的拟薄水铝石的成胶率≥95%、拟薄水铝石中Al2O3·H2O的含量≥70%(重量)。 A quasi boehmite with monoprotic acid the reaction, the resulting aluminum hydroxide glue acid value (millimoles per gram of alumina Al2O3 system corresponding monoprotic acid) is 3 to 5, a solids content of 15 % to 25%, pseudoboehmite, boehmite gel is used to rate ≧ 95%, pseudoboehmite, boehmite content of Al2O3 · H2O ≧ 70% (by weight). 制备镁浆M1和镁浆M2所用的轻质氧化镁的比表面积≥100m2/g、MgO含量≥95%。 The specific surface area and the preparation of the magnesium slurry M1 M2 light magnesium oxide slurry of magnesium used ≥100m2 / g, MgO content of ≥95%.

在实验室对实施例1至实施例11所制备的三效剂样品进行评价的方法如下:硫转移评价:实验装置为石英管反应器,内径11mm,固定床,取0.2克样品评价。 In the laboratory the method of Example 1 was evaluated to Triple Action samples prepared according to Example 11 as follows: Sulfur Transfer Evaluation: experimental apparatus is a quartz tube reactor, an inner diameter of 11mm, a fixed bed, take 0.2 g sample for evaluation. 做SO2吸附评价时,气体总流量200ml/min,其中空气流量40ml/min(O2占4%),SO2流量2~4ml/min,约占1%~2%,以N2平衡。 In doing SO2 adsorption evaluation, the total gas flow rate of 200ml / min, wherein the air flow rate of 40ml / min (O2 accounted for 4%), SO2 flow rate of 2 ~ 4ml / min, about 1% to 2%, in order to balance N2. 吸附时间一般在30min,基本上饱和吸附,温度700℃。 In general the adsorption time 30min, substantially saturated adsorption, temperature 700 ℃. 解吸时,解吸气体为H2,流量40ml/min。 Desorption, the desorption gas is H2, flow rate 40ml / min. 解吸时间30min,温度分540℃和700℃两种。 Desorption time 30min, temperature and divided into two 540 ℃ 700 ℃. 如此反复吸附、解吸,循环次数达六次以上,测定一定温度和气氛条件下三效剂对SO2的平均吸附率和平均解吸率,以此来判断其质量优劣。 This repeated adsorption, desorption, more than six cycles of measurement of average SO2 adsorption rate and the desorption rate of the average atmospheric conditions at a temperature and a three-way agents, in order to determine the merits of its quality. 吸附率和解吸率越高,三效剂性能越好。 The higher the adsorption rate and the desorption rate, the better the performance of the three-way agents.

在相同的条件下,实验室测得用于福建某炼厂的加拿大三效剂,其对SO2的饱和吸附率为45%。 Under the same conditions, measured in the laboratory for a three-way Canadian refinery Fujian agent, which is saturated adsorption of SO2 is 45%.

降氮助燃评价:实验装置为石英管反应器,沸腾床,实验时取3克样品评价。 Combustion Jiangdan assessment: experimental apparatus is a quartz tube reactor, ebullating bed, 3 grams of sample for evaluation experiment. 针对其CO助燃效果评价时,混合气体为CO含量10000ppmv,O2含量1%,N2平衡的混合气体。 When evaluated for their effect CO combustion, the mixed gas is CO content 10000ppmv, O2 content of 1%, a mixed gas of N2 balance. 针对NOx降解实验时,混合气体为CO含量10000ppmv,NO含量200ppmv,O2含量0.3%,N2平衡。 For the NOx degradation test, a mixed gas of CO content 10000ppmv, NO content 200ppmv, O2 content of 0.3%, N2 balance. 测定不同温度下气体反应后的成分,即可知其转化率。 After the reaction gas composition measured at different temperatures, to know the conversion rate. 表3和表4为转化率为50%和90%时不同实例样品的对应温度。 Tables 3 and 4 for the conversion rate corresponding to different instances of the temperature of the sample 50% and 90%. 温度越低,说明降氮助燃活性越强。 The lower the temperature, the stronger Jiangdan combustion activity.

表1为对实施例1至实施例11所得的样品进行硫转移试验时所测得的吸附率和解吸率。 Table 1 Example adsorption rate and the desorption rate of the sample measured 11 obtained in Examples 1 through embodiment for sulfur transfer test.

表1 Table 1

表2为对实施例1至实施例11所得的样品进行NOx和CO的转化试验时所测得的转化率为50%、90%时的对应温度的数据。 Table 2 shows the data measured during test Example 1 Conversion of NOx and CO to the sample obtained in Example 11 was 50% conversion, the temperature corresponding to 90% of.

表2 Table 2

实施例12为工业制备三效剂方法,为喷雾干燥,以50Kg成品为例。 Example 12 is a three-way method for industrial preparation agent, is spray dried to Example 50Kg finished.

(实施例12)于搅拌釜中依次加入73.90千克水,3.97千克冰醋酸以及19.47千克拟薄水铝石,以每分钟350转的速度高速搅拌30分钟,得胶液酸值(体系中每克氧化铝Al2O3对应的单质子酸的毫摩尔数)为4、固含量为20%的氢氧化铝胶A,所采用的拟薄水铝石的成胶率≥95%、拟薄水铝石中Al2O3·H2O的含量≥70%(重量)。 (Example 12) in a stirred autoclave was added sequentially 73.90 kg water, 3.97 kg of glacial acetic acid and 19.47 kg quasi boehmite, high-speed stirring at a speed of 350 revolutions per minute for 30 minutes (per gram of the system to give an acid number of glue the quasi boehmite alumina Al2O3 millimoles corresponding monoprotic acid) as 4, a solids content of 20% aluminum hydroxide gel a, the gelation rate employed ≥95%, pseudoboehmite, boehmite Al2O3 · H2O content ≥70% (by weight). 于搅拌釜中依次加入31.65千克水和7.27千克轻质氧化镁,搅拌均匀后(约5分钟),缓慢加入21.64千克冰醋酸,以每分钟350转的速度高速搅拌30分钟,得镁浆M1。 In a stirred autoclave was added sequentially 31.65 kg water and 7.27 kg of light magnesia, stir (about 5 minutes), 21.64 kg of glacial acetic acid was slowly added, with stirring at 350 revolutions per minute for a high speed for 30 minutes to obtain slurry of magnesium M1. 于搅拌釜中依次加入53.29千克水和7.27千克轻质氧化镁,搅拌均匀,得镁浆M2。 In a stirred autoclave was added sequentially 53.29 kg water and 7.27 kg of light magnesia, uniformly stirred to obtain a magnesium slurry M2. 镁浆M1及M2所用的轻质氧化镁的比表面积≥100m2/g、MgO含量≥95%。 Magnesium pulp M1 and M2 of the specific surface area of ​​light magnesia used ≥100m2 / g, MgO content of ≥95%. 将12.059千克Fe(NO3)3·9H2O与15千克氟碳铈矿粉分别制成50%的水溶液。 The 12.059 kg Fe (NO3) 3 · 9H2O and 15 kg bastnaesite ore were made 50% aqueous. 其中氟碳铈矿粉中、化学式为(Ce,La)(CO3)F的氟碳铈矿的含量≥93%(重量),氟碳铈矿粉中的稀土氧化物含量≥70%(重量),稀土氧化物中的稀土配分Ce>>La、Ce≥45%(重量)。 Wherein bastnaesite ore, the chemical formula (Ce, La) (CO3) content bastnaesite F of ≥93% (by weight), rare earth oxide content of bastnasite ore ≥70% (by weight) , rare earth oxide REE Ce >> La, Ce≥45% (by weight). 将1.607千克偏钒酸铵溶于草酸,草酸的量以偏钒酸铵在水中全部溶解为限,而制成10%的草酸水溶液。 The 1.607 kg of ammonium metavanadate was dissolved in oxalic acid, oxalic acid in the amount of ammonium metavanadate was dissolved in water all limited, to prepare a 10% aqueous solution of oxalic acid. 将上述铝胶A、镁浆M1、镁浆M2、硝酸铁与氟碳铈矿的水溶液、偏钒酸铵的草酸溶液依次加入搅拌釜中混合,以每分钟350转的速度高速搅拌30分钟。 The above-mentioned alumina gel A, magnesium pulp M1, magnesium slurry M2, an aqueous solution of ferric nitrate and bastnaesite, oxalic acid solution of ammonium metavanadate were sequentially added with stirring mixing tank, a high-speed stirring at 350 revolutions per minute for 30 minutes. 将所得浆料于300℃喷雾干燥,压力4MPa,蒸发量为50至150Kg/h,半成品粒径分布在80~120μm的部分的含量≥80%(重量)。 The resulting slurry was spray-dried at 300 deg.] C, the pressure 4MPa, evaporation of 50 to 150Kg / h, the particle size distribution in the semi-finished part 80 ~ 120μm content of ≥80% (by weight). 然后于500℃焙烧80分钟,即得三效剂成品。 Then baked 80 minutes at 500 ℃, i.e., to obtain the finished three agonists. 焙烧后所制得的三效剂中的吸附剂的成1分为MgAl1.8Fe0.2O4·MgO,作为氧化催化剂的CeO2和V2O5分散在吸附剂中,作为结构助剂的CeFO也分散在吸附剂中。 After firing three adsorbent agonist prepared in 1 is divided into MgAl1.8Fe0.2O4 · MgO, V2O5 and CeO2 as the oxidation catalyst is dispersed in the adsorbent, as a structural aid CeFO be dispersed in the adsorbent in.

将按本实施例的条件制得的三效剂应用于石油裂化催化工艺中,以不加任何三效剂为比照标准,使用本发明的三效剂(其藏量占总藏量2%)后,第一级再生器出口烟气中的二氧化硫的与比照标准相比是0.33,所以本发明三效剂对二氧化硫的一再脱除率为67%;本发明三效剂对二氧化硫的二再脱除率更高,为81%。 Conditions under which the three-way agents will be present embodiment is applied to a catalytic cracking process of petroleum in order without any contrast agent is a standard three-way, three-way use of the present invention (the total storage amount which reserves 2%) after the first stage of the regenerator flue gas outlet sulfur dioxide compared with the standard 0.33 contrast, the present invention is a three-way repeated removal of sulfur dioxide agent was 67%; three-way agents of the invention sulfur dioxide is then off two In addition to a higher rate, 81%. 而在相同的条件下,用于福建某炼厂的加拿大三效剂对二氧化硫的一再脱除率为40%。 While under the same conditions, for a Canadian refinery Fujian Triple Action repeated removal of sulfur dioxide was 40%. 本发明三效剂对二再烟气NOx脱除率为92%。 The present invention further Triple Action dimethyl flue gas NOx removal rate was 92%.

将本实施例所得的三效剂进行X射线衍射试验得到图1所示的X射线衍射图。 The Triple Action embodiment of the present embodiment obtained by X-ray diffraction to obtain X-ray diffraction test shown in FIG. 当按上述实验室对三效剂进行评价的方法吸附SO2后,吸附时间为30分钟,得到图2所示的X射线衍射图。 When the method of the three-agonist was evaluated according to the above laboratory adsorption SO2, the adsorption time of 30 minutes, to obtain X-ray diffraction pattern shown in FIG. 从两衍射图可知:三效剂吸附SO2后,二氧化铈和氟氧化铈的共晶物的特征峰消失,只剩下二氧化铈的特征峰;氧化镁的特征峰消失;尖晶石的特征峰未变。 From the two diffraction pattern can be seen: the three-way adsorbed SO2, characteristic peaks of ceria and eutectic cerium oxyfluoride disappears, leaving only the characteristic peaks of ceria; disappearance of characteristic peak of magnesium oxide; spinel characteristic peaks unchanged.

Claims (21)

  1. 1.一种硫转移脱氮助燃三效剂,包括吸附剂和氧化催化剂,氧化催化剂分散在吸附剂中,氧化催化剂包括五氧化二钒和含稀土铈的化合物二氧化铈;其特征在于:还具有分散在吸附剂中的结构助剂含稀土铈的化合物氟氧化铈;吸附剂是具有下式的类尖晶石复合氧化物:AB2-xB′xO4·yAO式中,A为碱土金属元素Mg,B为IIIA族金属元素Al,B′为过渡金属元素Fe,x为0.01~0.5,y为0.2~1.2。 A three-way combustion denitrification sulfur transfer agent, and the oxidation catalyst comprises an adsorbent, the adsorbent is dispersed in an oxidation catalyst, the oxidation catalyst comprises vanadium pentoxide and ceria rare earth-containing compound cerium; characterized in that: further a fluorine compound of cerium oxide dispersed in the adsorbent aids rare earth-containing cerium; spinel sorbent is a composite oxide having the formula: AB2-xB'xO4 · yAO formula, a is an alkaline earth metal element Mg , B is a group IIIA metals Al, B 'is a transition metal element Fe, x is 0.01 ~ 0.5, y is 0.2 to 1.2.
  2. 2.根据权利要求1所述的硫转移脱氮助燃三效剂,其特征在于:x为0.05~0.4,y为0.4~1.2。 2. Sulfur according to claim 1 according to the three-way transfer of nitrogen and combustion agent, wherein: x is 0.05 ~ 0.4, y is 0.4 to 1.2.
  3. 3.根据权利要求2所述的硫转移脱氮助燃三效剂,其特征在于:x为0.05~0.20,y为0.8~1.0。 According to claim 2, wherein the sulfur transfer agent is a three-way nitrogen and combustion, wherein: x is 0.05 ~ 0.20, y is from 0.8 to 1.0.
  4. 4.根据权利要求1所述的硫转移脱氮助燃三效剂,其特征在于:吸附剂的成分为MgAl1.99Fe0.01O4·MgO、MgAl1.95Fe0.05O4·MgO、MgAl1.90Fe0.10O4·MgO、MgAl1.85Fe0.15O4·MgO、MgAl1.80Fe0.20O4·MgO、MgAl1.60Fe0.40O4·MgO、MgAl1.80Fe0.20O4·0.4MgO、MgAl1.80Fe0.20O4·0.6MgO、MgAl1.80Fe0.20O4·0.8MgO、MgAl1.80Fe0.20O4·1.0MgO或MgAl1.80Fe0.20O4·1.2MgO。 Sulfur according to claim 1, wherein said three-way transfer of nitrogen and combustion agent, wherein: component adsorbent is MgAl1.99Fe0.01O4 · MgO, MgAl1.95Fe0.05O4 · MgO, MgAl1.90Fe0.10O4 · MgO , MgAl1.85Fe0.15O4 · MgO, MgAl1.80Fe0.20O4 · MgO, MgAl1.60Fe0.40O4 · MgO, MgAl1.80Fe0.20O4 · 0.4MgO, MgAl1.80Fe0.20O4 · 0.6MgO, MgAl1.80Fe0.20O4 · 0.8 MgO, MgAl1.80Fe0.20O4 · 1.0MgO or MgAl1.80Fe0.20O4 · 1.2MgO.
  5. 5.根据权利要求1所述的硫转移脱氮助燃三效剂,其特征在于:硫转移脱氮助燃三效剂中的含稀土铈的化合物占硫转移脱氮助燃三效剂的重量百分比为20%至35%,氧化催化剂中的五氧化二钒占硫转移脱氮助燃三效剂的重量百分比为2%至4%,其余为吸附剂。 The nitrogen and sulfur transfers according to claim 1 Triple Action combustion, characterized in that: a compound containing a rare earth cerium three-way nitrogen and sulfur transfer agent account for combustion combustion three-way nitrogen and sulfur transfer agent weight percent 20 to 35%, the vanadium pentoxide oxidation catalyst accounts for the denitrification of combustion sulfur transfer agent by weight of the three-way percentage of 2-4%, the remainder being absorbent.
  6. 6.根据权利要求5所述的硫转移脱氮助燃三效剂,其特征在于:硫转移脱氮助燃三效剂中的含稀土铈的化合物所用的原料为氟碳铈矿粉。 6. Sulfur according to claim 5, wherein the three-way transfer of nitrogen and combustion agent, wherein: the denitrification of combustion sulfur transfer starting compound of Cerium-containing triple effect agent used is bastnaesite ore.
  7. 7.根据权利要求5所述的硫转移脱氮助燃三效剂,其特征在于:氧化催化剂中的五氧化二钒所用的原料为偏钒酸铵。 7. The sulfur claimed in claim 5 Nitrogen combustion three transfer agonist, wherein: vanadium pentoxide oxidation catalyst raw materials used for the ammonium metavanadate.
  8. 8.一种制备硫转移脱氮助燃三效剂的方法,所述的硫转移脱氮助燃三效剂包括吸附剂和分散在吸附剂中的氧化催化剂和结构助剂,氧化催化剂包括含稀土铈的化合物二氧化铈和五氧化二钒;结构助剂是含稀土铈的化合物氟氧化铈;吸附剂是具有通式为AB2-xB′xO4·yAO的类尖晶石复合氧化物,式中:A为碱土金属元素Mg,B为IIIA族金属元素Al,B′为过渡金属元素Fe,x为0.01~0.5,y为0.2~1.2;该方法具有以下步骤:①将氟碳铈矿粉与水搅拌混合得到氟碳铈矿粉的悬浮液待用;将偏钒酸铵与水及有机酸混合得到偏钒酸铵的有机酸水溶液待用;将氧化铝的水合物与水及单质子酸搅拌得到氢氧化铝胶待用;将轻质氧化镁与水、单质子酸搅拌得到镁盐浆料待用;将轻质氧化镁与水搅拌得到氢氧化镁浆料待用;将三价铁盐溶于水中得到三价铁的水溶液待用;其中氟碳铈 A method for the preparation of sulfur transfer agent of the three-way nitrogen and combustion, the combustion of nitrogen and sulfur transfer agent comprises an adsorbent and a three-way oxidation catalyst structure and auxiliaries, oxidation catalyst is dispersed in the adsorbent comprises a rare earth-containing cerium ceria and vanadium pentoxide compound; structure aid is a compound containing a rare earth cerium oxyfluoride cerium; adsorbent having the formula AB2-xB'xO4 · yAO a spinel composite oxide, wherein: an alkaline earth metal element A is Mg, B is a group IIIA metals Al, B 'is a transition metal element Fe, x is 0.01 ~ 0.5, y is from 0.2 to 1.2; the method having the following: ① From the bastnaesite ore with water bastnasite ore stirred and mixed to obtain a suspension stand; ammonium metavanadate was mixed with water and an organic acid to obtain an aqueous solution of an organic acid ammonium metavanadate stand; alumina hydrate with water and stirred monoprotic acid aluminum hydroxide gel obtained stand; the water with light magnesium oxide, magnesium monoprotic acid slurry was stirred stand; the light magnesia stirred with water to give magnesium hydroxide slurry stand; the ferric was dissolved in water to obtain an aqueous solution of ferric stand; wherein bastnasite 粉的用量按成品中含稀土铈的化合物占成品总重量的20%至35%而定,偏钒酸铵的用量按成品中五氧化二钒占成品总重量的2%至4%而定,氧化铝的水合物、轻质氧化镁以及三价铁盐的用量按所需的AB2-xB′xO4·yAO的化学成分以及成品中吸附剂占成品总重量的61%至78%而定;②将步骤①所得的氢氧化铝胶、镁盐浆料、氢氧化镁浆料、氟碳铈矿粉的悬浮液、偏钒酸铵有机酸溶液以及三价铁盐溶液混合得到混合液;③将混合液进行干燥,得到半成品;④将半成品在400~800℃下焙烧1~2小时得到成品。 The amount of the compound according to the finished powder containing rare earth cerium accounting for 20-35% of the total weight of the finished product depends, ammonium metavanadate, vanadium pentoxide in an amount representing a finished 2-4% of the total weight of the finished product depends, hydrate, light magnesium oxide and the amount of ferric alumina desired chemical composition AB2-xB'xO4 · yAO finished adsorbent and accounted 61-78% depending on the total weight of the finished press; ② the step ① obtained aluminum hydroxide gel, magnesium slurry, magnesium hydroxide slurry, bastnaesite ore suspension, ammonium metavanadate, and organic acid mixed solution of iron salt solution to obtain a mixture of trivalent; ③ the the mixture was dried, to give semi-finished products; ④ semi-finished product to be finished at 400 ~ 800 ℃ calcined for 1-2 hours.
  9. 9.根据权利要求8所述的硫转移脱氮助燃三效剂的制备方法,其特征在于:步骤①中的氟碳铈矿粉中、化学式为(Ce,La)(CO3)F的氟碳铈矿的含量≥93%(重量),氟碳铈矿粉中的稀土氧化物含量≥70%(重量),稀土氧化物中的稀土配分Ce>>La、Ce≥45%(重量)。 According to claim 8, wherein the sulfur transfer agent method for preparing a three-way nitrogen and combustion, characterized by the steps of: ① in bastnaesite ore, the chemical formula (Ce, La) (CO3) F fluorocarbon content of cerium ore ≥93% (by weight), rare earth oxide content of bastnasite ore ≥70% (by weight), rare earth oxide REE Ce >> La, Ce≥45% (by weight).
  10. 10.根据权利要求8所述的硫转移脱氮助燃三效剂的制备方法,其特征在于:步骤①中与偏钒酸铵混合的有机酸为草酸,草酸的量以偏钒酸铵在水中全部溶解为下限。 Sulfur transfer according to claim 8 prepared according to the method denitrification Triple Action combustion, wherein: the step ① was mixed with ammonium metavanadate in the amount of organic acid is oxalic acid, ammonium metavanadate in water all dissolved the lower limit.
  11. 11.根据权利要求8所述的硫转移脱氮助燃三效剂的制备方法,其特征在于:步骤①中由拟薄水铝石与单质子酸反应、制得胶液酸值为2~6、固含量为15%至25%(重量)的氢氧化铝胶,其中的拟薄水铝石的成胶率≥95%、拟薄水铝石中Al2O3·H2O的含量≥70%(重量),其中的单质子酸为硝酸或醋酸。 Sulfur transfer according to claim 8 prepared according to the method denitrification Triple Action combustion, wherein: the step ① by quasi boehmite single protic acid to obtain an acid value of from 2 to 6 glue a solids content of 15 to 25% (by weight) of aluminum hydroxide gel, wherein the pseudo-boehmite gel-forming rate ≥95%, pseudoboehmite, boehmite Al2O3 · H2O content of ≥70% (by weight) wherein the monoprotic acid is nitric acid or acetic acid.
  12. 12.根据权利要求11所述的硫转移脱氮助燃三效剂的制备方法,其特征在于:步骤①中的拟薄水铝石与单质子酸混合时的搅拌速度为每分钟300至600转。 Nitrogen and sulfur transfer according to claim 11, wherein the preparation of the three-way combustion agent, characterized in that: the agitation speed pseudo boehmite single step ① protonic acid is from 300 to 600 revolutions per minute .
  13. 13.根据权利要求11所述的硫转移脱氮助燃三效剂的制备方法,其特征在于:单质子酸为硝酸,胶液酸值为3~5。 13. The sulfur according to claim 11, wherein the three-way transfer agent in preparing the denitrification of combustion, wherein: monoprotic acid is nitric acid, an acid value of from 3 to 5 glue.
  14. 14.根据权利要求8所述的硫转移脱氮助燃三效剂的制备方法,其特征在于:步骤①中的制备镁盐浆料以及制备氢氧化镁浆料的轻质氧化镁的比表面积≥100m2/g、MgO含量≥95%(重量),制备镁盐浆料的单质子酸为醋酸或/和硝酸,醋酸或/和硝酸所用的量依其与MgO充分反应的摩尔比而定,镁盐浆料以及氢氧化镁浆料的固含量为10%~14%(重量)。 14. The sulfur according to claim 8, the three-way transfer agent is prepared denitrification combustion, characterized in that: a slurry preparing a magnesium salt and a specific surface area of ​​light magnesia magnesium hydroxide slurry prepared in step ① ≥ 100m2 / g, MgO content of ≥95% (by weight), the amount of magnesium slurry was prepared monoprotic acid is acetic acid and / or nitric acid, acetic acid and / or nitric acid is used according to its fully reacted with a molar ratio of MgO may be, magnesium and the solids content of the slurry of magnesium hydroxide slurry of the salt is from 10% to 14% (by weight).
  15. 15.根据权利要求14所述的硫转移脱氮助燃三效剂的制备方法,其特征在于:步骤①中制备镁盐浆料时,先将轻质氧化镁与水搅拌均匀后、再加入冰醋酸或/和硝酸与氧化镁反应完全制得醋酸镁或/和硝酸镁,冰醋酸或/和硝酸与氧化镁反应时的搅拌速度为每分钟300至600转。 15. The sulfur according to claim 14, the three-way transfer agent is prepared denitrification combustion, characterized in that: the step ① When magnesium slurry was prepared, the first light magnesium oxide with water Stir, then addition of ice acetic acid and / or reaction with magnesium nitrate stirring speed when fully prepared magnesium acetate and / or magnesium nitrate, or acetic acid / magnesium oxide with nitric acid and the reaction is 300 to 600 revolutions per minute.
  16. 16.根据权利要求8所述的硫转移脱氮助燃三效剂的制备方法,其特征在于:步骤①中的三价铁盐为硝酸铁。 16. The sulfur according to claim 8, the three-way transfer agent is prepared denitrification combustion, characterized in that: in the step ① ferric iron nitrate.
  17. 17.根据权利要求8至16之一所述的硫转移脱氮助燃三效剂的制备方法,其特征在于:步骤②中混合时的搅拌速度为每分钟300至600转。 17. 8 Sulfur according to one of claims 16 three-way transfer agent is prepared denitrification combustion, wherein: the stirring speed when mixing step ② of 300 to 600 revolutions per minute.
  18. 18.根据权利要求8至16之一所述的硫转移脱氮助燃三效剂的制备方法,其特征在于:步骤③中的干燥为喷雾干燥,温度为300至350℃,压力为3.0至5.0Mpa,蒸发量为50至150Kg/h,半成品的粒径分布在80~120μm的部分的含量≥80%(重量)。 18. Nitrogen and sulfur transfer claim 8 to 16 prepared according to one of the three-way combustion agent, wherein: the drying step is a spray drying ③, a temperature of 300 to 350 deg.] C, a pressure of from 3.0 to 5.0 mpa, evaporation of 50 to 150Kg / h, the particle size distribution of the semi-finished part 80 ~ 120μm content of ≥80% (by weight).
  19. 19.根据权利要求8至16之一所述的硫转移脱氮助燃三效剂的制备方法,其特征在于:步骤③中的干燥为烘箱干燥,温度为100至150℃。 8 to 19. The sulfur according to one of claims 16 three-way transfer agent is prepared denitrification combustion, wherein: the drying step ③ the drying oven, a temperature of 100 to 150 ℃.
  20. 20.根据权利要求8至16之一所述的硫转移脱氮助燃三效剂的制备方法,其特征在于:步骤④中焙烧过程采用缓慢升温的方法,焙烧温度400~500℃,焙烧时间为80至100分钟。 20. Nitrogen and sulfur transfer claim 8 according to any one of the three-way agent 16 Preparation of combustion, wherein: the step ④ the method slowly warmed during firing, the firing temperature is 400 ~ 500 ℃, roasting time 80 to 100 minutes.
  21. 21.由权利要求1所述的三效剂,在降低催化裂化再生烟气中的硫氧化物、氮氧化物和一氧化碳含量中的应用。 21. A triple-effect by the agent according to claim 1, application of flue gas sulfur oxides, nitrogen oxides and carbon monoxide content in the regenerated catalytic cracking reduced.
CN 02153284 2002-11-26 2002-11-26 Agent with three effect, sulphur transfers, denitrification and combustion supporting as well as its preparing method CN1319631C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 02153284 CN1319631C (en) 2002-11-26 2002-11-26 Agent with three effect, sulphur transfers, denitrification and combustion supporting as well as its preparing method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 02153284 CN1319631C (en) 2002-11-26 2002-11-26 Agent with three effect, sulphur transfers, denitrification and combustion supporting as well as its preparing method

Publications (2)

Publication Number Publication Date
CN1480246A true CN1480246A (en) 2004-03-10
CN1319631C true CN1319631C (en) 2007-06-06

Family

ID=34148788

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 02153284 CN1319631C (en) 2002-11-26 2002-11-26 Agent with three effect, sulphur transfers, denitrification and combustion supporting as well as its preparing method

Country Status (1)

Country Link
CN (1) CN1319631C (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100478424C (en) 2004-08-31 2009-04-15 中国石油化工股份有限公司;中国石油化工股份有限公司石油化工科学研究院 Hydrocarbon oil cracking method

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5108979A (en) * 1991-02-25 1992-04-28 Intercat, Inc. Synthetic spinels and processes for making them
US5422332A (en) * 1993-07-30 1995-06-06 Intercat, Inc. Processes for reacting bastnaesite with metal oxides
US5914293A (en) * 1994-06-01 1999-06-22 Bp Amoco Corporation Absorbent and process for removing sulfur oxides from a gaseous mixture

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5108979A (en) * 1991-02-25 1992-04-28 Intercat, Inc. Synthetic spinels and processes for making them
US5422332A (en) * 1993-07-30 1995-06-06 Intercat, Inc. Processes for reacting bastnaesite with metal oxides
US5914293A (en) * 1994-06-01 1999-06-22 Bp Amoco Corporation Absorbent and process for removing sulfur oxides from a gaseous mixture

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
FCC再生烟气的脱硫助剂研究进展 朱仁发 李承烈,化工进展,第3期 2000;调变组分对流化催化裂化助剂脱硫性能的影响 朱仁发 谭乐成 王金安,华东理工大学学报,第26卷第2期 2000;流化催化裂化脱硫添加剂的研究进展 朱仁发 李承烈,化工科技,第8卷第1期 2000 *

Also Published As

Publication number Publication date Type
CN1480246A (en) 2004-03-10 application

Similar Documents

Publication Publication Date Title
Liang et al. Oxygen activation on Cu/Mn–Ce mixed oxides and the role in diesel soot oxidation
US4522937A (en) Preparative process for alkaline earth metal, aluminum-containing spinels
US4472532A (en) Preparative process for alkaline earth metal, aluminum-containing spinels
US5795553A (en) Nitrogen oxide adsorbing material
US20050207956A1 (en) Mixed metal oxide sorbents
US4018706A (en) Catalysts for purifying exhaust and waste gases
US5643542A (en) Process for simultaneously reducing the amounts of hydrocarbons, carbon monoxide and nitrogen oxides contained in the exhaust gas from an internal combustion engine
US5141906A (en) Catalyst for purifying exhaust gas
US4476245A (en) Preparative process for alkaline earth metal, aluminum-containing spinels
US20090191108A1 (en) Zirconium/Praseodymium Oxide NOx Traps and Prufication of Gases Containing Nitrogen Oxides (NOx) Therewith
EP0494388A1 (en) Process for removing nitrogen oxides from exhaust gases
US20080020925A1 (en) Composition Based On Oxides Of Zirconium, Praseodymium, Lanthanum Or Neodymium, Method For The Preparation And Use Thereof In A Catalytic System
US20020044901A1 (en) Desulfurization of gases with cerium oxide microdomains
US5821190A (en) Catalyst comprising iridium, alkaline metal, alkaline earth or rare earth metal, and metal carbide or metal nitride
US6281164B1 (en) SOx additive systems based upon use of multiple particle species
CN103769137A (en) Preparation method of high-strength flue gas denitration catalyst
WO1997048480A1 (en) Hydrotalcite sulfur oxide sorption
Li et al. CO2 capture performance of synthetic sorbent prepared from carbide slag and aluminum nitrate hydrate by combustion synthesis
US20100329954A1 (en) High specific surface area mixed oxide of cerium and of another rare earth, preparation method and use in catalysis
US8158551B2 (en) Catalyst compositions for the treatment of vehicular exhaust gases comprise zirconium oxide and cerium oxide, and have a high reducibility and a stable specific surface area
US6048821A (en) SOx additive systems based upon use of multiple particle species
Hodjati et al. NOx sorption–desorption study: application to diesel and lean-burn exhaust gas (selective NOx recirculation technique)
US20100040523A1 (en) High specific surface/reducibility catalyst/catalyst support compositions comprising oxides of zirconium, cerium and lanthanum and of yttrium, gadolinium or samarium
WO2008046920A1 (en) Highly acidic composition containing zirconium and silicon oxides and an oxide of at least one element selected from titanium, aluminium, tungsten, molybdenum, cerium, iron, tin, zinc, and manganese
CN102824922A (en) Integrated honeycomb SCR (selective catalytic reduction) catalyst for low-temperature smoke denitration and preparation method of catalyst

Legal Events

Date Code Title Description
C06 Publication
C10 Request of examination as to substance
C14 Granted
C56 Change in the name or address of the patentee

Owner name: BEIJING SANJU ENVIRONMENTAL PROTECTION AND NEW MAT

Free format text: FORMER NAME OR ADDRESS: SANJU ENVIRONMENT PROTECTION NEW MATERIAL CO., LTD., BEIJING

ASS Succession or assignment of patent right

Owner name: SHENYANG KAITE CATALYST CO., LTD.

Free format text: FORMER OWNER: BEIJING SANJU NEW ENVIRONMENTAL PROTECTION MATERIALS CO., LTD.

Effective date: 20090828

C41 Transfer of the right of patent application or the patent right
C57 Notification of unclear or unknown address
C41 Transfer of the right of patent application or the patent right
ASS Succession or assignment of patent right

Owner name: BEIJING SJ ENVIRONMENTAL PROTECTION AND NEW MATERI

Free format text: FORMER OWNER: SHENYANG KAITE CATALYST CO., LTD.

Effective date: 20140924

COR Bibliographic change or correction in the description

Free format text: CORRECT: ADDRESS; FROM: 110000 SHENYANG, LIAONING PROVINCE TO: 100080 HAIDIAN, BEIJING