CN106799234A - Rare earth-based SCR catalyst for diesel oil vehicle and preparation method of rare earth-based SCR catalyst - Google Patents

Rare earth-based SCR catalyst for diesel oil vehicle and preparation method of rare earth-based SCR catalyst Download PDF

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CN106799234A
CN106799234A CN201611252517.5A CN201611252517A CN106799234A CN 106799234 A CN106799234 A CN 106799234A CN 201611252517 A CN201611252517 A CN 201611252517A CN 106799234 A CN106799234 A CN 106799234A
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rare earth
composite oxide
catalyst
mass
based
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CN201611252517.5A
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李兆强
王艳
赵文怡
张丞
马志鸿
张旭霞
王荣
宋静
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包头稀土研究院
瑞科稀土冶金及功能材料国家工程研究中心有限公司
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/92Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9404Removing only nitrogen compounds
    • B01D53/9409Nitrogen oxides
    • B01D53/9413Processes characterised by a specific catalyst
    • B01D53/9418Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002Mixed oxides other than spinels, e.g. perovskite
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32Manganese, technetium or rhenium
    • B01J23/36Rhenium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889Manganese, technetium or rhenium
    • B01J23/8896Rhenium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2258/00Sources of waste gases
    • B01D2258/01Engine exhaust gases
    • B01D2258/012Diesel engines and lean burn gasoline engines
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00Constitutive chemical elements of heterogeneous catalysts
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection
    • Y02A50/20Air quality improvement or preservation
    • Y02A50/23Emission reduction or control
    • Y02A50/232Catalytic converters
    • Y02A50/2322Catalytic converters for exhaust after-treatment of internal combustion engines in vehicles
    • Y02A50/2325Selective Catalytic Reactors [SCR]
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02TCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00Road transport of goods or passengers
    • Y02T10/10Internal combustion engine [ICE] based vehicles
    • Y02T10/20Exhaust after-treatment
    • Y02T10/24Selective Catalytic Reactors for reduction in oxygen rich atmosphere

Abstract

The invention relates to a rare earth-based SCR catalyst for a diesel oil vehicle and a preparation method of the rare earth-based SCR catalyst. According to the catalyst, cordierite honeycomb ceramic is taken as a carrier and is coated with coating layer slurry, and the coating layer slurry mainly contains rare earth-based powder, a binder, an additive and water; and the rare earth-based powder contains the following four active components: the first active component is one or more of cerium-niobium composite oxide, cerium-tin composite oxide, cerium-yttrium composite oxide and cerium-lanthanum composite oxide, the second active component is one or more of manganese-samarium composite oxide, zirconium-hafnium composite oxide, zinc-erbium composite oxide, iron-copper composite oxide, copper-hafnium composite oxide and zirconium-aluminum composite oxide, the third active component is rhenium oxide, and the fourth active component is titanium-tungsten powder. The rare earth-based SCR catalyst has the advantages that the low temperature performance is good, an operation temperature window is wide, and the conversion rate of NOx reaches above 70% at 150 DEG C, is more than 90% at 180 DEG C and is 100% at 200-500 DEG C.

Description

一种柴油车用稀土基SCR催化剂及制备方法 For a diesel vehicle, and a rare earth-based SCR catalyst preparation method

技术领域 FIELD

[0001]本发明涉及一种柴油车用稀土基SCR催化剂及制备方法,属于催化还原方法净化机动车尾气排放技术领域。 [0001] The present invention relates to a diesel vehicle, and a rare earth-based SCR catalyst preparation method, belonging to the catalytic reduction method for purifying vehicle exhaust art.

背景技术 Background technique

[0002]柴油机由于在动力性、经济性和可靠性方面有着汽油机不可比拟的优势,特别是⑶2排放低,其用途已不再仅局限于船用和大型商用乘用车的动力系统,而是已逐步扩展到各类车型上,柴油轿车在欧美市场的占有率已达到40%以上。 [0002] As the diesel engine with a gasoline engine unparalleled advantages in power, economy and reliability, especially low ⑶2 emissions, its use is no longer limited to large-scale power systems for marine and commercial passenger vehicles, but has gradually extended to all types of vehicles, diesel cars in Europe and America market share has reached 40%. 我国政府在汽车产业规划中也大力支持柴油车的发展。 My Government strongly supports the development of diesel vehicles in the automotive industry planning. 但与此同时,柴油车尾气排放的氮氧化物(NOx)等污染排放问题也曰趋突出,N(k是酸雨、光化学烟雾、雾霾的主要元凶之一。为了防治环境污染,我国颁布了《车用压燃式、气体燃料点燃式发动机与汽车排气污染物排放限值及测量方法(中国ni、iv、 V阶段》(GB117691-2005),规定了柴油车的NOx排放标准。2015年1月1日,我国全面开始实施国IV排放标准,2〇17年1月1日,开始实施国V排放标准。因此,对柴油车尾气排放的NOx治理迫在眉睫。 At the same time, nitrogen oxides, diesel exhaust emissions (NOx) emissions and other pollution also said increasingly prominent, N (k is acid rain, one of photochemical smog, haze is the main culprit. In order to prevent and control environmental pollution, China promulgated "compression ignition gas fueled engine and ignition automobile exhaust pollutant emission limits and measurement methods (China ni, iv, V phase" (GB117691-2005), a predetermined standard NOx emissions of diesel vehicles. 2015 January 1st, our country began to implement a comprehensive national IV emission standards, 2 billion in 17 years on January 1, the country began to implement V emission standards. Therefore, NOx control for diesel exhaust emissions is imminent.

[0003]选择性催化还原法(SCR)是目前应用最为广泛的柴油车N(k净化技术,它是在特定催化剂作用下,用氨或其他还原剂选择性的将NOx还原为N2的方法。对于车用柴油机,尤其是公交车、洒水车、扫地车等低速行驶的柴油车型,在运行过程中尾气排放温度仅有30%的时间超过200°C,而70%的时间均低于200°C。因此,柴油车用SCR催化剂必须在保证较宽操作温度窗口的同时具有优异的低温性能。CN103736497 B与CN104338545 A中公开了一种处理柴油机尾气中N(k的SCR催化剂,虽然工作温度窗口较宽,但都使用了剧毒物质钒,且其低温性能较差。CN103908970 B公开的整体式SCR蜂窝催化剂,虽然在160-55(TC范围内NOz转化率大于85%,但是活性物质仍主要为钒。CN105032446 A公布了一种用于柴油车尾气净化的低温型SCR催化剂,其活性组分为氧化铁与氧化锰。该类催化剂200°C时N(k转化率较高, [0003] Selective Catalytic Reduction (SCR) is the most widely used diesel N (k purification technology, it is in particular a catalyst, with ammonia or other reducing agents for the selective reduction of NOx to N2 method. for vehicles with diesel engines, especially buses, sprinkler, etc. sweeper low speed diesel vehicle, during operation of only 30% longer than the 200 ° C temperature of exhaust emission, while 70% of the time were lower than 200 ° C. Thus, the SCR catalyst for diesel must ensure a wider operating temperature window while having excellent low temperature performance and .CN103736497 B CN104338545 a discloses Although operating temperature window for processing diesel exhaust gas N (k of the SCR catalyst, wide, but the use of highly toxic vanadium, and the monolithic honeycomb SCR catalysts poor low temperature properties .CN103908970 B disclosed, although 160-55 (TC within a range of greater than 85% conversion NOz, but is still mainly active substance published vanadium .CN105032446 a low temperature SCR catalyst for purification of diesel exhaust, the active component iron oxide and manganese oxide. such catalysts when 200 ° C N (k higher conversion rate, 操作温度窗口较窄,400°C时N(k转化率开始下降。CN 103127951 B中公开了一种用于柴油车尾气脱硝的分子筛型低温SCR催化剂,该类催化剂以铜、铁元素作为活性组分,基本可以满足低温高转化的要求,其在200 °C时NOz转化率大于90%,完全转化的温度窗口是250-450 °C。但是相比于稀土基催化剂,铁铜分子筛催化剂成本较高。CN101234345A、CN101234346 B 与CN101357328 A中分别公开了一种环境友好的稀土基催化剂,该类催化剂用于固定源烟气脱硝领域,活性组分主要为Ce02,其机械性能及热稳定性好,但是活性温度窗口是250-400°C,低温段(200°C左右)活性较差。 Narrow operating temperature window, when the 400 ° C N (k conversion rate began to decline .CN 103127951 B discloses a molecular sieve-type low temperature SCR catalyst for diesel exhaust gas denitration catalyst such as copper, iron as an active ingredient points to meet the basic requirements of low temperature and high conversions, the conversion rate at 200 ° C NOz greater than 90%, complete conversion temperature window is 250-450 ° C., but compared to the rare earth-based catalyst, the molecular sieve catalyst costs than iron-copper high .CN101234345A, CN101234346 B respectively with CN101357328 a discloses a rare earth-based environmentally friendly catalysts, such catalysts for flue gas denitrification art stationary sources, mainly the active ingredient CeO2, good mechanical properties and thermal stability, However, the active window is the temperature of 250-400 ° C, low temperature section (approximately 200 ° C) poor activity.

[0004] 基于此,为了满足日益严格的尾气排放法规要求,开发无毒、高效、低温性能好、操作温度窗口宽的稀土基柴油车SCR催化剂,低成本的实现柴油车尾气的高效脱硝,具有重要的现实意义。 [0004] Based on this, in order to meet increasingly stringent emissions regulations, the development of non-toxic, highly efficient, low temperature performance, wide operating temperature window of a rare earth-based SCR catalyst diesel, cost efficient denitration achieved in diesel exhaust, having important practical significance.

发明内容 SUMMARY

[0005] 本发明的目的是针对现有柴油车用催化剂在200°C左右NOx转化率不高的问题,提供一种成本低、低温活性高、操作温度窗口宽、抗水及二氧化硫性能好、制备方法简单、环境友好的柴油车用稀土基SCR催化剂及制备方法。 [0005] The object of the present invention is directed to conventional diesel catalyst at about 200 ° C NOx conversion rate is not high, to provide a low cost, high activity at low temperature, a wide operating temperature window, and good anti-sulfur performance water, rare earth-based SCR catalyst and a preparation method of simple, environmentally friendly diesel vehicle.

[0006] 本发明的技术方案如下: 一种柴油车用稀土基SCR催化剂,其特征是:以堇青石蜂窝陶瓷为载体涂覆涂层浆液, 涂层浆液主要由稀土基粉体、粘结剂、添加剂和水组成;其中稀土基粉体的成分包括四种活性组分:第一活性组分为铈铌复合氧化物、铈锡复合氧化物、铈钇复合氧化物和铈镧复合氧化物中的一种或几种,第二活性组分为锰钐复合氧化物、锆铪复合氧化物、锌铒复合氧化物、铁铜复合氧化物、铜铪复合氧化物、锆铝复合氧化物中的一种或几种,第三活性组分为氧化铼,第四活性组分为钛钨粉。 [0006] aspect of the present invention is as follows: A rare earth-based SCR using diesel catalysts, characterized in that: the cordierite honeycomb ceramic support coated with the slurry coating, slurry coating powder mainly composed of rare earth-based binder , additives and water; wherein the rare earth-based powder composition comprising four active ingredients: a first active component is niobium composite oxide of cerium, cerium-tin composite oxide, a composite oxide of cerium, yttrium and lanthanum cerium composite oxide one or more second active component samarium manganese composite oxide, a composite oxide of zirconium, hafnium, erbium complex of zinc oxide, a composite oxide of iron and copper, copper oxide, hafnium complex, aluminum zirconium composite oxide one or several, third active component rhenium oxide, a fourth active component is titanium tungsten powder.

[0007] 在所述的稀土基粉体中第一活性组分的质量占稀土基粉体总质量的5_18%,第二活性组分的质量占稀土基粉体总质量的1.5-10%,第三活性组分的质量为稀土基粉体总质量的0 • 1-5%,第四活性组分的质量为稀土基粉体总质量的67-93 • 4%。 [0007] In the rare earth-based powder according to the quality of the first active ingredient accounted 5_18% of total mass rare earth-based powder, the active mass of the second component accounts for 1.5 to 10 mass% of the total rare earth-based powder, quality of the third active ingredient is 0 • 1-5% of the total mass of the rare earth-based powder, the active mass of the fourth component is 67-93 • 4% of the total mass of a powder of a rare earth group.

[0008] 所述涂层浆液中粘结剂为懦米胶。 [0008] The slurry coating binder is gum coward meters.

[0009] 所述涂层浆液中添加剂为微晶纤维素,且其质量为稀土基粉体总质量的0.01% - 5%〇 [0009] The slurry coating additive is microcrystalline cellulose, and a mass of 0.01% of the total mass of the rare earth-based powder - 5% billion

[0010] 所述的柴油车用稀土基SCR催化剂的制备方法,其特征在于包括如下合成步骤: (1) 浆液配制:将稀土基粉体与粘结剂按质量比例为0 • 5-7.5:1加入到120mL去离子水中; (2) 浆液球磨:将步骤(1)所得浆液经行星式球磨机研磨,转速400转/分,运行时间5-60 min,研磨后浆液粒度①5Q)控制在1〇〇-1〇〇〇nm范围内; (3) 增加添加剂:在球磨后的浆液中加入微晶纤维素,并搅拌反应l-3h; (4) 涂层涂覆:将称量质量后的堇青石载体浸入步骤(3)所得的涂层浆液中,浸入高度控制到0_3-0_5 cm,然后使用真空装置迅速提拉,之后用气枪吹去孔道内多余液体,6(rC下干燥1 h。 [0010] The method of preparing a diesel vehicle rare earth-based SCR catalyst, comprising the following synthesis steps: (1) a slurry preparation: rare earth-based powder and a binder mass ratio of 0 • 5-7.5: 1 was added to 120mL of deionized water; (2) milling the slurry: step (1) the resulting slurry was a planetary ball mill, the rotational speed of 400 rev / min, run time of 5-60 min, the slurry particle size after milling ①5Q) controlled 1〇 the square-1〇〇〇nm range; (3) increasing additives: microcrystalline cellulose was added to the slurry after the ball mill, and the reaction was stirred for l-3h; (4) coating is applied: the mass weighed after Viola bluestone step of immersing the carrier (3) coating the resulting slurry, was immersed in a highly controlled to 0_3-0_5 cm, then rapidly pulling a vacuum apparatus, after the blow off excess liquid within the bore with an air gun, 6 (rC dried 1 h.

[0011] (5)重复上述涂覆操作直至催化剂涂层上载量占堇青石载体质量的50—80%,重复涂覆后催化剂的干燥温度为10(TC,之后在450-650 °C下焙烧4h即可制得所需催化剂。 [0011] (5) the above-described coating operation was repeated until the catalyst carrier accounted for 50-80% of the coating mass of the cordierite carrier, the drying temperature after the coating of the catalyst was repeated 10 (TC, after firing at 450-650 ° C 4h to obtain the desired catalyst.

[0012]所述的柴油车用稀土基SCR催化剂制备方法,其特征在于涂层的脱落质量占涂层总质量的0.5%及以下。 [0012] The diesel vehicles rare earth-based SCR catalyst preparation method, wherein the coating off 0.5% by mass of the total mass of the coating and below.

[0013]所述的稀土基催化剂主要是用于柴油车SCR领域,具体反应条件如下:模拟柴油车尾气中气体体积比组成为:100—150〇ppm N〇, 100-1500 ppm NH3,6-15% 02,0-20% H20,Ar 为载气,空速(61^)为3〇〇〇〇-1〇〇00(^-1。顺3/剌本积比为〇_5_1_5,气体检测系统为配有气体池的傅里叶变换红外分析伩。 [0013] The rare earth-based catalyst are mainly used in diesel vehicles SCR art, specific reaction conditions are as follows: simulated diesel exhaust gas in a volume ratio composition: 100-150〇ppm N〇, 100-1500 ppm NH3,6- 15% 02,0-20% H20, Ar as a carrier gas, the space velocity (61 ^) is 3〇〇〇〇-1〇〇00 (^ - 3 1 cis / volume ratio present 〇_5_1_5 punching, gas detection system with a gas cell Fourier transform infrared analysis of Xin.

[00M]采用上述技术方案,本发明的技术效果有: 1.本发明所制备的柴油车用稀土基SCR催化剂低温性能好,操作温度窗口宽,在15(rc 时N(k的转化率达7〇%以上,iso -C时NOx的转化率大于9〇%,2〇0_500 °C范围内NCk的转化率为100%,性能优于市场在售的传统VW-Ti型SCR催化剂和进口含稀土元素Ce的非钒基SCR催化剂。 _5] 2•本鋼_j細㈣车腦土基SGR催化織有健_硫巾毒、抗抗水热老化性能。 [00M] With the above technical solution, the technical effect of the present invention are: 1. The diesel vehicles of the present invention prepared in a rare earth-based SCR catalyst temperature performance, wide operating temperature window, at 15 N (when the conversion rate k rc ( 7〇% or more, when the conversion rate of NOx iso -C 9〇% greater than the conversion rate of the 2〇0_500 ° C range NCk 100% better performance than the traditional market contained in the VW-Ti-type SCR catalyst inlet and sold of Ce non vanadium-based SCR catalysts. _5] 2 • BX _j iv fine soil car brain health group SGR catalytic woven with towel _ sulfur poisoning, water-resistant anti-heat aging properties.

附图说明 BRIEF DESCRIPTION

[0016]图1是本发明中的稀土基SCR催化剂与市场在售的VW-Ti型催化剂和进口含稀土元素Ce的非钒基SCR催化剂的N(k转化性能对比曲线。 [0016] FIG. 1 is a rare earth-based SCR catalyst of the present invention and Market of Ce non-N-containing vanadium-based SCR catalyst (k conversion performance graph comparing the VW-Ti catalyst inlet and sale.

[0017]图2是本发明中的稀土基SCR催化剂在高硫环境下的N(k转化性能曲线。 [0017] FIG. 2 is in a high sulfur environment N rare earth-based SCR catalyst of the present invention (k conversion performance curves.

[0018] 图3是本发明中的稀土基SCR催化剂在不同空速下的NOx转化性能曲线。 [0018] FIG. 3 is a rare earth-based SCR catalyst of the present invention, NOx conversion performance curves at different airspeed.

[0019] 图4是本发明中的稀土基SCR催化剂在不同水热老化条件下的Mk转化性能曲线。 [0019] FIG. 4 is a rare earth-based SCR catalyst of the present invention Mk conversion performance curves at different hydrothermal aging conditions.

具体实施方式 Detailed ways

[0020] 下面将根据具体实施例对本发明进行进一步说明。 [0020] The present invention will now be further described with reference to specific embodiments.

[0021] 实施例1: 一种低温性能好操作温度窗口宽的柴油车用稀土基SCR催化剂的制备方法,具体合成步骤如下: (1)浆液配制:称量稀土基粉体48g,糯米胶20 g加入到去120mL离子水中。 [0021] Example 1: A cryogenic operating temperature window of good performance diesel vehicle width preparing a rare earth-based SCR catalyst, the specific synthetic steps as follows: (1) a slurry preparation: rare earth-based powder weighing 48g, glutinous rice glue 20 g DI water was added to 120mL go. 对于稀土基粉体,含有的铈铌复合氧化物为粉体总质量的10%,铁铜复合氧化物为粉体总质量的2%,氧化铼为粉体总质量的〇• 28%,其余为钛妈粉,合成方法为传统沉积沉淀法,沉淀剂为氨水。 For the rare earth-based powder, a cerium-containing niobium composite oxide is 10% of the total mass of the powder, iron-copper composite oxide powder 2% of the total mass, the total mass of rhenium oxide powder square • 28%, the remainder titanium mother powder, synthetic methods for the conventional deposition precipitation method, a precipitation agent is ammonia. [0022] (2)浆液球磨:浆液经行星式球磨机研磨,转速400转/分,运行时间10 min,最终浆液粒度D5Q为721 nm。 [0022] (2) milling the slurry: The slurry by a planetary ball mill, the rotational speed of 400 rev / min, run time 10 min, final slurry particle size D5Q of 721 nm.

[0023] (3)增加微晶纤维素:在步骤(2)中球磨后的浆液中加入〇.〇68g微晶纤维素,并搅拌反应lh。 [0023] (3) Microcrystalline cellulose increases: the slurry in step (2) was added after milling 〇.〇68g microcrystalline cellulose, and the reaction stirred for lh.

[0024] (4)涂层涂覆:将质量为2 • 〇94 g的堇青石载体浸入步骤(3)所得的涂层浆液中,透入高度控制到〇.3-0.5 cm,然后使用真空装置迅速提拉,之后用气枪吹去孔道内多余液体, 60°C下干燥1 h。 [0024] (4) coating is applied: the mass of 〇94 g 2 • immersing the cordierite carrier in step (3) coating the resulting slurry, to control penetration height cm & lt 〇.3-0.5, then vacuum quickly pulling apparatus, then blow off excess liquid within the bore with an air gun, dried at 60 ° C 1 h.

[0025] (5)重复上述涂覆操作3次,重复涂覆后催化剂的干燥温度为100°C,之后在500°C 下焙烧4 h,取出称量整体式催化剂的质量为3.371g。 [0025] (5) the above-described coating operation was repeated three times, the drying temperature after the coating of the catalyst was repeated 100 ° C, then calcined for 4 h at 500 ° C, remove Weigh monolithic catalyst is 3.371g. 催化剂上载率=(涂覆后催化剂质量-堇青石载体质量)/堇青石载体质量*100%,按照上述计算公式计算得到催化剂涂层的上载率为61%。 The catalyst-carrying rate = (mass of catalyst after coating - cordierite carrier mass) / * 100% cordierite carrier mass, calculated according to the above formula was 61% upload catalyst coating.

[0026] (6)将焙烧后的催化剂在超声清洗仪中超声30 min,110°C下干燥lh后称重。 [0026] (6) The catalyst was calcined ultrasound by the ultrasonic cleaner for 30 min after drying weighed lh at 110 ° C. 催化剂脱落率=(超声后催化剂质量-超声前催化剂质量)/超声前催化剂质量*100%,按此计算公式得到催化剂涂层的脱落率为0.03%。 The catalyst falling rate = (mass of catalyst after sonication - mass of catalyst prior to irradiation) / mass of catalyst * 100% prior to irradiation, this calculation formula obtained catalyst coating dropping rate 0.03%.

[0027] 实施例2: 一种低温性能好操作温度窗口宽的柴油车用稀土基SCR催化剂的制备方法,具体合成步骤如下: (1)浆液配制:称量稀土基粉体48g,糯米胶24 g加入到120mL去离子水中。 [0027] Example 2: A cryogenic operating temperature window of good performance diesel vehicle width preparing a rare earth-based SCR catalyst, the specific synthetic steps as follows: (1) a slurry preparation: rare earth-based powder weighing 48g, glutinous rice glue 24 g was added to 120mL of deionized water. 对于稀土基粉体,含有的铈镧复合氧化物为粉体总质量的13%,锰钐复合氧化物为粉体总质量的2.5%, 氧化铼为粉体总质量的〇• 28%,其余为钛钨粉,合成方法为传统沉积沉淀法,沉淀剂为氨水。 For the rare earth-based powder, a lanthanum cerium composite oxide containing 13% of the total mass of the powder, samarium manganese composite oxide powder of 2.5% of the total mass, the total mass of rhenium oxide powder square • 28%, the remainder titanium tungsten powder, conventional synthetic methods for the deposition-precipitation method, a precipitation agent is ammonia.

[0028] (2)浆液球磨:浆液经行星式球磨机研磨,转速400转/分,运行时间1〇min,最终浆液粒度D5q为615 nm。 [0028] (2) milling the slurry: The slurry by a planetary ball mill, the rotational speed of 400 rev / min, run time 1〇min, D5q final slurry particle size was 615 nm.

[0029] (3)增加微晶纤维素:在步骤(2)中球磨后的浆液中加入O.lSOg微晶纤维素,并搅拌反应lh。 [0029] (3) Microcrystalline cellulose increases: the slurry in step (2) was added after milling O.lSOg microcrystalline cellulose, and the reaction stirred for lh.

[0030] (4)涂层涂覆:将质量为2.038 g的堇青石载体浸入步骤(3)所得的涂层浆液中,浸入高度控制到〇.3-0.5 cm,然后使用真空装置迅速提拉,之后用气枪吹去孔道内多余液体, 60°C下干燥1 h。 [0030] (4) coating is applied: the mass of a cordierite carrier was immersed in 2.038 g in step (3) coating the resulting slurry, was immersed into 〇.3-0.5 cm & lt height control, and then rapidly pulled using a vacuum means inside, followed by an air gun blow off the excess liquid channels, dried 1 h at 60 ° C.

[0031] (5)重复上述涂覆操作3次,重复涂覆后催化剂的干燥温度为100°C,之后在500°C 下焙烧4 h,取出称量整体式催化剂的质量为3.465g。 [0031] (5) the above-described coating operation was repeated three times, the drying temperature after the coating of the catalyst was repeated 100 ° C, then calcined for 4 h at 500 ° C, remove Weigh monolithic catalyst is 3.465g. 催化剂上载率=(涂覆后催化剂质量-堇青石载体质量)/堇青石载体质量*100%,按照上述计算公式计算得到催化剂涂层的上载率为70%。 The catalyst-carrying rate = (mass of catalyst after coating - cordierite carrier mass) / * 100% cordierite carrier mass, calculated according to the above formula catalyst coating on the carrier was 70%.

[0032] (6)将焙烧后的催化剂在超声清洗仪中超声30 min,110°C下干燥lh后称重。 [0032] (6) The catalyst was calcined ultrasound by the ultrasonic cleaner for 30 min after drying weighed lh at 110 ° C. 催化剂脱落率率=(超声后催化剂质量-超声前催化剂质量)/超声前催化剂质量*100%,按此计算公式得到催化剂涂层的脱落率为〇• 〇8%。 The catalyst falling rate ratio = (mass of catalyst after sonication - mass of catalyst prior to irradiation) / mass of catalyst * 100% prior to irradiation, this calculation formula was obtained off the catalyst coating • square 〇8%.

[0033] 实施例3: 一种低温性能好操作温度窗口宽的柴油车用稀土基SCR催化剂的制备方法,具体合成步骤如下: (1)浆液配制:称量稀土基粉体48g,糯米胶28 g加入到120mL去离子水中。 [0033] Example 3: A cryogenic operating temperature window of good performance diesel vehicle width preparing a rare earth-based SCR catalyst, the specific synthetic steps as follows: (1) a slurry preparation: rare earth-based powder weighing 48g, glutinous rice glue 28 g was added to 120mL of deionized water. 对于稀土基粉体,含有的铈锡复合氧化物为粉体总质量的13.5%,铜铪复合氧化物为粉体总质量的3.1%,氧化铼为粉体总质量的0.35%,其余为钛钨粉,合成方法为传统沉积沉淀法,沉淀剂为氨水。 For the rare earth-based powder, cerium-tin composite oxide containing 13.5% of the total mass of the powder, copper-hafnium composite oxide 3.1% of the total mass of powder, rhenium oxide was 0.35% of the total mass of the powder, the remainder being titanium tungsten powder, conventional synthetic methods for the deposition-precipitation method, a precipitation agent is ammonia.

[0034] (2)浆液球磨:浆液经行星式球磨机研磨,转速400转/分,运行时间10 min,最终浆液粒度D5Q为586 nm。 [0034] (2) milling the slurry: The slurry by a planetary ball mill, the rotational speed of 400 rev / min, run time 10 min, final slurry particle size D5Q of 586 nm.

[0035] (3)增加微晶纤维素:在步骤(2)中球磨后的浆液中加入〇.279g微晶纤维素,并搅拌反应lh。 [0035] (3) Microcrystalline cellulose increases: the slurry in step (2) was added after milling 〇.279g microcrystalline cellulose, and the reaction stirred for lh.

[0036] (4)涂层涂覆:将质量为1.995 g的堇青石载体浸入步骤(3)所得的涂层浆液中,浸入高度控制到0• 3-0•5 cm,然后使用真空装置迅速提拉,之后用气枪吹去孔道内多余液体, 60°C下干燥1 h。 [0036] (4) coating is applied: the mass of 1.995 g of the cordierite carrier was immersed in step (3) coating the resulting slurry, was immersed in a highly controlled to 0 • 3-0 • 5 cm, then rapidly vacuum apparatus pulling, after blow off excess liquid within the bore with an air gun, dried at 60 ° C 1 h.

[0037] (5)重复上述涂覆操作3次,重复涂覆后催化剂的干燥温度为10(rc,之后在50(rc 下焙烧4 h,取出称量整体式催化剂的质量为3.350g。催化剂上载率=(涂覆后催化剂质量-堇青石载体质量)/堇青石载体质量*1〇〇%,按照上述计算公式计算得到催化剂涂层的上载率为68%。 [0037] (5) the above-described coating operation was repeated three times, after repeated drying temperature of the coated catalyst 10 (rc, after 50 (rc calcined at 4 h, taken Weigh monolithic catalyst is 3.350g. The catalyst upload rate = (mass of catalyst after coating - cordierite carrier mass) / * 1〇〇 cordierite carrier mass%, calculated according to the above catalyst coating formula upload 68%.

[0038] (6)将焙烧后的催化剂在超声清洗仪中超声3〇min,11(TC下干燥lh后称重。催化剂脱落率率=(超声后催化剂质量-超声前催化剂质量)/超声前催化剂质量*100%,按此计算公式得到催化剂涂层的脱落率为〇• 〇5%。 [0038] (6) The catalyst was calcined in the ultrasonic cleaning ultrasonic instrument 3〇min, dried weighed 11 lh (TC catalyst falling rate ratio = (mass of catalyst after sonication - mass of catalyst prior to irradiation) / ultrasound before * 100% by mass of the catalyst, this calculation formula was obtained off the catalyst coating • square 〇5%.

[0039] 对比例1: 将市场在售的传统VW-Ti型SCR催化剂进行解剖,取载体规格与实施例中载体规格相同的催化剂。 [0039] Comparative Example 1: The traditional markets dissected VW-Ti type sold SCR catalyst, the carrier takes the same specifications in Example Catalyst carrier specifications.

[0040] 对比例2 将市场在售的进口含稀土元素Ce的非钒基SCR催化剂进行解剖,取载体规格与实施例中载体规格相同的催化剂。 [0040] Non-vanadium-based SCR catalysts Comparative Example 2 containing the market in the sale of Ce inlet were dissected, the carrier taking the same specifications and the specifications of the catalyst carrier embodiment embodiment.

[0041]将以上实施例与对比例中的催化剂进行SCR脱硝性能测试:反应气体组成为(体积比):500 ppm N0,500 ppm NH;b,8% 〇2,Ar为载气,空速50 000 h_1。 [0041] The above embodiments and the comparative catalyst for SCR denitration performance test: Composition of reaction gas (volume ratio): 500 ppm N0,500 ppm NH; b, 8% 〇2, Ar as a carrier gas, a space velocity 50 000 h_1. 气体检测系统为配有气体池的傅里叶变换红外分析仪。 Gas detection system with a gas cell Fourier transform infrared analyzer. ' ^ '^

[0042] 活性测试结果见附图1。 [0042] Activity Test results See Fig. 1.

[0043]从上述测试结果可知,本发明所制备的柴油车用稀土基SCR催化剂在150。 [0043] From the above test results, diesel vehicles of the present invention prepared with a rare earth-based SCR catalyst 150. (:时N(k 的转化率达7〇%以上,l8〇°C时NOx的转化率大于90%,2〇〇-500°C范围内NOx的转化率为100%, 性能优于市场在售的SCR催化剂。 (: When N (conversion rate k 7〇% or more, l8〇 ° C when the conversion rate of NOx is greater than 90%, within the range of-500 ° C 2〇〇 NOx conversion was 100%, the performance is better than the market the sale of SCR catalyst.

[0044] 实施例4 催化剂性能检测试验:对实施例1合成的催化剂进行耐硫性试验、不同空速试验和水热老化试验。 [0044] Example 4 Catalyst Performance Testing Test: The catalyst synthesized in Example 1 is sulfur tolerance test, different test airspeed and hydrothermal aging test.

[0045] 试验结果见附图2、附图3和附图4。 [0045] The test results are shown in Figure 2, Figures 3 and 4 drawings.

[0046]附图2是本发明中实施例1在高硫环境下的NOx转化性能曲线。 [0046] Example 1 Figure 2 is a high sulfur environments in the NOx conversion performance curve of the present invention. 从图中可以看出,本发明的催化剂经过200 ppm S〇2,375°C下老化100 h性能基本没有变化。 As can be seen from the figure, the catalyst of the present invention at 200 ppm after aging 100 h S〇2,375 ° C substantially no change in properties. 众所周知,国V标准柴油中硫含量仅为10 ppm,说明本催化剂具有很好的耐硫性能。 It is well known standard State V diesel sulfur content of only 10 ppm, the catalyst of the present description has good resistance to sulfur poisoning.

[0047] 附图3是本发明中实施例1在不同空速下的NOx转化性能曲线。 [0047] Figure 3 is different from Example 1 at space velocities of NOx conversion performance curve of the present invention. 从图中可以看出,本发明的催化剂脱硝性能随空速的增加有所降低,但是降低并不很明显,当空速达到100 000 h_1时,150 °C时N(k转化率仍保持在65%以上,180°C时Mk转化率大于80%,200-500°C时NOx转化率大于95%,说明本发明的稀土基催化剂具有很好的抗高空速性能。 As can be seen from the figure, the denitration performance of the catalyst of the present invention increases as airspeed decreased, but the decrease is not apparent, when the airspeed 100 000 h_1 time when 150 ° C N (k conversion rate remained at 65 % or more, 180 ° C Mk when the conversion is greater than 80%, when 200-500 ° C NOx conversion was greater than 95%, described rare earth-based catalyst of the invention has good resistance to high speed performance.

[0048] 附图4是本发明中实施例1在不同水热老化条件下的NOz转化性能曲线。 [0048] Figure 4 is different from Example 1 in the hydrothermal aging conditions NOz conversion performance curve of the present invention. 测试气体组成为(体积比):500 ppm N0,500 ppm NH3,8% 02,10% H20,Ar为载气,空速50 000 h_1。 The test gas composition (volume ratio): 500 ppm N0,500 ppm NH3,8% 02,10% H20, Ar as a carrier gas, space velocity 50 000 h_1. 气体检测系统为配有气体池的傅里叶变换红外分析仪。 Gas detection system with a gas cell Fourier transform infrared analyzer. 本催化剂按照传统VW-Ti型SCR催化剂的老化条件550°C 75h和600°C 50h进行老化后,性能下降并不明显,150°C时NOx转化率仍保持在70%以上,180 °C时NOx转化率大于75%,200-500°C时NOx转化率大于90%,说明本催化剂具有很好的抗水热老化性能。 After this aging the catalyst according to a conventional aging conditions VW-Ti-type SCR catalyst 550 ° C 75h and 600 ° C 50h, no significant performance degradation, when 150 ° C NOx conversion rate remained at over 70%, 180 ° C NOx conversion rate greater than 75%, when 200-500 ° C NOx conversion is greater than 90%, indicating that this catalyst has good resistance to hydrothermal aging properties.

[0049] 从上述检测结果可以看出,本发明的稀土基催化剂具有低温性能好,操作温度窗口宽,抗硫、抗高空速和抗水热性能优越等特点。 [0049] As can be seen from the above test results, the rare earth-based catalyst of the present invention have good low temperature performance, wide operating temperature window, anti-sulfur, anti-high speed and excellent anti-hot water performance characteristics. 可以满足日益严格的尾气排放法规要求, 也可以解决我国镧铈大量积压等问题,对开拓新型低成本、环境友好的NH3-SCR催化剂有重要的科学意义和应用价值。 To meet increasingly stringent emissions regulations, can also solve the large backlog of lanthanum, cerium and other issues, to develop new low-cost, environmentally friendly NH3-SCR catalysts have important scientific significance and application value.

Claims (6)

1. 一种柴油车用稀土基SCR催化剂,其特征是:以堇青石蜂窝陶瓷为载体涂覆涂层浆液,涂层浆液主要由稀土基粉体、粘结剂、添加剂和水组成;其中稀土基粉体的成分包括四种活性组分:第一活性组分为铈铌复合氧化物、铈锡复合氧化物、铈钇复合氧化物和铈镧复合氧化物中的一种或几种,第二活性组分为锰钐复合氧化物、锆铪复合氧化物、锌铒复合氧化物、铁铜复合氧化物、铜铪复合氧化物、锆铝复合氧化物中的一种或几种,第三活性组分为氧化铼,第四活性组分为钛钨粉。 A rare earth-based SCR using diesel catalysts, characterized in that: the cordierite honeycomb ceramic support coated with the slurry coating, slurry coating is mainly composed of rare earth-based powder, a binder, additives and water; wherein the rare earth powder component group includes four active ingredients: a first active component is one or more niobium composite oxide of cerium, cerium-tin composite oxide, a composite oxide of cerium, yttrium and lanthanum composite oxide of cerium, of two active components samarium manganese composite oxide, a composite oxide of zirconium, hafnium, erbium complex of zinc oxide, iron-copper composite oxide, a composite oxide of copper, hafnium, zirconium aluminum complex oxide is one or more, third active component rhenium oxide, a fourth active component is titanium tungsten powder.
2. 根据权利要求1所述的柴油车用稀土基SCR催化剂,其特征是:在所述的稀土基粉体中第一活性组分的质量占稀土基粉体总质量的5-18%,第二活性组分的质量占稀土基粉体总质量的1.5-10%,第三活性组分的质量为稀土基粉体总质量的0.1-5%,第四活性组分的质量为稀土基粉体总质量的67-93.4%。 The diesel vehicles according to claim 1 with a rare earth-based SCR catalyst, characterized in that: in said first rare earth-based powder mass active ingredient accounts for 5-18% of the total mass of the rare earth-based powder, quality of the second active ingredient accounts for 1.5 to 10 mass% of the total rare earth-based powder, the active mass of the third component is 0.1 to 5% of the total mass of the rare earth-based powder, the active mass of the fourth component is a rare earth group 67-93.4% of the total mass of the powder.
3. 根据权利要求1所述的柴油车用稀土基SCR催化剂,其特征是:所述涂层浆液中粘结剂为糯米胶。 The diesel vehicles according to claim 1 with a rare earth-based SCR catalyst, characterized in that: the binder of the coating slurry glutinous adhesive.
4. 根据权利要求1所述的柴油车用稀土基SCR催化剂,其特征是:所述涂层浆液中添加剂为微晶纤维素,且其质量为稀土基粉体总质量的〇. 01% - 5%。 The diesel vehicles according to claim 1 with a rare earth-based SCR catalyst, characterized in that: the coating slurry additive is microcrystalline cellulose, and the mass of the total mass of the rare earth-based powder square 01% -. 5%.
5.—种根据权利要求1〜4所述的柴油车用稀土基SCR催化剂的制备方法,其特征是:包括如下合成步骤: (1) 浆液配制:将稀土基粉体与粘结剂按质量比例为0.5-7.5:1加入到120mL去离子水中; (2) 衆液球磨:将步骤⑴所得衆液经彳丁星式球磨机研磨,转速4〇〇转/分,运彳了时间5- 60 min,研磨后浆液粒度①50)控制在loo-iooo nm范围内; (3) 增加添加剂:在球磨后的浆液中加入微晶纤维素,并搅拌反应nh; 、(4)涂层涂覆:将称量质量后的堇青石载体浸入步骤(3)所得的涂层浆液中,浸入高度控制到0.3-0.5 cm,然后使用真空装置迅速提拉,之后用气枪吹去孔道内多余液体,㈤。 5.- The kinds of diesel vehicles according to claim 1 ~ 4 The preparation method of a rare earth-based SCR catalyst, which is characterized in: comprising the following synthesis steps: (1) a slurry preparation: rare earth-based powder with a binder by mass ratio of 0.5-7.5: 1 was added to 120mL of deionized water; (2) all liquid milling: the step by the left foot ⑴ butoxy all planetary ball mill resulting solution 4〇〇 speed rev / min, the run time left foot 5-60 min, the slurry after grinding a particle size ① 50) is controlled within the range of loo-iooo nm; (3) increasing additives: microcrystalline cellulose was added to the slurry after the ball mill, and the reaction was stirred nh;, (4) coating is applied: the cordierite carrier mass weighed after immersing step (3) coating the resulting slurry, was immersed in a highly controlled to 0.3-0.5 cm, then rapidly pulling a vacuum apparatus, after the blow off excess liquid within the bore, (v) using an air gun. C下千燥1 h; (5)重复上述涂覆操作直至催化剂涂层上载量占堇青石载体质量的5〇_8〇%,重复涂覆后催化剂的干燥温度为100°C,之后在450-65〇°C下焙烧4h即可制得所需催化剂。 C under dry in 1 h; (5) the coating operation is repeated until the catalyst on said washcoat loading amount 5〇_8〇% by mass of the cordierite carrier, the drying temperature after the coating of the catalyst was repeated 100 ° C, after 450 4h calcination to obtain the desired catalyst -65〇 ° C.
6.根据权利要求5所述的柴油车用稀土基SCR催化剂的制备方法,其特征是:涂层的脱落质量占涂层总质量的0.5%及以下。 The diesel vehicles according to claim 5 by preparing a rare earth-based SCR catalyst, characterized in that: shedding quality of the coating of 0.5% of the total mass of the coating and below.
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