WO2014134855A1 - 一种用于柴油车尾气脱硝的低温scr催化剂及其制备方法 - Google Patents

一种用于柴油车尾气脱硝的低温scr催化剂及其制备方法 Download PDF

Info

Publication number
WO2014134855A1
WO2014134855A1 PCT/CN2013/074063 CN2013074063W WO2014134855A1 WO 2014134855 A1 WO2014134855 A1 WO 2014134855A1 CN 2013074063 W CN2013074063 W CN 2013074063W WO 2014134855 A1 WO2014134855 A1 WO 2014134855A1
Authority
WO
WIPO (PCT)
Prior art keywords
molecular sieve
scr catalyst
catalyst
low
vehicle exhaust
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/CN2013/074063
Other languages
English (en)
French (fr)
Inventor
刘志昆
李云
林涛
陈耀强
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SICHUAN ZHONGZI EXHAUST PURGE CO Ltd
Original Assignee
SICHUAN ZHONGZI EXHAUST PURGE CO Ltd
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
Application filed by SICHUAN ZHONGZI EXHAUST PURGE CO Ltd filed Critical SICHUAN ZHONGZI EXHAUST PURGE CO Ltd
Priority to US14/771,797 priority Critical patent/US10179328B2/en
Priority to EP13876929.4A priority patent/EP2965812B1/en
Publication of WO2014134855A1 publication Critical patent/WO2014134855A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
    • B01J29/14—Iron group metals or copper
    • B01J29/146—Y-type faujasite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9404—Removing only nitrogen compounds
    • B01D53/9409—Nitrogen oxides
    • B01D53/9413—Processes characterised by a specific catalyst
    • B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
    • B01J29/042—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing iron group metals, noble metals or copper
    • B01J29/044—Iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
    • B01J29/072—Iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
    • B01J29/106—Y-type faujasite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • B01J29/7615—Zeolite Beta
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0213—Preparation of the impregnating solution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20738—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20761—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/50—Zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/50—Zeolites
    • B01D2255/502—Beta zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/50—Zeolites
    • B01D2255/504—ZSM 5 zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional [3D] monoliths
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies

Definitions

  • the present invention belongs to the technical field of catalyst preparation, it is particularly the zeolite SCR catalyst preparation technical field, and particularly relates to a method for low temperature conversion of NO x purifying exhaust gas of diesel type zeolite SCR catalyst and its preparation.
  • the vehicle is idling or in a low speed condition exhaust gas temperature mostly below 200 ° C, in which case conventional-type vanadium-titanium-tungsten SCR temperature window of 280 ° C- 400 ° C, at a low temperature can not meet the NO x purification .
  • conventional-type vanadium-titanium-tungsten SCR temperature window of 280 ° C- 400 ° C at a low temperature can not meet the NO x purification .
  • the long-term use of precious metals in large quantities, especially the use of metal vanadium not only has high production costs, pollution to the environment, but also serious damage to the human body.
  • the invention discloses a low temperature for denitration of diesel vehicle exhaust gas according to the deficiencies of the prior art.
  • the first problem to be solved by the present invention is to provide a catalyst composition which does not use precious metals or/and metal vanadium, but uses metallic copper and iron as composite active components and is harmless to the human body;
  • One problem is to provide a new method for preparing a composite active component molecular sieve type SCR catalyst, which not only meets the requirements of low temperature and high conversion but also has good durability and sulfur resistance.
  • Low-temperature SCR catalyst for denitration of diesel vehicle exhaust gas is realized by the following technical solutions: Low-temperature SCR catalyst uses a molecular sieve as a carrier and an SCR catalyst with copper and iron metal elements as active components.
  • the copper is calculated by Cu 2+ to account for 2 to 4% of the total mass of the molecular sieve, and the iron is calculated as Fe 3+ to account for 3 to 5% of the total mass of the molecular sieve.
  • copper is 3% of the total mass of the molecular sieve calculated as Cu 2+ and iron is 4% of the total mass of the molecular sieve calculated as Fe 3+ .
  • the above carrier is selected from molecular sieves having a spatial dendritic pore structure. Such as selected from ZSM-5 or Y molecular sieves.
  • the preparation method of the low temperature SCR catalyst of the invention comprises the following steps:
  • 1 molecular sieve pretreatment accurately weigh the molecular sieve and heat it in an oven at 90 °C for 4 hours, down to room temperature;
  • the first equal volume impregnation Detecting the specific pore volume of the material after drying, adding 1 molecular sieve powder to the reaction vessel, and dissolving the iron salt and the soluble copper salt solid by Cu 2+ and Fe 3+ respectively: Cu 2+ accounts for 1 ⁇ 2% of the total mass of the molecular sieve, and Fe 3+ accounts for 1.5 ⁇ 2.5% of the total mass of the molecular sieve, with Cu 2+ and Fe 3+ Total amount: Cu 2+ and Fe 3+ account for 2.5 ⁇ 4.5% of the total molecular sieve to form an aqueous solution.
  • the total volume of the solution the mass of the molecular sieve X is the pore volume.
  • the solution is slowly added in the form of a spray, stirring constantly, spraying Stirring was continued for 1 hour after completion; then stirred at 60 ° C for 1 hour, warmed to 80 ° C, and continuously stirred to a fine powder;
  • Drying and removing water Take out the powder in 2, put it into a stainless steel plate, and dry it at 120 ° C for 2 hours in a ventilated oven to remove the surface moisture and pass through a 40 mesh sieve;
  • Pulp coating The powder obtained by adding 5 is added to a binder, prepared into a slurry, coated on a carrier, and calcined to obtain a catalyst.
  • the active component of the present invention may be subjected to an equal volume impregnation method, one, two or more times, preferably two equal volume impregnations.
  • an equal volume impregnation method one, two or more times, preferably two equal volume impregnations.
  • the present invention dissolves the iron salt and the soluble copper salt, preferably their respective nitrates.
  • the invention adopts zeolite molecular sieve as a raw material, and the active component enters the molecular sieve skeleton through various loading means, and is dried, calcined and the like to form a special catalyst coating, coated on a ceramic or metal substrate to form a monolithic catalyst, through a special active ingredient, can significantly reduce the ignition temperature of the NO x to 150 ° C, and has a certain durability for practical significance denitration urban conditions cool-running diesel exhaust.
  • the raw material of the technology of the present invention is a molecular sieve having a spatial dendritic channel structure, and the ZSM-5, Y and the like are selected, the active component is loaded into the pores of the zeolite material, and the active component is uniformly dispersed to the carrier by drying, calcining and the like. In the surface pores. Thereby forming a catalyst coating with higher stability and selectivity.
  • the coating material has been tested, including XRD, BET method, particle size, surface acidity, NH 3 adsorption, etc., which proves that the material has a high specific surface area and pore size at the use temperature, excellent surface acidity and NH 3 absorption/desorption. , suitable for the requirements of NO reduction reaction.
  • the coating has good catalytic activity. After hydrothermal aging and sulfur resistance test, the catalyst still maintains high low temperature activity, which is more suitable for the diesel vehicle market in China.
  • the present invention does not use precious metals or/and metal vanadium, but uses copper and iron-bismuth metal as composite active components to reduce the cost, and is harmless to the human body and environmentally friendly.
  • the preparation method of the catalyst of the invention is simple and convenient, and the raw material requirement is not high, and a plurality of small volume equal volume impregnation methods are adopted, and the active ion dispersion is more uniform and the utilization ratio is improved, thereby improving the low temperature. Catalytic activity and durability.
  • FIG. 1 is an SCR catalyst of the present invention, NO x conversion performance curves in a high sulfur environment
  • FIG. 2 is an SCR catalyst of the present invention, NO x conversion performance curves at different space velocities
  • Figure 3 is an SCR catalyst of the present invention, different NO x conversion performance curve hydrothermal aging conditions
  • Figure 4 is a NOx emission of the SCR catalytic converter of the present invention before and after the steady state test of the engine gantry Value (g/kwh).
  • Molecular sieve pretreatment The molecular sieve was accurately weighed and heated in an oven at 90 °C for 4 hours to remove impurities such as moisture adsorbed on the surface and lowered to room temperature. This example uses a BEA or Y type molecular sieve.
  • the first equal volume impregnation Detecting the specific pore volume of the material after drying, adding 1 molecular sieve powder to the reaction vessel, and dissolving the iron salt and the soluble copper salt solid by Cu 2+ and Fe 3+ respectively: Cu 2+ accounting for 1 to 2% of the total mass of the molecular sieve, 1.5 ⁇ 2.5% of the total mass of Fe 3+ molecular sieve accounted for, the total amount of Fe 3+ and Cu 2+ total: total Cu 2+ and Fe 3+ molecular sieve accounted 2.5 ⁇
  • the ratio of 4.5% is determined into an aqueous solution.
  • the total volume of the solution the mass of the molecular sieve.
  • the solution is slowly added in the form of a spray. Stirring is continued. Stirring is continued for 1 hour after spraying. Then, the mixture is stirred at 60 ° C for 1 hour. Stir to a fine powder at 80 ° C;
  • Drying and removing water Take out the powder in 2, put it into a stainless steel plate, and dry it at 120 ° C for 2 hours in a ventilated oven to remove the surface moisture and pass through a 40 mesh sieve;
  • Pulp coating The powder is made into a slurry having a solid content of 40% to 42%. The slurry is coated on a cordierite ceramic carrier, dried in an electric blast drying oven, and placed in a box-type electric resistance furnace, and calcined at room temperature of 300 ° C (lhr) ⁇ 550 ° C (2 hr). A low temperature SCR catalyst is produced.
  • the powder was taken out, placed in a stainless steel pan, and dried in a ventilated oven at 120 ° C for 2 hours to remove surface moisture and passed through a 40 mesh sieve.
  • the obtained powder was added to the reaction vessel, and an equal amount of the solution was again added for spraying and drying.
  • the obtained powder was calcined at 550 ° C for 2 hours to obtain a dark red powder; a binder was added to the dark red powder to prepare a slurry, which was coated in a cell size of 400 cells/in 2 and a volume of 38.4 ml of cordierite ceramic honeycomb carrier.
  • dry roasting that is, a low temperature SCR catalyst.
  • a conventional V-Ti-W type SCR catalyst commercially available on the market was dissected, and a catalyst having the same carrier specifications as in the carrier of Example 1 was obtained.
  • the catalysts in the above examples and comparative examples were subjected to an activity evaluation test.
  • the test conditions are as follows: Gas volume composition: Nitric oxide: 500 ppm, ammonia: 500 ppm, carbon dioxide: 5%, water vapor: 4.5%, oxygen: 14%, nitrogen: equilibrium gas; space velocity: ⁇ OOOh ⁇ o
  • the three catalysts prepared have a good NOx conversion temperature and are suitable for the purification of diesel exhaust gas.
  • Example 2 In comparison with the comparative examples, Example 2, Example 3, and Example 4 all have a lower light-off temperature and a larger transition temperature window for NOx. It is shown that the low temperature SCR catalyst of the present invention has better catalytic performance than the conventional V-Ti-W type SCR catalyst.
  • Example 3 had a lower light-off temperature and a maximum conversion temperature window for NOx, indicating that the catalyst of Example 3 had the highest catalytic performance.
  • FIG. 1 is a graph showing the NOx conversion performance of an SCR catalyst in a high sulfur environment in the present invention. It can be seen that the performance of this catalyst has not decreased after 200 PP m SO2, 200 ° C 29 hr aging (equivalent to 25,000 km in 670 ppm fuel oil); after 600 PP m S02, 200 ° C After 29 hr aging (equivalent to 25,000 km of fuel with a sulphur content of 2000 ppm), it still has very effective performance. Now the diesel fuel has a sulfur content of 350 PP m. Therefore, the catalyst has good sulfur resistance. The results are shown in Table 2 below T 50 /°CT 90 /°C Fresh 157 196-565
  • FIG 3 is an SCR catalyst of the present invention, NO x conversion performance curves at different hydrothermal aging conditions. It can be seen that the performance of the catalyst is not significantly deteriorated according to the aging conditions of the conventional V-Ti-W type SCR catalyst at 550 ° C for 75 hr and 600 ° C for 50 hr; and according to the more severe 670 ° C 64 hr high temperature After aging, it still has very effective performance. Therefore, the catalyst has good resistance to hydrothermal aging. The results are shown in Table 4 below Fresh 157 196-565
  • Figure 4 is a graph showing the NOx emission values of the SCR catalyst of the present invention before and after the steady state test of the engine gantry. It can be seen from the figure that after the addition of the SCR catalytic converter of the present invention, the average NOj emission value is 2.8 g/kwh, which meets the national IV standard. (Engine model: WP7, 4.2L, National IV standard is 3.5g/kwh. Bench test is carried out using the test procedure specified by China Standard Country IV.) Has better catalytic performance.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Biomedical Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Analytical Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Catalysts (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
  • Exhaust Gas After Treatment (AREA)

Abstract

提供一种用于柴油车尾气脱硝的低温SCR催化剂及其制备方法。所述催化剂以分子筛作为载体，以铜、铁金属元素作为活性组分。所述催化剂制备方法包括：分子筛预处理、多次等体积浸渍、浸渍后干燥除水、焙烧，最后制浆涂覆制成。所述催化剂不采用贵金属，而是采用铜、铁贱金属作为活性组分，降低了成本，并对人体无害、对环境友好。所述催化剂制备方法简便易行，对原料要求不高，采用多次少量的等体积浸渍方法，与现有常规制备方法相比，活性离子分散更加均匀，提高了利用率，从而达到提高低温催化活性及耐久性的目的。

Description

技术领域
本发明属于催化剂制备技术领域， 尤其属于分子筛 SCR催化剂制备技 术领域， 特别涉及一种用于低温转化 NOx气体的柴油车尾气净化的分子筛 型 SCR催化剂及其制备。
背景技术
柴油机以其低油耗、 高功率比的特点得到越来越广泛的应用， 但是由 于柴油机缸内的高压高温产生的氮氧化物 NOx带来了严重的环境问题， 加 剧了空气质量的恶化， 我国对安装柴油发动机的道路车辆提高了排放标准， 目前在净化柴油车尾气 NOx方面选择性催化还原 （SCR ) 技术是主流技术， 而应用最多的是尿素 -SCR系统， 其原理是通过在 SCR催化转化器前端喷射 一定比例的尿素溶液， 通过尿素水解或热解产生的氨气作为还原剂在催化 剂表面来选择性还原 NOx， 而其核心部件一 SCR催化转化器的研制有一个很 大的不足， 即在车辆怠速或低速工况下尾气温度大多低于 200°C，在此种情 况下传统钒钛钨型 SCR的温度窗口为 280 °C— 400 °C，不能满足低温下的 NOx 净化。 同时长期、 大量使用贵金属、 特别是使用金属钒不仅生产成本高， 对环境造成污染， 对人体也有十分严重的损害。
由此开发更能适应低温高转化率、 对环境更友好的 SCR催化剂是目前 催化剂行业一直在努力探索的方向。
发明内容 本发明根据现有技术的不足公开了一种用于柴油车尾气脱硝的低温
SCR催化剂及其制备方法。本发明要解决的第一个问题是提供一种不采用贵 金属或 /和金属钒， 而是采用金属铜、 铁作为复合活性组分， 对人体无害的 催化剂组成； 本发明要解决的第二个问题是提供一种新的方法制备复合活 性组分分子筛型 SCR催化剂， 既满足低温高转化的要求又具有较好的耐久、 抗硫性能。
本发明用于柴油车尾气脱硝的低温 SCR催化剂由以下技术方案实现： 低温 SCR催化剂以分子筛作为载体， 以铜、 铁金属元素作为活性组分 的 SCR催化剂。
所述铜以 Cu2+计算占分子筛总质量的 2〜4%， 铁以 Fe3+计算占分子筛 总质量的 3〜5%。
优选铜以 Cu2+计算占分子筛总质量的 3%， 铁以 Fe3+计算占分子筛总质 量的 4%。
上述载体选自具有空间树枝状孔道结构的分子筛。 如选自 ZSM-5或 Y 型分子筛。
本发明低温 SCR催化剂制备方法包括以下步骤：
①分子筛预处理：准确称取分子筛并在 90 °C烘箱中通空气加热 4小时， 降到室温；
②第一次等体积浸渍： 检测①干燥后材料的比孔容， 将①分子筛粉料 加入反应釜， 将可溶解铁盐和可溶解铜盐固体以 Cu2+、 Fe3+分别计： Cu2+占 分子筛总质量的 1〜2%、 Fe3+占分子筛总质量的 1.5〜2.5%， 以 Cu2+和 Fe3+ 总量计： Cu2+和 Fe3+占分子筛总量 2.5〜4.5%的比例配成水溶液， 溶液的总 体积 =分子筛的质量 X比孔容， 溶液以喷雾的形式缓慢加入， 不断搅拌， 喷 完后继续搅拌 1小时； 然后在 60°C搅拌 1小时， 升温至 80°C， 持续搅拌至 细粉状；
③干燥除水： 取出②中的粉末， 装入不锈钢盘， 在通风烘箱内 120°C 烘 2小时除去表面水分， 过 40目筛；
④第二次等体积浸渍： 将③所得分子筛加入反应釜， 重复②③浸渍步 骤；
⑤焙烧： 将④所得的粉料于 55CTC煅烧 2小时， 自然降至室温， 得到 暗红色粉末；
⑥制浆涂覆： 将⑤所得粉末加入粘接剂， 制备成浆液， 涂覆于载体上， 干燥焙烧制得催化剂。
本发明活性组分采用等体积浸渍方法， 可以进行一次、 两次或多次， 优选两次等体积浸渍。 实验证明采用多次等体积浸渍使金属铜和金属铁催 化剂成分分布更均匀， 活性更优， 性能更稳定。
本发明可溶解铁盐和可溶解铜盐优选其各自的硝酸盐。
本发明采用沸石分子筛作为原料， 将活性成分通过多种负载手段进入 分子筛骨架， 经过干燥、 焙烧等处理制成特殊的催化剂涂层， 涂覆在陶瓷 或金属基体上形成整体式催化剂，通过特殊的活性组分，可以大幅降低 NOx 的起燃温度到 150°C， 且具有一定的耐久性，对城市工况低温运行的柴油车 尾气脱硝具有现实意义。 本发明技术的原材料为具有空间树枝状孔道结构的分子筛，选用 ZSM- 5、 Y等类型， 将活性组分负载到沸石材料孔道中， 再通过干燥、 焙烧等步 骤使活性组分均匀分散到载体表面孔隙中。 从而形成稳定性和选择性更高 的催化剂涂层。
涂层材料经过检测， 包括 XRD、 B.E.T.法、 粒度、 表面酸性、 NH3吸附 性等的检测， 证明材料具有使用温度下高的比表面积和孔径， 优良的表面 酸性及 NH3吸 /脱附性， 适合 NO 化还原反应的要求。
通过涂层催化活性评价， 涂层具有良好的催化活性， 经过水热老化及 耐硫试验， 催化剂仍然保持较高的低温活性， 更加适合中国城市工况的柴 油车市场需要。
本发明不采用贵金属或 /和金属钒， 而是采用铜、 铁贱金属作为复合活 性组分降低了成本， 并对人体无害、 对环境友好。 本发明的催化剂制备方 法简便易行， 对原料要求不高， 采用多次少量的等体积浸渍方法， 与现有 常规制备方法相比， 活性离子分散更加均匀， 提高了利用率， 从而达到提 高低温催化活性及耐久性的目的。
附图说明
图 1是本发明中 SCR催化剂在高硫环境下的 NOx转化性能曲线； 图 2是本发明中 SCR催化剂在不同空速下的 NOx转化性能曲线； 图 3是本发明中 SCR催化剂在不同水热老化条件下的 NOx转化性能曲 线；
图 4是本发明 SCR催化转化器在发动机台架稳态试验前后的 NOx排放 值 （g/kwh)。
具体实施方式
下面通过实施例对本发明进行进一步的描述， 本实施例只用于对本发 明进行进一步的说明， 但不能理解为对本发明保护范围的限制， 本领域的 技术人员可以根据上述内容作出一些非本质的改进和调整属于本发明保护 的范围。
实施例 1
低温 SCR催化剂制备
①分子筛预处理:准确称取分子筛并在 90 °C烘箱中通空气加热 4小时， 除去表面吸附的水分等杂质， 降到室温。 本例采用 BEA或 Y型分子筛。
②第一次等体积浸渍： 检测①干燥后材料的比孔容， 将①分子筛粉料 加入反应釜， 将可溶解铁盐和可溶解铜盐固体以 Cu2+、 Fe3+分别计： Cu2+占 分子筛总质量的 1〜2%、 Fe3+占分子筛总质量的 1.5〜2.5%， 以 Cu2+和 Fe3+ 总量计： Cu2+和 Fe3+占分子筛总量 2.5〜4.5%的比例配成水溶液， 溶液的总 体积 =分子筛的质量 X比孔容， 溶液以喷雾的形式缓慢加入， 不断搅拌， 喷 完后继续搅拌 1小时； 然后在 60°C搅拌 1小时， 升温至 80°C， 持续搅拌至 细粉状；
③干燥除水： 取出②中的粉末， 装入不锈钢盘， 在通风烘箱内 120°C 烘 2小时除去表面水分， 过 40目筛；
④第二次等体积浸渍： 将③所得分子筛加入反应釜， 重复②③浸渍步 骤； ⑤焙烧： 将④所得的粉料于 550°C煅烧 2小时， 自然降至室温， 得到 暗红色粉末；
⑥制浆涂覆： 将粉料制成固含量为 40%~42%的浆料。 将浆料涂覆在堇 青石陶瓷载体上， 放入电热鼓风干燥箱干燥后， 再放入箱式电阻炉内， 按 照从室温 300°C ( lhr) ^550 °C (2hr) 焙烧后即制得低温 SCR催化剂。
实施例 2
Cu2+和 Fe3+质量比为 2:5的低温 SCR催化剂制备
准确称取 200g分子筛并在 90°C烘箱中通空气加热 4小时， 除去表面 吸附的水分等杂质， 降到室温。 检测其比孔容， 并将其加入反应釜。 将硝 酸铜 [Cu(N03)2.3H20]7.56g，硝酸铁 [Fe(NO3)3.9H2O]36.07g溶于 103.85ml去离 子水中， 搅拌至溶解。 将溶液缓慢加入分子筛中， 不断搅拌， 溶液加完后 继续搅拌 1小时。取出粉末， 装入不锈钢盘， 在通风烘箱内 120°C烘 2小时 除去表面水分， 过 40目筛。 将所得粉末加入反应釜， 再次加入等量的溶液 进行喷雾并干燥。将所得的粉料于 550°C煅烧 2小时， 得到暗红色粉末； 暗 红色粉末中加入粘接剂，制备成浆液，涂覆在孔目数 400cell/in2，体积 38.4ml 堇青石陶瓷蜂窝载体上， 干燥焙烧， 即得低温 SCR催化剂。
实施例 3
Cu2+和 Fe3+质量比为 3:4的低温 SCR催化剂制备
准确称取 200g分子筛并在 90°C烘箱中通空气加热 4小时， 除去表面 吸附的水分等杂质， 降到室温。 检测其比孔容， 并将其加入反应釜。 将硝 酸铜 [Cu(N03)2.3H20]11.34g， 硝酸铁 [Fe(N03)3.9H20]28.86g溶于 105.89ml去 离子水中， 搅拌至溶解。 其他与实施例 2同样操作。
实施例 4
Cu2+和 Fe3+质量比为 4:3的低温 SCR催化剂制备
准确称取 200g分子筛并在 90°C烘箱中通空气加热 4小时， 除去表面 吸附的水分等杂质， 降到室温。 检测其比孔容， 并将其加入反应釜。 将硝 酸铜 [Cu(N03)2.3H20]15.13g， 硝酸铁 [Fe(N03)3.9H20]21.64g溶于 107.93ml去 离子水中， 搅拌至溶解。 其他与实施例 2同样操作。
比较例 1
将市场上在售的传统 V-Ti-W型 SCR催化剂进行解剖， 取载体规格与实 施例 1中载体规格相同的催化剂。
检测结果
将以上实施例与比较例中的催化剂进行活性评价试验。 试验条件如下 气体体积组成： 一氧化氮： 500ppm， 氨气： 500ppm， 二氧化碳： 5%， 水蒸气： 4.5 % , 氧气： 14%, 氮气： 平衡气； 空速： ^OOOh^ o
活性评价结果如下表 1
NOx
T50/°C W°C
实施例 2 165 210-568
实施例 3 157 196-565
实施例 4 150 192-530 比较例 1 214 255-452 从上表 1可以得知：
( 1 ) 制备的 3种催化剂具有很好的 NOx转化温度， 适用目前柴油车 尾气净化需要。
( 2 ) 与比较例对比， 实施例 2， 实施例 3， 实施例 4均具有对 NOx更 低的起燃温度和更大的转化温度窗口。 说明本发明的低温 SCR催化剂比传 统 V-Ti-W型 SCR催化剂具有更好的催化性能。
( 3 ) 在实施例 2， 实施例 3， 实施例 4中， 实施例 3对 NOx的起燃温 度较低和转化温度窗口最大， 说明实施例 3催化剂的催化性能最高。
实施例 5
催化剂性能检测实验
用实施例 3制备的催化剂进行相关检测实验。 通过耐硫性实验、 不同 空速实验、 水热老化实验以及台架试验的结果， 可看出本发明制备的催化 剂对 NOx具有优良的低温起燃活性以及高硫、 高空速、 高温度下的稳定性。
图 1是本发明中 SCR催化剂在高硫环境下的 NOx转化性能曲线。 图中 可以看出， 本催化剂经过 200PPm SO2， 200°C29hr老化 （相当于在含硫量 670ppm的燃油中运行 25000公里）后，性能基本没有下降；在经过 600PPm S02, 200°C 29hr老化（相当于在含硫量 2000ppm的燃油中运行 25000公里） 后， 仍具有非常有效的性能。 而现在柴油车用油的硫含量为 350PPm， 所以 说， 本催化剂具有很好的耐硫性能。 结果如下表 2
Figure imgf000010_0001
T50/°C T90/°C 新鲜 157 196-565
200ppm S02, 200°C 29hr老化后 158 198-558
600ppm S02, 200°C 29hr老化后 176 230-492 图 2是本发明中 SCR催化剂在不同空速下的 NOx转化性能曲线。 图中 可以看出， 本催化剂的 NOx转化性能随空速的升高而有所降低， 但降低的 并不明显， 在 110,000 1空速条件下， 仍具有非常有效的性能。 所以说， 本催化剂具有很好的空速性能。 结果如下表 3
Figure imgf000011_0001
图 3是本发明中 SCR催化剂在不同水热老化条件下的 NOx转化性能曲 线。 图中可以看出， 本催化剂按照传统 V-Ti-W型 SCR催化剂的老化条件 550°C 75hr和 600°C 50hr进行老化后， 性能下降的并不明显； 而按照更加恶 劣的 670°C64hr高温老化后， 仍具有非常有效的性能。 所以说， 本催化剂 具有很好的抗水热老化性能。 结果如下表 4
Figure imgf000011_0002
新鲜 157 196-565
550°C75hrs老化后 168 216-563
600°C50hrs老化后 171 239-574
670°C 64hrs老化后 172 244->555
图 4是本发明 SCR催化剂在发动机台架稳态试验前后的 NOx排放值。 图中可以看出， 加装本发明 SCR催化转化器后， NOj 平均排放值为 2.8 g/kwh , 达到国 IV标准。 （发动机型号： WP7， 4.2L, 国 IV标准为 3.5g/kwh。 采用中国标准国 IV规定的测试规程， 进行台架试验。） 具有更好的催化性能。

Claims

权 利 要 求 书
1、 一种用于柴油车尾气脱硝的低温 SCR催化剂， 其特征是： 以分子筛作为 载体， 以铜、 铁金属元素作为复合活性组分的 SCR催化剂。
2、 根据权利要求 1所述的用于柴油车尾气脱硝的低温 SCR催化剂， 其特征 是：所述铜以 Cu2+计算占分子筛总质量的 2〜4%， 铁以 Fe3+计算占分子筛总 质量的 3〜5%。
3、 根据权利要求 2所述的用于柴油车尾气脱硝的低温 SCR催化剂， 其特征 是： 所述铜以 Cu2+计算占分子筛总质量的 3%， 铁以 Fe3+计算占分子筛总质 量的 4%。
4、根据权利要求 1至 3任一项所述的用于柴油车尾气脱硝的低温 SCR催化 剂， 其特征是： 所述载体选自具有空间树枝状孔道结构的分子筛。
5、根据权利要求 4所述的低温 SCR催化剂，其特征是：所述载体选自 ZSM-5、 或 Y型分子筛。
6、 一种用于柴油车尾气脱硝的低温 SCR催化剂的制备方法， 其特征是包括 以下步骤：
①分子筛预处理：准确称取分子筛，在 90°C烘箱中通空气加热 4小时， 降到室温；
②第一次等体积浸渍： 检测①干燥后材料的比孔容， 将①分子筛粉料 加入反应釜， 将可溶解铁盐和可溶解铜盐固体以 Cu2+、 Fe3+分别计： Cu2+占 分子筛总质量的 1〜2%、 Fe3+占分子筛总质量的 1.5〜2.5%， 以 Cu2+和 Fe3+ 总量计： Cu2+和 Fe3+占分子筛总量 2.5〜4.5%的比例配成水溶液， 溶液的总 体积 =分子筛的质量 X比孔容， 溶液以喷雾的形式缓慢加入， 不断搅拌， 喷 完后继续搅拌 1小时； 然后在 60°C搅拌 1小时， 升温至 80°C， 持续搅拌至 细粉状；
③干燥除水： 取出②中的粉末， 装入不锈钢盘， 在通风烘箱内 120°C 烘 2小时除去表面水分， 过 40目筛；
④第二次等体积浸渍： 将③所得分子筛加入反应釜， 重复②③浸渍步 骤；
⑤焙烧： 将④所得的粉料于 55CTC煅烧 2小时， 自然降至室温， 得到 暗红色粉末；
⑥制浆涂覆： 将⑤所得粉末加入粘接剂， 制备成浆液， 涂覆于载体上， 干燥焙烧制得催化剂。
7、 根据权利要求 6所述的用于柴油车尾气脱硝的低温 SCR催化剂的制备方 法， 其特征是： 所述等体积浸渍进行一次、 两次或多次。
8、根据权利要求 6所述的用于柴油车尾气脱硝的低温 SCR催化剂的制备方 法， 其特征是： 所述可溶解铁盐和可溶解铜盐均为其各自的硝酸盐。
PCT/CN2013/074063 2013-03-05 2013-04-11 一种用于柴油车尾气脱硝的低温scr催化剂及其制备方法 Ceased WO2014134855A1 (zh)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US14/771,797 US10179328B2 (en) 2013-03-05 2013-04-11 Low temperature SCR catalyst for denitrating diesel vehicle exhaust, and preparation method thereof
EP13876929.4A EP2965812B1 (en) 2013-03-05 2013-04-11 Low-temperature scr catalyst for denitrating diesel vehicle exhaust, and preparation method thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201310068345.6A CN103127951B (zh) 2013-03-05 2013-03-05 一种用于柴油车尾气脱硝的低温scr 催化剂及其制备方法
CN201310068345.6 2013-03-05

Publications (1)

Publication Number Publication Date
WO2014134855A1 true WO2014134855A1 (zh) 2014-09-12

Family

ID=48488777

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2013/074063 Ceased WO2014134855A1 (zh) 2013-03-05 2013-04-11 一种用于柴油车尾气脱硝的低温scr催化剂及其制备方法

Country Status (4)

Country Link
US (1) US10179328B2 (zh)
EP (1) EP2965812B1 (zh)
CN (1) CN103127951B (zh)
WO (1) WO2014134855A1 (zh)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113398919A (zh) * 2021-06-08 2021-09-17 安徽元琛环保科技股份有限公司 一种城市污泥制备涂覆式脱硝催化剂的方法
CN113617348A (zh) * 2021-09-13 2021-11-09 中国石油化工股份有限公司 一种分子筛负载TiO2光催化材料及其制备方法和应用
CN114247467A (zh) * 2021-12-31 2022-03-29 武汉智宏思博环保科技有限公司 一种双金属改性的usy型分子筛催化剂及其制备方法
CN115591575A (zh) * 2022-11-01 2023-01-13 兖矿科技有限公司（Cn） 一种脱硝催化剂及其制备方法和应用

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015125496A1 (en) * 2014-02-21 2015-08-27 Toyota Jidosha Kabushiki Kaisha SELECTIVE NOx REDUCTION CATALYST
CN104014364B (zh) * 2014-06-19 2017-02-15 中国石油大学(北京) 一种脱硝铜基分子筛催化剂、制备方法及其用途
CN104607239A (zh) * 2014-12-29 2015-05-13 清华大学苏州汽车研究院（吴江） 铜铁复合基scr催化剂及其制备方法
CN105214720B (zh) * 2015-10-14 2017-11-10 无锡威孚环保催化剂有限公司 用于机动车尾气nox消除的分子筛催化剂的制备方法
CN105413740A (zh) * 2015-11-06 2016-03-23 无锡威孚环保催化剂有限公司 高效Fe-SCR整体式催化剂的制备方法
CN105597810B (zh) * 2015-12-21 2017-10-10 河南东大高温节能材料有限公司 一种高活性中低温scr脱硝催化剂的制备方法
CN106984357B (zh) * 2017-04-17 2019-10-15 中自环保科技股份有限公司 一种用于柴油车尾气净化的scr催化剂及其制备方法
CN107552088B (zh) * 2017-09-20 2020-03-13 大连海事大学 一种复合分子筛脱硝催化剂及其制备方法和应用
CN109289907A (zh) * 2018-09-21 2019-02-01 四川大学 碱土金属改性的铜基分子筛nh3-scr催化剂及其制备方法
CN109174173B (zh) * 2018-09-30 2019-10-15 中自环保科技股份有限公司 一种分子筛scr催化剂制备方法及其制备的催化剂
CN110681412A (zh) * 2019-07-17 2020-01-14 凯龙蓝烽新材料科技有限公司 一种耐高温高活性Cu基SCR催化剂及其制备方法
US12168951B2 (en) 2020-04-21 2024-12-17 Cummins Inc. Systems and methods for selective catalytic reduction and/or ammonia slip catalyst sulfur protection
CN112371166A (zh) * 2020-10-19 2021-02-19 江苏大学 一种二次改性分子筛整体式scr催化剂的制备方法
CN113713852B (zh) * 2021-08-03 2024-05-03 浙江三元龙兴科技股份有限公司 满足柴油车低NOx排放用的催化剂及其生产方法
CN113926385A (zh) * 2021-10-25 2022-01-14 上海洁昊环保股份有限公司 一种尿素催化热解制氨的设备及方法
CN114247465A (zh) * 2021-11-24 2022-03-29 中煤科工集团西安研究院有限公司 一种宽温无钒脱硝催化剂、制备方法及其应用
CN115364892B (zh) * 2022-08-05 2024-03-01 东风商用车有限公司 用于柴油车尾气后处理系统的钒基催化剂及其制备方法
CN117920335B (zh) * 2023-12-19 2026-04-21 福州大学 一种抗so2中毒的低温脱硝催化剂及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101450322A (zh) * 2007-12-05 2009-06-10 中国科学院大连化学物理研究所 一种用于N2O直接分解的Fe/ZSM-5催化剂的制备方法
US20120039759A1 (en) * 2010-08-13 2012-02-16 Ut-Battelle, Llc Zeolite-based scr catalysts and their use in diesel engine emission treatment
WO2012025617A1 (en) * 2010-08-27 2012-03-01 Technical University Of Denmark Mordenite - type zeolite scr catalysts with iron or copper

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3841990A1 (de) * 1988-12-14 1990-06-21 Degussa Verfahren zur reduktion von stickoxiden aus abgasen
US5024981A (en) * 1989-04-20 1991-06-18 Engelhard Corporation Staged metal-promoted zeolite catalysts and method for catalytic reduction of nitrogen oxides using the same
US6248684B1 (en) * 1992-11-19 2001-06-19 Englehard Corporation Zeolite-containing oxidation catalyst and method of use
CN101549290B (zh) * 2009-03-06 2012-07-04 无锡科立泰科技有限公司 复合金属氧化物及低温氨选择性催化还原氮化物催化剂
WO2010121257A1 (en) * 2009-04-17 2010-10-21 Johnson Matthey Public Limited Company Small pore molecular sieve supported copper catalysts durable against lean/rich aging for the reduction of nitrogen oxides
US9516559B2 (en) * 2010-01-20 2016-12-06 Blackberry Limited Methods of performing cell change without receiving description of resources in a target cell
DE102010007626A1 (de) * 2010-02-11 2011-08-11 Süd-Chemie AG, 80333 Kupferhaltiger Zeolith vom KFI-Typ und Verwendung in der SCR-Katalyse
US8987162B2 (en) * 2010-08-13 2015-03-24 Ut-Battelle, Llc Hydrothermally stable, low-temperature NOx reduction NH3-SCR catalyst
KR101177684B1 (ko) * 2011-12-06 2012-08-27 주식회사 이엔드디 ＬＰＧ를 환원제로 사용하는 ＮＯｘ 제거용 ＳＣＲ 촉매
CN102614910B (zh) * 2012-03-16 2014-01-01 北京工业大学 用于氨选择性催化消除NOx的SAPO-34负载Cu-Fe催化剂的制备方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101450322A (zh) * 2007-12-05 2009-06-10 中国科学院大连化学物理研究所 一种用于N2O直接分解的Fe/ZSM-5催化剂的制备方法
US20120039759A1 (en) * 2010-08-13 2012-02-16 Ut-Battelle, Llc Zeolite-based scr catalysts and their use in diesel engine emission treatment
WO2012025617A1 (en) * 2010-08-27 2012-03-01 Technical University Of Denmark Mordenite - type zeolite scr catalysts with iron or copper

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP2965812A4 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113398919A (zh) * 2021-06-08 2021-09-17 安徽元琛环保科技股份有限公司 一种城市污泥制备涂覆式脱硝催化剂的方法
CN113617348A (zh) * 2021-09-13 2021-11-09 中国石油化工股份有限公司 一种分子筛负载TiO2光催化材料及其制备方法和应用
CN113617348B (zh) * 2021-09-13 2023-07-04 中国石油化工股份有限公司 一种分子筛负载TiO2光催化材料及其制备方法和应用
CN114247467A (zh) * 2021-12-31 2022-03-29 武汉智宏思博环保科技有限公司 一种双金属改性的usy型分子筛催化剂及其制备方法
CN115591575A (zh) * 2022-11-01 2023-01-13 兖矿科技有限公司（Cn） 一种脱硝催化剂及其制备方法和应用
CN115591575B (zh) * 2022-11-01 2024-06-07 山东能源集团有限公司 一种脱硝催化剂及其制备方法和应用

Also Published As

Publication number Publication date
CN103127951A (zh) 2013-06-05
US20160023195A1 (en) 2016-01-28
EP2965812A1 (en) 2016-01-13
EP2965812B1 (en) 2021-10-27
US10179328B2 (en) 2019-01-15
CN103127951B (zh) 2015-02-04
EP2965812A4 (en) 2016-11-30

Similar Documents

Publication Publication Date Title
WO2014134855A1 (zh) 一种用于柴油车尾气脱硝的低温scr催化剂及其制备方法
CN102166522B (zh) 一种烟气脱硝催化剂及其制备和应用
CN102941088B (zh) 一种同时去除CO、CH、NOx、PM催化剂及其制备方法
WO2020063360A1 (zh) 一种分子筛scr催化剂制备方法及其制备的催化剂
CN103263912B (zh) 一种柴油车尾气净化催化剂及其制备方法
CN102728383B (zh) 一种高温稳定的整体式汽车尾气净化催化剂的制备方法
CN102188971B (zh) 一种柴油车尾气四效催化剂及其制备方法和应用
CN107282101B (zh) 一种用于柴油车尾气净化的sapo-34分子筛催化剂的原位负载改性方法
CN106582794A (zh) 基于改性分子筛和水滑石衍生氧化物的柴油机用催化剂及制备和应用
CN111167487A (zh) 一种多功能催化剂及其制备方法和应用
CN104174412A (zh) 一种用于汽车尾气净化的三效催化剂及其制备方法
CN107552088B (zh) 一种复合分子筛脱硝催化剂及其制备方法和应用
CN104338545A (zh) 一种应用于柴油机尾气氮氧化物净化的高效scr催化剂
CN103962126A (zh) 一种用于氮氧化合物选择性催化还原的催化剂及制备方法
CN114733563B (zh) 一种Cu-CHA与H-AEI的复合催化剂及其制备方法与应用
CN102000600B (zh) 整体式常温微量氮氧化物净化材料及其制备方法
CN109590017A (zh) 基于复合主催化剂和水滑石衍生氧化物的柴油机用催化剂及其制备方法
CN103611563B (zh) 一种scr催化剂及其制备方法
CN111167508A (zh) 一种用于高温尾气的氨氧化催化剂及其制备方法
CN102000507B (zh) 用于柴油车尾气处理的还原气注入及四效催化净化系统
CN111939917B (zh) 一种具有良好抗硫性能的dpf催化剂及其制备方法
CN102580764A (zh) 一种用于净化氮氧化物的催化剂及其制备方法
CN106268790B (zh) 抗水热老化及耐硫IrPdPt/IrPd催化剂及其制备方法与应用
CN100371072C (zh) 稀燃汽油车尾气排放氮氧化物选择性还原催化剂制备方法
CN108435170A (zh) 一种低温co起燃的氧化型催化剂及其制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13876929

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2013876929

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 14771797

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE