JPS6291246A - Catalyst for reducing nitrogen oxide and its preparation - Google Patents
Catalyst for reducing nitrogen oxide and its preparationInfo
- Publication number
- JPS6291246A JPS6291246A JP60229523A JP22952385A JPS6291246A JP S6291246 A JPS6291246 A JP S6291246A JP 60229523 A JP60229523 A JP 60229523A JP 22952385 A JP22952385 A JP 22952385A JP S6291246 A JPS6291246 A JP S6291246A
- Authority
- JP
- Japan
- Prior art keywords
- amorphous alloy
- catalyst
- surface area
- alloy powder
- specific surface
- 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.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 34
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims description 48
- 238000002360 preparation method Methods 0.000 title description 2
- 239000000843 powder Substances 0.000 claims abstract description 31
- 229910000808 amorphous metal alloy Inorganic materials 0.000 claims abstract description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000002425 crystallisation Methods 0.000 claims abstract description 11
- 230000008025 crystallization Effects 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 10
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 9
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 7
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 7
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 7
- 239000010955 niobium Substances 0.000 claims abstract description 7
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000010936 titanium Substances 0.000 claims abstract description 7
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 6
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000002344 surface layer Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- 230000000694 effects Effects 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000005300 metallic glass Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 241000345998 Calamus manan Species 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910018502 Ni—H Inorganic materials 0.000 description 1
- 229910018559 Ni—Nb Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000005280 amorphization Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical group [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229960001730 nitrous oxide Drugs 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 235000012950 rattan cane Nutrition 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- 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
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)
Landscapes
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】 イ、産業上の利用分野 本発明は窒素酸化物還元用触媒に関する。[Detailed description of the invention] B. Industrial application fields The present invention relates to a catalyst for reducing nitrogen oxides.
口、従来技術
公害防止のため、廃ガス中に含まれる窒素酸化物は、大
気中への排出に先立って窒素に還元し、無害化する必要
がある。そのためには、上記還元反応に適当な触媒の使
用が不可欠であり、従来からこの目的に使用する各種の
触媒が提案されている。還元剤としては、実用上の観点
から主として一酸化炭素を使用する場合が多く、これに
適した触媒としては、例えば白金、パラジウム、ロジウ
ム、ルテニウム等の貴金属や酸化銅（ＣｕＯ１Ｃｕ２０
）等が用いられている。BACKGROUND OF THE INVENTION To prevent pollution, nitrogen oxides contained in waste gas must be reduced to nitrogen and rendered harmless before being discharged into the atmosphere. For this purpose, it is essential to use a suitable catalyst for the above-mentioned reduction reaction, and various catalysts have been proposed for this purpose. Carbon monoxide is often used as the reducing agent from a practical standpoint, and suitable catalysts include noble metals such as platinum, palladium, rhodium, and ruthenium, and copper oxide (CuO1Cu20).
) etc. are used.
上記の貴金属触媒は高価であるので経済上の問題があり
、酸化物触媒では３００℃以下の温度での一酸化窒素（
ＮＯ）の還元反応に於ける窒素（Ｎ２）への転化率が低
下し、また、生成物に酸化二窒素（Ｎ２０）が生ずると
いう問題がある。また、非品質合金を触媒に通用するこ
とは、熱的不安定が懸念され、結晶化を起こす温度領域
での使用が疑問視されていた。The above-mentioned noble metal catalysts are expensive and therefore pose an economic problem, while oxide catalysts have nitrogen monoxide (nitrogen monoxide) at temperatures below 300°C.
There is a problem that the conversion rate of NO) to nitrogen (N2) in the reduction reaction decreases, and dinitrogen oxide (N20) is produced as a product. Furthermore, there are concerns about thermal instability in using non-quality alloys as catalysts, and there have been doubts about their use in temperature ranges where crystallization occurs.
ハ０発明の目的
本発明は、上記のような従来の触媒が有する問題を解消
し、３００℃以下の温度領域でも酸化窒素の還元反応に
高活性、高選択性を示す酸化窒素還元用触媒及びその製
造方法を提供することを目的としている。Object of the Invention The present invention solves the problems of conventional catalysts as described above, and provides a nitrogen oxide reduction catalyst and a nitrogen oxide reduction catalyst that exhibits high activity and selectivity in the nitrogen oxide reduction reaction even in a temperature range of 300°C or lower. The purpose of this invention is to provide a manufacturing method for the same.
二６発明の構成
本発明の第一の発明は、ニッケルを３５〜７０原子％、
イツトリウム、チタン、ジルコニウム、ハフニウム、ニ
オブ及びランタンの１種又は２種以上を合計で３０〜６
５原子％含有する非晶質合金粉末の表面層が部分的に結
晶化されていて、比表面積が５ｒｒｒ／ｇ以上とされて
いる窒素酸化物還元用触媒に係る。26 Constitution of the Invention The first invention of the present invention is to contain 35 to 70 atomic % of nickel.
30 to 6 in total of one or more of yttrium, titanium, zirconium, hafnium, niobium, and lanthanum
The present invention relates to a catalyst for reducing nitrogen oxides, in which the surface layer of amorphous alloy powder containing 5 atomic % is partially crystallized and has a specific surface area of 5 rrr/g or more.
本発明の第二の発明は、ニッケルを３５〜７０原子％、
イツトリウム、チタン、ジルコニウム、ハフニウム、ニ
オブ及びランタンの１種又は２種以上を合計で３０〜６
５原子％含有する非晶質合金粉末を製造する工程と、前
記非晶質合金粉末を２５０℃以上結晶化温度未満の範囲
内の温度で水素を含む雰囲気中で処理して表面積を増加
させる工程とを有する、非晶質合金粉末の表面が部分的
に結晶化されていて、比表面積が５ｎ？／ｇ以上とされ
ている窒素酸化物還元用触媒の製造方法に係る。The second invention of the present invention includes 35 to 70 at% of nickel,
30 to 6 in total of one or more of yttrium, titanium, zirconium, hafnium, niobium, and lanthanum
A step of producing an amorphous alloy powder containing 5 at%, and a step of increasing the surface area by treating the amorphous alloy powder in an atmosphere containing hydrogen at a temperature within a range of 250° C. or higher and lower than the crystallization temperature. The surface of the amorphous alloy powder is partially crystallized and has a specific surface area of 5n? /g or more.
ホ９発明の作用効果
最初に、窒素酸化物の一酸化炭素による還元反応につい
て、−酸化窒素（Ｎｏ）の還元反応を例に挙げて説明す
る。−酸化窒素以外の窒素酸化物、Ｎ２Ｏ３、ＮＯ２、
Ｎ２Ｏ５，ＮＯ３等の還元反応についても原理的には同
様である。E9 Functions and Effects of the Invention First, the reduction reaction of nitrogen oxides with carbon monoxide will be explained by taking the reduction reaction of -nitrogen oxide (No) as an example. - Nitrogen oxides other than nitrogen oxides, N2O3, NO2,
The same principle applies to the reduction reactions of N2O5, NO3, etc.
−酸化窒素（ＮＯ）の−酸化炭素（Ｃ○）による還元反
応（以下、Ｎｏ／Ｃｏ反応と呼ぶ。）は、次の反応式に
より表わされる。The reduction reaction of -nitrogen oxide (NO) with -carbon oxide (CO) (hereinafter referred to as No/Co reaction) is represented by the following reaction formula.
２ＮＯ＋２ＣＯ−Ｎ２＋ＣＯ２
従来の還元反応は、Ｎ２への選択率が高い５００℃近辺
の高温域で行われていた。2NO+2CO-N2+CO2 Conventional reduction reactions have been carried out in a high temperature range around 500° C. where the selectivity to N2 is high.
本発明者は、非晶質合金触媒の調整やその触媒特性に関
する研究の過程で、ニッケルのほかに特定の１種又は２
種以上の元素を含む非晶質合金粉末を出発物質として調
整された触媒は、部分的に結晶化した状態において３０
０℃以下でのＮｏ／Ｃ０反応に対して高活性を示し、か
つ、高選択性を示すことを見出した。In the course of research on the preparation of amorphous alloy catalysts and their catalytic properties, the present inventor discovered that in addition to nickel, one or more specific
A catalyst prepared using an amorphous alloy powder containing more than one element as a starting material has a crystallization temperature of 30
It has been found that it exhibits high activity and high selectivity for the No/C0 reaction at temperatures below 0°C.
上記特定の元素とは、イツトリウム、チタン、ジルコニ
ウム、ハフニウム、ニオブ及ヒランタンからなる群から
選ばれた１種又は２種以上であり、それらの量について
は、ニッケルは３５〜７０原子％、上記特定の元素（２
種以上の場合は合計量）は３０〜６５原子％である。The specific element mentioned above is one or more selected from the group consisting of yttrium, titanium, zirconium, hafnium, niobium, and hylanthane, and the amount of these elements is 35 to 70 at% for nickel, element (2
In the case of more than one species, the total amount) is 30 to 65 atomic %.
ニッケルが３５原子％未満及び７０原子％を越えると触
媒としての活性が低くなる。If the content of nickel is less than 35 atom % or more than 70 atom %, the activity as a catalyst will be low.
上記他の成分元素の合計量が３０原子％未満では、後述
する比表面積増大が顕著ではなく、また、これが６５原
子％を越えると、触媒自身の活性が低下する。If the total amount of the other component elements is less than 30 at %, the specific surface area increase described below will not be significant, and if it exceeds 65 at %, the activity of the catalyst itself will decrease.
上記の非晶質合金粉末は、微粉末である程望ましく、比
表面積が略１ ｒｄ、／ ｇ以上であることが特に好ま
しい。The finer the amorphous alloy powder is, the more desirable it is, and it is particularly preferable that the specific surface area is approximately 1 rd,/g or more.
本発明にあっては、ニッケルに添加する成分として、イ
ツトリウム、ジルコニウム、ハフニウム、ニオブ及びラ
ンタンを用いる。これらを含有する非晶質ニッケル合金
は水素吸蔵能力を有する。従って、上記非晶質ニッケル
合金は、２５０°Ｃ以上で水素の吸蔵、放出に伴い、微
粉化して新たに活性な表面を作り出し、比表面積が５ｍ
／ｇ以上に増大して一層活性化する。この処理で部分的
な結晶化が起こるが、安定な高活性を示し、触媒として
頗る好都合である。In the present invention, yttrium, zirconium, hafnium, niobium, and lanthanum are used as components added to nickel. Amorphous nickel alloys containing these have hydrogen storage ability. Therefore, the above-mentioned amorphous nickel alloy absorbs and releases hydrogen at temperatures above 250°C, becomes fine powder, creates a new active surface, and has a specific surface area of 5 m2.
/g or more and becomes even more active. Although partial crystallization occurs during this treatment, it exhibits stable and high activity, making it extremely useful as a catalyst.
先に本出願人の一人は、広い化学組成範囲に亘って熔融
金属から容易に非晶質金属粉を製造する方法を提供する
ことを目的とし、熔融金属に対して濡れ性の小さな表面
層を有し２ｍ／秒以上の周速度で回転しているロール表
面に熔融金属をノズルを経由して供給し、該熔融金属を
微細な溶融金属滴に分断したのち、引き続いて該溶融金
属滴を１０ｍ／秒以上の周速度で回転している金属回転
体に衝突させて急冷凝固させる非晶質金属粉の製造方法
（特開昭５８−６９０７号公報）を提示した。本発明に
基づく触媒を構成する非晶質全屈粉末は、上記の方法に
よって容易に製造することができる。Previously, one of the applicants of the present invention aimed to provide a method for easily producing amorphous metal powder from molten metal over a wide chemical composition range. The molten metal is supplied via a nozzle to the surface of a roll rotating at a circumferential speed of 2 m/sec or more, and the molten metal is divided into fine molten metal droplets. A method for producing amorphous metal powder (JP-A-58-6907) was proposed in which the metal powder is rapidly solidified by colliding with a metal rotating body rotating at a circumferential speed of 1/2 or more. The amorphous powder constituting the catalyst according to the present invention can be easily produced by the method described above.
本発明に基づ（触媒は、前記化学組成を有する非晶質合
金粉末を水素を含む２５０℃以上の雰囲気中で処理する
ことにより、前述のように表面積が著しく増大され、活
性化が促進される。この結果として部分的に結晶化を伴
うが、触媒活性は安定化する。然し、この処理は非晶質
合金粉末の結晶化温度よりも低い温度で行うのが良い。Based on the present invention, the catalyst is produced by treating an amorphous alloy powder having the above chemical composition in an atmosphere containing hydrogen at a temperature of 250°C or higher, thereby significantly increasing the surface area and promoting activation. Although this results in partial crystallization, the catalytic activity is stabilized.However, this treatment is preferably carried out at a temperature lower than the crystallization temperature of the amorphous alloy powder.
結晶化温度以上の処理では、高活性な触媒調整は困難に
なる。If the temperature is higher than the crystallization temperature, it becomes difficult to prepare a highly active catalyst.
本発明に基づく窒素酸化物還元用触媒は、前記のように
構成されていることにより、３００℃以下で使用して活
性と選択性に優れ、長期間使用しても安定である。The catalyst for reducing nitrogen oxides according to the present invention is configured as described above, and therefore has excellent activity and selectivity when used at temperatures below 300° C., and is stable even when used for a long period of time.
へ、実施例 以下、実施例を挙げて本発明を具体的に説明する。To, Example The present invention will be specifically described below with reference to Examples.
ス］直糺よ
前記特開昭５８−６９０７号公報に記載の方法によって
比表面積０．８ｒｒｆ／ｇのＮ １ａＪＺ ｒｊｔ （
元素記号に付した数字は、当該元素成分の原子％を表わ
す。N 1aJZ rjt (
The number attached to the element symbol represents the atomic percent of the element component.
以下、同様。）非晶質合金粉末を製造した。この非晶質
合金粉末０．３ ｇをステンレス鋼管製反応管に充虜し
、水素ガス５０ｃｃ／ｗｉｎ ｓ温度２６３℃で７時間
の処理を施した。この処理によって粉末の表面層部分の
結晶化が進み、比表面積は０．８ｒｒｆ／ｇから１７．
０ｒｒｒ／ｇに著しく増大した。（ＢＥＴ法による測定
）
以下、引き続きＮｏ／Ｃｏ反応を遂行した。Same below. ) An amorphous alloy powder was produced. A stainless steel reaction tube was filled with 0.3 g of this amorphous alloy powder, and treated with 50 cc/wins of hydrogen gas at a temperature of 263° C. for 7 hours. This treatment promotes crystallization of the surface layer portion of the powder, and the specific surface area increases from 0.8rrf/g to 17.
It increased significantly to 0 rrr/g. (Measurement by BET method) Subsequently, the No/Co reaction was carried out.
Ｎｏ／Ｃｏ反応は流通方式で行い、反応ガス組成は、Ｎ
０２５００ｐｐｎ＋ 、 Ｃ０２０００〜２５００ｐ
ｐｍ 、残部はヘリウムガスで、流速１２ｃｃ／ｗｉｎ
、反応温度２５０℃とした。定常状態での物質収支は
下記表に示す通りである。The No/Co reaction is carried out in a flow system, and the reaction gas composition is N.
02500ppn+, C02000~2500p
pm, the remainder is helium gas, flow rate 12cc/win
, the reaction temperature was 250°C. The steady state material balance is shown in the table below.
表 （ｐｐｍ ）
上記の結果から、反応中Ｎ ｚ Ｏの生成はなく、略当
量のＮｏ及びＣＯが消費され、略当量のＣＯ２及び１／
２当量のＮ２が生成している。即ち、この触媒は２５０
℃でのＮｏ／Ｃｏ反応に使用し高活性、かつ高選択性を
示している。Table (ppm) From the above results, there was no generation of NzO during the reaction, approximately equivalent amounts of No and CO were consumed, and approximately equivalent amounts of CO2 and 1/2 were consumed.
2 equivalents of N2 are produced. That is, this catalyst has 250
It has been used in No/Co reactions at ℃ and shows high activity and selectivity.
上記のＮｏ／Ｃｏ反応を５０時間実施し、反応生成物中
４Ｎ２及びＣＯ２の量を測定した。その結果は図面に示
す通りであって、空間速度Ｓ、Ｖ。The above No/Co reaction was carried out for 50 hours, and the amounts of 4N2 and CO2 in the reaction product were measured. The results are as shown in the drawing, with space velocities S and V.
高活性、高選択性を示すことが確認された。It was confirmed that it exhibits high activity and high selectivity.
災籐皿ｌ工主
Ｎ１ＩｚＴｉ＃非晶質合金粉末（実施例２）及びＮ１ｕ
ＨｆＪｚ非晶質合金粉末（実施例３）について前記実施
例１に於けると同様の水素ガスによる前処理を施した。Disaster rattan dish l builder N1IzTi# amorphous alloy powder (Example 2) and N1u
The HfJz amorphous alloy powder (Example 3) was pretreated with hydrogen gas in the same manner as in Example 1 above.
その結果、比表面積はいずれも０．８ｒｒｒ／ｇから１
０ｒｒｒ／ｇへと増大した。これら粉末について前記実
施例１に於けると同様のＮｏ／ＣＯ反応試験を１０時間
行った。上記反応は定常的に進み、２５０℃で両者共前
記Ｎｉ１ＪＺｒＪ７非晶質合金触媒と同様の高選択性を
示し、ＮｏのＮ２への転化率はいずれも９０％であった
。As a result, the specific surface area ranged from 0.8 rrr/g to 1
It increased to 0rrr/g. These powders were subjected to the same No/CO reaction test as in Example 1 for 10 hours. The above reaction proceeded steadily, and at 250° C., both exhibited high selectivity similar to that of the Ni1JZrJ7 amorphous alloy catalyst, and the conversion rate of No to N2 was 90% in both cases.
尖上遡土エエ
Ｎｉ−Ｚｒ系非晶質合金触媒のＮｉ（！：Ｚｒとの原子
比が触媒活性に及ぼす影響を調べた。The effect of the atomic ratio of Ni(!:Zr) on the catalytic activity of the Ni-Zr amorphous alloy catalyst was investigated.
Ｎ ｉ り１１ Ｚ ｒ Ｊ６非晶質合金粉末（実施例
４）及びＮ ｉ ｅ＃ Ｚ ｒ ｔ−非晶質合金粉末（
実施例５）について前記実施例１に於けると同様の水素
ガスによる前処理を施した。その結果、比表面積はいず
れも０．８ｒｒｆ／ｇから２Ｏｒ＋？／ｇへと増大した
。これら粉末について前記実施例１に於けると同様のＮ
Ｏ／ＣＯ反応試験を１０時間行った。ＮＯのＮ２への転
化率は、実施例４では１００％、実施例５では９０％で
あった。Ｎｔの含有量７０原子％迄Ｎｉ−Ｚｒ系触媒で
はＮｉの増加に伴ってＮＯのＮ２への転化率は上昇する
。また、反応前後に於ける物質収支の測定から、両触媒
共、略１００％の選択性を示すことが確認された。N i 11 Z r J6 amorphous alloy powder (Example 4) and N i e# Z r t-amorphous alloy powder (
Regarding Example 5), the same pretreatment with hydrogen gas as in Example 1 was performed. As a result, the specific surface area ranged from 0.8rrf/g to 2Or+? /g. For these powders, the same N
The O/CO reaction test was conducted for 10 hours. The conversion rate of NO to N2 was 100% in Example 4 and 90% in Example 5. In a Ni--Zr catalyst with an Nt content of 70 at %, the conversion rate of NO to N2 increases as the Ni content increases. Furthermore, it was confirmed from measurements of mass balance before and after the reaction that both catalysts exhibited approximately 100% selectivity.
以上の各実施例から、部分的に結晶化された本発明に基
づく触媒は、３００℃以下の低い温度でも長時間高活性
と高選択性を示し、−酸化炭素による窒素酸化物還元反
応用に使用して頗る好適であることが解る。From the above examples, it can be seen that the partially crystallized catalyst according to the present invention exhibits high activity and high selectivity for a long time even at low temperatures below 300°C, and is suitable for the nitrogen oxide reduction reaction with -carbon oxide. It turns out that it is very suitable for use.
以上の例は、Ｎｉ−Ｚｒ系、Ｎｔ−Ｔｉ系及びＮｉ−Ｈ
ｆ系非晶質合金触媒についての例であるが、Ｎ１−Ｙ系
、Ｎｉ−Ｎｂ系及びＮｉ −Ｌａ系非晶質合金触媒につ
いての実験でも略同様の結果が得られた。なお、Ｌａに
替えて又はその一部を置換してセリウムその他のランク
ニドの１種又は２種を用いても同様の結果が得られるの
は言う迄もない。また、前記成分に加えて、非晶質化を
促進する硼素、珪素、燐、砒素、テルルの１種又は２種
以上を含有させることも可能である。The above examples include Ni-Zr system, Nt-Ti system and Ni-H
This is an example of an f-based amorphous alloy catalyst, but substantially similar results were obtained in experiments using N1-Y, Ni-Nb, and Ni-La amorphous alloy catalysts. It goes without saying that similar results can be obtained even if one or two of cerium and other rank nitrides are used in place of La or in place of a portion thereof. In addition to the above components, it is also possible to contain one or more of boron, silicon, phosphorus, arsenic, and tellurium, which promote amorphization.
図面は、Ｎｉ々７．ｒＨ非晶質合金触媒を使用して一酸
化炭素による一酸化窒素の還元を２５０ ”Ｃで行った
ときの、ｃｏ２及びＮ２生成量を経時的に示すグラフで
ある。The drawings are Ni7. FIG. 2 is a graph showing the amount of CO2 and N2 produced over time when reduction of nitrogen monoxide by carbon monoxide is carried out at 250"C using an rH amorphous alloy catalyst.
Claims (1)
ン、ジルコニウム、ハフニウム、ニオブ及びランタンの
１種又は２種以上を合計で３０〜６５原子％含有する非
晶質合金粉末の表面層が部分的に結晶化されていて、比
表面積が５ｍ＾２／ｇ以上とされている窒素酸化物還元
用触媒。 ２、ニッケルを３５〜７０原子％、イットリウム、チタ
ン、ジルコニウム、ハフニウム、ニオブ及びランタンの
１種又は２種以上を合計で３０〜６５原子％含有する非
晶質合金粉末を製造する工程と、前記非晶質合金粉末を
２５０℃以上結晶化温度未満の範囲内の温度で水素を含
む雰囲気中で処理して表面積を増加させる工程とを有す
る、非晶質合金粉末の表面が部分的に結晶化されていて
、比表面積が５ｍ＾２／ｇ以上とされている窒素酸化物
還元用触媒の製造方法。[Claims] 1. An amorphous alloy powder containing 35 to 70 atomic percent of nickel and 30 to 65 atomic percent of one or more of yttrium, titanium, zirconium, hafnium, niobium, and lanthanum in total. A catalyst for reducing nitrogen oxides whose surface layer is partially crystallized and whose specific surface area is 5 m^2/g or more. 2. A step of producing an amorphous alloy powder containing 35 to 70 at% nickel and a total of 30 to 65 at% of one or more of yttrium, titanium, zirconium, hafnium, niobium, and lanthanum; a step of increasing the surface area by treating the amorphous alloy powder in an atmosphere containing hydrogen at a temperature within a range of 250° C. or higher and lower than the crystallization temperature, the surface of the amorphous alloy powder being partially crystallized; A method for producing a catalyst for reducing nitrogen oxides, which has a specific surface area of 5 m^2/g or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60229523A JPS6291246A (en) | 1985-10-15 | 1985-10-15 | Catalyst for reducing nitrogen oxide and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60229523A JPS6291246A (en) | 1985-10-15 | 1985-10-15 | Catalyst for reducing nitrogen oxide and its preparation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6291246A true JPS6291246A (en) | 1987-04-25 |
Family
ID=16893501
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60229523A Pending JPS6291246A (en) | 1985-10-15 | 1985-10-15 | Catalyst for reducing nitrogen oxide and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6291246A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012170900A (en) * | 2011-02-22 | 2012-09-10 | Denso Corp | Exhaust gas purification catalyst |
-
1985
- 1985-10-15 JP JP60229523A patent/JPS6291246A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012170900A (en) * | 2011-02-22 | 2012-09-10 | Denso Corp | Exhaust gas purification catalyst |
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