JP2000037623A - Preparation of oxidizing catalyst - Google Patents

Preparation of oxidizing catalyst

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Publication number
JP2000037623A
JP2000037623A JP10209543A JP20954398A JP2000037623A JP 2000037623 A JP2000037623 A JP 2000037623A JP 10209543 A JP10209543 A JP 10209543A JP 20954398 A JP20954398 A JP 20954398A JP 2000037623 A JP2000037623 A JP 2000037623A
Authority
JP
Japan
Prior art keywords
niobium
catalyst
silica
raw material
oxalic acid
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.)
Granted
Application number
JP10209543A
Other languages
Japanese (ja)
Other versions
JP4166334B2 (en
JP2000037623A5 (en
Inventor
Satoshi Fukushima
聡史 福島
Satoru Komada
悟 駒田
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.)
Asahi Chemical Industry Co Ltd
Original Assignee
Asahi Chemical Industry 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 Asahi Chemical Industry Co Ltd filed Critical Asahi Chemical Industry Co Ltd
Priority to JP20954398A priority Critical patent/JP4166334B2/en
Publication of JP2000037623A publication Critical patent/JP2000037623A/en
Publication of JP2000037623A5 publication Critical patent/JP2000037623A5/ja
Application granted granted Critical
Publication of JP4166334B2 publication Critical patent/JP4166334B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/52Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

PROBLEM TO BE SOLVED: To obtain an excellent yield of an unsaturated carboxylic acid by a method wherein an aqueous suspension containing oxalic acid and a niobium compound is cooled to obtain a suspension, and a niobium-containing liquid to be obtained by removing by separating a solid content from the suspension is adjusted to a specific mol ratio of oxalic acid/niobium, and is used as a niobium stock solution. SOLUTION: In preparation of a composite oxide catalyst containing niobium to be used for a gas phase catalyst oxidation reaction of an alkane, and manufacture of unsaturated carboxylic acid using the said catalyst, an aqueous suspension containing oxalic acid and niobium compound is cooled to obtain a suspension. Then, a niobium-containing solution to be obtained by removing by separating a solid content from the suspension is adjusted to 2 to 4, preferably 2 to 3.5 in a mol ratio of oxalic acid/niobium, and the product is used as a niobium stock solution. The niobium compound to be used is one or more kinds to be selected from niobic acid and niobium hydrogenoxalate. Further a catalyst is allowed to support silica, and a content of the silica is 20 to 60 wt.% of total weight ratio of the silica supporting catalyst comprising a catalytic component and silica.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】[0001]

【発明の属する技術分野】本発明は、アルカンの気相接
触酸化反応に用いるニオブを含む複合酸化物触媒の調製
方法、および該触媒を用いる不飽和カルボン酸の製造方
法に関する。
The present invention relates to a method for preparing a niobium-containing composite oxide catalyst for use in a gas phase catalytic oxidation reaction of alkanes, and a method for producing an unsaturated carboxylic acid using the catalyst.

【0002】[0002]

【従来の技術】不飽和カルボン酸の製造方法としては、
従来、プロピレン、イソブテンなどのオレフィンを触媒
の存在下高温で酸素と接触反応させ、アクロレイン、メ
タクロレインなどのアルデヒド化合物を経由して、二段
階で製造する方法が最も一般的な方法として知られてい
る。一方、近年オレフィンに替わってアルカン出発原料
に用い、触媒の存在下で気相接触酸化反応させて不飽和
カルボン酸を製造する方法が着目されている。
2. Description of the Related Art As a method for producing an unsaturated carboxylic acid,
Conventionally, olefins such as propylene and isobutene are brought into contact with oxygen at a high temperature in the presence of a catalyst, and acrolein and methoxide compounds such as methacrolein are produced in two steps. I have. On the other hand, in recent years, attention has been paid to a method of producing an unsaturated carboxylic acid by using it as an alkane starting material instead of olefin and subjecting it to a gas phase catalytic oxidation reaction in the presence of a catalyst.

【0003】例えば、プロパン、イソブタンを気相接触
酸化させて一段でアクリル酸、メタクリル酸を製造する
ための触媒として、B−P−O系触媒(特公平6−11
720号公報)、Bi−Mo−V−Ag−O系触媒(特
開平2−83348号公報)、P−V−Au/Ag−O
系触媒(特開平5−178774号公報)、ピリジンで
処理されたP−Mo−O系触媒(上田ら、Chemis
try Letters,1995年,p.541)、
Mo−Sb−P−O系触媒(欧州特許第0010902
号明細書)、P−Mo−V−O系触媒(特開平4−59
739)などが提案されている。しかしながら、これら
の触媒は、目的とするアクリル酸あるいはメタクリル酸
の収率、あるいは選択率が十分満足できるものではい。
一方ニオブを含む触媒の例として、Mo−V−Te−N
b−O系触媒(特開平6−279351号公報、特開平
7−10801号公報、特開平10−36311号公
報、特開平10−57813号公報)、Mo−V−Sb
−Nb−O系触媒(特開平9−278680号公報、特
開平9−316023号公報、特開平10−36311
号公報、特開平10−45664号公報、特開平10−
57813号公報、特開平10−118491号公報、
特開平10−120617号公報、特開平10−128
112号公報)などが提案されている。これらニオブを
使用する触媒に関する公報では、触媒の調製に用いるニ
オブの原料として、シュウ酸ニオブアンモニウム塩、ニ
オブ酸、シュウ酸水素ニオブ、Nb2 5 、NbCl5
などのハロゲン化物、Nb(OC2 5 5 などのアル
コキシドを使用することが記載されている。これらのニ
オブ化合物を用いて調製された触媒は、アクリル酸の高
い選択率を有しているが、プロパンの転化率を高める
と、アクリル酸の選択率の低下が著しいという問題があ
った。上記特開平7−10801号公報、特開平10−
57813号公報では、触媒調製過程において、触媒を
粉砕する工程をさらに加えたり、触媒を酸素含有ガス気
流中で加熱処理する工程を加えるなどして、アクリル酸
の選択率を改善する方法を開示しているが、触媒調製方
法が煩雑になるなどの問題があった。
For example, as a catalyst for producing acrylic acid and methacrylic acid in a single step by subjecting propane and isobutane to gas-phase catalytic oxidation, BPO catalysts (JP-B-6-11)
720), a Bi-Mo-V-Ag-O-based catalyst (JP-A-2-83348), PV-Au / Ag-O
Based catalyst (JP-A-5-178774), P-Mo-O-based catalyst treated with pyridine (Ueda et al., Chemis
try Letters, 1995, p. 541),
Mo-Sb-PO catalyst (EP 0010902)
Specification), a P-Mo-VO catalyst (JP-A-4-59)
739) has been proposed. However, these catalysts do not sufficiently satisfy the target acrylic acid or methacrylic acid yield or selectivity.
On the other hand, as an example of a catalyst containing niobium, Mo-V-Te-N
b-O-based catalysts (JP-A-6-279351, JP-A-7-10801, JP-A-10-36311, JP-A-10-57813), Mo-V-Sb
-Nb-O based catalysts (JP-A-9-278680, JP-A-9-316023, JP-A-10-36311)
JP-A-10-45664, JP-A-10-45664
57813, JP-A-10-118491,
JP-A-10-120617 and JP-A-10-128
112) has been proposed. In the publications concerning catalysts using niobium, as raw materials of niobium used for preparing the catalyst, niobium ammonium oxalate, niobate, niobium hydrogen oxalate, Nb 2 O 5 , NbCl 5 are used.
The use of a halide such as Nb (OC 2 H 5 ) 5 is described. The catalysts prepared using these niobium compounds have a high selectivity for acrylic acid, but have a problem that when the conversion of propane is increased, the selectivity for acrylic acid is significantly reduced. JP-A-7-10801 and JP-A-10-108
No. 57813 discloses a method for improving the selectivity of acrylic acid by adding a step of pulverizing the catalyst or adding a step of heating the catalyst in an oxygen-containing gas stream in the catalyst preparation process. However, there has been a problem that the catalyst preparation method becomes complicated.

【0004】[0004]

【発明が解決しようとする課題】本発明は、アルカンの
転化率が高い場合であっても、不飽和カルボン酸の高い
選択率を有し、結果的に優れた不飽和カルボン酸収率を
達成できるニオブ含有触媒の調製方法および該触媒を用
いた不飽和カルボン酸の製造方法を提供することを目的
とするものである。
SUMMARY OF THE INVENTION The present invention has a high selectivity for unsaturated carboxylic acids even when the alkane conversion is high, and consequently achieves an excellent unsaturated carboxylic acid yield. It is an object of the present invention to provide a method for preparing a niobium-containing catalyst and a method for producing an unsaturated carboxylic acid using the catalyst.

【0005】[0005]

【課題を解決するための手段】本発明者らは、プロパ
ン、イソブタンなどのアルカンを気相接触酸化させて不
飽和カルボン酸を製造するための、ニオブを含有する触
媒の調製方法について鋭意検討した結果、シュウ酸とニ
オブ化合物を含む水溶液または水性懸濁液を冷却後、濾
別して得られるニオブ含有液を原料として用いて調製し
た触媒が、優れた不飽和カルボン酸収率を与えることを
見出し、本発明を完成するに至った。
DISCLOSURE OF THE INVENTION The present inventors have intensively studied a method for preparing a niobium-containing catalyst for producing an unsaturated carboxylic acid by subjecting an alkane such as propane or isobutane to gas-phase catalytic oxidation. As a result, after cooling an aqueous solution or aqueous suspension containing oxalic acid and a niobium compound, it was found that a catalyst prepared using a niobium-containing liquid obtained by filtration as a raw material gave an excellent unsaturated carboxylic acid yield, The present invention has been completed.

【0006】すなわち、本発明は (1)アルカンを気相接触酸化反応させて不飽和カルボ
ン酸を製造するために用いられる、ニオブを含む触媒の
調製方法であって、シュウ酸とニオブ化合物を含む水溶
液または水性懸濁液を冷却して懸濁液を得、該懸濁液か
ら固形分を分離除去して得られるニオブ含有液を、シュ
ウ酸/ニオブのモル比2〜4に調整し、ニオブ原料液と
して用いることを特徴とするニオブ含有触媒の調製方
法、(2)該ニオブ化合物がニオブ酸およびシュウ酸水
素ニオブから選ばれる少なくとも1種類以上である
(1)に記載の触媒の調製方法、(3)該触媒が次の一
般式(I)で示される化合物であることを特徴とする
(1)または(2)に記載の触媒の調製方法、 Mo1VaNbbXcZdOn (I) (式中成分XはTeおよびSbから選ばれる少なくとも
1種類以上の元素を表し、成分ZはW、Cr、Ta、T
i、Zr、Hf、Mn、Re、Fe、Ru、Co、R
h、Ni、Pd、Pt、Ag、Zn、B、Al、Ga、
In、Ge、Sn、Pb、P、Bi、Y、希土類元素お
よびアルカリ土類元素から選ばれる少なくとも1種類以
上の元素を表し、a、b、c、d、nはMo1原子当た
りの原子比を表し、 0.1≦a≦1.0 0.01≦b≦1.0 0.01≦c≦1.0 0≦d≦1.0 であり、またnは他の元素の酸化状態によって決まる数
である。) (4)該触媒がシリカに担持されていることを特徴とす
る(1)〜(3)のいずれかに記載の触媒の調製方法、
(5)シリカの含有量が該触媒成分とシリカから成るシ
リカ担持触媒の全重量比の20〜60重量%であること
を特徴とする(4)に記載の触媒の調製方法、(6)該
シリカ担体の原料がアンモニウムイオンで安定化したゾ
ルであることを特徴とする(4)または(5)に記載の
触媒の調製方法、(7)アルカンを気相接触酸化反応さ
せて不飽和カルボン酸を製造するに際して、(1)〜
(6)のいずれかに記載の調製方法によって調整された
ニオブ含有触媒を用いることを特徴とする不飽和カルボ
ン酸の製造方法に関するものである。
That is, the present invention relates to (1) a method for preparing a catalyst containing niobium, which is used for producing an unsaturated carboxylic acid by subjecting an alkane to a gas phase catalytic oxidation reaction, comprising oxalic acid and a niobium compound. The aqueous solution or the aqueous suspension was cooled to obtain a suspension, and the niobium-containing liquid obtained by separating and removing the solid content from the suspension was adjusted to a oxalic acid / niobium molar ratio of 2 to 4 to obtain niobium. (2) a method for preparing a catalyst according to (1), wherein the niobium compound is at least one selected from niobic acid and niobium hydrogen oxalate; (3) The method for preparing a catalyst according to (1) or (2), wherein the catalyst is a compound represented by the following general formula (I): Mo1VaNbbXcZdOn (I) wherein component X is T e represents at least one element selected from the group consisting of W, Cr, Ta, and Tb.
i, Zr, Hf, Mn, Re, Fe, Ru, Co, R
h, Ni, Pd, Pt, Ag, Zn, B, Al, Ga,
In, Ge, Sn, Pb, P, Bi, Y, at least one element selected from the group consisting of rare earth elements and alkaline earth elements, a, b, c, d, and n represent the atomic ratio per Mo atom. 0.1 ≦ a ≦ 1.0 0.01 ≦ b ≦ 1.0 0.01 ≦ c ≦ 1.00 ≦ d ≦ 1.0, and n is determined by the oxidation state of other elements Is a number. (4) The method for preparing a catalyst according to any one of (1) to (3), wherein the catalyst is supported on silica.
(5) The method for preparing a catalyst according to (4), wherein the content of silica is 20 to 60% by weight based on the total weight ratio of the catalyst component and the silica-supported catalyst comprising silica. The method for preparing a catalyst according to (4) or (5), wherein the raw material of the silica carrier is a sol stabilized with ammonium ions, (7) an unsaturated carboxylic acid obtained by subjecting an alkane to a gas phase catalytic oxidation reaction. When manufacturing (1)-
(6) A method for producing an unsaturated carboxylic acid, comprising using a niobium-containing catalyst prepared by the preparation method according to any of (6).

【0007】以下、本発明を詳細に説明する。本発明で
はニオブ化合物として、ニオブ酸およびシュウ酸水素ニ
オブを好適に用いることができる。なお、ニオブ酸は水
酸化ニオブおよび酸化ニオブを含む。これらのニオブ化
合物は、固体または懸濁液の形で用いることができる。
ニオブ酸は使用前にアンモニア水および/または水で洗
浄することができる。
Hereinafter, the present invention will be described in detail. In the present invention, niobate and niobium hydrogen oxalate can be suitably used as the niobium compound. Note that niobic acid includes niobium hydroxide and niobium oxide. These niobium compounds can be used in solid or suspension form.
Niobic acid can be washed with aqueous ammonia and / or water before use.

【0008】これらのニオブ化合物は長期保存や脱水の
進行によって変質する場合がある。本発明においては、
製造直後の、変質をしていないニオブ化合物を使用する
ことが好ましいが、多少変質したニオブ化合物を使用し
てもよい。本発明の方法に用いるシュウ酸は、シュウ酸
無水物またはシュウ酸二水和物が好ましい。
[0008] These niobium compounds may be deteriorated due to long-term storage or progress of dehydration. In the present invention,
It is preferable to use an unaltered niobium compound immediately after production, but a slightly altered niobium compound may be used. The oxalic acid used in the method of the present invention is preferably oxalic anhydride or oxalic acid dihydrate.

【0009】水にこれらニオブ化合物とシュウ酸を加
え、攪拌することによって水溶液または水性懸濁液を得
ることができる。ニオブ化合物としてシュウ酸水素ニオ
ブを用いる場合は、シュウ酸を加えなくても水溶液また
は水性懸濁液を得ることができる。この水溶液または水
性懸濁液のニオブの濃度は、好ましくは0.2〜0.8
(mol−Nb/Kg−液)程度である。
An aqueous solution or suspension can be obtained by adding these niobium compounds and oxalic acid to water and stirring. When niobium hydrogen oxalate is used as the niobium compound, an aqueous solution or suspension can be obtained without adding oxalic acid. The concentration of niobium in the aqueous solution or suspension is preferably between 0.2 and 0.8.
(Mol-Nb / Kg-liquid).

【0010】仕込みのシュウ酸/ニオブモル比は3〜6
程度が好ましい。仕込みのシュウ酸/ニオブのモル比が
大きい場合は、ニオブ化合物の溶解を増すことはできる
が、次の冷却工程でシュウ酸の析出量が多くなり、シュ
ウ酸の利用率が低くなる。逆にシュウ酸/ニオブのモル
比が小さい場合は、溶解しないニオブ化合物が増え、ニ
オブの利用率が低くなることがある。
The charged oxalic acid / niobium molar ratio is 3-6.
The degree is preferred. When the charged oxalic acid / niobium molar ratio is large, the dissolution of the niobium compound can be increased, but the amount of precipitated oxalic acid increases in the next cooling step, and the utilization rate of oxalic acid decreases. Conversely, when the oxalic acid / niobium molar ratio is small, the amount of the insoluble niobium compound increases, and the niobium utilization may decrease.

【0011】次いで、この水溶液または水性懸濁液を冷
却することによって、溶解したシュウ酸の一部が析出、
沈殿が生じ、攪拌下、懸濁液を得ることができる。この
懸濁液から固形分を分離除去することによって、ニオブ
含有液を得ることができる。冷却は簡便には氷冷によっ
て、分離除去は簡便にはデカンテーションまたは濾過に
よって実施できる。
Next, by cooling the aqueous solution or the aqueous suspension, a part of the dissolved oxalic acid precipitates,
A precipitate forms and a suspension can be obtained with stirring. By separating and removing the solid content from the suspension, a niobium-containing liquid can be obtained. Cooling can be conveniently performed by ice cooling, and separation and removal can be conveniently performed by decantation or filtration.

【0012】このニオブ含有液のシュウ酸/ニオブのモ
ル比は、好ましくは2〜4であり、さらに好ましくは、
2〜3.5である。シュウ酸/ニオブのモル比の調整
は、ニオブ酸およびシュウ酸水素ニオブから選ばれるニ
オブ化合物、またはシュウ酸をニオブ含有液に添加して
行うこともできるが、仕込みのシュウ酸/ニオブのモル
比、ニオブの濃度および冷却温度を適宜制御することに
よって、直接、シュウ酸/ニオブのモル比が2〜4のニ
オブ含有液を得ることができる。
The oxalic acid / niobium molar ratio of the niobium-containing liquid is preferably 2 to 4, more preferably
2 to 3.5. The molar ratio of oxalic acid / niobium can be adjusted by adding a niobium compound selected from niobic acid and niobium hydrogen oxalate or an oxalic acid to a niobium-containing solution. By appropriately controlling the concentration of niobium and the cooling temperature, a niobium-containing liquid having a oxalic acid / niobium molar ratio of 2 to 4 can be directly obtained.

【0013】本発明で用いられる好ましい触媒は、下記
一般式(I)で示されるものである。 Mo1VaNbbXcZdOn (I) (式中成分XはTeおよびSbから選ばれる少なくとも
1種類以上の元素を表し、成分ZはW、Cr、Ta、T
i、Zr、Hf、Mn、Re、Fe、Ru、Co、R
h、Ni、Pd、Pt、Ag、Zn、B、Al、Ga、
In、Ge、Sn、Pb、P、Bi、Y、希土類元素お
よびアルカリ土類元素から選ばれる少なくとも1種類以
上の元素を表し、a、b、c、d、nはMo1原子当た
りの原子比を表し、 0.1≦a≦1.0 0.01≦b≦1.0 0.01≦c≦1.0 0≦d≦1.0 であり、またnは他の元素の酸化状態によって決まる数
である。) 本発明の触媒を製造するために用いる金属成分の原料は
特に限定されないが、下記の化合物を好適に用いること
ができる。
The preferred catalyst used in the present invention is represented by the following general formula (I). Mo1VaNbbXcZdOn (I) (wherein component X represents at least one element selected from Te and Sb, and component Z is W, Cr, Ta, T
i, Zr, Hf, Mn, Re, Fe, Ru, Co, R
h, Ni, Pd, Pt, Ag, Zn, B, Al, Ga,
In, Ge, Sn, Pb, P, Bi, Y, at least one element selected from the group consisting of rare earth elements and alkaline earth elements, a, b, c, d, and n represent the atomic ratio per Mo atom. 0.1 ≦ a ≦ 1.0 0.01 ≦ b ≦ 1.0 0.01 ≦ c ≦ 1.00 ≦ d ≦ 1.0, and n is determined by the oxidation state of other elements Is a number. The raw material of the metal component used for producing the catalyst of the present invention is not particularly limited, but the following compounds can be suitably used.

【0014】MoとVの原料はそれぞれ、ヘプタモリブ
デン酸アンモニウムとメタバナジン酸アンモニウムを好
適に用いることができる。TeとSbの原料は、それぞ
れ、テルル酸と酸化アンチモンを好適に用いることがで
きる。成分Zの原料は、それぞれの成分の有機酸塩、硝
酸塩、塩化物、水酸化物または酸化物などを用いること
ができる。
As the raw materials for Mo and V, ammonium heptamolybdate and ammonium metavanadate can be suitably used. As the raw materials for Te and Sb, telluric acid and antimony oxide can be suitably used, respectively. As a raw material of the component Z, an organic acid salt, a nitrate, a chloride, a hydroxide or an oxide of each component can be used.

【0015】シリカの原料は、シリカゾルを好適に用い
ることができる。アルカリ金属イオンで安定化させたシ
リカゾルよりも、アンモニウムイオンで安定化させたゾ
ルを用いることが好ましい。 (原料調合工程)ヘプタモリブデン酸アンモニウム、メ
タバナジン酸アンモニウムおよびテルル酸の混合液を調
製する。アンチモンを用いる場合は、メタバナジン酸ア
ンモニウム水溶液と酸化アンチモンからなるスラリーを
加熱させた後、ヘプタモリブデン酸アンモニウムを添加
し、場合によってはテルル酸を添加して混合液を調製す
る。
As a raw material of silica, a silica sol can be suitably used. It is preferable to use a sol stabilized with ammonium ions rather than a silica sol stabilized with alkali metal ions. (Raw material preparation step) A mixed solution of ammonium heptamolybdate, ammonium metavanadate and telluric acid is prepared. In the case of using antimony, a mixed solution is prepared by heating a slurry composed of an aqueous solution of ammonium metavanadate and antimony oxide, then adding ammonium heptamolybdate, and optionally adding telluric acid.

【0016】この混合液に、攪拌下、本発明で得られる
ニオブ原料液と、式(I)の成分Zを含む水溶液を添加
して原料調合液を得ることができる。シリカ担持触媒を
調製する場合は、攪拌下、この調合液にシリカゾルを添
加して、原料調合液を得ることができる。 (乾燥工程)原料調合工程で得られた調合液を噴霧乾燥
法または蒸発乾固法によって乾燥させ、乾燥粉体を得る
ことができる。噴霧乾燥法における噴霧化は遠心方式、
二流体ノズル方式または高圧ノズル方式によって行うこ
とができる。乾燥熱源は、スチーム、電気ヒーターなど
によって加熱された空気を用いることができる。熱風の
乾燥機入口温度は150〜300℃が好ましい。
[0016] To this mixed solution, under stirring, the niobium raw material liquid obtained in the present invention and an aqueous solution containing the component Z of the formula (I) can be added to obtain a raw material mixture. When preparing a silica-supported catalyst, a raw material mixture can be obtained by adding silica sol to this mixture under stirring. (Drying step) The preparation liquid obtained in the raw material preparation step is dried by a spray drying method or an evaporation to dryness method to obtain a dry powder. The atomization in the spray drying method is a centrifugal method,
It can be performed by a two-fluid nozzle system or a high-pressure nozzle system. As the drying heat source, air heated by steam, an electric heater, or the like can be used. The dryer inlet temperature of the hot air is preferably from 150 to 300C.

【0017】(焼成工程)乾燥工程で得られた乾燥粉体
を焼成することによって酸化物触媒を得ることができ
る。焼成は窒素などの実質的に酸素を含まないガス雰囲
気下、500〜700℃、好ましくは550〜650℃
で実施することができる。焼成時間は0.5〜20時
間、好ましくは1〜8時間である。焼成は回転炉、トン
ネル炉、管状炉および流動焼成炉などを用いることがで
き、酸素を実質的に含まないガスを流通させながら行う
ことができる。この焼成の前に、大気雰囲気下または空
気流通下、200〜400℃、0.1〜5時間、前焼成
をすることができる。
(Firing step) An oxide catalyst can be obtained by firing the dry powder obtained in the drying step. The firing is performed in a gas atmosphere substantially free of oxygen such as nitrogen at 500 to 700 ° C, preferably 550 to 650 ° C.
Can be implemented. The firing time is 0.5 to 20 hours, preferably 1 to 8 hours. The firing can be performed using a rotary furnace, a tunnel furnace, a tubular furnace, a fluidized-bed firing furnace, or the like, and can be performed while flowing a gas substantially containing no oxygen. Before this calcination, pre-calcination can be performed at 200 to 400 ° C. for 0.1 to 5 hours under an atmosphere of air or flowing air.

【0018】本発明の酸化物触媒を用いて、アルカンを
気相接触酸化反応させて不飽和カルボン酸を製造する方
法において、原料のアルカンとしては特に限定されない
が、プロパン、イソブタンを用いるのが好ましい。アル
カンは必ずしも高純度である必要はなく、不純物とし
て、炭素数の異なるアルカンやアルケンなどを少量含有
していても何ら問題はない。
In the method of producing an unsaturated carboxylic acid by subjecting an alkane to a gas phase catalytic oxidation reaction using the oxide catalyst of the present invention, the raw material alkane is not particularly limited, but it is preferable to use propane or isobutane. . The alkane does not necessarily need to be of high purity, and there is no problem even if it contains a small amount of an alkane or alkene having a different carbon number as an impurity.

【0019】原料の分子状酸素としては純酸素を使用す
ることができるが、特に高い純度は要求されないので、
空気または純酸素で富化した空気を用いてもよい。ま
た、場合によっては、希釈ガスとして水蒸気、ヘリウ
ム、ネオン、アルゴン、炭酸ガス、窒素などを供給して
もよい。反応に供給する原料ガス中の組成比は特に限定
されるものではないが、アルカン:酸素:水蒸気:希釈
ガス=1:0.1〜10.0:0〜70:0〜20で実
施されるのが好ましく、より好ましくは、1:0.1〜
5.0:0〜40:0〜20である。
Although pure oxygen can be used as the molecular oxygen of the raw material, since a particularly high purity is not required,
Air or air enriched with pure oxygen may be used. In some cases, steam, helium, neon, argon, carbon dioxide, nitrogen, or the like may be supplied as a dilution gas. Although the composition ratio in the raw material gas supplied to the reaction is not particularly limited, the alkane: oxygen: water vapor: diluent gas = 1: 0.1 to 10.0: 0 to 70: 0 to 20 is used. And more preferably 1: 0.1 to
5.0: 0 to 40: 0 to 20.

【0020】反応の圧力は、大気圧下、加圧下または減
圧下で実施しても良いが、好ましくは0.1〜10at
m、さらに好ましくは1〜3atmである。反応温度は
280℃〜500℃で実施することができるが、好まし
くは280℃〜450℃である。原料ガスと触媒との接
触時間は0.1〜30(sec・g/cc)、好ましく
は0.1〜10(sec・g/cc)である。
The reaction may be carried out under atmospheric, increased or reduced pressure, but preferably from 0.1 to 10 atm.
m, more preferably 1 to 3 atm. The reaction can be carried out at a temperature of from 280 ° C to 500 ° C, preferably from 280 ° C to 450 ° C. The contact time between the raw material gas and the catalyst is 0.1 to 30 (sec · g / cc), preferably 0.1 to 10 (sec · g / cc).

【0021】反応方式は、固定床方式、流動床方式、移
動床方式などを採用できるが、本反応は発熱反応である
ことから、反応器内の温度制御を容易に行うことができ
る流動床反応方式が好ましい。本発明においては、アル
カンの転化率が高い場合であっても、不飽和カルボン酸
の高い選択率を達成することができるが、反応に供給す
る原料ガスの組成比を調整して、アルカンの転化率を低
くすると、目的生成物である不飽和カルボン酸の逐次分
解を抑制できるので、不飽和カルボン酸の選択率を更に
高めることができる。この場合、反応器の流出物から不
飽和カルボン酸を分離し、未反応のアルカンを回収して
再度反応器に供給してもよい。
As the reaction system, a fixed bed system, a fluidized bed system, a moving bed system and the like can be adopted. However, since this reaction is an exothermic reaction, a fluidized bed reaction system in which the temperature in the reactor can be easily controlled is provided. The system is preferred. In the present invention, even when the conversion of the alkane is high, a high selectivity of the unsaturated carboxylic acid can be achieved, but the conversion of the alkane is controlled by adjusting the composition ratio of the raw material gas supplied to the reaction. When the rate is reduced, the sequential decomposition of the unsaturated carboxylic acid as the target product can be suppressed, so that the selectivity of the unsaturated carboxylic acid can be further increased. In this case, the unsaturated carboxylic acid may be separated from the effluent of the reactor, and the unreacted alkane may be recovered and supplied to the reactor again.

【0022】[0022]

【発明の実施の形態】以下に本発明を、ニオブ原料液の
製造実施例、触媒の製造実施例およびプロパンの気相接
触酸化反応によるアクリル酸の製造実施例を用いて詳細
に説明するが、本発明は、その要旨を越えない限り、こ
れら実施例に限定されるものではない。
BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to a production example of a niobium raw material liquid, a production example of a catalyst, and a production example of acrylic acid by a gas phase catalytic oxidation reaction of propane. The present invention is not limited to these examples unless it exceeds the gist.

【0023】なお、以下の実施例におけるプロパン転化
率、アクリル酸選択率、アクリル酸収率は各々次式で定
義される。 プロパン転化率(%) =(反応したプロパンのモル
数) /(供給したプロパンのモル数)×100 アクリル酸選択率(%)=(生成したアクリル酸のモル
数)/(反応したプロパンのモル数)×100 アクリル酸収率(%) =(生成したアクリル酸のモル
数)/(供給したプロパンのモル数)×100
The propane conversion, acrylic acid selectivity, and acrylic acid yield in the following examples are defined by the following equations, respectively. Propane conversion (%) = (moles of propane reacted) / (moles of propane supplied) × 100 Acrylic acid selectivity (%) = (moles of acrylic acid produced) / (moles of reacted propane) Number) × 100 Acrylic acid yield (%) = (mol number of generated acrylic acid) / (mol number of supplied propane) × 100

【0024】[0024]

【実施例1】(ニオブ原料液の調製)水6562gにN
2 5 として80.0重量%を含有するニオブ酸66
4.0gとシュウ酸二水和物〔H2 2 4 ・2H
2 O〕2774.0gを混合した。仕込みのシュウ酸/
ニオブのモル比は5.5、仕込みのニオブ濃度は0.4
(mol−Nb/Kg−液)である。この混合液を95
℃で1時間加熱撹拌することによって、ニオブが溶解し
た水溶液を得た。この水溶液を静置、氷冷後、固体を吸
引濾過によって濾別し、ニオブ含有液を得た。このニオ
ブ含有液のシュウ酸/ニオブのモル比は下記の分析によ
り2.6であった。
Example 1 (Preparation of niobium raw material liquid) N was added to 6562 g of water.
Niobic acid 66 containing 80.0% by weight as b 2 O 5
4.0 g of oxalic acid dihydrate [H 2 C 2 O 4 .2H
2 O] 2774.0 g were mixed. Prepared oxalic acid /
The niobium molar ratio was 5.5, and the charged niobium concentration was 0.4.
(Mol-Nb / Kg-solution). 95 of this mixture
By heating and stirring at 1 ° C. for 1 hour, an aqueous solution in which niobium was dissolved was obtained. The aqueous solution was allowed to stand, cooled with ice, and then the solid was separated by suction filtration to obtain a niobium-containing liquid. The oxalic acid / niobium molar ratio of this niobium-containing liquid was 2.6 according to the following analysis.

【0025】るつぼにこのニオブ含有液10gを精秤
し、95℃で一夜乾燥後、600℃で1時間熱処理し、
Nb2 5 0.625gを得た。この結果から、ニオブ
濃度は0.47(mol−Nb/Kg−液)であった。
300mlのガラスビーカーにこのニオブ含有液3gを
精秤し、約80℃の熱水200mlを加え、続いて1:
1硫酸10mlを加えた。得られた溶液をホットスター
ラー上で液温70℃に保ちながら、攪拌下、1/4規定
KMnO4 を用いて滴定した。KMnO4 によるかすか
な淡桃色が約30秒以上続く点を終点とした。シュウ酸
の濃度は、滴定量から次式に従って計算した結果、1.
22(mol−シュウ酸/Kg)であった。 2KMnO4 +3H2SO4 +5H224→K2SO4
2MnSO4+10CO2+8H2O 得られたニオブ含有液は、シュウ酸/ニオブのモル比を
調整することなく、下記の触媒調製のニオブ原料液とし
て用いた。 (触媒の調製)触媒成分の組成式がMo10.32Nb
0.12Te0.22nであって、SiO2含有量30重量%の
シリカ担持触媒を次のようにして調製した。
In a crucible, 10 g of this niobium-containing liquid was precisely weighed, dried at 95 ° C. overnight, and heat-treated at 600 ° C. for 1 hour.
0.625 g of Nb 2 O 5 was obtained. From these results, the niobium concentration was 0.47 (mol-Nb / Kg-solution).
In a 300 ml glass beaker, 3 g of the niobium-containing liquid was precisely weighed, and 200 ml of hot water at about 80 ° C. was added.
10 ml of 1 sulfuric acid was added. The obtained solution was titrated with 1 / 4N KMnO 4 with stirring while maintaining the liquid temperature at 70 ° C on a hot stirrer. The point at which the faint pale pink color by KMnO 4 continued for about 30 seconds or more was determined as the end point. The concentration of oxalic acid was calculated from the titer according to the following equation.
22 (mol-oxalic acid / Kg). 2KMnO 4 + 3H 2 SO 4 + 5H 2 C 2 O 4 → K 2 SO 4 +
2MnSO 4 + 10CO 2 + 8H 2 O The obtained niobium-containing liquid was used as a niobium raw material liquid for the following catalyst preparation without adjusting the molar ratio of oxalic acid / niobium. (Preparation of catalyst) The composition formula of the catalyst component is Mo 1 V 0.32 Nb
A 0.12 Te 0.22 O n, to prepare a SiO 2 content of 30 wt% silica supported catalyst as follows.

【0026】水2300gにヘプタモリブデン酸アンモ
ニウム〔(NH46Mo724・4H2O〕546.7
g、メタバナジン酸アンモニウム〔NH4VO3〕11
6.3gおよびテルル酸〔H6TeO6〕156.9gを
順次加え、60℃に加熱して溶解した後、30℃まで冷
却して混合水溶液を得た。次いでこの混合水溶液に、上
記のニオブ原料液785.0gおよびシリカとして30
重量%を含有するシリカゾル1000gを順次添加して
混合し、触媒原料調合液を得た。この原料調合液を遠心
式噴霧乾燥機にて入口温度が240℃、出口温度が14
5℃で乾燥し、微小球状の乾燥粉体を得た。得られた乾
燥粉体を大気雰囲気下275℃で2時間焼成した。この
粉体85gを直径1インチのSUS製管に充填し、15
0Ncc/minの窒素ガス流通下、600℃で2時間
焼成してシリカ担持触媒を得た。(プロパンの酸化反
応)触媒2gを内径10mmの固定床型反応管に充填
し、反応温度380℃、反応圧力常圧下にプロパン:O
2:H2O:He=1:3.2:14:12.1のモル比
の混合ガスを接触時間3.0(sec・g/cc)で通
過させた。得られた結果を表1に示す。
[0026] Ammonium heptamolybdate in water 2300g [(NH 4) 6 Mo 7 O 24 · 4H 2 O ] 546.7
g, ammonium metavanadate [NH 4 VO 3 ] 11
6.3 g and 156.9 g of telluric acid [H 6 TeO 6 ] were sequentially added and dissolved by heating to 60 ° C., followed by cooling to 30 ° C. to obtain a mixed aqueous solution. Next, 785.0 g of the above-mentioned niobium raw material liquid and 30% as silica were added to this mixed aqueous solution.
1000 g of silica sol containing 1% by weight was sequentially added and mixed to obtain a catalyst raw material mixture. This raw material mixture was centrifuged by a centrifugal spray drier at an inlet temperature of 240 ° C and an outlet temperature of 14 ° C.
It was dried at 5 ° C. to obtain a fine spherical dry powder. The obtained dry powder was calcined at 275 ° C. for 2 hours in an air atmosphere. 85 g of this powder was filled into a 1-inch diameter SUS tube,
The mixture was calcined at 600 ° C. for 2 hours under a nitrogen gas flow of 0 Ncc / min to obtain a silica-supported catalyst. (Oxidation reaction of propane) 2 g of the catalyst was charged into a fixed-bed type reaction tube having an inner diameter of 10 mm, and propane: O
A mixed gas having a molar ratio of 2 : 3.2: 14: 12.1 with 2 : H2O: He was passed with a contact time of 3.0 (sec.g / cc). Table 1 shows the obtained results.

【0027】なお、接触時間は次式で定義される。 接触時間(sec・g/cc)=(W/F)×273/
(273+T) (ここで、Wは充填触媒量(g)、Fは原料混合ガス流
量(Ncc/sec)、そしてTは反応温度(℃)であ
る。)
The contact time is defined by the following equation. Contact time (sec · g / cc) = (W / F) × 273 /
(Where W is the amount of the charged catalyst (g), F is the raw material mixed gas flow rate (Ncc / sec), and T is the reaction temperature (° C.))

【0028】[0028]

【実施例2】(ニオブ原料液の調製)実施例1のシュウ
酸/ニオブのモル比2.6のニオブ含有液に、さらにシ
ュウ酸/ニオブのモル比3.0となるようにシュウ酸二
水和物〔H224・2H2O〕を加え、加熱して溶解さ
せた後、30℃まで冷却した。得られた液を下記の触媒
調製のニオブ原料液として用いた。このニオブ原料液中
のニオブ濃度は実施例1と同様にして分析した結果、
0.46(mol−Nb/Kg−液)であった。 (触媒の調製)触媒成分の組成式がMo10.32Nb
0.12Te0.22nであって、SiO2含有量30重量%の
シリカ担持触媒を、上記のニオブ原料液を用い、その使
用量を802.1gとした他は実施例1と同様にして調
製してシリカ担持触媒を得た。 (プロパンの酸化反応)得られた触媒を用いて、実施例
1と同じ条件でプロパンの酸化反応を行った。結果を表
1に示す。
Example 2 (Preparation of niobium raw material liquid) The oxalic acid / niobium molar ratio of 2.6 was added to the niobium-containing liquid of Example 1, and oxalic acid / niobium was further added to the oxalic acid / niobium molar ratio of 3.0. A hydrate [H 2 C 2 O 4 .2H 2 O] was added and dissolved by heating, and then cooled to 30 ° C. The obtained liquid was used as a niobium raw material liquid for preparing the following catalyst. As a result of analyzing the niobium concentration in the niobium raw material liquid in the same manner as in Example 1,
0.46 (mol-Nb / Kg-solution). (Preparation of catalyst) The composition formula of the catalyst component is Mo 1 V 0.32 Nb
0.12 A Te 0.22 O n, the SiO 2 content of 30 wt% of silica-supported catalyst, using the above-mentioned niobium raw material liquid, and other usage was with 802.1g was prepared in the same manner as in Example 1 Thus, a silica-supported catalyst was obtained. (Propane oxidation reaction) Propane oxidation reaction was carried out using the obtained catalyst under the same conditions as in Example 1. Table 1 shows the results.

【0029】[0029]

【比較例1】(ニオブ原料液の調製)実施例1と同様に
して得られる、ニオブが溶解したシュウ酸/ニオブのモ
ル比5.5の液を氷冷することなく、そのまま下記の触
媒調製のニオブ原料液として用いた。このニオブ原料液
中のニオブ濃度は実施例1と同様にして分析した結果、
0.41(mol−Nb/Kg−液)であった。 (触媒の調製)触媒成分の組成式がMo10.32Nb
0.12Te0.22nであって、SiO2含有量30重量%の
シリカ担持触媒を、上記のニオブ原料液を用い、その使
用量を899.9gとした他は実施例1と同様にして調
製してシリカ担持触媒を得た。 (プロパンの酸化反応)得られた触媒を用いて、実施例
1と同じ条件でプロパンの酸化反応を行った。結果を表
1に示す。
Comparative Example 1 (Preparation of Niobium Raw Material Liquid) A liquid having a molar ratio of oxalic acid / niobium of 5.5 in which niobium was dissolved and obtained in the same manner as in Example 1 was used without cooling with ice and the following catalyst was prepared. Was used as a niobium raw material liquid. As a result of analyzing the niobium concentration in the niobium raw material liquid in the same manner as in Example 1,
0.41 (mol-Nb / Kg-solution). (Preparation of catalyst) The composition formula of the catalyst component is Mo 1 V 0.32 Nb
0.12 A Te 0.22 O n, the SiO 2 content of 30 wt% of silica-supported catalyst, using the above-mentioned niobium raw material liquid, and other usage was with 899.9g was prepared in the same manner as in Example 1 Thus, a silica-supported catalyst was obtained. (Propane oxidation reaction) Propane oxidation reaction was carried out using the obtained catalyst under the same conditions as in Example 1. Table 1 shows the results.

【0030】[0030]

【実施例3】(ニオブ原料液の調製)水782gにNb
25として80.0重量%を含有するニオブ酸66.4
gとシュウ酸二水和物〔H224・2H2O〕151.
3gを混合した。仕込みのシュウ酸/ニオブのモル比は
3.0、仕込みのニオブ濃度は0.4(mol−Nb/
Kg−液)である。この混合液を95℃で1時間加熱撹
拌することによって、不溶ニオブ成分を含む水性懸濁液
を得た。この水性懸濁液を静置、氷冷後、固体を濾別
し、ニオブ含有液を得た。このニオブ含有液中のニオブ
濃度およびシュウ酸/ニオブのモル比は、それぞれ、実
施例1と同様にして分析した結果、0.41(mol−
Nb/Kg−液)および2.8であった。このニオブ含
有液は、シュウ酸/ニオブのモル比を調整することなく
下記の触媒調製のニオブ原料液として用いた。 (触媒の調製)触媒成分の組成式がMo10.32Nb
0.12Te0.22nであって、SiO2含有量30重量%の
シリカ担持触媒を、上記のニオブ原料液を用い、その使
用量を899.9gとした他は実施例1と同様にして調
製してシリカ担持触媒を得た。 (プロパンの酸化反応)得られた触媒を用いて、実施例
1と同じ条件でプロパンの酸化反応を行った。結果を表
1に示す。
Example 3 (Preparation of niobium raw material liquid) Nb was added to 782 g of water.
66.4 niobic acid containing 80.0% by weight as 2 O 5
g oxalic acid dihydrate [H 2 C 2 O 4 · 2H 2 O ] 151.
3 g were mixed. The charged oxalic acid / niobium molar ratio was 3.0, and the charged niobium concentration was 0.4 (mol-Nb /
Kg-liquid). This mixture was heated and stirred at 95 ° C. for 1 hour to obtain an aqueous suspension containing an insoluble niobium component. This aqueous suspension was allowed to stand, cooled with ice, and then the solid was separated by filtration to obtain a niobium-containing liquid. The niobium concentration and the oxalic acid / niobium molar ratio in this niobium-containing liquid were analyzed in the same manner as in Example 1, and as a result, 0.41 (mol-
Nb / Kg-solution) and 2.8. This niobium-containing liquid was used as a niobium raw material liquid for the following catalyst preparation without adjusting the molar ratio of oxalic acid / niobium. (Preparation of catalyst) The composition formula of the catalyst component is Mo 1 V 0.32 Nb
0.12 A Te 0.22 O n, the SiO 2 content of 30 wt% of silica-supported catalyst, using the above-mentioned niobium raw material liquid, and other usage was with 899.9g was prepared in the same manner as in Example 1 Thus, a silica-supported catalyst was obtained. (Propane oxidation reaction) Propane oxidation reaction was carried out using the obtained catalyst under the same conditions as in Example 1. Table 1 shows the results.

【0031】[0031]

【実施例4】(ニオブ原料液の調製)水4084gにN
25として80.0重量%を含有するニオブ酸66
4.0gとシュウ酸二水和物〔H224・2H2O〕2
52.0gを混合した。仕込みのシュウ酸/ニオブのモ
ル比は0.5、仕込みのニオブ濃度は0.8(mol−
Nb/Kg−液)である。この混合液を95℃で1時間
加熱撹拌することによって、不溶ニオブ成分を含む水性
懸濁液を得た。この水性懸濁液を静置、氷冷後、固体を
濾別し、ニオブ含有液を得た。このニオブ含有液中のニ
オブ濃度およびシュウ酸/ニオブのモル比は、それぞ
れ、実施例1と同様にして分析した結果、0.16(m
ol−Nb/Kg−液)および2.2であった。このニ
オブ含有液にさらに、シュウ酸/ニオブのモル比3.0
となるようにシュウ酸二水和物を加え、加熱して溶解さ
せた後、30℃まで冷却した。得られた液を下記の触媒
調製のニオブ原料液として用いた。この液中のニオブ濃
度は実施例1と同様にして分析した結果、0.158
(mol−Nb/Kg−液)であった。 (触媒の調製)触媒成分の組成式がMo10.32Nb
0.12Te0.22nであって、SiO2含有量30重量%の
シリカ担持触媒を、上記のニオブ原料液を用い、その使
用量を2335.2gとした他は実施例1と同様にして
調製してシリカ担持触媒を得た。 (プロパンの酸化反応)得られた触媒を用いて、実施例
1と同じ条件でプロパンの酸化反応を行った。結果を表
1に示す。
Example 4 (Preparation of niobium raw material liquid) N was added to 4084 g of water.
Niobic acid 66 containing 80.0% by weight as b 2 O 5
4.0g oxalic acid dihydrate [H 2 C 2 O 4 · 2H 2 O ] 2
52.0 g were mixed. The charged oxalic acid / niobium molar ratio was 0.5, and the charged niobium concentration was 0.8 (mol-
Nb / Kg-liquid). This mixture was heated and stirred at 95 ° C. for 1 hour to obtain an aqueous suspension containing an insoluble niobium component. This aqueous suspension was allowed to stand, cooled with ice, and then the solid was separated by filtration to obtain a niobium-containing liquid. The niobium concentration and the oxalic acid / niobium molar ratio in the niobium-containing liquid were analyzed in the same manner as in Example 1, and as a result, 0.16 (m
ol-Nb / Kg-solution) and 2.2. This niobium-containing liquid was further added with a oxalic acid / niobium molar ratio of 3.0.
Then, oxalic acid dihydrate was added to the mixture, and the mixture was dissolved by heating, and then cooled to 30 ° C. The obtained liquid was used as a niobium raw material liquid for preparing the following catalyst. As a result of analyzing the niobium concentration in this solution in the same manner as in Example 1, the niobium concentration was 0.158.
(Mol-Nb / Kg-solution). (Preparation of catalyst) The composition formula of the catalyst component is Mo 1 V 0.32 Nb
0.12 A Te 0.22 O n, the SiO 2 content of 30 wt% of silica-supported catalyst, using the above-mentioned niobium raw material liquid, and other usage was with 2335.2g was prepared in the same manner as in Example 1 Thus, a silica-supported catalyst was obtained. (Propane oxidation reaction) Propane oxidation reaction was carried out using the obtained catalyst under the same conditions as in Example 1. Table 1 shows the results.

【0032】[0032]

【実施例5】(ニオブ原料液の調製)実施例1と同様に
してシュウ酸/ニオブのモル比2.6のニオブ原料液を
得た。 (触媒の調製)組成式がMo10.32Nb0.12Te0.22
nで示される触媒を、次の様にして調製した。
Example 5 (Preparation of a niobium raw material liquid) A niobium raw material liquid having a molar ratio of oxalic acid / niobium of 2.6 was obtained in the same manner as in Example 1. (Preparation of catalyst) The composition formula is Mo 1 V 0.32 Nb 0.12 Te 0.22
The catalyst represented by O n, was prepared in the following manner.

【0033】水1650gにヘプタモリブデン酸アンモ
ニウム〔(NH46Mo724・4H2O〕390.5
g、メタバナジン酸アンモニウム〔NH4VO3〕83.
1gおよびテルル酸〔H6TeO6〕112.0gを順次
加え、60℃に加熱して溶解した後、30℃まで冷却し
て混合水溶液を得た。次いでこの混合水溶液に、上記の
ニオブ原料液560.7gを添加して混合し、触媒原料
調合液を得た。この原料調合液を遠心式噴霧乾燥機にて
入口温度が240℃、出口温度が145℃で乾燥し、微
小球状の乾燥粉体を得た。得られた乾燥粉体を大気雰囲
気下275℃で2時間焼成した。この粉体85gを直径
1インチのSUS製管に充填し、150Ncc/min
の窒素ガス流通下、600℃で2時間焼成して触媒を得
た。 (プロパンの酸化反応)得られた触媒を用いて、接触時
間を1.5(sec・g/cc)とした以外は実施例1
と同じ条件でプロパンの酸化反応を行った。結果を表1
に示す。
[0033] Ammonium heptamolybdate in water 1650g [(NH 4) 6 Mo 7 O 24 · 4H 2 O ] 390.5
g, ammonium metavanadate [NH 4 VO 3 ] 83.
1 g and telluric acid [H 6 TeO 6 ] 112.0 g were sequentially added and dissolved by heating to 60 ° C., followed by cooling to 30 ° C. to obtain a mixed aqueous solution. Next, 560.7 g of the above-mentioned niobium raw material liquid was added to and mixed with this mixed aqueous solution to obtain a catalyst raw material preparation liquid. This raw material mixture was dried with a centrifugal spray drier at an inlet temperature of 240 ° C. and an outlet temperature of 145 ° C. to obtain a fine spherical dry powder. The obtained dry powder was calcined at 275 ° C. for 2 hours in an air atmosphere. 85 g of this powder was filled into a SUS tube having a diameter of 1 inch, and 150 Ncc / min.
The mixture was calcined at 600 ° C. for 2 hours under a nitrogen gas flow to obtain a catalyst. (Propane oxidation reaction) Example 1 was repeated except that the contact time was 1.5 (sec · g / cc) using the obtained catalyst.
The propane oxidation reaction was carried out under the same conditions as described above. Table 1 shows the results
Shown in

【0034】[0034]

【比較例2】(ニオブ原料液の調製)比較例1と同様に
してシュウ酸/ニオブのモル比5.5のニオブ原料液を
得た。 (触媒の調製)組成式がMo10.32Nb0.12Te0.22
nで示される触媒を、上記のニオブ原料液を用い、そ
の使用量を642.8gとした他は実施例5と同様にし
て調製して触媒を得た。 (プロパンの酸化反応)得られた触媒を用いて、実施例
5と同じ条件でプロパンの酸化反応を行った。結果を表
1に示す。
Comparative Example 2 (Preparation of Niobium Raw Material Liquid) A niobium raw material liquid having a oxalic acid / niobium molar ratio of 5.5 was obtained in the same manner as in Comparative Example 1. (Preparation of catalyst) The composition formula is Mo 1 V 0.32 Nb 0.12 Te 0.22
The catalyst represented by O n, using the above-mentioned niobium raw material liquid, and other usage was with 642.8g was obtained a catalyst was prepared in the same manner as in Example 5. (Oxidation reaction of propane) Using the obtained catalyst, an oxidation reaction of propane was carried out under the same conditions as in Example 5. Table 1 shows the results.

【0035】[0035]

【実施例6】(ニオブ原料液の調製)水1000gにN
25として14.9重量%を含有するシュウ酸水素ニ
オブ917gを混合した。仕込みのニオブ濃度は0.5
4(mol−Nb/Kg−液)である。この混合液を9
5℃で1時間加熱撹拌することによって、溶解液を得
た。実施例1と同様にしてシュウ酸/ニオブのモル比を
分析した結果、5.2であった。この溶解液を静置、氷
冷後、固体を濾別してニオブ含有液を得た。このニオブ
含有液中のニオブ濃度およびシュウ酸/ニオブのモル比
は、それぞれ、実施例1と同様にして分析した結果、
0.66(mol−Nb/Kg−液)および2.4であ
った。このニオブ含有液にさらに、シュウ酸/ニオブの
モル比3.0、ニオブ濃度0.46(mol−Nb/K
g−液)となるようにシュウ酸二水和物〔H224
2H2O〕と水を加え、加熱、撹拌して溶解させた後、
30℃まで冷却した。得られた液を下記の触媒調製のニ
オブ原料液として用いた。 (触媒の調製)触媒成分の組成式がMo10.32Nb
0.12Te0.22nであって、SiO2含有量30重量%の
シリカ担持触媒を、上記のニオブ原料液を用いた他は、
実施例2と同様にして調製してシリカ担持触媒を得た。 (プロパンの酸化反応)得られた触媒を用いて、実施例
1と同じ条件でプロパンの酸化反応を行った。結果を表
1に示す。
Example 6 (Preparation of niobium raw material liquid) N was added to 1000 g of water.
917 g of niobium hydrogen oxalate containing 14.9% by weight as b 2 O 5 was mixed. Charged niobium concentration is 0.5
4 (mol-Nb / Kg-solution). 9
By heating and stirring at 5 ° C. for 1 hour, a solution was obtained. As a result of analyzing the oxalic acid / niobium molar ratio in the same manner as in Example 1, it was 5.2. The solution was allowed to stand, cooled on ice, and the solid was filtered off to obtain a niobium-containing solution. The niobium concentration and the oxalic acid / niobium molar ratio in this niobium-containing liquid were analyzed in the same manner as in Example 1, respectively.
0.66 (mol-Nb / Kg-solution) and 2.4. The niobium-containing solution was further added with a oxalic acid / niobium molar ratio of 3.0 and a niobium concentration of 0.46 (mol-Nb / K).
g-liquid) such that oxalic acid dihydrate [H 2 C 2 O 4.
2H 2 O] and water are added, and the mixture is dissolved by heating and stirring.
Cooled to 30 ° C. The obtained liquid was used as a niobium raw material liquid for preparing the following catalyst. (Preparation of catalyst) The composition formula of the catalyst component is Mo 1 V 0.32 Nb
A 0.12 Te 0.22 O n, the SiO 2 content of 30 wt% of the silica supported catalyst, except for using the above-mentioned niobium raw material liquid,
A silica-supported catalyst was prepared in the same manner as in Example 2. (Propane oxidation reaction) Propane oxidation reaction was carried out using the obtained catalyst under the same conditions as in Example 1. Table 1 shows the results.

【0036】[0036]

【実施例7】(ニオブ原料液の調製)実施例1と同様に
してシュウ酸/ニオブのモル比2.6のニオブ原料液を
得た。 (触媒の調製)組成式がMo10.32Nb0.06Sb0.16
nで示される触媒を、次のようにして調製した。
Example 7 (Preparation of a niobium raw material liquid) A niobium raw material liquid having a molar ratio of oxalic acid / niobium of 2.6 was obtained in the same manner as in Example 1. (Preparation of catalyst) The composition formula is Mo 1 V 0.32 Nb 0.06 Sb 0.16
The catalyst represented by O n, was prepared as follows.

【0037】水1850gにメタバナジン酸アンモニウ
ム〔NH4VO3〕92.5gを加え、加熱して溶解した
後、三酸化アンチモン〔Sb23〕の粉末57.6gを
加え、スラリーを得た。得られたスラリーを95〜10
0℃で10時間加熱還流し、次いでヘプタモリブデン酸
アンモニウム〔(NH46Mo724・4H2O〕43
5.1gを加え溶解させた。この混合液を約10℃に冷
却してから、上記のニオブ原料液312.4gを添加し
て、触媒原料調合液を得た。この原料調合液を遠心式噴
霧乾燥機にて入口温度が240℃、出口温度が145℃
で乾燥し、微小球状の乾燥粉体を得た。得られた乾燥粉
体を大気雰囲気下325℃で1時間焼成した。この粉体
85gを直径1インチのSUS製管に充填し、150N
cc/minの窒素ガス流通下、600℃で2時間焼成
して触媒を得た。 (プロパンの酸化反応)得られた触媒を用いて、接触時
間を2.0(sec・g/cc)とした以外は実施例1
と同じ条件でプロパンの酸化反応を行った。結果を表1
に示す。
92.5 g of ammonium metavanadate [NH 4 VO 3 ] was added to 1850 g of water and dissolved by heating, and then 57.6 g of antimony trioxide [Sb 2 O 3 ] powder was added to obtain a slurry. 95 to 10 of the obtained slurry
0 ℃ in 10 hours heating under reflux, followed by ammonium heptamolybdate [(NH 4) 6 Mo 7 O 24 · 4H 2 O ] 43
5.1 g was added and dissolved. After cooling this mixture to about 10 ° C., 312.4 g of the above-mentioned niobium raw material liquid was added to obtain a catalyst raw material preparation liquid. The raw material mixture was centrifugally spray-dried at an inlet temperature of 240 ° C. and an outlet temperature of 145 ° C.
To obtain a fine spherical dry powder. The obtained dry powder was calcined at 325 ° C. for 1 hour in an air atmosphere. 85 g of this powder was filled in a SUS tube having a diameter of 1 inch, and 150 N
The catalyst was obtained by calcining at 600 ° C. for 2 hours under a nitrogen gas flow of cc / min. (Oxidation reaction of propane) Example 1 was repeated except that the obtained catalyst was used and the contact time was 2.0 (sec · g / cc).
The propane oxidation reaction was carried out under the same conditions as described above. Table 1 shows the results
Shown in

【0038】[0038]

【実施例8】(ニオブ原料液の調製)実施例2と同様に
してシュウ酸/ニオブのモル比3.0のニオブ原料液を
得た。 (触媒の調製)組成式がMo10.32Nb0.06Sb0.16
nで示される触媒を、上記のニオブ原料液を用い、そ
の使用量を319.2gとした他は実施例7と同様にし
て調製して触媒を得た。 (プロパンの酸化反応)得られた触媒を用いて、実施例
7と同じ条件でプロパンの酸化反応を行った。結果を表
1に示す。
Example 8 (Preparation of niobium raw material liquid) A niobium raw material liquid having a molar ratio of oxalic acid / niobium of 3.0 was obtained in the same manner as in Example 2. (Preparation of catalyst) The composition formula is Mo 1 V 0.32 Nb 0.06 Sb 0.16
The catalyst represented by O n, using the above-mentioned niobium raw material liquid, and other usage was with 319.2g was obtained a catalyst was prepared in the same manner as in Example 7. (Propane oxidation reaction) Propane oxidation reaction was carried out using the obtained catalyst under the same conditions as in Example 7. Table 1 shows the results.

【0039】[0039]

【比較例3】(ニオブ原料液の調製)実施例3と同様に
してシュウ酸/ニオブのモル比5.5のニオブ原料液を
得た。 (触媒の調製)組成式がMo10.32Nb0.06Sb0.16
nで示される触媒を、上記のニオブ原料液を用い、そ
の使用量を358.1gとした他は実施例7と同様にし
て調製して触媒を得た。 (プロパンの酸化反応)得られた触媒を用いて、実施例
7と同じ条件でプロパンの酸化反応を行った。結果を表
1に示す。
Comparative Example 3 (Preparation of Niobium Raw Material Liquid) A niobium raw material liquid having a molar ratio of oxalic acid / niobium of 5.5 was obtained in the same manner as in Example 3. (Preparation of catalyst) The composition formula is Mo 1 V 0.32 Nb 0.06 Sb 0.16
The catalyst represented by O n, using the above-mentioned niobium raw material liquid, and other usage was with 358.1g was obtained a catalyst was prepared in the same manner as in Example 7. (Propane oxidation reaction) Propane oxidation reaction was carried out using the obtained catalyst under the same conditions as in Example 7. Table 1 shows the results.

【0040】[0040]

【表1】 [Table 1]

【0041】[0041]

【発明の効果】本発明により、簡便に調製されるニオブ
の原料液を用いて、不飽和カルボン酸を高い収率で得る
ことができる。
According to the present invention, an unsaturated carboxylic acid can be obtained in a high yield by using a raw material solution of niobium which is easily prepared.

フロントページの続き (51)Int.Cl.7 識別記号 FI テーマコート゛(参考) B01J 23/84 B01J 23/84 Z 23/89 23/89 Z 27/057 27/057 Z C07C 51/215 C07C 51/215 57/05 57/05 // C07B 61/00 300 C07B 61/00 300 Fターム(参考) 4G069 AA01 AA03 AA08 AA09 AA14 BA01A BA02A BA02B BA04A BA05A BA37 BB04A BB04B BB06A BB06B BB20C BC08A BC17A BC18A BC21A BC22A BC23A BC25A BC26A BC26B BC32A BC35A BC38A BC40A BC52A BC54A BC54B BC55A BC55B BC55C BC56A BC58A BC59A BC59B BC60A BC62A BC64A BC66A BC67A BC68A BC70A BC71A BC72A BC75A BD03A BD07A BD10A BD10B BE08C CB07 CB17 DA06 EA01Y FA01 FA02 FB04 FB14 FB30 FB57 FC02 4H006 AA02 AC46 BA05 BA06 BA07 BA08 BA09 BA10 BA11 BA12 BA13 BA14 BA15 BA16 BA19 BA20 BA21 BA23 BA24 BA25 BA26 BA30 BA31 BA35 BA55 BA75 BA85 BC13 BC32 BE30 BS10 4H039 CA65 CC30 Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat II (reference) B01J 23/84 B01J 23/84 Z 23/89 23/89 Z 27/057 27/057 Z C07C 51/215 C07C 51 / 215 57/05 57/05 // C07B 61/00 300 C07B 61/00 300 F-term (reference) 4G069 AA01 AA03 AA08 AA09 AA14 BA01A BA02A BA02B BA04A BA05A BA37 BB04A BB04B BB06A BB06B BB20C BC08A BC17A BC18A BC21A BC32A BC35A BC38A BC40A BC52A BC54A BC54B BC55A BC55B BC55C BC56A BC58A BC59A BC59B BC60A BC62A BC64A BC66A BC67A BC68A BC70A BC71A BC72A BC75A BD03A BD07A BD10A BD10B BE08C CB07 AC11 BA01 BA01 BA01 BA01 BA01 BA01 BA02 BA12 BA13 BA14 BA15 BA16 BA19 BA20 BA21 BA23 BA24 BA25 BA26 BA30 BA31 BA35 BA55 BA75 BA85 BC13 BC32 BE30 BS10 4H039 CA65 CC30

Claims (7)

【特許請求の範囲】[Claims] 【請求項1】 アルカンを気相接触酸化反応させて不飽
和カルボン酸を製造するために用いられる、ニオブを含
む触媒の調製方法であって、シュウ酸とニオブ化合物を
含む水溶液または水性懸濁液を冷却して懸濁液を得、該
懸濁液から固形分を分離除去して得られるニオブ含有液
を、シュウ酸/ニオブのモル比2〜4に調整し、ニオブ
原料液として用いることを特徴とするニオブ含有触媒の
調製方法。
1. A method for preparing a catalyst containing niobium, which is used for producing an unsaturated carboxylic acid by subjecting an alkane to a gas phase catalytic oxidation reaction, comprising an aqueous solution or an aqueous suspension containing oxalic acid and a niobium compound. Is cooled to obtain a suspension, and a niobium-containing liquid obtained by separating and removing a solid content from the suspension is adjusted to a molar ratio of oxalic acid / niobium of 2 to 4 to be used as a niobium raw material liquid. A method for preparing a niobium-containing catalyst.
【請求項2】 該ニオブ化合物がニオブ酸およびシュウ
酸水素ニオブから選ばれる少なくとも1種類以上である
請求項1に記載の触媒の調製方法。
2. The method according to claim 1, wherein the niobium compound is at least one member selected from niobic acid and niobium hydrogen oxalate.
【請求項3】 該触媒が次の一般式(I)で示される化
合物であることを特徴とする請求項1または2に記載の
触媒の調製方法。 Mo1VaNbbXcZdOn (I) (式中成分XはTeおよびSbから選ばれる少なくとも
1種類以上の元素を表し、成分ZはW、Cr、Ta、T
i、Zr、Hf、Mn、Re、Fe、Ru、Co、R
h、Ni、Pd、Pt、Ag、Zn、B、Al、Ga、
In、Ge、Sn、Pb、P、Bi、Y、希土類元素お
よびアルカリ土類元素から選ばれる少なくとも1種類以
上の元素を表し、a、b、c、d、nはMo1原子当た
りの原子比を表し、 0.1≦a≦1.0 0.01≦b≦1.0 0.01≦c≦1.0 0≦d≦1.0 であり、またnは他の元素の酸化状態によって決まる数
である。)
3. The method according to claim 1, wherein the catalyst is a compound represented by the following general formula (I). Mo1VaNbbXcZdOn (I) (wherein component X represents at least one element selected from Te and Sb, and component Z is W, Cr, Ta, T
i, Zr, Hf, Mn, Re, Fe, Ru, Co, R
h, Ni, Pd, Pt, Ag, Zn, B, Al, Ga,
In, Ge, Sn, Pb, P, Bi, Y, at least one element selected from the group consisting of rare earth elements and alkaline earth elements, a, b, c, d, and n represent the atomic ratio per Mo atom. 0.1 ≦ a ≦ 1.0 0.01 ≦ b ≦ 1.0 0.01 ≦ c ≦ 1.00 ≦ d ≦ 1.0, and n is determined by the oxidation state of other elements Is a number. )
【請求項4】 該触媒がシリカに担持されていることを
特徴とする請求項1〜3のいずれか1項に記載の触媒の
調製方法。
4. The method according to claim 1, wherein the catalyst is supported on silica.
【請求項5】 シリカの含有量が該触媒成分とシリカか
ら成るシリカ担持触媒の全重量比の20〜60重量%で
あることを特徴とする請求項4に記載の触媒の調製方
法。
5. The method according to claim 4, wherein the content of silica is 20 to 60% by weight based on the total weight ratio of the catalyst component and the silica-supported catalyst comprising silica.
【請求項6】 該シリカ担体の原料がアンモニウムイオ
ンで安定化したゾルであることを特徴とする請求項4ま
たは請求項5に記載の触媒の調製方法。
6. The method for preparing a catalyst according to claim 4, wherein the raw material of the silica carrier is a sol stabilized with ammonium ions.
【請求項7】 アルカンを気相接触酸化反応させて不飽
和カルボン酸を製造するに際して、請求項1〜6のいず
れか1項に記載の調製方法によって調整されたニオブ含
有触媒を用いることを特徴とする不飽和カルボン酸の製
造方法。
7. A process for producing an unsaturated carboxylic acid by subjecting an alkane to a gas phase catalytic oxidation reaction, wherein a niobium-containing catalyst prepared by the preparation method according to any one of claims 1 to 6 is used. For producing unsaturated carboxylic acids.
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