JP2806480B2 - Method for producing 2,6-dichlorobenzonitrile - Google Patents
Method for producing 2,6-dichlorobenzonitrileInfo
- Publication number
- JP2806480B2 JP2806480B2 JP1177960A JP17796089A JP2806480B2 JP 2806480 B2 JP2806480 B2 JP 2806480B2 JP 1177960 A JP1177960 A JP 1177960A JP 17796089 A JP17796089 A JP 17796089A JP 2806480 B2 JP2806480 B2 JP 2806480B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- reaction
- dichlorotoluene
- dbn
- alumina
- 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.)
- Expired - Fee Related
Links
- YOYAIZYFCNQIRF-UHFFFAOYSA-N 2,6-dichlorobenzonitrile Chemical compound ClC1=CC=CC(Cl)=C1C#N YOYAIZYFCNQIRF-UHFFFAOYSA-N 0.000 title claims description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000003054 catalyst Substances 0.000 claims description 38
- 239000011148 porous material Substances 0.000 claims description 19
- DMEDNTFWIHCBRK-UHFFFAOYSA-N 1,3-dichloro-2-methylbenzene Chemical compound CC1=C(Cl)C=CC=C1Cl DMEDNTFWIHCBRK-UHFFFAOYSA-N 0.000 claims description 15
- RYMMNSVHOKXTNN-UHFFFAOYSA-N 1,3-dichloro-5-methyl-benzene Natural products CC1=CC(Cl)=CC(Cl)=C1 RYMMNSVHOKXTNN-UHFFFAOYSA-N 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims description 7
- 150000004706 metal oxides Chemical class 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 20
- 238000000034 method Methods 0.000 description 15
- 238000000465 moulding Methods 0.000 description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- -1 bromine compound Chemical class 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- PMJNEQWWZRSFCE-UHFFFAOYSA-N 3-ethoxy-3-oxo-2-(thiophen-2-ylmethyl)propanoic acid Chemical compound CCOC(=O)C(C(O)=O)CC1=CC=CS1 PMJNEQWWZRSFCE-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000004009 herbicide Substances 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- AZFUOHYXCLYSQJ-UHFFFAOYSA-N [V+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound [V+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O AZFUOHYXCLYSQJ-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000010457 zeolite 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、2,6−ジクロルトルエンの気相接触アンモ
オキシデーションによる、2,6−ジクロルベンゾニトリ
ル（以下DBNと略する）の製造方法に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to the production of 2,6-dichlorobenzonitrile (hereinafter abbreviated as DBN) by gas-phase catalytic ammoxidation of 2,6-dichlorotoluene. It relates to a manufacturing method.
DBNはそれ自体、除草剤として重要であるばかりでな
く同様に除草剤中間体、農園芸用殺虫剤の中間体とし
て、又、各種医薬、染料、高分子などの中間体又は原料
として広く利用されている極めて重要な化合物である。DBN itself is not only important as a herbicide, but is also widely used as an intermediate for herbicides, intermediates for agricultural and horticultural insecticides, and as intermediates or raw materials for various drugs, dyes, and polymers. Is a very important compound.
（従来の技術） 2,6−ジクロルトルエンをアンモオキデーションによ
りDBNに転化せしめる反応は公知である。古くは例えば
Ｖ系触媒を用い流動接触反応によりDBNを合成する方法
（特公昭43−10623号公報）、同様にＶ−Fe系触媒を用
いて合成する方法（特公昭43−5386号公報）、Ｖ−Ｐ系
触媒を用いて合成する方法（特開昭53−121738号公報）
などが知られている。(Prior Art) A reaction for converting 2,6-dichlorotoluene to DBN by amooxidation is known. For example, a method of synthesizing DBN by a fluid catalytic reaction using a V-based catalyst (Japanese Patent Publication No. 43-10623), a method of synthesizing using a V-Fe-based catalyst similarly (Japanese Patent Publication No. 43-5386), Method of synthesizing using VP catalyst (JP-A-53-121738)
Etc. are known.
しかしながらこれらの触媒系は目的とするDBNの収率
の点で満足できるものではない。この主たる原因は、望
まれるアンモオキシデーションの主反応の他に、原料2,
6−ジクロルトルエンの燃焼により、結果として生じる
塩化アンモニウムを副生する副反応が競争的に、しかも
相当量、起こるためである。However, these catalyst systems are not satisfactory in terms of the target DBN yield. This is mainly due to the main reaction of the desired ammoxidation,
The combustion of 6-dichlorotoluene causes competitive and considerable side reactions to produce the resulting ammonium chloride.
この副反応を制御する目的で、例えばＶ−Ｐ系触媒を
用い、流動接触反応によりDBNを合成する際に、臭素化
合物を反応系に添加する方法（特開昭60−67454号公
報）、及びＶ−Fe−Sb系に更に必要な場合、前３成分に
加え他の金属成分を更に４種以上、組み合わせた触媒系
を用い、同様に流動触媒反応によりDBNを合成する方法
（特開昭63−250357号公報）などが提案されている。For the purpose of controlling this side reaction, for example, a method of adding a bromine compound to a reaction system when synthesizing DBN by a fluidized contact reaction using a VP-based catalyst (JP-A-60-67454), and In the case where the V-Fe-Sb system is further required, a method of synthesizing DBN by a fluid catalytic reaction using a catalyst system in which four or more other metal components are combined in addition to the above three components (Japanese Patent Application Laid-Open No. Sho 63) -250357) and the like.
しかし例えば前者のように第三物質を反応系に添加す
る方法はそれ自体経済的に有利であるとは言い難いし、
又、目的とするDBNの不純物の混入という見地からも問
題が残るものである。又例えば後者のように好結果を得
る為には時として８種以上の金属酸化物を組み合わせた
触媒系を用いる方法も、やはりその触媒自体の経済性
や、系の調整方法から合理的とは言い難いものである。However, the method of adding the third substance to the reaction system as in the former, for example, cannot be said to be economically advantageous in itself,
Further, the problem remains from the viewpoint of contamination of the target DBN with impurities. For example, in order to obtain good results as in the latter case, sometimes a method using a catalyst system combining eight or more metal oxides is not rational due to the economics of the catalyst itself or the method of adjusting the system. It is hard to say.
更に一般にこれ等のアンモオキシデーションは、前記
副反応が局部高温加熱により、より増大するものと考え
られているため、通常は流動接触反応、すなわち流動床
方式により行われているが、この流動床方式は、大規模
な設備形態を招き易く、生産物とのバランスによって
は、しばしば採算に合わない事態に落ち入る欠点を有す
るものである。More generally, such ammoxidation is usually carried out by a fluidized contact reaction, that is, a fluidized bed method, since the side reaction is considered to be increased by local high-temperature heating. The method has a disadvantage that it tends to cause a large-scale equipment configuration and often falls into an unprofitable state depending on a balance with a product.
固定床方式を採ればこの種の問題は少なからず軽減さ
れるものであるが、先に述べた局部加熱の不具合を補っ
て、余りある良好な触媒種の開発が今もって望まれると
ころである。The use of a fixed bed system can alleviate this kind of problem to some extent. However, it is still desired to develop a sufficiently good catalyst species to compensate for the above-mentioned problem of local heating.
（本発明が解決しようとする問題） 本発明は工業的に有利な方法でDBNを製造する方法を
提供するものであり、更に具体的には、Ｖ−Mo−Cr−Ｐ
系金属酸化物触媒をγ−アルミナに担持させ、その細孔
分布を制御した成型触媒を用いる事により、2,6−ジク
ロルトルエンのアンモオキシデーションから高収率、高
選択率でDBNを製造する方法を提供するものである。(Problem to be solved by the present invention) The present invention provides a method for producing DBN by an industrially advantageous method, and more specifically, V-Mo-Cr-P
Production of DBN with high yield and high selectivity from ammoxidation of 2,6-dichlorotoluene by using γ-alumina carrying a metal oxide based catalyst and using a molded catalyst whose pore distribution is controlled It provides a way to:
（問題を解決する為の手段） 本発明によるDBNの製造方法は、2,6−ジクロルトルエ
ンをアンモニア及び酸素を含む気体でアンモオキシデー
ションする際に、Va、Mob、Crc、Pd、Oe（式中ａ、ｂ、
ｃ、ｄ、ｅは原子比は示し、ａ＝１の時ｂ＝0.05〜10、
ｃ＝0.1〜30、ｄ＝0.05〜10、ｅは他の原子価から必然
的にとる数を示す。）なる組成を有する金属酸化物をγ
−アルミナに担持させ、かつその担持物の細孔分布にお
いて、500Å〜10μの範囲内のマクロポアズの細孔容積
が少なくとも0.1cc/g以上を保つように成型された触媒
を用いる事を特徴とするものである。(Means for Solving the Problem) The method for producing DBN according to the present invention is characterized in that when ammoxidation of 2,6-dichlorotoluene with a gas containing ammonia and oxygen, Va, Mob, Crc, Pd, Oe ( Where a, b,
c, d and e indicate atomic ratios, and when a = 1, b = 0.05-10,
c = 0.1 to 30, d = 0.05 to 10, and e represents a number inevitable from other valences. The metal oxide having the composition
-Characterized by using a catalyst which is supported on alumina, and which is molded so that the pore volume of macropores in the range of 500Å to 10μ is maintained at least 0.1 cc / g or more in the pore distribution of the supported material. Things.
本発明に係る触媒に用いる金属酸化物組成は前記一般
式で示した範囲内であるならばいかなる組成でも良い
が、好ましくは前記一般式においてａを１とするならば
ｂ＝0.1〜１、ｃ＝0.5〜３、ｄ＝0.1〜３なる組成範囲
を持つ金属酸化物系である。（ｅは同様に他の原子価か
ら必然的にとる数を示す。） これら各成分の出発原料としては、それぞれの金属の
酸化物、ハロゲン化物、硫酸塩、アンモニウム塩など一
般的に触媒を調整する際に用いられる多くの種類の中か
ら選ぶ事ができる。The composition of the metal oxide used in the catalyst according to the present invention may be any composition as long as it is within the range shown by the above general formula. Preferably, if a is 1 in the above general formula, b = 0.1 to 1, c = 0.5-3 and d = 0.1-3. (E is also a number necessarily taken from other valences.) As a starting material for each of these components, generally, a catalyst such as an oxide, halide, sulfate, ammonium salt of each metal is prepared. You can choose from the many types that are used when doing so.
例えばバナジウム成分を導入するためには、五酸化バ
ナジウム、メタバナジン酸アンモニウム、硝酸バナジウ
ム、ハロゲン化バナジウム類などが用いられるし、モリ
ブデン成分を導入にするためにはパラモリブデン酸アン
モニウム、メタモリブデン酸アンモニウム、三酸化モリ
ブデン、ハロゲン化モリブデン類などが用いられる。
又、クロム成分を導入するためには例えは重クロム酸ア
ンモニウム、クロム酸アンモニウム、硝酸クロムなどが
用いられ、リン成分を導入するためにはリン酸、リン酸
塩、次亜リン酸、五酸化リンなどが用いられる。For example, to introduce a vanadium component, vanadium pentoxide, ammonium metavanadate, vanadium nitrate, vanadium halides and the like are used.To introduce a molybdenum component, ammonium paramolybdate, ammonium metamolybdate, Molybdenum trioxide, molybdenum halides and the like are used.
In order to introduce a chromium component, for example, ammonium bichromate, ammonium chromate, chromium nitrate, etc. are used, and to introduce a phosphorus component, phosphoric acid, phosphate, hypophosphorous acid, pentoxide, etc. Phosphorus or the like is used.
本発明におけるこれら各成分の調整には、この種の金
属酸化物触媒を調整する場合に良く用いられる一般的な
方法が適用できる。例えば水にバナジウム化合物を溶解
しそれにリン化合物を添加し、更にクロム化合物及びモ
リブデン化合物の水溶液を加え均一化し、これを担体を
加え充分に含浸させる。次にこれを蒸発乾固させ、それ
を焼成したのち必要な成型をする事により得られる。For adjusting each of these components in the present invention, a general method often used for adjusting such a metal oxide catalyst can be applied. For example, a vanadium compound is dissolved in water, a phosphorus compound is added thereto, and an aqueous solution of a chromium compound and a molybdenum compound is further added to homogenize the mixture. Next, it is obtained by evaporating it to dryness, baking it and performing necessary molding.
本発明の重要な点は、このようにして成型した触媒の
細孔分布にある。An important point of the present invention lies in the pore distribution of the catalyst thus molded.
通常アンモオキシデーションのような気相接触反応に
用いられる工業用触媒は、その強度的劣化を防ぐため、
又、固定床方式を採るならば圧損を避ける為、成型して
用いられ、その際使用される担体には各種シリカ、アル
ミナ、ゼオライトなどが適当とされている。本発明に要
望される細孔分布特性を有する担体は多種あるが、成型
された上で活性を保持、又は増強し、前記のように望ま
しくは、固定床方式において使用してもなお、充分な触
媒活性を発現させるための担体としてはγ−アルミナが
望ましい。Industrial catalysts usually used for gas-phase catalytic reactions such as ammoxidation, to prevent their strength deterioration,
If a fixed bed system is adopted, it is molded and used in order to avoid pressure loss, and various types of silica, alumina, zeolite and the like are considered to be suitable for the carrier used at that time. Although there are various types of carriers having the pore distribution characteristics required in the present invention, the activity is maintained or enhanced after being molded, and as described above, it is preferable that the carrier be sufficiently used even in a fixed bed system. Γ-alumina is desirable as a carrier for exhibiting catalytic activity.
γ−アルミナであれば特に種類は問わないが調整する
上で各金属成分を含浸させるためには200メッシュより
細かいγ−アルミナを使用する事が望ましい。Any kind of γ-alumina can be used, but it is preferable to use γ-alumina finer than 200 mesh in order to impregnate each metal component for adjustment.
これ等、各金属成分のγ−アルミナへの担持率は、主
触媒となるバナジウムを基準として、担持させたV2O5対
Al2O3の量比が約１〜30（V2O5wt/Al2O3wt）％の範囲内
であれば良いが、好ましくは２〜20（V2O5wt/Al2O3wt）
％の範囲である。The loading ratio of each metal component on γ-alumina was determined based on the amount of V 2 O 5 supported on the basis of vanadium as the main catalyst.
Al ratio of 2 O 3 may be within a range of about 1~30 (V 2 O 5 wt / Al 2 O 3 wt)% , but preferably 2~20 (V 2 O 5 wt / Al 2 O 3 wt)
% Range.
このようにして調整された金属酸化物−γ−アルミナ
触媒は、それに強度を付与せしめるために成型を施され
るが、その際必要ならばベントナイト、アルミナゾル、
シリカゾル等のバインダーを加える事も可能である。The metal oxide-γ-alumina catalyst adjusted in this manner is subjected to molding in order to give it strength, in which case if necessary, bentonite, alumina sol,
It is also possible to add a binder such as silica sol.
成型法は一般的には押出し成型、圧縮成型、打錠成型
あるいはマルメライザーによる形成等の方法が採られる
が、本発明が要求する細孔分布特性すなわち500Å〜10
μの範囲内のマクロポアズの細孔容積が少なくも0.1cc/
g以上を保つように成型するためには過度の圧縮、又は
打錠は好ましくなく、押出し法又はマルメライザーによ
る成型法、もしくは15kg/cm2以下の打錠圧にて成型する
打錠成型法などが好ましい。The molding method is generally a method such as extrusion molding, compression molding, tablet molding or formation with a marmellaizer, but the pore distribution characteristics required by the present invention, that is, 500 to 10
The pore volume of macropores in the μ range is at least 0.1 cc /
Excessive compression to mold to keep the above g, or tablet is undesirable, extrusion or molding by Marumerizer, or 15 kg / cm 2 or less tabletting molding method for molding by tableting pressure etc. Is preferred.
本発明が要求するこのマクロポアズの細孔容積は、ミ
クロポアズ及びメソポアズ内で主として行なわれる主反
応（アンモオシデーション）を補い、同時に同細孔内で
行なわれる副反応（過度の反応熱蓄積による燃焼の結
果、塩化アンモニウムを副制生する反応）を軽減する為
には必須のものである。本発明は、このようにして調整
した細孔分布特性を持つ成型触媒が充填されている反応
器へ、2,6−ジクロルトルエン、アンモニア及び酸素を
含有する気体を導入する事によって行なう。The pore volume of this macro poise required by the present invention complements the main reaction (ammoxidation) mainly performed in micro poise and meso poise, and simultaneously the side reaction (combustion due to excessive reaction heat accumulation) performed in the same pore. As a result, it is indispensable to reduce the reaction of by-producing ammonium chloride). The present invention is carried out by introducing a gas containing 2,6-dichlorotoluene, ammonia and oxygen into a reactor filled with a shaped catalyst having pore distribution characteristics thus adjusted.
これら、導入ガスは窒素及び他の不活性気体、例えば
水蒸気、二酸化炭素、一酸化炭素などを含んでいても良
く、酸素を含有する気体としては空気は用いるのが経済
的に望ましい。These introduced gases may include nitrogen and other inert gases such as water vapor, carbon dioxide, carbon monoxide, and the like, and it is economically desirable to use air as the oxygen-containing gas.
導入ガス中の2,6−ジクロルトルエンの濃度は0.5〜15
モル％の範囲内であれば良いが好ましくは１〜７モル％
の範囲である。同様にガス中の2,6−ジクロルトルエン
とアンモニアと酸素のモル比は、2,6−ジクロルトルエ
ン：アンモニア：酸素＝1:1〜10:1.5〜10であれば良い
が、好ましくは1:1.5〜7:2〜７の範囲である。The concentration of 2,6-dichlorotoluene in the introduced gas is 0.5 to 15
Although it may be within the range of mol%, preferably 1 to 7 mol%
Range. Similarly, the molar ratio of 2,6-dichlorotoluene to ammonia and oxygen in the gas may be 2,6-dichlorotoluene: ammonia: oxygen = 1: 1 to 10: 1.5 to 10, but is preferably 1: 1.5-7: 2-7.
反応温度は300〜600℃で良いが、好ましくは320〜420
℃の範囲である。The reaction temperature may be 300 to 600 ° C., preferably 320 to 420
It is in the range of ° C.
反応は常圧、加圧、減圧いずれの状態でも行ないうる
が、望ましくは常圧から3kg/cm2Gの範囲内で行なうのが
良い。接触時間は、反応が実施される条件における、ガ
ス容積基準で0.5〜50秒で良いが、好ましくは２〜25秒
の範囲である。The reaction can be carried out under any of normal pressure, increased pressure and reduced pressure, but is preferably carried out within a range from normal pressure to 3 kg / cm 2 G. The contact time may be 0.5 to 50 seconds, preferably 2 to 25 seconds, based on the gas volume under the conditions in which the reaction is carried out.
反応は固定床方式あるいは流動床方式のいずれでも良
いが前記の通り本触媒の特性を生かすためには固定床方
式が好ましい。The reaction may be carried out in a fixed bed system or a fluidized bed system, but as described above, the fixed bed system is preferable in order to make use of the characteristics of the present catalyst.
（発明の効果） 本発明のＶ−Mo−Cr−Ｐ系／γ−アルミナ担持触媒
は、その触媒組成及びその細孔分布特性から、2,6−ジ
クロルトルエンよりDBNを製造するアンモオキシデーシ
ョンに対して、すぐれた活性及び選択性を発現する。従
って、本発明の触媒を使用する事により産業上重要な化
合物であるDBNを高収率で得る事ができ、従来の方法に
比べ工業的に有利に実施する事ができる。(Effect of the Invention) The V-Mo-Cr-P-based / γ-alumina-supported catalyst of the present invention has an ammoxidation for producing DBN from 2,6-dichlorotoluene based on its catalyst composition and its pore distribution characteristics. Expresses excellent activity and selectivity. Therefore, by using the catalyst of the present invention, DBN which is an industrially important compound can be obtained in a high yield, and it can be carried out industrially more advantageously than the conventional method.
以下、実施例によって本発明を具体的に説明するが、
本発明はこれにより限定されるものではない。Hereinafter, the present invention will be described specifically with reference to Examples.
The present invention is not limited by this.
なお、以下実施例に記載される2,6−ジクロルトルエ
ンの転化率、DBNの収率、DBNの選択率、塩化アンモニウ
ムの副生率は次の定義に従って計算した。The conversion of 2,6-dichlorotoluene, the yield of DBN, the selectivity of DBN, and the by-product rate of ammonium chloride described in the following Examples were calculated according to the following definitions.
なお、実施例において触媒、金属酸化物組成中の酸素
については他の元素の原子価から自然に決まる値である
ので記載を省略した。 In the examples, the description of oxygen in the catalyst and metal oxide composition is omitted because it is a value naturally determined from the valence of other elements.
実施例１ メタバナジン酸アンモニウム200gを純水4lに懸濁させ
80℃に加熱した。これに50gのシュウ酸を少しずつ加
え、完全に均一溶液とした。次に85％リン酸200gとあら
かじめ３の純水に溶かした、クロム酸アンモニウム、
及び同様に２の純水に溶かしたモリブデン酸アンモニ
ウム90gをそれぞれ添加し、撹拌下、均一溶液とした。
この溶液に200メッシュより細かい、活性γ−アルミナ
を2600g添加し、80℃で２時間撹拌して金属成分を充分
に含浸させた。これを蒸発乾固した後、空気流中500℃
で５時間焼成した。この焼成触媒７に対して３の割合
（wt/wt）で、バインダーとしてベントナイトを加え、
適当量の水及びヒドロキシエチルセルロースと共に混練
りした。これを3mmφ×３〜7mmに押出し成型した後、空
気流中500℃にて５時間焼成した目的とする触媒を得
た。Example 1 200 g of ammonium metavanadate was suspended in 4 l of pure water.
Heated to 80 ° C. To this, 50 g of oxalic acid was added little by little to make a completely homogeneous solution. Next, ammonium chromate, previously dissolved in 200 g of 85% phosphoric acid and 3 pure waters,
Similarly, 90 g of ammonium molybdate dissolved in the pure water of No. 2 was added, respectively, to obtain a homogeneous solution with stirring.
To this solution, 2600 g of active γ-alumina finer than 200 mesh was added and stirred at 80 ° C. for 2 hours to sufficiently impregnate the metal component. After evaporating this to dryness, 500 ℃ in air stream
For 5 hours. Bentonite was added as a binder at a ratio of 3 (wt / wt) to the calcined catalyst 7,
Kneaded with an appropriate amount of water and hydroxyethyl cellulose. This was extruded to 3 mmφ × 3 to 7 mm, and then calcined at 500 ° C. for 5 hours in an air stream to obtain a desired catalyst.
このようにして得られた触媒の担持率は６％、組成は
V1、Mo0.3、Cr1、Ｐ0.7である。又、この触媒の細孔分
布をポアサイザーにより水銀圧入法で測定したところ50
0Å〜10μの範囲内のマクロポアズの細孔容積は0.13cc/
gの値を示した。The loading of the catalyst thus obtained is 6%, and the composition is
V 1 , Mo 0.3 , Cr 1 , and P 0.7 . The pore distribution of this catalyst was measured by a mercury intrusion method using a pore sizer.
The pore volume of macropoise in the range of 0Å to 10μ is 0.13cc /
The value of g is shown.
この触媒を内径が１インチの固定床反応器に層長が44
cmとなるように充填し（約200g）、反応器をアルミナ流
動浴に浸して、温度を340〜350℃に保った。The catalyst was placed in a fixed-bed reactor having an inner diameter of 1 inch and a bed length of 44 inches.
cm (about 200 g) and the reactor was immersed in an alumina fluidized bath to maintain the temperature at 340-350 ° C.
2,6−ジクロルトルエン、2.8モル％、アンモニア11.2
モル％、酸素11.2モル％、窒素74.8モル％を含む混合ガ
スを反応器に導入し、触媒層内の最高温度が360℃を超
えないよう流動浴を調整しながら反応させた。この時、
空塔線速度は4.1cm/秒に、接触時間は10.7秒に保った。2,6-dichlorotoluene, 2.8 mol%, ammonia 11.2
A mixed gas containing mol%, 11.2 mol% of oxygen, and 74.8 mol% of nitrogen was introduced into the reactor, and the reaction was performed while adjusting the fluidized bath so that the maximum temperature in the catalyst layer did not exceed 360 ° C. At this time,
The superficial linear velocity was kept at 4.1 cm / sec and the contact time was kept at 10.7 sec.
その後、2,6−ジクロルトルエンの添加率は95.1％、D
BNの収率は85％、選択率は90.1％、副生率は9.9％であ
った。Thereafter, the addition ratio of 2,6-dichlorotoluene was 95.1%,
The yield of BN was 85%, the selectivity was 90.1%, and the by-product rate was 9.9%.
比較例1. 実施例１と同様に調整、混練した触媒を打錠圧30kg/c
m2にて3mmφ×3mmに打錠成型した。Comparative Example 1. A catalyst prepared and kneaded in the same manner as in Example 1 was subjected to tableting pressure of 30 kg / c.
It was tableted to 3 mmφ × 3 mm in m 2 .
同様に焼成した後、この触媒の細孔分布を測定したと
ころ500Å〜10μの範囲内のマクロポアズの細孔容積は
0.06cc/gの値を示した。この触媒を用いて実施例１と同
一条件で反応を行なったところ、2,6−ジクロルトルエ
ンの転化率は96.9％、DBNの収率は77.8％、選択率は80.
5％、副生率は21.2％であった。After calcination in the same manner, when the pore distribution of this catalyst was measured, the pore volume of macropores in the range of 500Å to 10μ was
It showed a value of 0.06 cc / g. When the reaction was carried out under the same conditions as in Example 1 using this catalyst, the conversion of 2,6-dichlorotoluene was 96.9%, the yield of DBN was 77.8%, and the selectivity was 80.
The by-product rate was 51.2%.
実施例２ 実施例１において空塔線速度を8.3cm/秒に、接触時間
を5.3秒に、又、触媒層内の最高温度が380℃を超えない
ように変更した以外は実施例１と同様に反応を実施し
た。その結果、2,6−ジクロルトルエンの転化率は90.2
8、DBNの収率は79.5％、選択率は88.5％、副生率は11.4
であった。Example 2 Same as Example 1 except that the superficial linear velocity was changed to 8.3 cm / sec, the contact time was changed to 5.3 seconds, and the maximum temperature in the catalyst layer was not exceeded 380 ° C. The reaction was carried out. As a result, the conversion of 2,6-dichlorotoluene was 90.2
8, DBN yield 79.5%, selectivity 88.5%, by-product rate 11.4
Met.
実施例３〜５ 実施例１においてV:P又はMoの原子比を変えて触媒を
調整した以外は実施例１と同様に反応を実施した。マク
ロポアズの細孔容積を含む結果を表−Ｉに示した。Examples 3 to 5 The reaction was carried out in the same manner as in Example 1 except that the catalyst was adjusted by changing the atomic ratio of V: P or Mo. The results, including macropore pore volume, are shown in Table-I.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭60−67454（ＪＰ，Ａ) 特開 昭63−250357（ＪＰ，Ａ) 特開 昭53−121738（ＪＰ，Ａ) 特公 昭39−21243（ＪＰ，Ｂ１) 特公 昭45−5386（ＪＰ，Ｂ１) (58)調査した分野(Int.Cl.6，ＤＢ名) C07C 255/50 C07C 253/28──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-60-67454 (JP, A) JP-A-63-250357 (JP, A) JP-A-53-121738 (JP, A) 21243 (JP, B1) JP-B-45-5386 (JP, B1) (58) Fields investigated (Int. Cl. 6 , DB name) C07C 255/50 C07C 253/28
Claims (1)
酸素を含む気体でアンモオキシデーションする際にVaMo
bCrcPdOe（式中ａ、ｂ、ｃ、ｄ、ｅは原子比を示し、ａ
＝１の時ｂ＝0.05〜10、ｃ＝0.1〜30、ｄ＝0.05〜10、
ｅは他の原子価から必然的にとる数を示す。） なる組成を有する金属酸化物触媒を、γ−アルミナに担
持たせ、かつその担持物の細孔分布において、500Å〜1
0μの範囲内のマクロポアズの細孔容積が少なくとも0.1
cc/g以上を保つように成型された触媒を用いる事を特徴
とする、2,6−ジクロルベンゾニトリルの製造方法。(1) When ammoxidation of 2,6-dichlorotoluene with a gas containing ammonia and oxygen, VaMo
bCrcPdOe (where a, b, c, d, and e indicate an atomic ratio, and a
= 1, b = 0.05-10, c = 0.1-30, d = 0.05-10,
e indicates a number necessarily taken from other valences. ) A metal oxide catalyst having the following composition is supported on γ-alumina, and the pore distribution of the supported material is 500Å to 1
The pore volume of macropoise in the range of 0μ is at least 0.1
A method for producing 2,6-dichlorobenzonitrile, characterized by using a catalyst molded to maintain cc / g or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1177960A JP2806480B2 (en) | 1989-07-12 | 1989-07-12 | Method for producing 2,6-dichlorobenzonitrile |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1177960A JP2806480B2 (en) | 1989-07-12 | 1989-07-12 | Method for producing 2,6-dichlorobenzonitrile |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0344362A JPH0344362A (en) | 1991-02-26 |
| JP2806480B2 true JP2806480B2 (en) | 1998-09-30 |
Family
ID=16040090
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1177960A Expired - Fee Related JP2806480B2 (en) | 1989-07-12 | 1989-07-12 | Method for producing 2,6-dichlorobenzonitrile |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2806480B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08337543A (en) * | 1995-06-13 | 1996-12-24 | Kureha Chem Ind Co Ltd | Production of 2,6-dichloro-3,5-di(secondary or tertiary alkyl)toluene |
| AU2003242614A1 (en) | 2002-06-04 | 2003-12-19 | Tessenderlo Chemie S.A. | Method for the preparation of halogenated benzonitriles |
| JP5353095B2 (en) * | 2008-07-22 | 2013-11-27 | 三菱瓦斯化学株式会社 | Method for producing aromatic nitrile |
| WO2010143690A1 (en) | 2009-06-11 | 2010-12-16 | 三菱瓦斯化学株式会社 | Ammoxidation catalyst and method for producing nitrile compound using the same |
-
1989
- 1989-07-12 JP JP1177960A patent/JP2806480B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0344362A (en) | 1991-02-26 |
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