JPH0245433A - Production of dichlorobenzene - Google Patents
Production of dichlorobenzeneInfo
- Publication number
- JPH0245433A JPH0245433A JP63192862A JP19286288A JPH0245433A JP H0245433 A JPH0245433 A JP H0245433A JP 63192862 A JP63192862 A JP 63192862A JP 19286288 A JP19286288 A JP 19286288A JP H0245433 A JPH0245433 A JP H0245433A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- zeolite
- molecular oxygen
- reaction
- present
- 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
Links
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229940117389 dichlorobenzene Drugs 0.000 title claims abstract 5
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000010457 zeolite Substances 0.000 claims abstract description 20
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 17
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 15
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 13
- 239000007789 gas Substances 0.000 claims abstract description 13
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000005660 chlorination reaction Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 abstract description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 abstract description 2
- 229910052786 argon Inorganic materials 0.000 abstract description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 2
- 239000001569 carbon dioxide Substances 0.000 abstract description 2
- 239000001307 helium Substances 0.000 abstract description 2
- 229910052734 helium Inorganic materials 0.000 abstract description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 abstract description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 abstract description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011261 inert gas Substances 0.000 abstract description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 abstract description 2
- 239000002917 insecticide Substances 0.000 abstract 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 16
- 239000000460 chlorine Substances 0.000 description 16
- 229910052801 chlorine Inorganic materials 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 229910052680 mordenite Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- -1 trichlorobenzene Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 1
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 235000010582 Pisum sativum Nutrition 0.000 description 1
- 240000004713 Pisum sativum Species 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 229910052675 erionite Inorganic materials 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001640 fractional crystallisation Methods 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 239000000077 insect repellent Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur 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
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
イ）発明の目的
〔産業上の利用分野〕
本発明は、ベンゼン（以下ＢＺと略記する）および／ま
たはモノクロロベンゼン（以下ＣＢと略記する）を気相
塩素化し、ジクロロベンゼン（以下ＤＣＢと略記する）
を製造する方法に関するものである。Detailed Description of the Invention A) Purpose of the Invention [Industrial Field of Application] The present invention is directed to gas-phase chlorination of benzene (hereinafter abbreviated as BZ) and/or monochlorobenzene (hereinafter abbreviated as CB). Chlorobenzene (hereinafter abbreviated as DCB)
The present invention relates to a method for manufacturing.
ＤＣＢは工業的に重要な化合物であり、多くの製品の原
料中間体として用いられている。DCB is an industrially important compound and is used as a raw material intermediate for many products.
ＤＣＨにはバラジクロロベンゼン（以下ＰＤＣＢと略記
する）、オルトジクロロベンゼン（以下０ＤＣＢと略記
する）およびメタジクロロベンゼン（以下ＭＤＣＢと略
記する）の三種の異性体が存在する。このうちＰＤＣ［
３は最も需要が多く、防虫剤の他にエンジニアリング・
プラスチックであるポリフェニレンサルファイドの原料
として注目されている。There are three isomers of DCH: varadichlorobenzene (hereinafter abbreviated as PDCB), orthodichlorobenzene (hereinafter abbreviated as 0DCB), and metadichlorobenzene (hereinafter abbreviated as MDCB). Of these, PDC [
Type 3 has the highest demand, and in addition to insect repellents, it is also used in engineering and
It is attracting attention as a raw material for the plastic polyphenylene sulfide.
従来ＤＣＢは塩化第二鉄等のフリーデルタラット型触媒
を用い、ＢＺまたはＣＢを塩素化して製造されている。Conventionally, DCB has been produced by chlorinating BZ or CB using a free delta rat type catalyst such as ferric chloride.
しかしながらこの方法ではＰＤＣＢの選択率は約６０％
と低く、利用価値の低い０ＤＣＢが多く副生ずる。However, with this method, the selectivity of PDCB is about 60%.
0DCB with low utility value is produced as a by-product.
これを改良するため硫黄、セレン系の無機あるいは有機
化合物を塩化第二鉄と併用する方法が提案されている。To improve this, a method has been proposed in which sulfur and selenium-based inorganic or organic compounds are used in combination with ferric chloride.
この方法では、ＰＤＣＢの選択率は７０〜８０％と改善
されるものの、塩化第二鉄を触媒とする反応において一
般に見られるトリクロロベンゼン等の高次塩素化ベンゼ
ンの副生が多いという問題が残されている。また、これ
らの触媒で汚染された反応生成物から触媒を除去するた
めに水洗等の工程が必要であり、触媒の再利用は極めて
難しい。Although this method improves the selectivity of PDCB to 70-80%, there remains the problem that there are many by-products of higher chlorinated benzenes such as trichlorobenzene, which are commonly found in reactions using ferric chloride as a catalyst. has been done. In addition, steps such as water washing are required to remove the catalyst from reaction products contaminated with these catalysts, making reuse of the catalyst extremely difficult.
また、近年ゼオライトを触媒とするＢＺおよび／または
ＣＢの選択的塩素化について、いくつかの提案がなされ
ている０例えば、特開昭５９−１６３３２９号公報には
、Ｌ型ゼオライトを触媒とする液相塩素化反応が開示さ
れている。この反応におけるＰＤＣＢの選択率は８０〜
９０％と高いものの、触媒活性が短時間で低下するとい
う欠点がある。また、特開昭６１−１７１．４４号公報
には、オフレタイトーエリオナイト系ゼオライトを触媒
とする気相塩素化反応が開示されている。この反応にお
けるＰＤＣＢの選択率も８５〜９０％と高く、また、塩
素とＢＺおよび／またはＣＢを予め混合することなく、
それぞれ別々にゼオライト触媒層に供給することにより
、触媒の寿命を改善できるとされているが、触媒寿命の
改善は充分なものとはいえない。In addition, in recent years, several proposals have been made regarding the selective chlorination of BZ and/or CB using zeolite as a catalyst. A phase chlorination reaction is disclosed. The selectivity of PDCB in this reaction is 80~
Although it is as high as 90%, it has the disadvantage that the catalyst activity decreases in a short period of time. Further, Japanese Patent Application Laid-open No. 171.44/1988 discloses a gas phase chlorination reaction using an offretite erionite zeolite as a catalyst. The selectivity of PDCB in this reaction is as high as 85 to 90%, and without premixing chlorine with BZ and/or CB,
It is said that the life of the catalyst can be improved by supplying each of them separately to the zeolite catalyst bed, but the improvement in the life of the catalyst cannot be said to be sufficient.
本発明者らは、触媒としてゼオライトを用い、ＢＺおよ
び／またはＣＢを気相塩素化反応させＤＣＢを製造する
にあたり、ＰＤＣＢの選択率が高く、かつ長い触媒寿命
を提供し得る、工業的に有利なりＣＢの製造方法につき
鋭意研究を重ねた結果、本発明を完成した。The present inventors used zeolite as a catalyst to produce DCB by gas-phase chlorination reaction of BZ and/or CB, and found an industrially advantageous method that can provide high selectivity for PDCB and a long catalyst life. As a result of extensive research into the manufacturing method of Nari CB, the present invention was completed.
口）発明の構成
〔課題を解決する為の手段〕
本発明は、触媒としてゼオライトを用い、ＢＺおよび／
またはＣＢを気相塩素化反応させることによりＤＣＢを
製造するにあたり、分子状酸素の存在下に反応させるこ
とを特徴とするＤＣＢの製造方法である。g) Structure of the invention [Means for solving the problem] The present invention uses zeolite as a catalyst, and BZ and/or
Alternatively, in producing DCB by subjecting CB to a gas phase chlorination reaction, the method is characterized in that the reaction is carried out in the presence of molecular oxygen.
本発明において触媒として使用するゼオライトは、通常
、結晶性アルミノシリケートと呼ばれるものであり、本
発明においては特に制限されるものではないが、モルデ
ナイト系ゼオライトが好適に用いられる。ゼオライトの
中には天然に存在するものもあるが、合成することも可
能であり、本発明においては天然ゼオライトと合成ゼオ
ライトのどちらを用いても差し支えないが、不純物が少
なく、結晶化度の高い合成ゼオライトがより好適である
。The zeolite used as a catalyst in the present invention is usually called a crystalline aluminosilicate, and although it is not particularly limited in the present invention, mordenite zeolite is preferably used. Some zeolites exist naturally, but they can also be synthesized, and in the present invention, either natural zeolite or synthetic zeolite can be used, but zeolites with fewer impurities and a high degree of crystallinity can be used. Synthetic zeolites are more preferred.
ゼオライトは通常、Ｎａイオン、Ｋイオン等の金属陽イ
オンを含有するが、本発明においてはこのようなアルカ
リ金属イオンまたはアルカリ土類金属イオンを含有する
ゼオライトが好ましい。Zeolite usually contains metal cations such as Na ions and K ions, and in the present invention, zeolites containing such alkali metal ions or alkaline earth metal ions are preferred.
触媒の形状については、特に制限はな（、反応の形式に
よって任意に選択することが出来、粉末状、顆粒状、球
状、筒状、環状などがある。またゼオライトはガラスピ
ーズのような不活性充填材と混合して用いることが出来
る。There are no particular restrictions on the shape of the catalyst (it can be arbitrarily selected depending on the type of reaction, and may be powdered, granular, spherical, cylindrical, cyclic, etc.). It can be used in combination with a filler.
本発明におけるＢＺまたはＣＢに対する塩素の供給モル
比は、ＢＺを基準として塩素が０．１〜３．０が好まし
く、更に好ましくは０．５〜２．０である。ＢＺまたは
ＣＢに対する塩素の供給モル比が低くすぎるとＰＤＣＢ
の収率が低（なる恐れがあり、高すぎると高次塩素化物
の副生量が増大する可能性がある。また、本発明におい
ては単体の塩素が特に好ましく用いられる。In the present invention, the molar ratio of chlorine supplied to BZ or CB is preferably 0.1 to 3.0, more preferably 0.5 to 2.0, based on BZ. If the molar ratio of chlorine supplied to BZ or CB is too low, PDCB
If the yield is too high, the amount of by-products of higher chlorinated products may increase.Also, in the present invention, elemental chlorine is particularly preferably used.
本発明において反応系内に存在させる分子状酸素の割合
は、ＢＺまたは／およびＣＢを基準としたモル比で０．
０２〜２０が好ましい。０．０２未満では触媒寿命の改
善効果があまり期待できず、２０を超えても、それ以上
の改善効果の増大が期待できない場合がある。In the present invention, the proportion of molecular oxygen present in the reaction system is 0.00 molar ratio based on BZ or/and CB.
02-20 is preferred. If it is less than 0.02, no significant effect of improving the catalyst life can be expected, and even if it exceeds 20, no further increase in the improvement effect may be expected.
分子状酸素は単独で存在させても良いが、他のガスを併
存させることが望ましく、併存可能なガスとしては窒素
、ヘリウム、アルゴン等の不活性ガス、二酸化炭素、塩
化水素等が挙げられ、安全性、経済性等の点で空気が特
に好ましい。Molecular oxygen may be present alone, but it is desirable to coexist with other gases, and examples of gases that can coexist include inert gases such as nitrogen, helium, and argon, carbon dioxide, and hydrogen chloride. Air is particularly preferred in terms of safety, economy, etc.
他のガスを併存させた場合の分子状酸素の割合は、他の
ガスと分子状酸素の合計量に対し分子状酸素が５〜５０
容量％が好ましい、５容量％未満では必要かつ充分な量
の分子状酸素を存在させるために、触媒層体積を膨大と
する必要が生じる可能性があり、また５０容量％を越え
るとＢＺ等の有機物の燃焼につながる恐れがある。The ratio of molecular oxygen when other gases coexist is 5 to 50% of the total amount of other gases and molecular oxygen.
Volume % is preferable; if it is less than 5 volume %, it may be necessary to increase the volume of the catalyst layer in order to make the necessary and sufficient amount of molecular oxygen exist, and if it exceeds 50 volume %, BZ etc. May lead to combustion of organic matter.
本発明において、ＢＺおよび／またはＣＢ、塩素および
分子状酸素を触媒層と接触させる方法としては、各成分
を事前に混合してから接触させても、また各成分を別々
に供給することにより接触させても差し支えない。In the present invention, BZ and/or CB, chlorine, and molecular oxygen may be brought into contact with the catalyst layer by mixing each component in advance and then contacting, or by supplying each component separately. I don't mind if you let me.
ゼオライトと、ＢＺおよび／またはＣＢ、塩素若しくは
分子状酸素を接触させる割合としては、接触時間−Ｗ／
Ｆ （ｓｅｃ） （ただしＷ （ｃｃ） ：ゼオライ
ト、 Ｆ （ｃｃ／ｓｅｅ ） ： Ｂ Ｚおよび
／またはＣＢ、塩素および分子状酸素並びにその他のガ
スを併用するときはこれを含めたガスの合計供給量〕で
表して、０．５〜５００ ｓｅｃの範囲が好ましく、更
に好ましくは１〜１００ｓｅｃの範囲である。The ratio of contacting zeolite with BZ and/or CB, chlorine or molecular oxygen is as follows: contact time - W/
F (sec) (where W (cc): zeolite, F (cc/see): B Z and/or CB, chlorine and molecular oxygen, and when other gases are used together, the total supply amount of gas including these. ], preferably in the range of 0.5 to 500 sec, more preferably in the range of 1 to 100 sec.
０．５ｓｅｃ未満では十分な塩素転化率が得られるとは
云えず、５００ｓｅｃを越えても触媒量を増加する効果
が期待できない可能性がある。If it is less than 0.5 sec, it cannot be said that a sufficient chlorine conversion rate can be obtained, and even if it exceeds 500 sec, the effect of increasing the amount of catalyst may not be expected.
本発明は気相反応であり、反応温度は１００″Ｃ〜４０
０°Ｃが好ましく、更に好ましくは１５０℃〜３００°
Ｃである。反応温度が１００″Ｃ未満では十分な塩素転
化率が得られるとは云えず、４００°Ｃを越えるとＰＤ
ＣＢの選択率が低下する恐れがある。The present invention is a gas phase reaction, and the reaction temperature is 100"C to 40"C.
0°C is preferable, more preferably 150°C to 300°
It is C. If the reaction temperature is less than 100"C, it cannot be said that a sufficient chlorine conversion rate can be obtained, and if the reaction temperature exceeds 400"C, PD
There is a possibility that the selectivity of CB will decrease.
本発明の実施に際しては、用いられる装置の形式につい
ては特に制限はなく、通常の固定床で良いが、流動床あ
るいは移動床であっても実施可能である。When carrying out the present invention, there are no particular restrictions on the type of apparatus used, and a conventional fixed bed may be used, but a fluidized bed or moving bed may also be used.
反応後の生成物の分離、精製は水洗等の手段を必要とす
ることなく、分溜及び晶析等一般の分離精製手段を用い
れば良い。Separation and purification of the product after the reaction does not require means such as washing with water, and may be performed using general separation and purification means such as fractional distillation and crystallization.
以下、実施例および比較例にもとづいて本発明を具体的
に説明する。The present invention will be specifically described below based on Examples and Comparative Examples.
実施例および比較例
反応は通常の固定床反応装置を用い、反応管（パイレッ
クス製；３０１φｘ５００ｍｍＬ）にモルデナイト型ゼ
オライト（日本化学工業型の商品名ゼオスターＮＭ１０
０Ｐ）１０ｃｃとガラスピーズ９０ｃｃの混合物を充填
し、反応温度２００ ”Ｃにおいて、ＢＺ：塩素：空気
（実施例）またはＢＺ：塩素：窒素（比較例）＝１：に
１（モル比）で、Ｗ／Ｆ （接触時間）＝５ｓｅｃでこ
れらを供給し反応をｊテった。Examples and Comparative Examples Reactions were carried out using an ordinary fixed bed reactor, and mordenite type zeolite (Nihon Kagaku Kogyo type trade name Zeostar NM10) was placed in a reaction tube (manufactured by Pyrex; 301φ x 500 mmL).
Filled with a mixture of 10 cc of 0P) and 90 cc of glass peas at a reaction temperature of 200 ''C, BZ: chlorine: air (example) or BZ: chlorine: nitrogen (comparative example) = 1:1 (molar ratio), These were supplied at W/F (contact time) = 5 sec to carry out the reaction.
流出する反応生成物および未反応塩素量を一定時間毎に
分析した。その結果を第１表に示す。またＰＤＣＢ選択
率および塩素転化率の経時変化を第１図に示す。The reaction products flowing out and the amount of unreacted chlorine were analyzed at regular intervals. The results are shown in Table 1. Further, Fig. 1 shows the changes over time in the PDCB selectivity and chlorine conversion rate.
ＰＤＣＢ選沢率は次式で定義した。The PDCB selection rate was defined by the following formula.
ＰＤＣＢ＋０ＤＣＢ＋ＭＤＣＢ 塩素転化率は次式で定義した。PDCB+0DCB+MDCB The chlorine conversion rate was defined by the following formula.
注）反応に使用したモルデナイト型ゼオライトは、ゼオ
スターＮＭ１００Ｐを１０〜１４メツシユに圧縮成型し
た後、３００°Ｃで３時間乾燥した。Note) The mordenite type zeolite used in the reaction was compression molded from Zeostar NM100P into 10 to 14 meshes, and then dried at 300°C for 3 hours.
ハ〕発明の効果
本発明によれば０ＤＣＢの副生を抑え、ＰＤＣＢを高い
選択率で製造することが出来、更に触媒寿命が長く、か
つ塩素転化率を長時間高率に維持することが出来、工業
的に極めて有利にＤＣＢを製造することが出来る。C] Effects of the invention According to the present invention, it is possible to suppress the by-product of 0DCB, produce PDCB with high selectivity, and furthermore, the catalyst life is long and the chlorine conversion rate can be maintained at a high rate for a long time. , DCB can be produced industrially with great advantage.
第１図は本発明の実施例および比較例によるＢ２の塩素
転化率、ＰＤＣＢ選沢率の経時変化を示すグラフである
。FIG. 1 is a graph showing changes over time in the chlorine conversion rate of B2 and the PDCB selection rate in Examples and Comparative Examples of the present invention.
Claims (1)
たはモノクロロベンゼンを気相塩素化反応させることに
よりジクロロベンゼンを製造するにあたり、分子状酸素
の存在下に反応させることを特徴とするジクロロベンゼ
ンの製造方法。1. A method for producing dichlorobenzene, which is characterized by carrying out the reaction in the presence of molecular oxygen when producing dichlorobenzene by subjecting benzene and/or monochlorobenzene to a gas phase chlorination reaction using zeolite as a catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63192862A JPH0699333B2 (en) | 1988-08-03 | 1988-08-03 | Method for producing dichlorobenzene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63192862A JPH0699333B2 (en) | 1988-08-03 | 1988-08-03 | Method for producing dichlorobenzene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0245433A true JPH0245433A (en) | 1990-02-15 |
| JPH0699333B2 JPH0699333B2 (en) | 1994-12-07 |
Family
ID=16298208
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63192862A Expired - Lifetime JPH0699333B2 (en) | 1988-08-03 | 1988-08-03 | Method for producing dichlorobenzene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0699333B2 (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4910658A (en) * | 1972-04-06 | 1974-01-30 |
-
1988
- 1988-08-03 JP JP63192862A patent/JPH0699333B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4910658A (en) * | 1972-04-06 | 1974-01-30 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0699333B2 (en) | 1994-12-07 |
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