CN1213585A - Benzonitrile chlorination for preparing pentachlorobenzonitrile catalyst and its application - Google Patents
Benzonitrile chlorination for preparing pentachlorobenzonitrile catalyst and its application Download PDFInfo
- Publication number
- CN1213585A CN1213585A CN 97116968 CN97116968A CN1213585A CN 1213585 A CN1213585 A CN 1213585A CN 97116968 CN97116968 CN 97116968 CN 97116968 A CN97116968 A CN 97116968A CN 1213585 A CN1213585 A CN 1213585A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- benzonitrile
- preparing
- chlorination
- metallic element
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A catalyst for preparing benzylnitrile pentachloride by chlorinating benzylnitrile uses activated carbon as carrier and one or more of metal elements including Mn, Fe, Ni, Cu, or Ru as active components (5-20 wt.%), which may exists in the form of nitrates or chlorides. Its advantages include use of fixed-bed reactor for easy operation, high transform rate of benzylnitrile up to 100%, high selectivity of resultant (greater than 96%) and long service life up to 200 hrs or more.
Description
The invention provides a kind of benzonitrile chlorination for preparing pentachlorobenzonitrcatalyst catalyst that is used for and reach benzonitrile chlorination for preparing pentachlorobenzonitrcatalyst reaction under the effect of this catalyst.
The pentachloro-benzonitrile can be reacted by benzonitrile and chlorine and make, for example U.S.3855264 proposed not use catalyst by benzonitrile directly and chlorine react the method for producing the pentachloro-benzonitrile, be reflected under 650～850 ℃ of high temperature and carry out, the conversion ratio of benzonitrile is 75.7%～94.9%.The Japan Patent spy opens clear 44-29853 and has invented with charcoal, active carbon, and bone black, blood charcoal etc. are made catalyst, and the chloride that adheres to alkali metal or alkaline-earth metal on these charcoals is produced the method for pentachloro-benzonitrile by benzonitrile and chlorine reaction as catalyst.Reaction temperature is 200～470 ℃, can reach more than 96% at the conversion ratio that reacts 1～2 hour benzonitrile that begins, and selectivity is 97～99%.After 10 hours, conversion ratio and selectivity all drop to below 90%.The spy opens clear 60-239452 and adopts flowing bed reactor, with the mixed thing that contains of the iron of powdered activated carbon (32～100 order) and powdery, zinc, chromium (or chloride of these metals) as catalyst, produce the pentachloro-benzonitrile by the reaction of benzonitrile and chlorine, the long running time of catalyst is 80 hours.The conversion ratio of benzonitrile～100%, the selectivity of pentachloro-benzonitrile～96%.The purity of pentachloro-benzonitrile reached 99.6% after thick product was purified.
The purpose of this invention is to provide and a kind ofly be used for the benzonitrile chlorination for preparing pentachlorobenzonitrcatalyst catalyst for reaction and utilize this catalyst to make benzonitrile and chlorine carry out prepared in reaction pentachloro-benzonitrile.Industrial easy-operating fixed bed reactors are adopted in this reaction, and the conversion ratio of benzonitrile almost can reach 100%, selectivity＞96% of product pentachloro-benzonitrile, and life of catalyst length can reach more than 200 hours.
For achieving the above object, the catalyst that is used for benzonitrile chlorination for preparing pentachlorobenzonitrcatalyst of the present invention is carrier with the active carbon, support in Mn, Fe, Ni, Cu or the Ru metallic element one or more as active component, metallic element can metal or the form of its salt exist, the weight content of activity component metal element accounts for 5～20% of catalyst.When multiple metallic element during, the service life that can improve catalyst, therefore, preferably adopt metal or its salt more than 2 kinds or 2 kinds as the metallic element of active component jointly as active component.The salt of metallic element can adopt the nitrate or the chloride of metal, and active carbon can adopt wood activated charcoal, active fruit shell carbon or coal activated carbon.
The Preparation of catalysts method of the present invention method for making of supported catalyst is routinely carried out, promptly be used as the nitrate and/or the aqueous chloride solution impregnated carrier active carbon of activity component metal, the active carbon of dipping active component is through room temperature～120 ℃ airing or oven dry, roasting is 3～10 hours in 200～220 ℃ of air, can obtain finished catalyst.
Utilize the above-mentioned catalyst that makes on fixed bed reactors, can carry out the chlorination reaction of benzylamine and chlorine.Catalyst can carry out prereduction before use, and the condition that prereduction is handled is: under 400～450 ℃, and logical H
2With Ar gaseous mixture reductase 12～4 hours.Catalyst of the present invention also can not carry out the prereduction processing and directly react, and can obtain result preferably equally.Being reflected under the normal pressure of benzylamine and chlorine carried out, and reaction temperature is 250～450 ℃, is preferably 300～350 ℃.The conversion ratio of the reactant benzonitrile of this reaction almost can reach 100%, and the selectivity height of product pentachloro-benzonitrile can be greater than 96%, can make the purity of pentachloro-benzonitrile reach 99.6% after thick product load is pure.
Below by embodiment technology of the present invention is given to illustrate further.
Embodiment 1 Preparation of catalysts 1～9
Get that the nitrate that contains catalyst activity component Mn, Fe, Ni, Cu or Ru metallic element or chlorinating agent are soluble in water makes the solution that volume is about 1.5 times in carrier, 20～40 purpose active carbons are immersed, in 120 ℃ of down oven dry 1 hour, catalyst 1～9 is made in 200 ℃ of following roastings 8 hours.Each components contents is listed in table 1 in the concrete catalyst.
The performance of embodiment 2 catalyst
The evaluation of the catalyst performance of embodiment 1 is carried out in internal diameter is the nickel pipe reactor of 25mm, and the loadings of catalyst is 300ml, before reaction under 400 ℃, feeding H
2With the Ar gaseous mixture, carry out 3 hours reduction.Reduce to reaction temperature then, feed reactant and react, reaction pressure is a normal pressure, and the benzonitrile charging rate is 5.5g/ hour, Cl
2Throughput is 7.0l/ hour, N
2Throughput is 7.51/ hour, changes different reaction temperatures, and the selectivity of its benzonitrile conversion ratio, pentachloro-benzonitrile and the result of the duration of runs are with listing in table 1.Reaction also can not carried out prereduction, feeds reactant and directly carries out chlorination reaction.
The performance of comparative example 1～3 catalyst
Press embodiment 1 described method preparation catalyst as a comparative example, and carry out the evaluation of catalyst by embodiment 2 identical conditions, the performance evaluation result of different catalyst of forming and catalyst is with listing in table 1.Be to adopt flowing bed reactor for comparative example 3 wherein, make catalyst with 40～80 order active carbons and 80～100 order Fe powder, other reaction conditions are identical with example 2.
The performance preface catalyst of table 1 catalyst is formed prereduction reaction temperature benzonitrile changes pentachloro-benzonitrile running time signal (carrier active carbon is 15g) degree (℃) between change rate (%) selectivity (%) (hour)
Embodiment 1 2.2gMn (NO
3)
2, 1.5gCu (NO
3)
2Have 350 100 96～99 206
5.5g FeCl
32 2.8gMn (NO
3)
2, 9.5gFeCl
3Have 350 100 96～98 185
0.8g?NiCl
2
Table 1 continues 3 12%FeCl
3, 0.5RuCl
3, do not have 370 100 94～97 146
32.2g Cn (NO
3)
24 8gMnCl
2, 2.9gNi (NO
3)
2There are not 450 100 95～97 1265 2.8gMn (NO
3)
2, 9.5gFeCl
3, do not have 350 100 94～97 166
0.8g NiCl
26 3gMnCl
2, 6g FeCl
3, do not have 300 100 95～98 223
0.8g RuCl
37 10g FeCl
3350 95 95～98 168 12g MnCl are arranged
2360 100 96～98 689 10g NiCl are arranged
2Have 340 100 96～98 95
Comparative example 1 2gKCl, 3gMgCl
2380 80～90 90～92 32 3gLiCl are arranged, and 2gKCl has 380 80～90 85～90 23 10g Fe not have 360 92 90～95 6
Result by the foregoing description and comparative example can see, catalyst of the present invention has very high activity and product selectivity for benzonitrile and chlorine reaction system pentachloro-benzonitrile, and since the high life of catalyst be suitable in industrial production, using.
Claims (4)
1. one kind is used for benzonitrile chlorination for preparing pentachlorobenzonitrcatalyst catalyst, it is characterized in that with the active carbon being carrier, support in Mn, Fe, Ni, Cu or the Ru metallic element one or more as active component, metallic element can metal or the form of its salt exist, the weight content of activity component metal element accounts for 5～20% of catalyst.
2. according to the described catalyst of claim 1, it is characterized in that the metallic element of active component adopts metal or its salt more than 2 kinds or 2 kinds.
3. according to the described catalyst of claim 1, it is characterized in that the nitrate or the chloride of the salt employing metal of metallic element, active carbon can adopt wood activated charcoal, active fruit shell carbon or coal activated carbon.
4. one kind by benzonitrile chlorination for preparing pentachlorobenzonitrcatalyst reaction, it is characterized in that it being to adopt the described catalyst of claim 1 to carry out.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97116968 CN1213585A (en) | 1997-10-05 | 1997-10-05 | Benzonitrile chlorination for preparing pentachlorobenzonitrile catalyst and its application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97116968 CN1213585A (en) | 1997-10-05 | 1997-10-05 | Benzonitrile chlorination for preparing pentachlorobenzonitrile catalyst and its application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1213585A true CN1213585A (en) | 1999-04-14 |
Family
ID=5174242
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 97116968 Pending CN1213585A (en) | 1997-10-05 | 1997-10-05 | Benzonitrile chlorination for preparing pentachlorobenzonitrile catalyst and its application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1213585A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100556537C (en) * | 2008-01-03 | 2009-11-04 | 厦门大学 | The Catalysts and its preparation method of propionic acid synthesized by ethanol carboxylation |
| CN105732427A (en) * | 2016-04-14 | 2016-07-06 | 湖北郡泰医药化工有限公司 | Novel method for synthesizing 3,4-dichlorobenzonitrile |
| CN107999060A (en) * | 2017-12-13 | 2018-05-08 | 西安凯立新材料股份有限公司 | A kind of supported ruthenium catalyst for handling organic wastewater with difficult degradation thereby and preparation method thereof |
| CN108339555A (en) * | 2017-01-24 | 2018-07-31 | 盐城恒盛化工有限公司 | A kind of method of support type chlorination catalyst and preparation method thereof and synthesis 4 chloro pyridine |
-
1997
- 1997-10-05 CN CN 97116968 patent/CN1213585A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100556537C (en) * | 2008-01-03 | 2009-11-04 | 厦门大学 | The Catalysts and its preparation method of propionic acid synthesized by ethanol carboxylation |
| CN105732427A (en) * | 2016-04-14 | 2016-07-06 | 湖北郡泰医药化工有限公司 | Novel method for synthesizing 3,4-dichlorobenzonitrile |
| CN108339555A (en) * | 2017-01-24 | 2018-07-31 | 盐城恒盛化工有限公司 | A kind of method of support type chlorination catalyst and preparation method thereof and synthesis 4 chloro pyridine |
| CN108339555B (en) * | 2017-01-24 | 2021-10-29 | 盐城恒盛化工有限公司 | Supported chlorination catalyst, preparation method thereof and method for synthesizing tetrachloropyridine |
| CN107999060A (en) * | 2017-12-13 | 2018-05-08 | 西安凯立新材料股份有限公司 | A kind of supported ruthenium catalyst for handling organic wastewater with difficult degradation thereby and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4308176A (en) | Catalyst and method for producing said catalyst | |
| EP0184413B1 (en) | Process for the production of chlorine | |
| KR102583541B1 (en) | Method for producing vinyl chloride | |
| US5506273A (en) | Catalyst for hydrogenation and method for hydrogenation therewith | |
| US3933883A (en) | Methanation catalyst and process of use | |
| US3876557A (en) | Metallic catalyst | |
| US4186112A (en) | Catalyst for reducing carbon monoxide with hydrogen | |
| CN101357337B (en) | Heavy oil hydrogenating treatment catalyst and preparation method thereof | |
| CN109046362A (en) | A kind of preparation method and applications of carbon-coated nano CuZnAl catalyst | |
| US5663112A (en) | Cerous chloride-chromic oxide catalyst for producing chlorine, methods for producing the same and a method for producing chlorine | |
| CN101491762B (en) | Load hydrogenation catalyst for trickle bed and preparation method thereof | |
| CN1213585A (en) | Benzonitrile chlorination for preparing pentachlorobenzonitrile catalyst and its application | |
| CN114289028A (en) | Non-noble metal catalyst for preparing succinic anhydride by maleic anhydride liquid-phase continuous hydrogenation and preparation method thereof | |
| CN102803130B (en) | Method for hydrogen chloride oxidation at a catalyst having low surface roughness | |
| CN102333589A (en) | Catalyst for hydrogen chloride oxidation comprising ruthenium and silver and/or calcium | |
| JP2004209408A (en) | Catalyst for reforming hydrocarbon and method for reforming hydrocarbon | |
| CN110975884A (en) | Preparation method of transition metal-containing catalyst for preparing benzaldehyde by selectively oxidizing toluene | |
| JP3552766B2 (en) | Ammonia synthesis catalyst and its preparation method | |
| JPS647974B2 (en) | ||
| CN101434536B (en) | Method for preparing phthalandione by selective oxidation | |
| JP3500617B2 (en) | Method for producing hexafluorocyclobutane | |
| CN111036268B (en) | Alumina composite material, preparation method and application thereof, and synthetic method of n-valeronitrile | |
| US4146503A (en) | Process for preparing a catalyst for reducing carbon monoxide | |
| US5767166A (en) | Process for producing mixtures of methanol and higher alcohols | |
| CN109622006B (en) | Catalyst for preparing low-grade aliphatic amine from ammonia-containing synthesis gas and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| REG | Reference to a national code |
Ref country code: HK Ref legal event code: GR Ref document number: 1055040 Country of ref document: HK |