CN104549569B - A kind of method of the catalyst recovery of metribuzin intermediate oxidation reaction - Google Patents
A kind of method of the catalyst recovery of metribuzin intermediate oxidation reaction Download PDFInfo
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- CN104549569B CN104549569B CN201410850030.1A CN201410850030A CN104549569B CN 104549569 B CN104549569 B CN 104549569B CN 201410850030 A CN201410850030 A CN 201410850030A CN 104549569 B CN104549569 B CN 104549569B
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Abstract
The invention discloses a kind of method of the catalyst recovery of metribuzin intermediate oxidation reaction, belong to Industrial Catalysis field.The method for the catalyst recovery that metribuzin intermediate oxidation reacts in the present invention concretely comprises the following steps：By ruthenium catalyst to be washed and the mass ratio 1 of cleaning solvent:1~4 addition cleaning solvent, reconciles pH to 9~14, and backflow washing is carried out after stirring 2h, and the condition of described backflow washing is to be washed at 20~80 DEG C 1~24 hour, then stands, settles, filtering obtains the catalyst of recovery.Recovery method technique of the present invention is simple, and operating process is easy, low in the pollution of the environment, is adapted to industrial production, cost is low, has obvious economic benefit, social benefit and the market competitiveness.
Description
Technical field
The invention belongs to Industrial Catalysis field, more particularly to a kind of catalyst recovery of metribuzin intermediate oxidation reaction
Method.
Background technology
Ru is the VIIIth race's element, and Ru metal, oxide and metallo-organic compound can be effective as all kinds of chemistry
The catalyst of reaction, it is widely used in industrial production and research and development, is one of important catalyst raw material.In agriculture
In the building-up process of medicine metribuzin, there is an intermediate ruthenium catalyst (catalyst ruthenium hereinafter referred to as Cat) catalysis oxidation.Should
Catalyst is by RuCl3Reaction is transformed into Ru (OH)4, i.e., by 2.5% hydroxide ruthenium, 66.7% water and 30.8% nanometer
The porous diatomite vehicle group of level into.Wherein, (1) process for synthetic catalyst is as shown in formula I and formula II.
RuCl3+NaOH→Ru(OH)3
Formula I；
Ru(OH)3+H2O2→Ru(OH)4
Formula II；
(2) it is as shown in Figure 1 to participate in reaction for catalyst.(3) catalyst action mechanism is as shown in Figure 2；Experiment finds Cat quilt covers
After 10 times, then when applying mechanically, reaction detection is difficult to reach terminal, need to constantly extend the time, and product yield is low, and impurity is more,
Show that Cat activity has reduced, constantly inactivation.At present, after hydroxide ruthenium inactivation, hydrochloric acid is usually added, carries out Leach reaction, mistake
After filtering out the insoluble matter in diatomite, obtain the aqueous solution containing ruthenium ion and finally give ruthenium trichloride.This method can be effective
Recovery ruthenium catalyst, but produce the excessive three wastes and the consumption energy, be not suitable for industrialized production.In order to solve this problem,
The reason for we inactivate to ruthenium catalyst is inquired into.
Above-mentioned Cat application methods are：When terminal is detected in the building-up process of agricultural chemicals metribuzin, after reaction, stop
Stirring, after standing a few hours, Cat is settled completely, is transferred supernatant liquor with vacuum, then is fed intake, and carries out next batch reaction.I
Find that Cat is applied mechanically 10 times after, then when applying mechanically, reaction detection is difficult to reach terminal, need to constantly extend the time, and product is received
Rate is low, and impurity is more, shows that Cat activity has reduced, constantly inactivation.The reason for we inactivate to Cat has carried out explore and study, hair
Caused organic matter especially some macromolecular compounds are to the porous of Cat during the main reason for now inactivating is due to raw material and reacted
Carrier generates blocking and surface parcel.The reason for specific Cat inactivations, is as follows：
1) initially, hydroxide ruthenium is distributed in porous carrier (as shown in Figure 3) well, but with use emphatically, raw material
With especially some macromolecular compounds (abbreviation greasy dirt) of caused organic matter in reaction to Cat porous carrier generate blocking and
Wrap up (as shown in Figure 4) in surface so that Cat can not contact raw material, and Cat specific surface area reduces, and the reaction time extends.
2) catalyst granules of greasy dirt parcel is easily enriched with blocking (as shown in Figure 5), and proportion is larger, easily sedimentation, and not
Easily it is dispersed with stirring so that Cat can not be contacted fully with raw material, and such Cat effective rate of utilization can reduce.
3) because greasy dirt proportion is small, the Cat particles (as shown in Figure 6) of greasy dirt parcel are when reaction terminates sedimentation, no
Free settling, can cause Cat loss, and have solid impurity in reaction product.And lack returning for effective above-mentioned catalyst at present
Receiving method.
The content of the invention
It is an object of the invention to overcome shortcoming and deficiency present in prior art, there is provided a kind of metribuzin intermediate oxygen
Change the method for the catalyst recovery of reaction.
The purpose of the present invention is achieved through the following technical solutions：A kind of catalyst recovery of metribuzin intermediate oxidation reaction
Method, concretely comprise the following steps：
By ruthenium catalyst to be washed and the mass ratio 1 of cleaning solvent:1~4 addition cleaning solvent, reconciles pH to 9~14,
Backflow washing is carried out after stirring 2h, the condition of described backflow washing is to be washed 1~24 hour at 20~80 DEG C, Ran Houjing
Put, settle, filtering obtains the catalyst of recovery.
Described cleaning solvent is methanol, ethanol, isopropanol, acetone, N,N-dimethylformamide, benzene,toluene,xylene
Deng；Preferably methanol and ethanol, can Reusability because methanol and alcohol solvent easily reclaim.
Described ruthenium catalyst is by RuCl3Reaction is transformed into Ru (OH)4, i.e., by 2.5% hydroxide ruthenium, 66.7%
Water and 30.8% nanometer porous diatomite support composition.Described ruthenium catalyst to be washed, it is in agricultural chemicals metribuzin
In building-up process, the Ru (OH) of 10 times is applied mechanically4Catalyst.
Preferably, by ruthenium catalyst to be washed and the mass ratio 1 of cleaning solvent:2 addition cleaning solvents.
Described regulation pH is to be adjusted with 30% liquid caustic soda.It is to keep the form of hydroxide ruthenium.
Described stirring purpose is the contact area for increasing ruthenium catalyst and cleaning solvent to be washed, and can preferably wash
Degreasing.
The condition of described backflow washing is preferably to be washed 8 hours at 65 DEG C.
The catalyst of the recovery of above-mentioned acquisition and original Ru (OH)4Catalyst carries out proportioning use, and described matches somebody with somebody
Than the catalyst reclaimed in use：Original Ru (OH)4The mass ratio of catalyst is 9:1.
In the building-up process of agricultural chemicals metribuzin, Ru (OH) is applied mechanically4Catalyst number increases so that hydrogen-oxygen in catalyst
The content for changing ruthenium gradually decreases, and catalytic efficiency reduces, wherein catalyst inactivation the main reason for be greasy dirt hole plug and carrier
Particle wrap up, so solve emphasis be how degreasing.Processing method before is mainly that calcining makes revivification of catalyst, still
Because calcining can produce solid waste and a large amount of energy consumptions, it is unfavorable for the long-term reuse of catalyst；The present invention is by have chosen
Suitable solvent, Ru (OH) is realized using solvent washing methods well4The recovery and recycling of catalyst.
The present invention is had the following advantages relative to prior art and effect：
The present invention is by have chosen suitable cleaning solvent, the blocking for being covered catalyst surface using solvent washing methods
The greasy dirt of hole and parcel carrier granular removes, and realizes Ru (OH) in the building-up process of agricultural chemicals metribuzin well4Catalyst
Recovery and recycling.Recovery method technique of the present invention is simple, and operating process is easy, low in the pollution of the environment, is adapted to work
Industry produces, and cost is low, has obvious economic benefit, social benefit and the market competitiveness.
Brief description of the drawings
Fig. 1 is the structural formula schematic diagram that catalyst participates in reaction.
Fig. 2 is the circulation schematic diagram of catalyst action mechanism.
Fig. 3 is the structural representation that hydroxide ruthenium is distributed in porous carrier.
Fig. 4 is greasy dirt to Ru (OH)4Porous carrier generate block and surface parcel structural representation.
Fig. 5 is that the catalyst granules of greasy dirt parcel is enriched with blocking structural representation.
Fig. 6 is the structural representation of the catalyst granules of greasy dirt parcel.
Embodiment
With reference to embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited
In this.
The described ruthenium catalyst for applying mechanically 10 times is that the Cat of 10 times has been applied mechanically in the building-up process of agricultural chemicals metribuzin
[i.e. Ru (OH)4Catalyst], wherein hydroxide ruthenium accounts for 2.5%.Then washed with solvent, comparative experiments result, determine detergent.
Embodiment 1
Specific experiment step：
By taking methanol as an example
The ruthenium catalyst for taking 20g to apply mechanically 10 times, the methanol solvate of quality such as then weigh, be mixed with, reconcile pH to 9
~14,8h is heated to reflux by stirring 2h, reflux temperature is 65 DEG C, then stands, settles, filters out the catalysis for having washed end
Agent.
According to the amount of washing rear catalyst, 1 (structure as shown in fig. 1) and sodium hypochlorite reaction during input is corresponding, inspection
In raw material I amount is surveyed after reaction, testing result is shown in Table 1.
After the detection reflection of the sodium hypochlorite reaction of table 1 in raw material I amount result
Wherein, described in table 1 in I and in II structure as shown in fig. 1.
From the experimental results, the effect that methanol and ethanol wash is much the same, than being wanted with the clean result of DMF, benzene, water
It is good, and alcoholic solvent is easy to recovery of applied.So our prioritizing selection alcohols are detergent, in addition, the low boiling point of methanol, the energy disappear
Consume small, therefore, our prioritizing selections methanol is detergent.
Embodiment 2
Using methanol as detergent, wash time is selected
Specific experiment step：
The ruthenium catalyst for taking 20g to apply mechanically 10 times, the methanol of quality such as then weigh, be mixed with, reconcile pH to 9~
14,8h is heated to reflux by stirring 2h, reflux temperature is 65 DEG C, then stands, settles, filters out the catalyst for having washed end.
According to the amount of washing rear catalyst, 1 and sodium hypochlorite reaction during input is corresponding, after detection reaction I in raw material
Amount, testing result are shown in Table 2.
After the detection reflection of the sodium hypochlorite reaction of table 2 in raw material I amount result
Wherein, described in table 1 in I and in II structure as shown in fig. 1.From the experimental results, when applying mechanically washing 8h
The catalyst filtered out, product yield reach maximum.As the extension of wash time, value are constant.So wash time is optimal is
8h。
Embodiment 3
The selection of catalysts and solvents ratio
Experimental procedure：
The ruthenium catalyst for taking 20g to apply mechanically 10 times, the methanol of quality such as then weigh, be mixed with, reconcile pH to 9~
14, by stirring 2h, 8h is heated to reflux, reflux temperature is 65 DEG C, then stands, settles, filters out the catalyst for having washed end.
According to the amount of washing rear catalyst, 1 and sodium hypochlorite reaction during input is corresponding, after detection reaction I in raw material
Amount, testing result are shown in Table 3.
After the detection reflection of the sodium hypochlorite reaction of table 3 in raw material I amount result
Wherein, described in table 1 in I and in II structure as shown in fig. 1.
From the experimental results, catalyst:Solvent=1:When 2, product yield reaches maximum, increases with the ratio of solvent
Greatly, it is worth constant.So the ratio of catalysts and solvents is 2.
The best approach of catalyst recovery is can be seen that from above-mentioned experiment is：It is heated to reflux, is washed with twice of methanol
8h.Because being applying mechanically before, catalyst has the loss of part, so, when directly applying mechanically the catalyst of recovery, it is impossible to reach new
The effect of catalyst processed, therefore, we have added 10% or so brand-new catalyst when applying mechanically recovery catalyst.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (1)
- A kind of 1. method of the catalyst recovery of metribuzin intermediate oxidation reaction, it is characterised in that：Concretely comprise the following steps：By Ru to be washed (OH)4The mass ratio 1 of catalyst and cleaning solvent:2 addition cleaning solvents, pH is adjusted with 30% liquid caustic soda To 9~14, backflow washing is carried out after stirring 2h, the condition of described backflow washing is to be washed 8 hours at 65 DEG C, Ran Houjing Put, settle, filtering obtains the catalyst of recovery；Described cleaning solvent is methanol and ethanol.
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| JPS60102943A (en) * | 1983-11-08 | 1985-06-07 | Daido Steel Co Ltd | Catalyst regenerating method |
| DE3445275A1 (en) * | 1984-12-12 | 1986-06-19 | Henkel KGaA, 4000 Düsseldorf | Process for reactivating ruthenium-containing supported catalysts. |
| CN1768954A (en) * | 2004-10-29 | 2006-05-10 | 中国石油化工股份有限公司 | Method for reproducing deactivation catalyst of carbon deposit |
| CN101584989A (en) * | 2009-07-13 | 2009-11-25 | 北京化工大学 | A kind of renovation process of catalyst for preparing low carbon olefin hydrocarbon by methanol |
| CN103540760A (en) * | 2013-09-26 | 2014-01-29 | 宁波大地化工环保有限公司 | Method for recovering ruthenium from waste ruthenium hydroxide/kieselguhr catalyst |
| CN103816923A (en) * | 2012-11-16 | 2014-05-28 | 万华化学集团股份有限公司 | Method for regenerating ruthenium hydrogenation catalyst |
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2014
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60102943A (en) * | 1983-11-08 | 1985-06-07 | Daido Steel Co Ltd | Catalyst regenerating method |
| DE3445275A1 (en) * | 1984-12-12 | 1986-06-19 | Henkel KGaA, 4000 Düsseldorf | Process for reactivating ruthenium-containing supported catalysts. |
| CN1768954A (en) * | 2004-10-29 | 2006-05-10 | 中国石油化工股份有限公司 | Method for reproducing deactivation catalyst of carbon deposit |
| CN101584989A (en) * | 2009-07-13 | 2009-11-25 | 北京化工大学 | A kind of renovation process of catalyst for preparing low carbon olefin hydrocarbon by methanol |
| CN103816923A (en) * | 2012-11-16 | 2014-05-28 | 万华化学集团股份有限公司 | Method for regenerating ruthenium hydrogenation catalyst |
| CN103540760A (en) * | 2013-09-26 | 2014-01-29 | 宁波大地化工环保有限公司 | Method for recovering ruthenium from waste ruthenium hydroxide/kieselguhr catalyst |
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