CN100448543C - Preparation method of Pd/resin catalyst - Google Patents
Preparation method of Pd/resin catalyst Download PDFInfo
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- CN100448543C CN100448543C CNB2006100456414A CN200610045641A CN100448543C CN 100448543 C CN100448543 C CN 100448543C CN B2006100456414 A CNB2006100456414 A CN B2006100456414A CN 200610045641 A CN200610045641 A CN 200610045641A CN 100448543 C CN100448543 C CN 100448543C
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Abstract
A Pd/resin catalyst for preparing methylisabutyl ketone from acetone with high activity and stability and long service life is prepared through preparing the Pd-contained exchange liquid, adding oxidant, heat treating, immersing resin in it for ion exchange, filtering and washing.
Description
1, technical field
The present invention relates to be used for Preparation of catalysts method, particularly a kind of Preparation of catalysts method by acetone and hydroformylation step synthesize methyl-isobutyl ketone by methylisobutanone synthesized from acetone.
2, background technology
Methyl iso-butyl ketone (MIBK) (being called for short MIBK) is a kind of important organic solvent, is mainly used in paint, cold coating, waxy oil dewaxing, also is one of raw material of producing by rubber antioxidant 4020, and is of many uses.
Traditional production method is a three-step approach, has problems such as contaminated environment, production cost height, flow process be numerous and diverse, is eliminated gradually.One-step method is the state-of-the-art technology of acetone (being called for short AC) synthesize methyl-isobutyl ketone, and this specification requirement catalyst must have difunctional, i.e. condensation dehydration and hydrogenating function.
The catalyst that is used for this technology mainly is divided into two classes: the first kind is an organic catalyst, as CN1069674A, US3666816, CN1255404A, CN1385241A, has used Pd/Al mostly
2O
3With the Pd/ molecular sieve catalyst, such catalyst advantage is that palladium is difficult for running off, not etching apparatus; Shortcoming is the reaction temperature height, reactivity is low, meet water catalyst strength and active decline comparatively fast, generate water in the synthetic MIBK course of reaction of acetone, the organic catalyst that is used for this reaction, after running 1000h, its intensity descends rapidly, because this deadly defect of such catalyst makes it that industrial application value not arranged.
Second class is an organic catalyst, i.e. Pd/ resin catalyst, this class catalyst are to be used for the synthetic MIBK commercial plant of acetone one-step method the earliest.Such catalyst generally adopts storng-acid cation exchange resin to immerse to contain and carries out in the aqueous solution of palladium that ion-exchange obtains.Because require such catalyst to possess condensation dehydrating function and hydrogenating function simultaneously, so when ion-exchange, the H on the resin on some sulfonate radical
+By Pd
2+Exchange is got off, Pd
2+As the hydrogenating function center, the H+ on another part sulfonate radical is as the condensation function center of catalyst behind hydrogen reducing.This shows H
+And Pd
2+Distribution situation on catalyst directly influences the coupling of two functions in the catalyst.The palladium catalyst too high levels, hydrogenation activity strengthens, and easily causes acetone directly to be generated isopropyl alcohol by hydrogenation.H on the catalyst sulfonate radical
+Too high levels, palladium content is low excessively, easily causes the isopropylidene acetone part that the condensation dehydration generates on the acid site not generated MIBK by hydrogenation, thereby influences activity of such catalysts and selectivity.
The disclosed Pd/ resin catalyst of US3953517, GB1010260, preparation process is a palladium nitrate aqueous solution dipping storng-acid cation exchange resin, shortcoming is that the utilization rate of palladium is low in the preparation process, catalyst in operation process on the resin sulfonate radical and palladium leakage is arranged, cause the condensation dehydration and the hydrogenating function of this catalyst not to match, cause the selectivity of acetone conversion and MIBK relatively poor, influential to catalyst life, await further raising.The sulfonate radical of Liu Shiing is corrosive to equipment in addition.
CN 1457927A discloses a kind of preparation method of palladium-resin catalyst.This method adopts the acid solution and the resin that contain palladium to carry out ion-exchange, wherein contains H in the palladium solution
+Concentration is that (quite concentration is 0.063～31.5g/100ml) to 0.01～5.0mol/L.The simple acid medium that adopts, the H in exchange liquid
+Can change the competitive Adsorption state in the ion exchange process when concentration is an amount of to a certain extent, but, cause the waste of precious metal palladium only by adding the not high problem of utilization rate that acid still can not solve palladium.This method gained activity of such catalysts and selectivity are still treated further raising in addition.
Summary of the invention
At the problem that prior art exists, the invention provides the preparation method of the high Pd/ resin catalyst of a kind of Metal Palladium utilization rate.When being used for by the methylisobutanone synthesized from acetone course of reaction by this method gained catalyst, its activity, selectivity and life-span all increase than existing catalyst.
The preparation method of Pd/ resin catalyst of the present invention, this method comprises the preparation that contains palladium exchange liquid, hydro-strong acidic cation exchange resin is immersed contain palladium exchange liquid and carry out ion-exchange, filtration and washing, wherein containing palladium exchange liquid is by containing the aqueous solution that palladium compound, water and oxidant are made into, wherein said oxidant is nitric acid and hydrogen peroxide, perhaps being nitric acid and hypochlorous acid, perhaps is nitric acid, hydrogen peroxide and hypochlorous acid.In exchange liquid, the concentration of nitric acid is 0.1～5.0g/100ml, is preferably 0.5～2.0g/100ml, and hydrogen peroxide and/or hypochlorous concentration are 0.05～5.0g/100ml, are preferably 0.1～2.0g/100ml.
The described palladium compound that contains is a palladium nitrate.
Wherein said resin was preferably heat-treated before immersing exchange liquid, and process is as follows: in the volume ratio of resin and water is 1: 1～1: 5 ratio, adds entry in hydro-strong acidic cation exchange resin, 80～180 ℃ of following constant temperature processing 4～8 hours.
In the described Pd/ resin catalyst, palladium content carries the palladium amount with catalyst (butt) and is calculated as 0.1wt%～0.8wt%.
The preferred strongly acidic styrene type cation exchange resin of described storng-acid cation exchange resin, preferably adopt the heatproof strongly acidic styrene type cation exchange resin, its preparation method is as introducing among the CN 1076385A, this heatproof resin building-up process is made up of polymerization, extracting, bromination, the sulfonation process of styrene and divinylbenzene, polymerization, bromination, sulfonation process are synthetic heatproof resin matrix and the step of introducing functional group, and extracting is a step of adjusting the polymer physics structure.The selected resin property index of the present invention is as follows: wet basis exchange capacity 4.00～4.35mol/g, wet density 0.65～0.82g/ml, percentage of water loss 45～62wt%, specific area 10～20m
2/ g, average pore size 10～15nm.
In the inventive method, described ion-exchange, filtration and washing process adopt the conventional method that is adopted when preparing the Pd/ resin catalyst, specific as follows: that the hydro-strong acidic cation exchange resin immersion is contained in the palladium exchange liquid, ion-exchange is carried out in stirring, be 10 minutes～5 hours swap time, leach resin, be washed with distilled water to neutrality, promptly get catalyst of the present invention.
The catalyst of the inventive method gained palladium on the resin before use needs become Metal Palladium with hydrogen reducing, adopts reduction in the device, and reducing condition is: reduction temperature is normal temperature～100 ℃, reduction pressure 1～6.0MPa, time is 4～8 hours, and the catalyst after the reduction need seal, can not ingress of air.
Course of reaction adopts fixed bed to go up charging continuously, and 100～150 ℃ of reaction temperatures, reaction pressure are 3.0～7.0MPa, acetone feed air speed 0.5～3.0h
-1(v), H
2(v) 300～1500, this reaction acetone water content must be less than 0.5wt%, hydrogen purity 〉=99v% for/AC.
In the inventive method, in exchange liquid, add oxidant, not only can increase substantially the utilization rate of palladium, and can also make the condensation dehydrating function of catalyst and hydrogenating function mate better, further improved activity of such catalysts and selectivity.
Owing to have unsettled sulfonate radical in the storng-acid cation exchange resin, cause at this part sulfonate radical of initial reaction stage and come off easily, and the palladium on the Pd/ resin catalyst exchanges on the sulfonate radical, because the existence of unstable sulfonate radical, be combined in the loss that easily thereupon comes off naturally of palladium on this part sulfonate radical, so the present invention adopts h type resin is heat-treated, make that unstable sulfonate radical removes in this catalyst, the leakage of catalyst runs initial stage sulfonate radical and palladium significantly reduces, reduce the corrosion of equipment, prolonged the service life of catalyst.
Catalyst of the present invention has good heatproof effect owing to adopt the heatproof h type resin to do carrier, makes range of reaction temperature widen (100～150 ℃), catalyst runs cycle stretch-out.
4, the specific embodiment
The present invention is described in further detail below in conjunction with embodiment; it should be noted; following examples are not limiting the scope of the invention, and those skilled in the art is in conjunction with specification of the present invention and can do suitable expansion in full, and these expansions all should be protection scope of the present invention.
Embodiment 1
A) heat treatment of h type resin
Hydrogen type strong acid heatproof styrene type cation exchange resin, rerum natura is as follows: moisture content 49wt%, specific surface 15m
2/ g, average pore size 10.5nm, wet basis exchange capacity 4.3mol/g, wet apparent density 0.75g/ml.Measure above-mentioned resin 200ml (wet basis), adding distil water 300ml places the 1000ml autoclave together, is heated to 150 ℃, and constant temperature 4 hours filters afterwards, is washed till neutrality.
B) palladium is carried in ion-exchange
The resin immersion 400ml of 200ml step a gained is contained in the exchange liquid of palladium 0.228g, nitric acid 0.8g/100ml, hydrogen peroxide 0.5g/100ml, stir 2.0h simultaneously, leach resin, be washed till neutrality with distilled water, catalyst WB-1 gets product.
Embodiment 2
With embodiment 1, different is among the step b in the 400ml exchange liquid, and palladium is 0.363g, and nitric acid content is 1.2g/100ml, hydrogen peroxide content 1.2g/100ml, catalyst WB-2.
Embodiment 3
With embodiment 1, different is among the step b in the 400ml exchange liquid, and palladium is 0.456g, nitric acid 1.8g/100ml, hypochlorous acid 1.5g/100ml, catalyst WB-3.
Comparative Examples 1
With embodiment 1, different is among the step b in the 400ml ion exchange liquid, and palladium is 0.363g, and nitric acid content is 1.89g/100ml, catalyst DB-1.
Comparative Examples 2
With embodiment 1, different is to be in the 400ml ion exchange liquid among the step b to contain palladium 0.456g by palladium nitrate aqueous solution, gets catalyst DB-2.
The utilization rate of more above-mentioned five kinds of palladium catalysts sees Table 1.
Table 1
| The catalyst numbering | Estimate to contain the Pd amount, wt% | Actual Pd amount, the wt% of containing | The Pd utilization rate, wt% |
| WB-1 WB-2 DB-1 WB-3 DB-2 | 0.3 0.47 0.47 0.6 0.6 | 0.29 0.46 0.44 0.58 0.55 | 96.7 97.8 93.6 96.7 91.7 |
By table 1 as seen, in palladium nitrate aqueous solution, add the catalyst DB-1 of salpeter solution gained separately, the utilization rate effect of precious metal palladium slightly is better than catalyst DB-2 by the palladium nitrate aqueous solution gained, and mix the catalyst WB-1, the WB-2 that add nitric acid and hydrogen peroxide or hypochlorous acid gained and WB-3 to the utilization rate of precious metal palladium apparently higher than Comparative Examples catalyst DB-1.In addition, the inventive method also helps exchanging the post processing of raffinate, and reduces the catalyst cost.
Comparative Examples 3
Omit step a in the example 1, step b makes catalyst DB-3 with embodiment 1.
Embodiment 4
The reaction unit of evaluate catalysts is internal diameter 25mm, the stainless steel tubular type flow reactor of long 1200mm, charging in the reaction, reaction mass flows out from reactor bottom, enters separator after cooling, circulation of gas phase tail gas or metering emptying, the liquid phase timing sampling is used gas chromatographic analysis; Sulfonate radical content is analyzed with chemical method in the liquid-phase product.
Get WB-1 catalyst 150ml, mix the reactor of packing into 10～40 order quartz sand 100ml that handled, airtight, reducing condition is: 100 ℃ of reaction temperatures, pressure 6.0MPa, 4 hours time.Operating condition and the results are shown in Table 2.
Get DB-3 catalyst 150ml and replace above-mentioned WB-1 catalyst, other condition is with the evaluation procedure of WB-1 catalyst.
Table 2WB-1, the active result of DB-4 catalyst runs
By table 2 data, can further specify catalyst of the present invention after Overheating Treatment, the start of run sulfonate radical runs off seldom, has alleviated the corrosion to equipment like this, can find out that also the initial activity of catalyst of the present invention all is higher than the comparative catalyst simultaneously.
Embodiment 5～9
Catalyst test apparatus and reducing condition are with embodiment 4.
Get catalyst 150ml, mix, the reactor of packing into after the dilution, concrete operating condition and the results are shown in Table 3 with 10～40 order quartz sand 100ml.
The operating condition of table 3 example 5～9 and result
| Embodiment | 5 | 6 | 7 | 8 | 9 |
| Catalyst numbering reaction temperature, ℃ reaction pressure, MPa air speed, h -1 H 2/ AC, (v) conversion ratio, mol% MIBK selectivity, mol% | WB-1 140 6.0 2.0 600 46.86 95.36 | WB-2 120 4.0 1.0 1000 47.01 96.13 | DB-1 120 4.0 1.0 1000 46.38 96.04 | WB-3 105 3.0 1.5 1500 32.04 96.78 | DB-2 105 3.0 1.5 1500 31.27 96.67 |
Claims (8)
1, a kind of preparation method of Pd/ resin catalyst, this method comprises the preparation that contains palladium exchange liquid, hydro-strong acidic cation exchange resin is immersed contain palladium exchange liquid and carry out ion-exchange, filtration and washing, and wherein containing palladium exchange liquid is by containing the aqueous solution that palladium compound, water and oxidant are made into; Described oxidant is nitric acid and hydrogen peroxide, perhaps is nitric acid and hypochlorous acid; In exchange liquid, the concentration of nitric acid is 0.1～5.0g/100ml, and hydrogen peroxide or hypochlorous concentration are 0.05～5.0g/100ml.
2, in accordance with the method for claim 1, it is characterized in that the concentration of nitric acid is 0.5～2.0g/100ml in exchange liquid, hydrogen peroxide or hypochlorous concentration are 0.1～2.0g/100ml.
3, in accordance with the method for claim 1, it is characterized in that the described palladium compound that contains is a palladium nitrate.
4, in accordance with the method for claim 1, it is characterized in that described resin heat-treated before immersing exchange liquid, process is as follows: the ratio that in the volume ratio of resin and water is 1: 1～1: 5, in hydro-strong acidic cation exchange resin, add entry, handled 4～8 hours at 80～180 ℃ of following constant temperature.
5, in accordance with the method for claim 1, it is characterized in that in the described Pd/ resin catalyst, palladium content is 0.1wt%～0.8wt%.
6, in accordance with the method for claim 1, it is characterized in that described storng-acid cation exchange resin is a strongly acidic styrene type cation exchange resin.
7, in accordance with the method for claim 6, the character that it is characterized in that described strongly acidic styrene type cation exchange resin is as follows: wet basis exchange capacity 4.00～4.35mol/g, wet density 0.65～0.82g/ml, percentage of water loss 45wt%～62wt%, specific area 10～20m
2/ g, average pore size 10～15nm.
8, in accordance with the method for claim 1, it is characterized in that described ion-exchange, filtration and washing process are as follows: the hydro-strong acidic cation exchange resin immersion is contained in the palladium exchange liquid, carry out ion-exchange, be 10 minutes～5 hours swap time, leach resin, be washed with distilled water to neutrality, promptly get the Pd/ resin catalyst.
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101549291B (en) * | 2009-05-08 | 2011-04-20 | 西安凯立化工有限公司 | Catalyst for removing dissolved oxygen in water and preparing method thereof |
| CN103801407A (en) * | 2012-11-08 | 2014-05-21 | 中国科学院大连化学物理研究所 | Preparation and applications of magnetic gamma-Fe2O3-HAP compound |
| CN104549501B (en) * | 2013-10-28 | 2017-05-17 | 中国石油化工股份有限公司 | Ethylidene diacetate method vinyl acetate catalyst and vinyl acetate synthesis method |
| CN105709840A (en) * | 2016-01-18 | 2016-06-29 | 张玲 | Method for producing palladium catalysts |
| CN107469865A (en) * | 2017-09-18 | 2017-12-15 | 吉林市道特化工科技有限责任公司 | A kind of method for preparing high degree of dispersion palladium resin catalyst and application |
| CN108097263B (en) * | 2017-12-25 | 2020-09-08 | 万华化学集团股份有限公司 | Method for preparing MIBK from industrial byproduct waste liquid acetone |
| CN111992249B (en) * | 2019-05-27 | 2021-12-24 | 中南大学 | Palladium/sulfonated (polymer-inorganic two-dimensional material) composite catalyst, preparation thereof and application thereof in catalyzing acetone hydrogenation |
| CN112439412B (en) * | 2019-09-02 | 2023-06-06 | 中国石油化工股份有限公司 | Refining agent for ethylene glycol hydrofining and preparation method thereof |
| CN114436794A (en) * | 2020-10-31 | 2022-05-06 | 中国石油化工股份有限公司 | Method for synthesizing methyl isoamyl ketone |
Citations (3)
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|---|---|---|---|---|
| US3953517A (en) * | 1967-09-08 | 1976-04-27 | Veba-Chemie Aktiengesellschaft | Process for preparing methyl isobutyl ketone and catalyst |
| CN1288782A (en) * | 1999-09-17 | 2001-03-28 | 中国石油化工集团公司 | Catalyst for synthesizing methyl isobutyl ketone with acetone and its preparation |
| CN1457927A (en) * | 2002-05-15 | 2003-11-26 | 中国石油化工股份有限公司 | Process for preparing palladium-resin catalyst |
-
2006
- 2006-01-09 CN CNB2006100456414A patent/CN100448543C/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3953517A (en) * | 1967-09-08 | 1976-04-27 | Veba-Chemie Aktiengesellschaft | Process for preparing methyl isobutyl ketone and catalyst |
| CN1288782A (en) * | 1999-09-17 | 2001-03-28 | 中国石油化工集团公司 | Catalyst for synthesizing methyl isobutyl ketone with acetone and its preparation |
| CN1457927A (en) * | 2002-05-15 | 2003-11-26 | 中国石油化工股份有限公司 | Process for preparing palladium-resin catalyst |
Non-Patent Citations (2)
| Title |
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| 强酸型阳离子交换树脂催化剂预处理研究. 霍稳周等.工业催化，第6期. 1999 |
| 强酸型阳离子交换树脂催化剂预处理研究. 霍稳周等.工业催化，第6期. 1999 * |
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