CN101024185A - Method for reactivating palledium/carbon catalyst - Google Patents
Method for reactivating palledium/carbon catalyst Download PDFInfo
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- CN101024185A CN101024185A CN 200710020627 CN200710020627A CN101024185A CN 101024185 A CN101024185 A CN 101024185A CN 200710020627 CN200710020627 CN 200710020627 CN 200710020627 A CN200710020627 A CN 200710020627A CN 101024185 A CN101024185 A CN 101024185A
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Abstract
The invention relates to a Pd carbon catalyst anew active method. The method did justice of inactivation catalyst to obtain anew active Pd /carbon catalyst supplied for the TA hydrorefining reaction. The method includes: use out threshold CO2 extract washing inactivation Pd/carbon catalyst; put the inactivation Pd/carbon catalyst into nitric acid solution to boil up; after drying park in the hartshorn; in addition add to PdCl2; after filtration get the catalyst prosome; catalyst prosome through NaOH and formaldehyde revert,drying get the anew active Pd/carbon catalyst.
Description
Technical field
The invention relates to the method for palladium/carbon catalyst reactivation, more specifically, is about the process for reactivation of deactivated palladium/carbon catalyst in the hydrofining reaction in p-phthalic acid (PTA) production technology.
Background technology
Well-known palladium/carbon catalyst is the special-purpose catalyst that is used for PTA hydrofining reaction process.Palladium/carbon catalyst in use, along with the growing up of the loss of Metal Palladium in the catalyst, palladium crystal grain, poisonous substance poisoning effect, deposit such as cover at factor, activity of such catalysts reduces gradually until complete deactivation.
Palladium is a rare metal, and the palladium/carbon catalyst price is more expensive.Deactivated palladium/carbon catalyst is suitably handled,, continued to use for the TA hydrofining reaction to recover its activity; Or deactivated palladium/carbon catalyst handled time, from wherein extracting Metal Palladium, it is recycling that palladium metal is obtained.
It is methods of handling about deactivated palladium/carbon catalyst that many patents are arranged.Chinese patent 89101887 discloses a kind of method of reactivation palladium/carbon catalyst: palladium/carbon catalyst is contacted 0.5h to 10h with 200 ℃～350 ℃ hot water, catalyst contacts 0.5h～10h with 100 ℃ with interior cold water more then, and last catalyst contacts 1h～10h with concentrated base solution again and finishes the reactivation process.Chinese patent 00112558.3 discloses a kind of method of online regeneration palladium/carbon catalyst: earlier material is switched to water, move 2～4 hours, then reactor is adjusted to 6.0～6.5MPa, 255～265 ℃ of temperature, feed aqueous slkali, move 4～8 hours, switch to water running again after 2～4 hours, finish the reactivation process of palladium/carbon catalyst.This class processing method is applicable to the palladium/carbon catalyst that level of deactivation is more shallow, and the palladium/carbon catalyst of or complete deactivation heavier to level of deactivation generally adopts the method for extracting palladium from catalyst.Chinese patent 95104435.4 discloses a kind of method that reclaims palladium from the heavier palladium/carbon catalyst of level of deactivation: palladium/carbon catalyst is put into roaster oxidizing roasting, the roasting ash boils removal of impurities with sulfuric acid solution acid, ash after the removal of impurities leaches palladium with chloridising, leachate exchanges further removal of impurities through cationic ion-exchange resin, exchange liquid closes purification through ammino, and reduction obtains palladium sponge.Chinese patent 200410033983.5 discloses the method that reclaims palladium in a kind of palladium/carbon catalyst of complete deactivation: the carbonate with alkali metal or alkaline-earth metal is additive, under 700～800 ℃, charcoal is taken off in the palladium/carbon catalyst oxidation of will giving up, refining smart slag of back gained and alkali-metal bisulphate reactant salt, generate the palladium salt of solubility, adopt electrolysis that palladium is separated then, obtain palladium metal.Chinese patent 96114679.6 discloses the method that reclaims palladium in a kind of palladium/carbon catalyst: the palladium/carbon catalyst that will give up carries out preliminary treatment, decomposes through peracid, makes palladium become the acid of chlorine palladium and enters solution; Chlorine palladium acid solution through the adsorption column of adsorbent is housed, after adsorbent is saturated, is taken out adsorbent,, pass through chemical refining again, obtain pure palladium powder through burning.There is the not high shortcoming of contaminated environment, resource utilization in these class methods.
At the more shallow palladium/carbon catalyst of level of deactivation, adopt the method for alkaline solution washing can recover catalyst activity.And the palladium/carbon catalyst heavier to level of deactivation, its palladium content has only 0.2～0.3%, adopt the method for alkaline solution washing can not recover its activity, the general employing burned the back and extracted wherein palladium by chemical method, and there is the not high shortcoming of contaminated environment, resource utilization in this method.
Summary of the invention
The purpose of this invention is to provide and a kind of the heavier palladium/carbon catalyst of level of deactivation is carried out the method for reactivation, make the palladium/carbon catalyst reactivation of inactivation, use for the TA hydrofining reaction again.
Main contents of the present invention are: deactivated palladium/carbon catalyst is carried out preliminary treatment, through supercritical CO
2Fluid extraction is restored the pore structure of catalyst, deactivated palladium/carbon catalyst is used dense HNO again
3Boil, spend deionised water again to neutral, the back oven dry; Then deactivated palladium/carbon catalyst is immersed in the deionized water, dropping ammonia drips a certain amount of PdCl more then
2With the mixture of ammonia, filter after stirring a period of time, spend deionised water; Drying, roasting, reduction process again obtain the palladium/carbon catalyst of reactivation.
The process for reactivation of palladium-carbon catalyst may further comprise the steps:
1, deactivated palladium/carbon catalyst is placed supercritical CO
2In the extraction kettle, CO
2Temperature be 40 ℃～100 ℃, pressure is 9.7MPa～20MPa, the processing time is 1h～10h;
2, with supercritical CO
2Deactivated palladium/carbon catalyst after the processing places HN03 solution, and its concentration is 10～60wt%, and acid-treated temperature is 40 ℃～120 ℃, and the time is 1h～10h, and the deactivated palladium/carbon catalyst after acid treatment spends deionised water to neutral and oven dry;
3, the deactivated palladium/carbon catalyst with oven dry places deionized water, and dropping ammonia makes the concentration of ammoniacal liquor remain on 0.01mol/L～1mol/L, and stirs 1h～10h;
4, by the 0.17-0.34% of the weight of handling deactivated palladium/carbon catalyst, take by weighing PdCl
2Be dissolved in an amount of ammoniacal liquor, form Pd (NH3)
4 2+Complex, and this drips of solution is added in the deactivated palladium/carbon catalyst that aforementioned ammoniacal liquor soaks goes, stir 1h～10h, refilter and obtain catalyst precarsor, and spend deionised water;
5, catalyst precarsor is placed deionized water, add thermal agitation and be warming up to 60 ℃, add NaOH solution, regulate the pH value about 8, NaOH concentration is 5%～30%WT, stir the back and add formalin, the concentration of formaldehyde is 37%WT, regulate the pH value all the time greater than 8 with NaOH, till the pH value no longer descends, be cooled to room temperature, filter, obtain after the drying catalyst after the reactivation.
CO in the step 1
2Temperature be preferably 50 ℃～80 ℃, preferred pressure is 9.7MPa～15MPa, the preferred time is 4h～7h;
HNO in the step 2
3Preferred concentration is 30wt%～50wt%, and the processing time is preferably 1～6h;
The ammonia concn preference is 0.1mol/L～0.5mol/L in the step 3, and mixing time is preferably 2h～6h;
In the step 4, mixing time is preferably 2h～6h;
Adopt reactivation technology of the present invention, be used after can the palladium/carbon catalyst that level of deactivation is darker activating again, the catalyst activity after the reactivation is quite active with fresh catalyst.This method is that the reactivation effect of palladium/carbon catalyst of loss of active component is more effective to those deactivation causes especially.
Embodiment:
The following examples will be described further method provided by the invention, but the present invention is not limited to embodiment.
The deactivated palladium/carbon catalyst that is used for following examples is from the palladium/carbon catalyst of changing because of inactivation in the PTA hydrofinishing industrial process, and the average quality mark of palladium is 0.32% in the deactivated palladium/carbon catalyst, and average specific surface area is 700m
2/ g.
The active method of conversion ratio that adopts of reactivation rear catalyst is estimated, it is 4-CBA content * 100% of conversion ratio=(the 4-CBA content of initial reaction stage 4-CBA content-last stage reaction)/initial reaction stage, test is carried out in autoclave, its reaction condition and PTA hydrogenation industrial condition are similar, promptly at 280 ℃, the condition of 6.8MPa is carried out hydrogenation reaction.
4-CBA is to carboxyl benzaldehyde
Embodiment 1
The 20g deactivated palladium/carbon catalyst is placed the supercritical CO 2 extraction kettle, and adding temperature is 50 ℃, and pressure is the supercritical CO of 12MPa
2, extraction 4h.
Will be through supercritical CO
2Decaying catalyst after the extraction places 30% HNO3 solution, and is heated to boiling, keeps 2h.Spend deionised water then to neutral, and oven dry.
The decaying catalyst of oven dry is placed the 200ml deionized water, dropping ammonia slowly then, ammonia concn reaches 0.1mol/L to the solution, and slowly stirs 2h.
The preparation of Pd solution by 0.34% of the weight of handling deactivated palladium/carbon catalyst, takes by weighing 0.062gPdCl
2, drip 20ml ammoniacal liquor, make PdCl
2Dissolving fully forms Pd (NH
3)
4Cl
2Solution in the deactivated palladium/carbon catalyst that soaks to aforementioned ammoniacal liquor before this solution slowly added, carries out suction filtration after stirring 3h, makes catalyst precarsor after spending deionised water.
Catalyst precarsor is placed the 100ml deionized water, be heated to 50 ℃, NaOH with 30% regulates about pH value to 8, after fully stirring, adds 37% formalin 10ml, the pH value that keeps solution during this time is all the time greater than 8, till the pH value no longer descends, be cooled to room temperature then, suction filtration, filter cake 120 ℃ of oven dry down, is promptly obtained the palladium/carbon catalyst of reactivation.
Embodiment 2～5
Change supercritical CO
2The temperature of extraction adopts 40 ℃, 60 ℃, 80 ℃, 100 ℃ supercritical CO
2Extraction inactivation palladium-carbon catalyst.All the other are with embodiment 1.
Embodiment 6～8
Change supercritical CO
2The pressure of extraction, the supercritical CO of employing 9.7MPa, 14MPa, 20MPa
2Extraction inactivation palladium-carbon catalyst.All the other are with embodiment 1
Embodiment 9～10
Change the temperature of nitric acid treatment inactivation palladium-carbon catalyst, the catalyst after adopting 60 ℃, 80 ℃ nitric acid treatment to wash.All the other are with embodiment 1
Embodiment 11～13
Change the concentration of WITH AMMONIA TREATMENT inactivation palladium-carbon catalyst, make the ammonia concn in the solution reach 0.05mol/L, 0.2mol/L, 1mol/L respectively.All the other are with embodiment 1
Embodiment 14～15
Change the reduction temperature of catalyst precarsor in the step 5, adopt 40 ℃, 80 ℃ of conditions to carry out the restoring operation of catalyst precarsor respectively.All the other are with embodiment 1
Embodiment 16
Change again the amount of supported palladium,, take by weighing 0.031g PdCl by 0.17% of the weight of handling deactivated palladium/carbon catalyst
2, all the other are with embodiment 1
Catalyst that each embodiment makes and industrial catalyst adopt above-mentioned activity of such catalysts appreciation condition to carry out activity rating, and its result is as shown in table 1.
| Catalyst | Conversion ratio |
| Industrial catalyst | 97.18％ |
| Embodiment 1 | 98.52％ |
| Embodiment 2 | ?93.48％ |
| Embodiment 3 | ?98.74％ |
| Embodiment 4 | ?99.16％ |
| Embodiment 5 | ?99.24％ |
| Embodiment 6 | ?97.22％ |
| Embodiment 7 | ?99.46％ |
| Embodiment 8 | ?99.42％ |
| Embodiment 9 | ?96.72％ |
| Embodiment 10 | ?95.47％ |
| Embodiment 11 | ?93.54％ |
| Embodiment 12 | ?98.56％ |
| Embodiment 13 | ?98.34％ |
| Embodiment 14 | ?98.36％ |
| Embodiment 15 | ?98.14％ |
| Embodiment 16 | ?99.13％ |
Claims (9)
1, the process for reactivation of palladium-carbon catalyst may further comprise the steps:
1), deactivated palladium/carbon catalyst is placed supercritical CO
2In the extraction kettle, CO
2Temperature be 40～100 ℃, pressure is 9.7MPa～20MPa, the processing time is 1～10h;
2), with supercritical CO
2Deactivated palladium/carbon catalyst after the processing places salpeter solution, and concentration is 10～60wt%, and the temperature of acid solution is 40 ℃～120 ℃, and the processing time is 1h～10h, and the deactivated palladium/carbon catalyst after acid treatment spends deionised water to neutral and oven dry;
3), the deactivated palladium/carbon catalyst of oven dry is placed deionized water, dropping ammonia makes the concentration of ammoniacal liquor remain on 0.01mol/L～1mol/L, and stirs 1h～10h;
4), by the 0.17-0.34% of the weight of handling deactivated palladium/carbon catalyst, take by weighing PdCl
2Be dissolved in an amount of ammoniacal liquor, form Pd (NH3)
4 2+Complex, and this drips of solution is added in the deactivated palladium/carbon catalyst that aforementioned ammoniacal liquor soaks goes, stir 1h～10h, filter and obtain catalyst precarsor, and spend deionised water;
5), catalyst precarsor is placed deionized water, add thermal agitation and be warming up to 60 ℃, add NaOH solution, regulate the pH value about 8, NaOH concentration is 5%～30%wt, stirs the back and adds formalin, the concentration of formaldehyde is 37%wt, regulate pH value all the time greater than 8 with NaOH, be cooled to room temperature, obtain the catalyst after the reactivation after filtration, the drying.
2, method according to claim 1 is characterized in that CO in the step 1
2Temperature be preferably 50 ℃～80 ℃.
3, method according to claim 1 is characterized in that CO in the step 1
2Pressure is preferably 9.7MPa～15MPa.
4, method according to claim 1 is characterized in that CO in the step 1
2Processing time is preferably 4h～7h.
5, method according to claim 1 is characterized in that step 2 acid concentration is preferably 30wt%～50wt%.
6, method according to claim 1 is characterized in that the processing time is preferably 1～6h in the step 2.
7, method according to claim 1 is characterized in that ammonia concn is preferably 0.1mol/L～0.5mol/L in the step 3.
8, method according to claim 1 is characterized in that mixing time is preferably 2h～6h in the step 3.
9, method according to claim 1 is characterized in that mixing time is preferably 2h～6h in the step 4.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103691452A (en) * | 2013-12-23 | 2014-04-02 | 江西汉氏铂业有限公司 | Activating method of inactive platinum/palladium catalyst |
| CN104588038A (en) * | 2013-11-03 | 2015-05-06 | 中国石油化工股份有限公司 | Regeneration method for deactivated heavy oil hydrogenation catalyst |
| CN105107552A (en) * | 2015-09-07 | 2015-12-02 | 广西梧州通轩林产化学有限公司 | Reactivation method of palladium-carbon catalyst for preparation of disproportionated rosin |
| CN114345325A (en) * | 2021-12-31 | 2022-04-15 | 河北海力香料股份有限公司 | Reactivation method of palladium/carbon catalyst |
| CN116020451A (en) * | 2022-12-22 | 2023-04-28 | 雅邦绿色过程与新材料研究院南京有限公司 | Palladium-carbon catalyst regeneration activation method for removing N-benzyl by hydrogenation based on N-heterocyclic alkane compound |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS549992B2 (en) * | 1973-09-05 | 1979-04-28 | ||
| US4164481A (en) * | 1978-01-27 | 1979-08-14 | The Dow Chemical Company | Process of regenerating a noble metal catalyst used in the reduction of organic nitro compounds |
| DE19618829A1 (en) * | 1996-05-10 | 1997-11-13 | Bayer Ag | Process for reactivating catalyst systems containing platinum metal |
| CN1276794C (en) * | 2003-04-29 | 2006-09-27 | 中国石油化工股份有限公司 | Reactivation method of loading type palladium catalyst |
-
2007
- 2007-03-16 CN CNB2007100206273A patent/CN100423835C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104588038A (en) * | 2013-11-03 | 2015-05-06 | 中国石油化工股份有限公司 | Regeneration method for deactivated heavy oil hydrogenation catalyst |
| CN103691452A (en) * | 2013-12-23 | 2014-04-02 | 江西汉氏铂业有限公司 | Activating method of inactive platinum/palladium catalyst |
| CN105107552A (en) * | 2015-09-07 | 2015-12-02 | 广西梧州通轩林产化学有限公司 | Reactivation method of palladium-carbon catalyst for preparation of disproportionated rosin |
| CN114345325A (en) * | 2021-12-31 | 2022-04-15 | 河北海力香料股份有限公司 | Reactivation method of palladium/carbon catalyst |
| CN114345325B (en) * | 2021-12-31 | 2022-11-22 | 河北海力香料股份有限公司 | Reactivation method of palladium/carbon catalyst |
| CN116020451A (en) * | 2022-12-22 | 2023-04-28 | 雅邦绿色过程与新材料研究院南京有限公司 | Palladium-carbon catalyst regeneration activation method for removing N-benzyl by hydrogenation based on N-heterocyclic alkane compound |
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|---|---|
| CN100423835C (en) | 2008-10-08 |
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