CN100453176C - Method for reactivating deactivated palladium/carbon catalyst - Google Patents
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- CN100453176C CN100453176C CNB2007100206269A CN200710020626A CN100453176C CN 100453176 C CN100453176 C CN 100453176C CN B2007100206269 A CNB2007100206269 A CN B2007100206269A CN 200710020626 A CN200710020626 A CN 200710020626A CN 100453176 C CN100453176 C CN 100453176C
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Abstract
The invention relates to an inactive Pd carbon catalyst rebirth 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 heat lye washing inactivation Pd/carbon catalyst; use water washing to neutrality; 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. The operation of inactivation catalyst no need high temperature high pressure and simply, the anew catalyst activity correspond with a verdure catalyst activity.
Description
Technical field
The invention relates to the method for palladium/carbon catalyst reactivation, more specifically, is the process for reactivation about 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.Chinese patent 2005100944663 discloses a kind of renovation process of catalyst of hydrofinishing terephthalic acid (TPA), with the palladium/carbon catalyst of inactivation after high temperature alkali cleaning, washing, salt acid soak, adopt the palladium of equivalent impregnation method load 0.05～0.2%, the palladium/carbon catalyst that obtains regenerating after drying, the reduction.This method is utilized again to the palladium/carbon catalyst carrier, only replenishes the effect that a spot of palladium can reach fresh catalyst, has the high advantage of resource utilization.But this method is handled decaying catalyst and is adopted high temperature high pressure process, still has inconvenience in operating process.
Summary of the invention
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.
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 the alkaline solution washing, the pore structure of catalyst is restored; Again deactivated palladium/carbon catalyst is handled with oxidizing acid, adopt the acid treatment deactivated palladium/carbon catalyst, can make the carbon carrier surface be rich in groups such as tradable hydroxyl, carboxyl, the palladium in the oxidable deactivated palladium/carbon catalyst of simultaneous oxidation makes palladium reach the purpose of disperseing again when being reduced; Spend deionised water again to neutral, the back oven dry; Then deactivated palladium/carbon catalyst is immersed in the deionized water, dropping ammonia then can make the group such as hydroxyl, carboxyl and the amino of carbon surface carry out ion-exchange behind the WITH AMMONIA TREATMENT deactivated palladium/carbon catalyst, make the carbon carrier surface be rich in tradable NH
4 +Group; Drip a certain amount of PdCl again
2With the mixture of ammonia, make Pd (NH
4)
4 2+Ion and carbon carrier surface NH
4 +Ion-exchange loads on the deactivated palladium/carbon catalyst palladium, makes palladium load to the advantage that has the palladium good dispersion on the carbon carrier by ion-exchange.Filter after stirring a period of time, spend deionised water; Drying, roasting, reduction process again obtain the palladium/carbon catalyst of reactivation.
The present invention includes following steps
1, with the alkaline solution washing of deactivated palladium/carbon catalyst with heat, to recover the pore structure of catalyst, its alkaline solution is meant water-soluble alkali metal, alkaline earth metal hydroxide, carbonate, bicarbonate etc., as NaOH, KOH, Na
2CO
3, NaHCO
3, K
2CO
3Deng, alkali concn is 1wt%～20wt%, and preferred concentration is 5%～10%, and the temperature of aqueous slkali is 20 ℃～150 ℃, and preferred temperature is 50 ℃～150 ℃.
2, spend deionised water deactivated palladium/carbon catalyst to neutrality again and be placed in the oxidizing acid solution, as nitric acid, perchloric acid etc.Its concentration is 10wt%～60wt%, and preferred concentration is 30wt%～50wt%, and acid-treated temperature is 40 ℃～120 ℃, and the time is 1h～10h, and the preferred time is 1h～6h.Deactivated palladium/carbon catalyst after oxidizing acid is handled 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 preferred concentration is 0.1mol/L～0.5mol/L, and slowly stirs 1h～10h, and the preferred time is 2h～6h.
4, by the 0.17-0.34% of the weight of handling deactivated palladium/carbon catalyst, take by weighing PdCl
2, be 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, the preferred time is 2h～6h, filters, and spends deionised water to neutral.
5, the desirable product of drying and roasting then, under 200 ℃～500 ℃, reduce 1～10h with hydrogen, preferred reduction temperature is 200 ℃～300 ℃, the preferred recovery time is 2h～5h, behind hydrogen reducing, promptly obtain the palladium/carbon catalyst of reactivation, can use for the TA hydrofining reaction again.
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 obvious to those deactivation causes especially, and the processing of decaying catalyst be need not HTHP, and is easy and simple to handle.
Embodiment:
The following examples will the present invention is described further, 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
With 10% NaOH solution washing, wash temperature is 80 ℃, spends deionised water then to neutral with the 20g deactivated palladium/carbon catalyst.
Decaying catalyst after the washing is placed 30% HNO
3In the solution, and be heated to boiling, keep 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 dry down at 120 ℃.At 300 ℃ of following roasting 4h, use hydrogen reducing 5h down at 200 ℃ at last then, promptly obtain the palladium/carbon catalyst of reactivation.
Embodiment 2～3
Change the concentration and the Temperature Treatment inactivation palladium-carbon catalyst of alkali, adopt 1%, 5% NaOH solution respectively, at the catalyst of 150 ℃ of washing inactivations.All the other are with embodiment 1.
Embodiment 4
The kind that changes alkali is handled the inactivation palladium-carbon catalyst, adopts the catalyst of KOH solution-treated inactivation.All the other are with embodiment 1.
Embodiment 5～8
Change the temperature of nitric acid treatment inactivation palladium-carbon catalyst, adopt the catalyst after 20 ℃, 40 ℃, 60 ℃, 80 ℃ the nitric acid treatment washing respectively.All the other are with embodiment 1
Embodiment 9～10
The concentration that changes nitric acid is handled the inactivation palladium-carbon catalyst, adopts the catalyst after 20%, 50% the nitric acid treatment washing respectively, and all the other are with embodiment 1.
Embodiment 11
The kind that changes acid is handled the inactivation palladium-carbon catalyst, and the perchloric acid of employing 10% is handled the catalyst after the washing, and all the other are with embodiment 1.
Embodiment 12～14
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 15
Change the baking temperature of catalyst precarsor, adopt 60 ℃ of dried catalyst precursor.All the other are with embodiment 1
Embodiment 16～17
Change the sintering temperature of catalyst prerequisite, adopt 400 ℃, 500 ℃ calcined catalyst precursors respectively.
Embodiment 18
Change the reduction temperature of catalyst precarsor, adopt 300 ℃, 400 ℃ reducing catalyst precursors respectively.
Embodiment 19
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.
Table 1
| Catalyst | Conversion ratio |
| Industrial catalyst | 97.18％ |
| Embodiment 1 | 99.41％ |
| Embodiment 2 | 96.34％ |
| Embodiment 3 | 99.12％ |
| Embodiment 4 | 99.35％ |
| Embodiment 5 | 95.68％ |
| Embodiment 6 | 95.33％ |
| Embodiment 7 | 98.82％ |
| Embodiment 8 | 98.26％ |
| Embodiment 9 | 99.50％ |
| Embodiment 10 | 97.25％ |
| Embodiment 11 | 98.32％ |
| Embodiment 12 | 96.85％ |
| Embodiment 13 | 97.67％ |
| Embodiment 14 | 95.43％ |
| Embodiment 15 | 98.73％ |
| Embodiment 16 | 95.36％ |
| Embodiment 17 | 93.65％ |
| Embodiment 18 | 94.78％ |
| Embodiment 19 | 99.62％ |
Sum up: the process for reactivation of the crude terephthalic acid Hydrobon catalyst that a kind of level of deactivation is darker, after this method is suitably handled decaying catalyst, again a certain amount of palladium of load obtains the palladium/carbon catalyst of reactivation, can use for the TA hydrofining reaction again.This method comprises: wash deactivated palladium/carbon catalyst with heat alkali liquid; Be washed with water to neutrality; Place nitric acid to boil processing deactivated palladium/carbon catalyst; Oven dry is placed in the ammonia spirit; An amount of Pd (the NH that adds configuration again
3)
4Cl
2Solution; Obtain catalyst precarsor behind the suction filtration; Obtain the palladium/carbon catalyst of reactivation behind catalyst precarsor drying, roasting, the hydrogen reducing.
Claims (6)
1, a kind of renovation process of inactivation Pd/carbon catalyst may further comprise the steps:
1) deactivated palladium/carbon catalyst is washed with aqueous slkali, alkali concn is 1wt%～20wt%, and the temperature of aqueous slkali is 20 ℃～150 ℃, and described alkali is the alkali metal soluble in water or hydroxide or the carbonate or the bicarbonate of alkaline-earth metal;
2) spend deionised water and in step 1), be placed on HNO through deactivated palladium/carbon catalyst to the neutrality of aqueous slkali washing
3In the solution, HNO
3Concentration is 10wt%～60wt%, HNO
3The temperature of solution is 40 ℃～120 ℃, and be 1h～10h standing time, through HNO
3Deactivated palladium/carbon catalyst after the solution-treated spends deionised water to neutral and oven dry;
3) 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 processed deactivated palladium/carbon catalyst, take by weighing PdCl
2, be dissolved in an amount of ammoniacal liquor, form Pd (NH
3)
4 2+Complex, and the complex solution that will obtain thus is added drop-wise in the deactivated palladium/carbon catalyst that the ammoniacal liquor of step 3) soaks and goes, and stirs 1h～10h, filters, and spends deionised water to neutral;
5) product that obtains dry then, calcination steps 4) reduces 1～10h with hydrogen under 200 ℃～500 ℃, promptly obtain the palladium/carbon catalyst of reactivation after the reduction.
2, method according to claim 1 is characterized in that: the described alkali in the step 1) is the hydroxide of alkali metal or alkaline-earth metal, and alkali concn is 5%～10wt%, and the temperature of aqueous slkali is 50 ℃～150 ℃.
3, method according to claim 2 is characterized in that: the described alkali in the step 1) is KOH or NaOH.
4, method according to claim 1 is characterized in that: step 2) middle HNO
3Concentration is 30wt%～50wt%, and be 1h～6h standing time.
5, method according to claim 1 is characterized in that: ammonia concn is 0.1mol/L～0.5mol/L in the step 3), and mixing time is 2h～6h.
6, method according to claim 1 is characterized in that: mixing time is 2h～6h in the step 4).
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| CNB2007100206269A CN100453176C (en) | 2007-03-16 | 2007-03-16 | Method for reactivating deactivated palladium/carbon catalyst |
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| CN100453176C true CN100453176C (en) | 2009-01-21 |
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