CN101811041B - Method for preparing crude terephthalic acid refined catalyst - Google Patents
Method for preparing crude terephthalic acid refined catalyst Download PDFInfo
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- CN101811041B CN101811041B CN2009100568841A CN200910056884A CN101811041B CN 101811041 B CN101811041 B CN 101811041B CN 2009100568841 A CN2009100568841 A CN 2009100568841A CN 200910056884 A CN200910056884 A CN 200910056884A CN 101811041 B CN101811041 B CN 101811041B
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Abstract
The invention relates to a method for preparing a crude terephthalic acid refined catalyst, which mainly aims at solving the problem that the active component of metal palladium microcrystallines of the catalyst in the prior art is distributed into micropores of the surface nearing the active carbon and has shallow penetration, and the Pd is easy to lose in the using process due to abrasion, therefore the activity of the catalyst is decreased and the stability is decreased. The method comprises the following steps of: preimpregnating an active carbon carrier by adopting a competitive adsorbent, filtering and drying to load an active component of metal palladium, and finally adding a reducing agent to reduce, and washing to obtain the finished catalyst. The invention well solves the problem, and can be applied to the industrial production of crude terephthalic acid refining.
Description
Technical field
The present invention relates to a kind of preparation method of crude terephthalic acid catalyst for refining, particularly about a kind of preparation method who is used for the refining support type Pd/carbon catalyst of crude terephthalic acid.
Background technology
The support type Pd/carbon catalyst is applicable to the refining of crude terephthalic acid, in the crude terephthalic acid carboxyl benzaldehyde impurity such as (being called for short 4-CBA) is carried out adopting the method for crystallization to separate purification subsequently after hydrogenation changes other compound into.Because Pd/carbon catalyst adopts single active constituent, so the distribution situation of Metal Palladium on carrier is very big to the influence of catalyst performance.
Because terephthalic acid (TPA) hydrofining reaction process is a first order reaction; Reaction speed is fast; React the inside that reactant is difficult to be penetrated into catalyst granules in the course of reaction; This just makes the reactive metal of granule interior because steric influence, and not reaching the bigger reactant molecule component of diameter can not play a role.At this moment, the high catalytic activity that shows of the reactive metal of outer surface.From the consideration that makes full use of noble metal, Pd/carbon catalyst is made eggshell type usually, promptly lets the basic load of active constituent palladium in the surface of carrier.The surface area that palladium contacts with reactant is big more, and activity is also good more.The catalyst that the eggshell type active constituent distributes has higher hydrogenation catalyst ability than the catalyst of distribution wider range.United States Patent (USP) 4476242 proposes to adopt the palladium salt solution impregnation absorbent charcoal carrier that is dissolved in organic solvent, and the active constituent palladium is all concentrated on the top layer of thickness less than 70～80 μ m.United States Patent (USP) 6066589 proposes to adopt prepreg method that dense palladium solution is loaded on the active carbon, is positioned at the top layer of carrier surface less than 50 μ m less than 50%Pd in the catalyst that makes, and remaining palladium is positioned at the top layer of 50～400 μ m.But the Pd/C catalyst that the eggshell type active constituent distributes is because surface abrasion causes the loss of palladium to cause catalysqt deactivation easily, so egg-shell catalyst active constituent palladium is distributed in outer surface unfavorable factor is also arranged.Preparing Pd distribution rational catalyst, is the key factor that improves catalytic performance, prolongs catalyst life.
Summary of the invention
Technical problem to be solved by this invention is to overcome that active constituent Metal Palladium crystallite is distributed in the micropore of active carbon near the surface in the catalyst that exists in the prior art; Infiltrate more shallow; In use, wearing and tearing run off because of causing palladium; Cause catalyst activity reduction and problem that stability reduces, a kind of preparation method of new crude terephthalic acid catalyst for refining is provided.The catalyst that this method makes is used for the hydrofinishing refining reaction of crude terephthalic acid, has minimizing and causes the loss of catalyst surface active component Metal Palladium because of wearing and tearing, the characteristics that catalyst stability is high, the life-span is long.
For solving the problems of the technologies described above; The technical scheme that the present invention adopts is following: a kind of preparation method of crude terephthalic acid catalyst for refining; With competitive adsorbate pre-preg absorbent charcoal carrier, filter and dry back loading active constituent Metal Palladium, add reducing agent at last it is reduced; Wash finished catalyst; The Metal Palladium percentage by weight is 0.1～5% in the catalyst that makes, and wherein has at least 45% palladium to be distributed in the top layer of carrier 0.2～20 μ m, and the top layer that is distributed in carrier surface to 0.2 μ m less than 10% palladium is arranged; Remainder is distributed in the internal layer that the degree of depth is 20～180 μ m, and it is at least a in 1～6 the low carbon organic acid aqueous solution that wherein used competitive adsorbate is selected from carbon number.
In the technique scheme; Described competitive adsorbate is selected from least a in citric acid, maleic acid, oxalic acid or the lactic acid that concentration is 0.01～0.5 mol, and preferred version is selected from least a in citric acid, maleic acid, oxalic acid or the lactic acid that concentration is 0.05～0.3 mol, and more preferably scheme is selected from the citric acid that concentration is 0.1～0.2 mol; The competitive adsorbate dipping temperature is 0～80 ℃; Preferable range is 10～50 ℃, and more preferably scope is 20～30 ℃, and dip time is 5～120 minutes; Preferable range is 10～60 minutes, and more preferably scope is 20～40 minutes; Baking temperature is 100～200 ℃, and preferable range is 110～150 ℃, and more preferably scope is 130～140 ℃.Palladium precursor preferred version is selected from least a in palladium bichloride, palladium oxide, acid chloride, palladium nitrate, the acid of chlorine palladium and basic salt thereof, the palladium amine complex, and more preferably scheme is selected from the acid of chlorine palladium.Reducing agent is selected from least a in formic acid, sodium formate, formaldehyde, hydrazine hydrate, glucose or the hydrogen, and preferred version is selected from sodium formate.
Select particle or pressed active carbon among the present invention for use, preferred particulates or moulding coconut husk charcoal, specific surface is 600～1800m
2/ g, preferable range is 800～1500m
2/ g; Pore volume is 0.30～0.85ml/g, and preferable range is 0.40～0.60ml/g; Wherein the grain graininess more than 90% is 4～8 orders.
With respect to prior art; It is activated carbon granule that improvements of the present invention are to have adopted competitive adsorbate to come the said carrier of pre-preg; Make that the adsorption site part on the said carrier is occupied; And then only have palladium to be distributed in the carrier outermost layer of the degree of depth, thereby can reduce the loss of the active palladium that causes because of wearing and tearing less than 0.2 μ m less than 10wt% (wt is a weight).Therefore, Pd/carbon catalyst of the present invention has good stability and long advantage of life-span.Each catalyst of the present invention's preparation has all obviously reduced the palladium abundance in the outermost layer (≤0.2 μ m), and this amount of being about to is controlled at less than 10wt%, thereby makes these catalyst have only very low palladium loss after 1000 hours in continued operation; In addition; The palladium component mainly is distributed in the skin (0.2～20 μ m), thereby has guaranteed the initial activity of these catalyst, promptly in intermittent reaction, reaches very high 4-CBA conversion ratio; And should activity still keep finely after 1000 hours, promptly have only a little reduction in continued operation.Therefore, catalyst of the present invention distributes through further optimization palladium and has reduced the palladium loss in the operating process, thereby has improved the stability of catalyst and prolonged catalyst life, has kept activity of such catalysts simultaneously, has obtained better technical effect.
To every kind of catalyst, in autoclave, carry out intermittent reaction, the initial activity of testing said catalyst is the 4-CBA conversion ratio that is reached, test condition is following: catalyst amount is 2.0 grams; The crude terephthalic acid amount is 30.0 grams; The 4-CBA amount is 1.0 grams; Reaction pressure is 8.0MPa (gauge pressure); With reaction temperature be 280 ℃.
To every kind of catalyst, in continuous apparatus, carry out successive reaction, test the active and corresponding palladium loss of operation of said catalyst, test condition is following: catalyst amount is 200.0 grams; Slurry flow is 3 kilograms/hour; Crude terephthalic acid content is 5wt%; 4-CBA content is 0.35wt%; Reaction pressure is 8.0MPa (gauge pressure); Reaction temperature is 280 ℃; With duration of the reaction be 1000 hours.
In the test process, the calculating of the conversion ratio of 4-CBA is undertaken by following formula:
In this manual, for following each embodiment and the prepared Pd/carbon catalyst of comparative example, wherein the percentage by weight of supported palladium is recorded by plasma atomic emission spectrometer (ICP-AES) analysis; Wherein the measure of spread of supported palladium is following: the palladium amount that is distributed in the palladium amount of the degree of depth≤20 μ m and is distributed in the degree of depth≤180 μ m records through electron probe power spectrum (EPMA); The palladium atomicity ratio that is distributed in the degree of depth≤0.2 μ m records through photoelectron spectroscopy (XPS).
In addition,, test, wherein use the high pressure liquid chromatographic analysis sample through the hydrofining reaction of crude terephthalic acid for following each embodiment and the prepared Pd/carbon catalyst of comparative example.
Through embodiment the present invention is done further elaboration below.
The specific embodiment
[embodiment 1]
Take by weighing 50 gram sheet coconut husk charcoals, the granularity of this coconut husk charcoal particle is 4～8 orders, and specific area is 1078 meters
2/ gram and pore volume are 0.47 milliliter/gram.Remove the dust and the surface porosity part of said coconut husk charcoal particle surface absorption; In the washing still, using concentration then is that the nitric acid of 0.5 mol carries out pickling, and wash temperature is that 80 ℃ and wash time are 1 hour; Then spend deionised water to neutral, following dry 2 hours at 120 ℃ at last.At room temperature using concentration is the said coconut husk charcoal of the aqueous citric acid solution pre-preg particle 15 minutes of 0.1 mol, filter then and 120 ℃ dry 2 hours down.Take by weighing 1.25 and restrain the chlorine palladium acid solution that contains palladium 20%; To wherein adding 15 gram deionized water preparation dipping solutions; Also to the dodecyl polyoxyethylene ether phosphate sylvite that wherein adds 0.45 gram, the pH value that adds an amount of sodium carbonate regulating solution then is 5.5, mends 5 at last and restrains the just said coconut husk charcoal of submergence particle of amount that deionized waters make solution; Utilize coconut husk charcoal particle after the said pre-preg of this solution impregnation about 1 minute, obtain said Pd/carbon catalyst.The Pd/carbon catalyst that is obtained was worn out 24 hours in air, reduced 4 hours down at 80 ℃ with sodium formate solution afterwards, with pure water washing to neutrality and drying, obtain catalyst prod A at last again.
[embodiment 2]
Repeat embodiment 1, just using concentration down at 50 ℃ is the said coconut husk charcoal of the lactic acid aqueous solution pre-preg particle 60 minutes of 0.4 mol, takes by weighing the chlorine palladium acid solution that 2.00 grams contain palladium 20%, obtains catalyst prod B.
[embodiment 3]
Repeat embodiment 1, just wherein the coconut husk charcoal carries out pickling without nitric acid, and using concentration down at 10 ℃ is the said coconut husk charcoal of the aqueous citric acid solution pre-preg particle 20 minutes of 0.2 mol, takes by weighing the chlorine palladium acid solution that 2.50 grams contain palladium 20%, obtains catalyst prod C.
[embodiment 4]
Repeat embodiment 1, just using concentration down at 70 ℃ is the said coconut husk charcoal of the maleic acid aqueous solution pre-preg particle 90 minutes of 0.5 mol, takes by weighing the chlorine palladium acid solution that 6.25 grams contain palladium 20%, obtains catalyst prod D.
[embodiment 5]
Repeat embodiment 1, just using concentration down at 20 ℃ is the said coconut husk charcoal of the oxalic acid aqueous solution pre-preg particle 5 minutes of 0.3 mol, takes by weighing the palladium nitrate solution that 0.50 gram contains palladium 20%, obtains catalyst prod E.
[embodiment 6]
Repeat embodiment 1, just using concentration down at 40 ℃ is the said coconut husk charcoal of the lactic acid aqueous solution pre-preg particle 5 minutes of 0.4 mol, takes by weighing the palladium nitrate solution that 3.50 grams contain palladium 20%, obtains catalyst prod F.
[embodiment 7]
Repeat embodiment 1, just using concentration down at 25 ℃ is the said coconut husk charcoal of the lactic acid aqueous solution pre-preg particle 30 minutes of 0.04 mol, takes by weighing the chlorine palladium acid solution that 8.75 grams contain palladium 20%, obtains catalyst prod G.
[embodiment 8]
Repeat embodiment 1; Just using concentration down at 35 ℃ is the said coconut husk charcoal of the aqueous citric acid solution pre-preg particle 30 minutes of lactic acid aqueous solution and 0.05 mol of 0.05 mol; Wherein take by weighing 11.25 and restrain the chlorine palladium acid solution that contains palladium 20%, obtain catalyst prod H.
[comparative example 1]
Repeat embodiment 1, just wherein coconut husk charcoal particle does not experience the competitive adsorbate pre-soak step, obtains catalyst prod I.
The palladium load capacity, the palladium that in following table 1, have provided each prepared in the foregoing description and comparative example catalyst distribute and the initial activity evaluation result.
Table 1
In following table 2, provided each prepared in the foregoing description and comparative example catalyst reaction Pd load capacity, Pd loss amount and operation activity rating result after 1000 hours in continuous evaluating apparatus.
Table 2
| Catalyst | Pd load capacity wt% (reacting after 1000 hours) | Pd loss amount wt% | 4-CBA conversion ratio % | Conversion ratio reduction amount % |
| A | 0.48 | 0.03 | ?97.9 | 1.1 |
| B | 0.76 | 0.05 | ?98.0 | 1.2 |
| C | 0.95 | 0.06 | ?98.3 | 1.1 |
| D | 2.43 | 0.06 | ?98.5 | 1.0 |
| E | 0.18 | 0.02 | ?84.5 | 1.2 |
| F | 1.36 | 0.04 | ?98.1 | 1.3 |
| G | 3.45 | 0.06 | ?98.2 | 1.4 |
| H | 4.40 | 0.08 | ?98.3 | 1.4 |
| I | 0.40 | 0.11 | ?95.5 | 4.3 |
Claims (7)
1. the preparation method of a crude terephthalic acid catalyst for refining; With competitive adsorbate pre-preg absorbent charcoal carrier, filter and dry back loading active constituent Metal Palladium, add reducing agent at last it is reduced; Wash finished catalyst; The Metal Palladium percentage by weight is 0.1～5% in the catalyst that makes, and wherein has at least 45% palladium to be distributed in the top layer of carrier 0.2～20 μ m, and the top layer that is distributed in carrier surface to 0.2 μ m less than 10% palladium is arranged; Remainder is distributed in the internal layer that the degree of depth is 20～180 μ m, and wherein used competitive adsorbate is selected from least a in citric acid, maleic acid, oxalic acid or the lactic acid aqueous solution; Described competitive Adsorption agent concentration is 0.01～0.5 mol, and dipping temperature is 0～80 ℃, and dip time is 5～120 minutes, and baking temperature is 100～200 ℃.
2. the preparation method of crude terephthalic acid catalyst for refining according to claim 1; It is characterized in that described competitive Adsorption agent concentration is 0.05～0.3 mol; Dipping temperature is 10～50 ℃, and dip time is 10～60 minutes, and baking temperature is 110～150 ℃.
3. the preparation method of crude terephthalic acid catalyst for refining according to claim 2; It is characterized in that described competitive adsorbate is selected from citric acid, concentration is 0.1～0.2 mol, and dipping temperature is 20～30 ℃; Dip time is 20～40 minutes, and baking temperature is 130～140 ℃.
4. the preparation method of crude terephthalic acid catalyst for refining according to claim 1 is characterized in that the palladium precursor is selected from least a in palladium bichloride, palladium oxide, acid chloride, palladium nitrate, the acid of chlorine palladium and basic salt thereof, the palladium amine complex.
5. the preparation method of crude terephthalic acid catalyst for refining according to claim 4 is characterized in that it is that the chlorine palladium is sour that the palladium precursor is selected from.
6. the preparation method of crude terephthalic acid catalyst for refining according to claim 1 is characterized in that said reducing agent is selected from least a in formic acid, sodium formate, formaldehyde, hydrazine hydrate, glucose or the hydrogen.
7. the preparation method of crude terephthalic acid catalyst for refining according to claim 6 is characterized in that said reducing agent is selected from sodium formate.
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| CN1457922A (en) * | 2002-05-16 | 2003-11-26 | 中国石化上海石油化工股份有限公司 | Hydrogenating catalyst for refining terephthalic acid |
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