CN102039122B - Palladium carbon catalyst for hydrofining crude terephthalic acid - Google Patents
Palladium carbon catalyst for hydrofining crude terephthalic acid Download PDFInfo
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Abstract
The invention relates to a palladium carbon catalyst for hydrofining crude terephthalic acid. The catalyst provided by the invention is mainly used for solving the following problem in the prior art: the active component palladium in the palladium carbon catalyst positioned on the surface of the carrier can easily run off due to abrasion, so that the activity of the catalyst is reduced, thereby shortening the service life of the catalyst. The technical scheme is as follows: shaped cocoanut carbon is used as the carrier, the active component palladium is loaded on the cocoanut carbon, and fluorocarbon resin is loaded on the surface of the catalyst. By utilizing the technical scheme, the problem in the prior art is solved; and the palladium carbon catalyst for hydrofining crude terephthalic acid can be used for hydrofining crude terephthalic acid in an industrial production mode.
Description
Technical field
The present invention relates to a kind of crude terephthalic acid Hydrobon catalyst that is used for.
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.U.S. Pat 4476242 proposes the active constituent palladium is all concentrated on the top layer of thickness less than 70～80 μ m.U.S. Pat 6066589 proposes and will be positioned at the top layer of carrier surface less than 50 μ m less than 50%Pd, 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; U.S. Pat 5723659 proposes can improve the anti-wear performance of catalyst at catalyst surface load silicone resin, but silicone resin costs an arm and a leg, and in practical application in industry, be difficult to realize, and the covering on surface is prone to come off.
Summary of the invention
Technical problem to be solved by this invention is to overcome that the active constituent Metal Palladium is distributed in activated carbon 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 new crude terephthalic acid Hydrobon catalyst that is used for is provided.This catalyst is used for the hydrofining reaction of crude terephthalic acid, has to reduce the loss that causes catalyst surface active component Metal Palladium because of wearing and tearing the advantage that catalyst stability is high, the life-span is long.
In order to solve the problems of the technologies described above; The technical scheme that the present invention adopts is following: a kind of crude terephthalic acid Hydrobon catalyst that is used for is a carrier with the coconut husk charcoal, the load active component palladium; Wherein in catalyst weight, contain 0.02～0.1% fluorocarbon resin at catalyst surface.
In the technique scheme, the carrier preferred version is particle or moulding coconut husk charcoal, and the specific surface preferable range is 800～1600m
2/ g, the pore volume preferable range is 0.35～0.80ml/g, wherein the particle more than 90% is at 4～8 orders; Palladium percentage by weight preferable range is 0.3～0.6%; The fluorocarbon resin preferred version is for being selected from least a in Kynoar (PVDF), polyurethane fluorine olefine resin (FEVE) or the PFPE polyurethane (CF-PU).
Preparation of catalysts method of the present invention is following:
1, select particle or pressed active carbon for use, preferred particulates or moulding coconut husk charcoal, specific surface is 800～1600m
2/ g, preferred 800～1200m
2/ g; Pore volume is 0.30～0.85ml/g, preferred 0.40～0.60ml/g; Wherein the grain graininess more than 90% is 4～8 orders.
2, remove the dust and surface porosity part of carbon surface absorption after, in the washing still, carry out pickling, the acid of employing is at least a in hydrochloric acid, nitric acid or the phosphoric acid, acid concentration is 0.1～5N, spends deionised water then to neutral, 100～200 ℃ of oven dry down.
3, adopt competitive adsorbate pre-preg absorbent charcoal carrier, filter oven dry then.Competitive adsorbate is at least a in citric acid, maleic acid, oxalic acid, the lactic acid.The concentration of competitive adsorbate is 0.01～0.5N.The competitive adsorbate dipping temperature is 0～50 ℃.Dip time is 5～60 minutes.Bake out temperature is 100～200 ℃.
4, active constituent aqueous solution adding surfactant and sodium carbonate are mixed with catalyst activity component solution, wherein the parent of palladium is with its chloride, oxide, acetate, nitrate, the acid of chlorine palladium and basic salt or palladium amine complex.Surfactant can be selected anion surfactant for use.Adopt methods such as dipping or sprinkling to make Pd be carried on the carrier active carbon surface then, preferred infusion process.Dipping temperature is 0～50 ℃.The percentage by weight of palladium is 0.1～5% in the catalyst.
5, catalyst in air aging 1～24 hour then adopts reducing agent to reduce processing.Reducing agent can adopt formic acid, sodium formate, formaldehyde, hydrazine hydrate, glucose and hydrogen.0～200 ℃ of reduction temperature, the recovery time is 0.5～10 hour.
6, will reduce good catalyst at 80～150 ℃ of dry 24h; Spray to catalyst surface with 0.02～0.1% fluorocarbon resin then, fluorocarbon resin is selected from least a in Kynoar (PVDF), polyurethane fluorine olefine resin (FEVE) or the PFPE polyurethane (CF-PU); At last at 120 ℃ of dry 24h.
Catalyst among the present invention is owing to adopt fluorocarbon resin spray treatment catalyst surface; Form the film of one deck difficult drop-off on the surface of catalyst, therefore can effectively reduce the loss that causes catalyst surface active component Metal Palladium because of wearing and tearing, improve the stability and the life-span of catalyst; Use catalyst of the present invention; Its abrasion can reach below 0.4%, and stability had preferably and to improve, and have obtained better technical effect.
Wear test: the catalyst 20g that handles well is put into beaker, add the 200ml pure water; Put into ultrasonoscope, handled 30 minutes; Put into 110 ℃ of dry 24h of baking oven behind the washing filtering, cooling back weighing, the counting loss rate is the abrasion of catalyst, with percentage calculation.
The powder that falls experiment: the catalyst 20～30g that handles well is washed 5～6 times with the 3L pure water, and the fine powder that filters is collected in the water filtration after the washing, dry back weighing.
The appreciation condition of catalyst in autoclave:
Catalyst amount: 2.0 grams
Crude terephthalic acid amount: 30.0 grams
4-CBA amount: 1.0 grams
Reaction pressure: 7.5Mpa
Reaction temperature: 280 ℃
Sample analysis adopts high pressure liquid chromatographic analysis.
The amount of the amount of≤20 μ m Pd and≤180 μ m Pd records through electron probe power spectrum (EPMA); ≤0.2 μ m top layer Pd atomicity ratio records through photoelectron spectroscopy (XPS).The percentage by weight of Pd is recorded by plasma atomic emission spectrometer (ICP-AES) analysis in the catalyst.
The burin-in process of catalyst: condition is identical with the appreciation condition of catalyst in the autoclave, and the reaction time is 72 hours.
Through embodiment the present invention is done further elaboration below.
The specific embodiment
[embodiment 1]
Take by weighing 50 grams, 4～8 orders, laminar cocoanut active charcoal, specific surface is 1100m
2/ g, pore volume are 0.52ml/g.After removing dust and the surface porosity part of surface adsorption, in the washing still, uses concentration to carry out pickling as the nitric acid of 0.5N, 80 ℃ of wash temperatures, spend deionised water to neutrality then at 1 hour pickling time.And it is following dry 2 hours at 120 ℃.Take by weighing 1.25 and restrain the chlorine palladium acid solution that contains palladium 20%; Again to the dodecyl polyoxyethylene ether phosphate sylvite and 0.05% citric acid that wherein add 0.1%; The pH value that uses 10% sodium carbonate regulating solution is 5.5, and the amount that adds deionized water to solution then just submergence absorbent charcoal carrier is advisable.With the catalyst activity component solution impregnating carrier, wear out and reduce with sodium formate solution after 24 hours, obtain catalyst prod with pure water washing to neutral also drying then.With percentage by weight is that 0.05% Kynoar (being called for short PVDF) dissolves in the 20ml acetone, adopts the spray gun of diameter 1.0～1.5mm to spray to catalyst surface; To spray good catalyst then and promptly wait required catalyst prod down in dry 24 hours at 120 ℃.
[embodiment 2～15]
Select for use the fluorocarbon resin of different fluorocarbon resins, different content to spray to catalyst surface, other catalyst preparation process is with embodiment 1, and concrete content is seen table 1.
[comparative example]
Do not add fluorocarbon resin, all the other are with embodiment 1.
The analysis data such as the following table of each instance: table 2 is a fresh catalyst; Table 3 is the catalyst of 72h after aging.
Table 1
Table 2
| Pd content (%) | 4-CBA conversion ratio (%) | Abrasion (%) | Powder (ppmw) falls | |
| [embodiment 1] | 0.498 | 98.4 | 0.41 | 48 |
| [embodiment 2] | 0.495 | 99.0 | 0.45 | 50 |
| [embodiment 3] | 0.496 | 98.6 | 0.40 | 48 |
| [embodiment 4] | 0.495 | 98.5 | 0.42 | 46 |
| [embodiment 5] | 0.494 | 98.6 | 0.38 | 47 |
| [embodiment 6] | 0.497 | 99.0 | 0.40 | 50 |
| [embodiment 7] | 0.495 | 98.4 | 0.43 | 52 |
| [embodiment 8] | 0.493 | 98.8 | 0.45 | 50 |
| [embodiment 9] | 0.496 | 98.3 | 0.48 | 49 |
| [embodiment 10] | 0.494 | 98.1 | 0.47 | 46 |
| [embodiment 11] | 0.495 | 98.4 | 0.40 | 46 |
| [embodiment 12] | 0.496 | 98.6 | 0.42 | 48 |
| [embodiment 13] | 0.493 | 98.2 | 0.46 | 51 |
| [embodiment 14] | 0.492 | 98.0 | 0.42 | 49 |
| [embodiment 15] | 0.495 | 98.1 | 0.43 | 53 |
| [comparative example] | 0.499 | 99.6 | 2.21 | 480 |
Table 3
| Pd content (%) | 4-CBA conversion ratio (%) | |
| [embodiment 1] | 0.481 | 97.7 |
| [embodiment 2] | 0.488 | 97.8 |
| [embodiment 3] | 0.486 | 97.5 |
| [embodiment 4] | 0.485 | 97.2 |
| [embodiment 5] | 0.488 | 97.6 |
| [embodiment 6] | 0.486 | 97.5 |
| [embodiment 7] | 0.487 | 97.4 |
| [embodiment 8] | 0.485 | 97.6 |
| [embodiment 9] | 0.486 | 97.4 |
| [embodiment 10] | 0.484 | 97.2 |
| [embodiment 11] | 0.486 | 97.1 |
| [embodiment 12] | 0.485 | 97.5 |
| [embodiment 13] | 0.483 | 97.3 |
| [embodiment 14] | 0.486 | 97.6 |
| [embodiment 15] | 0.484 | 97.4 |
| [comparative example] | 0.475 | 95.8 |
Claims (4)
1. one kind is used for the crude terephthalic acid Hydrobon catalyst, is carrier with the coconut husk charcoal, and the load active component palladium is characterized in that in catalyst weight, contains 0.02～0.1% fluorocarbon resin at catalyst surface;
The Preparation of catalysts method is following:
(1) selects moulding coconut husk charcoal for use;
(2) remove the dust and surface porosity part of carbon surface absorption after, in the washing still, carry out pickling, the acid of employing is at least a in hydrochloric acid, nitric acid or the phosphoric acid, acid concentration is 0.1～5N, spends deionised water then to neutral, 100～200 ℃ of oven dry down;
(3) adopt competitive adsorbate pre-preg coconut husk charcoal carrier, filter oven dry then; Competitive adsorbate is at least a in citric acid, maleic acid, oxalic acid, the lactic acid; The concentration of competitive adsorbate is 0.01～0.5N; The competitive adsorbate dipping temperature is 0～50 ℃, and dip time is 5～60 minutes, and bake out temperature is 100～200 ℃;
(4) active constituent aqueous solution adding surfactant and sodium carbonate are mixed with catalyst activity component solution, wherein the parent of palladium is with its chloride, oxide, acetate, nitrate, the acid of chlorine palladium and basic salt or palladium amine complex; Surfactant is selected anion surfactant for use; The method that adopts dipping then or spray makes Pd be carried on carrier coconut husk carbon surface; Dipping temperature is 0～50 ℃; The percentage by weight of palladium is 0.1～5% in the catalyst;
(5) catalyst in air aging 1～24 hour then adopts reducing agent to reduce processing; Reducing agent adopts formic acid, sodium formate, formaldehyde, hydrazine hydrate, glucose and hydrogen; 0～200 ℃ of reduction temperature, the recovery time is 0.5～10 hour;
(6) will reduce good catalyst 80～150 ℃ of dryings 24 hours, spray to catalyst surface with 0.02～0.1% fluorocarbon resin then, at last 120 ℃ of dryings 24 hours.
2. according to the said crude terephthalic acid Hydrobon catalyst that is used for of claim 1, it is characterized in that described carrier is a moulding coconut husk charcoal, specific surface is 800～1600m
2/ g, pore volume are 0.35～0.80ml/g, and wherein the particle more than 90% is at 4～8 orders.
3. according to the said crude terephthalic acid Hydrobon catalyst that is used for of claim 1, it is characterized in that the palladium weight content is 0.3～0.6% of a catalyst weight.
4. according to the said crude terephthalic acid Hydrobon catalyst that is used for of claim 1, it is characterized in that fluorocarbon resin is selected from least a in Kynoar, polyurethane fluorine olefine resin or the PFPE polyurethane.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4476242A (en) * | 1981-10-29 | 1984-10-09 | Standard Oil Company (Indiana) | Process for preparing palladium on carbon catalysts for purification of crude terephthalic acid |
| US5723659A (en) * | 1994-12-20 | 1998-03-03 | Engelhard Corporation | Process for the purification of aromatic polycarboxylic acids |
| US6066589A (en) * | 1997-05-19 | 2000-05-23 | Sud Chemie Mt. S.R.L. | Hydrogenation catalysts |
| CN101347730A (en) * | 2007-07-18 | 2009-01-21 | 中国石油化工股份有限公司 | Hydrogenation catalyst for refinement of crude terephthalic acid |
| CN101428218A (en) * | 2007-11-07 | 2009-05-13 | 中国石油化工股份有限公司 | P-benzene dicarboxylic acid hydrogen refining catalyst and preparation method thereof |
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2009
- 2009-10-13 CN CN2009102016408A patent/CN102039122B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4476242A (en) * | 1981-10-29 | 1984-10-09 | Standard Oil Company (Indiana) | Process for preparing palladium on carbon catalysts for purification of crude terephthalic acid |
| US5723659A (en) * | 1994-12-20 | 1998-03-03 | Engelhard Corporation | Process for the purification of aromatic polycarboxylic acids |
| US6066589A (en) * | 1997-05-19 | 2000-05-23 | Sud Chemie Mt. S.R.L. | Hydrogenation catalysts |
| CN101347730A (en) * | 2007-07-18 | 2009-01-21 | 中国石油化工股份有限公司 | Hydrogenation catalyst for refinement of crude terephthalic acid |
| CN101428218A (en) * | 2007-11-07 | 2009-05-13 | 中国石油化工股份有限公司 | P-benzene dicarboxylic acid hydrogen refining catalyst and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Michael R. Buchmeiser et al..Access to Well-Defined Heterogeneous Catalytic Systems via Ring-Opening Metathesis Polymerization (ROMP): Applications in Palladium(II)-Mediated Coupling Reactions.《J. Am. Chem. Soc.》.1999,第121卷(第48期),第11101页左栏第1段至第11107页右栏第4行. * |
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