CN102070441B - Method for catalytic hydrorefining of terephthalic acid - Google Patents
Method for catalytic hydrorefining of terephthalic acid Download PDFInfo
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- CN102070441B CN102070441B CN200910234627.2A CN200910234627A CN102070441B CN 102070441 B CN102070441 B CN 102070441B CN 200910234627 A CN200910234627 A CN 200910234627A CN 102070441 B CN102070441 B CN 102070441B
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- terephthalic acid
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- palladium
- hydrorefining
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Abstract
The invention discloses a method for catalytic hydrorefining of terephthalic acid. In the method, a palladium coordination compound is taken as a catalyst in aqueous solution, crude terephthalic acid is hydrogenated at the temperature of between 250 and 300 DEG C under the hydrogen pressure of 0.3 to 1MPa for 10 to 60 minutes, the products are cooled to room temperature, and the terephthalic acid is filtered out, wherein the palladium coordination compound is MaPdX4, (NH3)2PdX2 or Pd(NH3)4X2, or Pd(MTPPTS)2X2. The TA hydrorefining method can be carried out in a tank reactor or a tubular reactor, and the conventional TA hydrorefining equipment and process conditions are not needed to be changed basically. The catalyst is convenient to use, and the catalyst is 1 to 10 mass percent of a reactant 4-carboxybenzaldehyde based on transition metal. After the reaction is finished, a homogeneous catalyst is retained in a liquid phase, and is easily separated from a solid product; and the 4-CBA conversion rate is more than or equal to 95 percent.
Description
Technical field
The present invention relates to a kind of method with homogeneous catalyst catalytic hydrofinishing terephthalic acid.
Background technology
Pure terephthalic acid (PTA) is one of main raw material of polyester industrial, its production process is generally p-Xylol (PX) liquid phase air oxidation and becomes crude terephthalic acid (TA), then by hydrorefined method, remove the impurity in TA, obtain PTA product.Thick TA hydrofining is under High Temperature High Pressure, and thick TA and hydrogen are under the effect of catalyzer, and major impurity terephthalaldehydic acid (4-CBA) generates p-methylbenzoic acid (PT) with H-H reaction, and chromoplastid decomposes simultaneously, thereby reaches the refining object of TA.
The catalyzer that TA hydrofining reaction is used is to take a series of heterogeneous catalyst that palladium/carbon catalyst is representative, the palladium/carbon catalyst that the coconut carbon of take is carrier is the main flow of catalyst for refining industrial applications and production always, the support of the catalyst of development of new is one of TA Hydrobon catalyst research main contents always simultaneously, Engelhard company improves palladium-carbon catalyst, on palladium-carbon catalyst, apply the water-fast flexible materials that one deck is at least comprised of a kind of polymkeric substance, with the extending catalyst life-span; Degussa company adopts the titanium dioxide of high-ratio surface to make Pd/TiO2 catalyzer as carrier, is applied in TA unifining process, and the transformation efficiency of 4-CBA can reach 97.3%; Amoco company also useful titanium dioxide as the report of palladium carrier; Porous sintered metal and alloy thereof are also used as support of the catalyst.But palladium/carbon catalyst also exists after carrier pulverizing, and carbon granule enters into PTA product, affect the problems such as polyester quality, and other heterogeneous catalyst is not yet realized large-scale industrial application.
Summary of the invention
The title complex that the object of the invention is to develop palladium, as homogeneous catalyst, is applied in TA hydrofining reaction process.
For achieving the above object, the technical scheme of taking is in the present invention as follows:
A kind of method of catalytic hydrofinishing terephthalic acid, it is in the aqueous solution, the title complex of palladium is as catalyzer, by crude terephthalic acid, at 250-300 ℃, be under 0.3-1MPa condition with hydrogen partial pressure, hydrogenation 10-60 minute, be cooled to room temperature, filter out terephthalic acid, the title complex of described palladium is M
2pdX
4, (NH
3)
2pdX
2or Pd (NH
3)
4x
2, wherein M is positively charged ion (as: hydrogen ion, NH
4 +) and X be negatively charged ion [as halogen (particularly chlorine)], or Pd (MTPPTS)
2x
2, wherein M is that positively charged ion is [as hydrogen ion, alkalimetal ion (Na
+, K
+), NH
4 +], TPPTS is a triphenylphosphine three-sulfonic acid part, its molecular formula is: P (m-C
6h
4sO
3 -)
3, X is negatively charged ion [as halogen (particularly chlorine)].
The method of above-mentioned catalytic hydrofinishing terephthalic acid, the consumption of the palladium of the title complex of described palladium is the 1-10% of 4-aldehyde benzoic acid quality.
TA hydrofinishing process of the present invention can carry out in tank reactor or tubular reactor, substantially needn't change the hydrorefined equipment and process condition of existing TA.The use of catalyzer is very convenient, adds the homogeneous catalyst of dissolving in the deionized water of configuration TA slurry, mixes with reactant, jointly enters reactor, carries out catalytic hydrogenation reaction.Reaction conditions is consistent with existing TA hydrogenation conditions, at 250～300 ℃, under hydrogen partial pressure 0.3～1MPa condition, carries out hydrogenation reaction, catalyst levels be transition metal to the concentration of reactant 4-CBA 1%～10%.After reaction finishes, homogeneous catalyst is retained in liquid phase, can be separated with solid phase prod very easily, and transformation efficiency >=95% of 4-CBA.Homogeneous catalyst in liquid phase can adopt adsorbent method to be reclaimed, and selected sorbent material is activated carbon, ion exchange resin, macroporous silica gel etc.After upon adsorption dose of a certain amount of homogeneous catalyst of absorption, can adopt the method for traditional burning, chemical refining obtain palladium powder (referring to Wu Yuxiong etc., the recycling of palladium carbon catalyst, Chemical Engineering Technology and exploitation, 2003,32 (3): 29～30).
Embodiment
Embodiment:
The present invention is described further for the following examples.
The activity of homogeneous catalyst (Shanghai Jiu Shan Chemical Co., Ltd. provides) adopts the method for transformation efficiency to evaluate, it is 4-CBA content * 100% of transformation efficiency=(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 conditions and PTA solid-phase catalyst shortening industrial condition are similar, water is solvent, the concentration of TA is 20%, carries out hydrogenation reaction.
Embodiment 1～7
Respectively with Pd (NaTPPTS)
2cl
2, H
4pdCl
4, Pd (NH
3)
4cl
2, (NH
3)
2pdCl
2as the catalyzer of TA unifining process, result is as follows:
Note: catalyst levels is with transition metal, the quality of 4-CBA in reactant to be represented
Embodiment 8:
Catalyzer in liquid phase can be reclaimed by the method for solid absorption.Take the gac 10g that nitric acid treatment crosses and be placed in beaker, add and contain catalyzer H
4pdCl
4reaction after solution 100ml solution, wherein containing PdCl
20.1g (wherein palladium content 0.06g), after 8h absorption, takes out gac to analyze, and the palladium content in gac is 0.057g, and palladium yield is 95%.
Embodiment 9:
With Pd (NH
3)
4cl
2for example, the repeat performance of homogeneous catalyst is described.At 280 ℃, 0.5MPa, under 30 minutes conditions, reuses 3 times, and reaction result is as follows:
Claims (1)
1. the method for a catalytic hydrofinishing terephthalic acid, it is characterized in that: it is in the aqueous solution, the title complex of palladium is as catalyzer, by crude terephthalic acid, at 250-300 ℃, be under 0.3-1MPa condition with hydrogen partial pressure, hydrogenation 10-60 minute, be cooled to room temperature, filter out terephthalic acid, the title complex of described palladium is H
4pdCl
4, (NH
3)
2pdCl
2or Pd (NH
3)
4cl
2, or Pd (NaTPPTS)
2cl
2, wherein TPPTS is a triphenylphosphine three-sulfonic acid part, its molecular formula is: P (m-C
6h
4sO
3 -)
3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910234627.2A CN102070441B (en) | 2009-11-25 | 2009-11-25 | Method for catalytic hydrorefining of terephthalic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910234627.2A CN102070441B (en) | 2009-11-25 | 2009-11-25 | Method for catalytic hydrorefining of terephthalic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102070441A CN102070441A (en) | 2011-05-25 |
| CN102070441B true CN102070441B (en) | 2014-02-12 |
Family
ID=44029222
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910234627.2A Active CN102070441B (en) | 2009-11-25 | 2009-11-25 | Method for catalytic hydrorefining of terephthalic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102070441B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3584039A (en) * | 1967-08-30 | 1971-06-08 | Standard Oil Co | Fiber-grade terephthalic acid by catalytic hydrogen treatment of dissolved impure terephthalic acid |
| US4263452A (en) * | 1979-06-12 | 1981-04-21 | Mitsubishi Gas Chemical Company, Inc. | Process for purifying terephthalic acid |
| CN1205244A (en) * | 1997-05-19 | 1999-01-20 | 舒德化学公司 | Hydrogenation catalysts |
-
2009
- 2009-11-25 CN CN200910234627.2A patent/CN102070441B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3584039A (en) * | 1967-08-30 | 1971-06-08 | Standard Oil Co | Fiber-grade terephthalic acid by catalytic hydrogen treatment of dissolved impure terephthalic acid |
| US4263452A (en) * | 1979-06-12 | 1981-04-21 | Mitsubishi Gas Chemical Company, Inc. | Process for purifying terephthalic acid |
| CN1205244A (en) * | 1997-05-19 | 1999-01-20 | 舒德化学公司 | Hydrogenation catalysts |
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| Publication number | Publication date |
|---|---|
| CN102070441A (en) | 2011-05-25 |
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