CN105435812B - Hydrofining crude terephthalic acid catalyst and preparation method thereof - Google Patents
Hydrofining crude terephthalic acid catalyst and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to hydrofining crude terephthalic acid catalyst and preparation method thereof, after solving the acetic acid in PX washings removing crude terephthalic acid in the prior art, the problem of PX of residual can be used in the Pd/C catalyst poisonings of refinement of crude terephthalic acid.By using a kind of hydrofining crude terephthalic acid catalyst, using activated carbon as carrier, including Pd, Ir, Cu and Pb are the technical scheme of active component, available in the industrial production for producing p-phthalic acid.
Description
Technical field
The present invention relates to a kind of crude terephthalic acid refined catalyst, its preparation method and the crude terephthalic acid containing PX
Hydrofinishing process.
Background technology
The production technology of p-phthalic acid (PTA) is for raw material with paraxylene (PX), and oxidized reaction prepares thick right
Phthalic acid (CTA), CTA is crystallized again, filter, is sent into follow-up hydrofinishing unit after drying finally gives PTA products.It is dry
Dry unit is the operating unit that energy consumption is larger in PTA production processes, phenomena such as tubulation knot wall in drying machine easily occurs, corrodes, sternly
Ghost image rings PTA quality and yield, is the bottleneck of PTA Increasing Production and Energy Savings.And solvent is used to be washed to CTA filter cakes to remove second
Acid is a highly effective method, wherein being solvent to CTA Washing of Filter Cake (Chinese patent the most economic especially using PX
CN1129693 and solvent washing method remove the oil such as research Xu Shichang, Liu Huiwu, Luo Qiming of acetic acid in crude terephthalic acid
Chemical industry .2007,36 (7):694-698).But prior art can inevitably make a certain amount of PX remaining in final CTA filter cakes,
And the PX remained can be to the purification efficiency of reduction Pd/C catalyst, or even make catalyst poisoning and inactivate.
The content of the invention
One of problem to be solved by this invention is the vinegar in PX washing removing crude terephthalic acids in the prior art be present
After acid, the problem of PX of residual can be used in the Pd/C catalyst poisonings of refinement of crude terephthalic acid, there is provided one kind is used for thick right
Benzene dicarboxylic acid hydrogen refining catalyst, the catalyst, which has, is used for the characteristics of CTA hydrofinishings are not influenceed by PX.
The two of problem to be solved by this invention are the preparation methods of the catalyst of one of above-mentioned technical problem.
The three of problem to be solved by this invention are the crude terephthalic acids using the catalyst of one of above-mentioned technical problem
Hydrofinishing process.
One of in order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows：Crude terephthalic acid hydrogenation essence
Catalyst processed, using activated carbon as carrier, including Pd, Ir, Cu and Pb are active component.
In above-mentioned technical proposal, Pd contents are preferably 0.1~1wt%, more preferably 0.3~0.5wt%.
In above-mentioned technical proposal, Ir contents are preferably 0.01~0.05wt%, more preferably 0.02~0.03wt%.
In above-mentioned technical proposal, Cu contents are preferably 1~5wt%, more preferably 2~3wt%.
In above-mentioned technical proposal, Pb contents are preferably 0.005~0.01wt%, more preferably 0.005~0.006wt%.
In order to solve the above-mentioned technical problem two, technical scheme is as follows：Any of one of above-mentioned technical problem
The preparation method of catalyst described in technical scheme described in, including the steps：
A) impregnated and carried with the solution of the desired amount of compound containing Pd, compound containing Ir, compound containing Cu and the compound containing Pb
Body activated carbon；
B) Pd, Ir, Cu and Pb compound are reduced to metal simple-substance with reducing agent.
In above-mentioned technical proposal, described reducing agent be preferably in hydrogen, formaldehyde, hydrazine hydrate, formic acid or sodium formate at least
It is a kind of.
In order to solve the above-mentioned technical problem three, technical scheme is as follows：Hydrofining crude terephthalic acid
Method, in the presence of catalyst any one of the technical scheme in one of above-mentioned technical problem, using water as solvent, hydrogen and contain
PX crude terephthalic acid reacts to obtain p-phthalic acid.
In above-mentioned technical proposal, PX contents are preferably 0~20wt% in crude terephthalic acid, more preferably 0~10wt%.
PX contents are preferably greater than 0wt%.
In above-mentioned technical proposal, catalyst and the mass ratio of crude terephthalic acid inventory are preferably 1:(1~20), it is more excellent
Elect 1 as:(1~10).
When catalyst in the present invention is used for 4-CBA containing 3300ppm and 5wt%PX hydrofining crude terephthalic acid,
4-CBA is down to 70ppm, and transformation does not occur for paraxylene and catalyst is after 10 times are applied mechanically, and still keeps initial activity, achieve compared with
Good technique effect, substantially increases mithridatism of the Pd/C catalyst to PX, while also avoid PX loss.
Embodiment
【Embodiment 1】
The preparation of catalyst：It is that 0.4wt%, Ir content are to be first according to Pd contents in Pd-Ir-Cu-Pb/C catalyst
0.02wt%, Cu content are that 2wt% and Pb contents are the H that 0.005wt% weighs respective quality2PdCl4、IrCl3、CuCl2With
(CH3COO)2Pb simultaneously is dissolved in forming 250ml maceration extracts in 15wt% hydrochloric acid, and gained maceration extract and 50 grams of activated carbons are mixed
Close, impregnate 12h, 3h is then dried in vacuo at 110 DEG C obtains catalyst precursor, finally with the hydrogen diluted through 5 times of volume nitrogen
The lower 160 DEG C of reduction 3h filterings of gas 150ml/min, obtain Pd-Ir-Cu-Pb/C finished catalysts, are analyzed through ICP-AES, catalyst
In Pd contents be that 0.4wt%, Ir content are that 0.02wt%, Cu content are that 2wt% and Pb contents are 0.005wt%, for ease of
Compare, gained catalyst composition is listed in Table 1 below.
Evaluating catalyst：3300ppm p -carboxybenzaldehydes (4-CBA), 5wt%PX crude terephthalic acid 18g, water will be contained
42g and above-mentioned catalyst 2g is fitted into the titanium pressure vessel that capacity is 100ml, is filled with hydrogen 0.5MPa, is reacted at 280 DEG C
10min.Reaction product is analyzed, compared for convenience, analysis result is listed in Table 1 below.Catalyst is applied mechanically 10 times, and
The reaction product analysis result of the 10th time is also shown in Table 1 below.
【Embodiment 2】
The preparation of catalyst：It is that 0.1wt%, Ir content are to be first according to Pd contents in Pd-Ir-Cu-Pb/C catalyst
0.02wt%, Cu content are that 2wt% and Pb contents are the H that 0.005wt% weighs respective quality2PdCl4、IrCl3、CuCl2With
(CH3COO)2Pb simultaneously is dissolved in forming 250ml maceration extracts in 15wt% hydrochloric acid, and gained maceration extract is mixed with 50 grams of activated carbons,
12h is impregnated, 3h is then dried in vacuo at 110 DEG C obtains catalyst precursor, finally with the hydrogen diluted through 5 times of volume nitrogen
The lower 160 DEG C of reduction 3h filterings of 150ml/min, obtain Pd-Ir-Cu-Pb/C finished catalysts, are analyzed through ICP-AES, in catalyst
Pd contents be that 0.1wt%, Ir content are that 0.02wt%, Cu content are that 2wt% and Pb contents are 0.005wt%, for ease of than
Compared with, by gained catalyst composition be listed in Table 1 below.
Evaluating catalyst：3300ppm p -carboxybenzaldehydes (4-CBA), 5wt%PX crude terephthalic acid 18g, water will be contained
42g and above-mentioned catalyst 2g is fitted into the titanium pressure vessel that capacity is 100ml, is filled with hydrogen 0.5MPa, is reacted at 280 DEG C
10min.Reaction product is analyzed, compared for convenience, analysis result is listed in Table 1 below.Catalyst is applied mechanically 10 times, and
The reaction product analysis result of the 10th time is also shown in Table 1 below.
【Embodiment 3】
The preparation of catalyst：It is that 0.3wt%, Ir content are to be first according to Pd contents in Pd-Ir-Cu-Pb/C catalyst
0.02wt%, Cu content are that 2wt% and Pb contents are the H that 0.005wt% weighs respective quality2PdCl4、IrCl3、CuCl2With
(CH3COO)2Pb simultaneously is dissolved in forming 250ml maceration extracts in 15wt% hydrochloric acid, and gained maceration extract is mixed with 50 grams of activated carbons,
12h is impregnated, 3h is then dried in vacuo at 110 DEG C obtains catalyst precursor, finally with the hydrogen diluted through 5 times of volume nitrogen
The lower 160 DEG C of reduction 3h filterings of 150ml/min, obtain Pd-Ir-Cu-Pb/C finished catalysts, are analyzed through ICP-AES, in catalyst
Pd contents be that 0.3wt%, Ir content are that 0.02wt%, Cu content are that 2wt% and Pb contents are 0.005wt%, for ease of than
Compared with, by gained catalyst composition be listed in Table 1 below.
Evaluating catalyst：3300ppm p -carboxybenzaldehydes (4-CBA), 5wt%PX crude terephthalic acid 18g, water will be contained
42g and above-mentioned catalyst 2g is fitted into the titanium pressure vessel that capacity is 100ml, is filled with hydrogen 0.5MPa, is reacted at 280 DEG C
10min.Reaction product is analyzed, compared for convenience, analysis result is listed in Table 1 below.Catalyst is applied mechanically 10 times, and
The reaction product analysis result of the 10th time is also shown in Table 1 below.
【Embodiment 4】
The preparation of catalyst：It is that 0.5wt%, Ir content are to be first according to Pd contents in Pd-Ir-Cu-Pb/C catalyst
0.02wt%, Cu content are that 2wt% and Pb contents are the H that 0.005wt% weighs respective quality2PdCl4、IrCl3、CuCl2With
(CH3COO)2Pb simultaneously is dissolved in forming 250ml maceration extracts in 15wt% hydrochloric acid, and gained maceration extract is mixed with 50 grams of activated carbons,
12h is impregnated, 3h is then dried in vacuo at 110 DEG C obtains catalyst precursor, finally with the hydrogen diluted through 5 times of volume nitrogen
The lower 160 DEG C of reduction 3h filterings of 150ml/min, obtain Pd-Ir-Cu-Pb/C finished catalysts, are analyzed through ICP-AES, in catalyst
Pd contents be that 0.5wt%, Ir content are that 0.02wt%, Cu content are that 2wt% and Pb contents are 0.005wt%, for ease of than
Compared with, by gained catalyst composition be listed in Table 1 below.
Evaluating catalyst：3300ppm p -carboxybenzaldehydes (4-CBA), 5wt%PX crude terephthalic acid 18g, water will be contained
42g and above-mentioned catalyst 2g is fitted into the titanium pressure vessel that capacity is 100ml, is filled with hydrogen 0.5MPa, is reacted at 280 DEG C
10min.Reaction product is analyzed, compared for convenience, analysis result is listed in Table 1 below.Catalyst is applied mechanically 10 times, and
The reaction product analysis result of the 10th time is also shown in Table 1 below.
【Embodiment 5】
The preparation of catalyst：It is that 1wt%, Ir content are to be first according to Pd contents in Pd-Ir-Cu-Pb/C catalyst
0.02wt%, Cu content are that 2wt% and Pb contents are the H that 0.005wt% weighs respective quality2PdCl4、IrCl3、CuCl2With
(CH3COO)2Pb simultaneously is dissolved in forming 250ml maceration extracts in 15wt% hydrochloric acid, and gained maceration extract is mixed with 50 grams of activated carbons,
12h is impregnated, 3h is then dried in vacuo at 110 DEG C obtains catalyst precursor, finally with the hydrogen diluted through 5 times of volume nitrogen
The lower 160 DEG C of reduction 3h filterings of 150ml/min, obtain Pd-Ir-Cu-Pb/C finished catalysts, are analyzed through ICP-AES, in catalyst
Pd contents be that 1wt%, Ir content are that 0.02wt%, Cu content are that 2wt% and Pb contents are 0.005wt%, for ease of comparing,
Gained catalyst composition is listed in Table 1 below.
Evaluating catalyst：3300ppm p -carboxybenzaldehydes (4-CBA), 5wt%PX crude terephthalic acid 18g, water will be contained
42g and above-mentioned catalyst 2g is fitted into the titanium pressure vessel that capacity is 100ml, is filled with hydrogen 0.5MPa, is reacted at 280 DEG C
10min.Reaction product is analyzed, compared for convenience, analysis result is listed in Table 1 below.Catalyst is applied mechanically 10 times, and
The reaction product analysis result of the 10th time is also shown in Table 1 below.
【Embodiment 6】
The preparation of catalyst：It is that 0.4wt%, Ir content are to be first according to Pd contents in Pd-Ir-Cu-Pb/C catalyst
0.01wt%, Cu content are that 2wt% and Pb contents are the H that 0.005wt% weighs respective quality2PdCl4、IrCl3、CuCl2With
(CH3COO)2Pb simultaneously is dissolved in forming 250ml maceration extracts in 15wt% hydrochloric acid, and gained maceration extract is mixed with 50 grams of activated carbons,
12h is impregnated, 3h is then dried in vacuo at 110 DEG C obtains catalyst precursor, finally with the hydrogen diluted through 5 times of volume nitrogen
The lower 160 DEG C of reduction 3h filterings of 150ml/min, obtain Pd-Ir-Cu-Pb/C finished catalysts, are analyzed through ICP-AES, in catalyst
Pd contents be that 0.4wt%, Ir content are that 0.01wt%, Cu content are that 2wt% and Pb contents are 0.005wt%, for ease of than
Compared with, by gained catalyst composition be listed in Table 1 below.
Evaluating catalyst：3300ppm p -carboxybenzaldehydes (4-CBA), 5wt%PX crude terephthalic acid 18g, water will be contained
42g and above-mentioned catalyst 2g is fitted into the titanium pressure vessel that capacity is 100ml, is filled with hydrogen 0.5MPa, is reacted at 280 DEG C
10min.Reaction product is analyzed, compared for convenience, analysis result is listed in Table 1 below.Catalyst is applied mechanically 10 times, and
The reaction product analysis result of the 10th time is also shown in Table 1 below.
【Embodiment 7】
The preparation of catalyst：It is that 0.4wt%, Ir content are to be first according to Pd contents in Pd-Ir-Cu-Pb/C catalyst
0.03wt%, Cu content are that 2wt% and Pb contents are the H that 0.005wt% weighs respective quality2PdCl4、IrCl3、CuCl2With
(CH3COO)2Pb simultaneously is dissolved in forming 250ml maceration extracts in 15wt% hydrochloric acid, and gained maceration extract is mixed with 50 grams of activated carbons,
12h is impregnated, 3h is then dried in vacuo at 110 DEG C obtains catalyst precursor, finally with the hydrogen diluted through 5 times of volume nitrogen
The lower 160 DEG C of reduction 3h filterings of 150ml/min, obtain Pd-Ir-Cu-Pb/C finished catalysts, are analyzed through ICP-AES, in catalyst
Pd contents be that 0.4wt%, Ir content are that 0.03wt%, Cu content are that 2wt% and Pb contents are 0.005wt%, for ease of than
Compared with, by gained catalyst composition be listed in Table 1 below.
Evaluating catalyst：3300ppm p -carboxybenzaldehydes (4-CBA), 5wt%PX crude terephthalic acid 18g, water will be contained
42g and above-mentioned catalyst 2g is fitted into the titanium pressure vessel that capacity is 100ml, is filled with hydrogen 0.5MPa, is reacted at 280 DEG C
10min.Reaction product is analyzed, compared for convenience, analysis result is listed in Table 1 below.Catalyst is applied mechanically 10 times, and
The reaction product analysis result of the 10th time is also shown in Table 1 below.
【Embodiment 8】
The preparation of catalyst：It is that 0.4wt%, Ir content are to be first according to Pd contents in Pd-Ir-Cu-Pb/C catalyst
0.05wt%, Cu content are that 1wt% and Pb contents are the H that 0.005wt% weighs respective quality2PdCl4、IrCl3、CuCl2With
(CH3COO)2Pb simultaneously is dissolved in forming 250ml maceration extracts in 15wt% hydrochloric acid, and gained maceration extract is mixed with 50 grams of activated carbons,
12h is impregnated, 3h is then dried in vacuo at 110 DEG C obtains catalyst precursor, finally with the hydrogen diluted through 5 times of volume nitrogen
The lower 160 DEG C of reduction 3h filterings of 150ml/min, obtain Pd-Ir-Cu-Pb/C finished catalysts, are analyzed through ICP-AES, in catalyst
Pd contents be that 0.4wt%, Ir content are that 0.05wt%, Cu content are that 1wt% and Pb contents are 0.005wt%, for ease of than
Compared with, by gained catalyst composition be listed in Table 1 below.
Evaluating catalyst：3300ppm p -carboxybenzaldehydes (4-CBA), 5wt%PX crude terephthalic acid 18g, water will be contained
42g and above-mentioned catalyst 2g is fitted into the titanium pressure vessel that capacity is 100ml, is filled with hydrogen 0.5MPa, is reacted at 280 DEG C
10min.Reaction product is analyzed, compared for convenience, analysis result is listed in Table 1 below.Catalyst is applied mechanically 10 times, and
The reaction product analysis result of the 10th time is also shown in Table 1 below.
【Embodiment 9】
The preparation of catalyst：It is that 0.4wt%, Ir content are to be first according to Pd contents in Pd-Ir-Cu-Pb/C catalyst
0.02wt%, Cu content are that 1wt% and Pb contents are the H that 0.005wt% weighs respective quality2PdCl4、IrCl3、CuCl2With
(CH3COO)2Pb simultaneously is dissolved in forming 250ml maceration extracts in 15wt% hydrochloric acid, and gained maceration extract is mixed with 50 grams of activated carbons,
12h is impregnated, 3h is then dried in vacuo at 110 DEG C obtains catalyst precursor, finally with the hydrogen diluted through 5 times of volume nitrogen
The lower 160 DEG C of reduction 3h filterings of 150ml/min, obtain Pd-Ir-Cu-Pb/C finished catalysts, are analyzed through ICP-AES, in catalyst
Pd contents be that 0.4wt%, Ir content are that 0.02wt%, Cu content are that 1wt% and Pb contents are 0.005wt%, for ease of than
Compared with, by gained catalyst composition be listed in Table 1 below.
Evaluating catalyst：3300ppm p -carboxybenzaldehydes (4-CBA), 5wt%PX crude terephthalic acid 18g, water will be contained
42g and above-mentioned catalyst 2g is fitted into the titanium pressure vessel that capacity is 100ml, is filled with hydrogen 0.5MPa, is reacted at 280 DEG C
10min.Reaction product is analyzed, compared for convenience, analysis result is listed in Table 1 below.Catalyst is applied mechanically 10 times, and
The reaction product analysis result of the 10th time is also shown in Table 1 below.
【Embodiment 10】
The preparation of catalyst：It is that 0.4wt%, Ir content are to be first according to Pd contents in Pd-Ir-Cu-Pb/C catalyst
0.02wt%, Cu content are that 3wt% and Pb contents are the H that 0.005wt% weighs respective quality2PdCl4、IrCl3、CuCl2With
(CH3COO)2Pb simultaneously is dissolved in forming 250ml maceration extracts in 15wt% hydrochloric acid, and gained maceration extract is mixed with 50 grams of activated carbons,
12h is impregnated, 3h is then dried in vacuo at 110 DEG C obtains catalyst precursor, finally with the hydrogen diluted through 5 times of volume nitrogen
The lower 160 DEG C of reduction 3h filterings of 150ml/min, obtain Pd-Ir-Cu-Pb/C finished catalysts, are analyzed through ICP-AES, in catalyst
Pd contents be that 0.4wt%, Ir content are that 0.02wt%, Cu content are that 3wt% and Pb contents are 0.005wt%, for ease of than
Compared with, by gained catalyst composition be listed in Table 1 below.
Evaluating catalyst：3300ppm p -carboxybenzaldehydes (4-CBA), 5wt%PX crude terephthalic acid 18g, water will be contained
42g and above-mentioned catalyst 2g is fitted into the titanium pressure vessel that capacity is 100ml, is filled with hydrogen 0.5MPa, is reacted at 280 DEG C
10min.Reaction product is analyzed, compared for convenience, analysis result is listed in Table 1 below.Catalyst is applied mechanically 10 times, and
The reaction product analysis result of the 10th time is also shown in Table 1 below.
【Embodiment 11】
The preparation of catalyst：It is that 0.4wt%, Ir content are to be first according to Pd contents in Pd-Ir-Cu-Pb/C catalyst
0.02wt%, Cu content are that 5wt% and Pb contents are the H that 0.005wt% weighs respective quality2PdCl4、IrCl3、CuCl2With
(CH3COO)2Pb simultaneously is dissolved in forming 250ml maceration extracts in 15wt% hydrochloric acid, and gained maceration extract is mixed with 50 grams of activated carbons,
12h is impregnated, 3h is then dried in vacuo at 110 DEG C obtains catalyst precursor, finally with the hydrogen diluted through 5 times of volume nitrogen
The lower 160 DEG C of reduction 3h filterings of 150ml/min, obtain Pd-Ir-Cu-Pb/C finished catalysts, are analyzed through ICP-AES, in catalyst
Pd contents be that 0.4wt%, Ir content are that 0.02wt%, Cu content are that 5wt% and Pb contents are 0.005wt%, for ease of than
Compared with, by gained catalyst composition be listed in Table 1 below.
Evaluating catalyst：3300ppm p -carboxybenzaldehydes (4-CBA), 5wt%PX crude terephthalic acid 18g, water will be contained
42g and above-mentioned catalyst 2g is fitted into the titanium pressure vessel that capacity is 100ml, is filled with hydrogen 0.5MPa, is reacted at 280 DEG C
10min.Reaction product is analyzed, compared for convenience, analysis result is listed in Table 1 below.Catalyst is applied mechanically 10 times, and
The reaction product analysis result of the 10th time is also shown in Table 1 below.
【Embodiment 12】
The preparation of catalyst：It is that 0.4wt%, Ir content are to be first according to Pd contents in Pd-Ir-Cu-Pb/C catalyst
0.02wt%, Cu content are that 2wt% and Pb contents are the H that 0.006wt% weighs respective quality2PdCl4、IrCl3、CuCl2With
(CH3COO)2Pb simultaneously is dissolved in forming 250ml maceration extracts in 15wt% hydrochloric acid, and gained maceration extract is mixed with 50 grams of activated carbons,
12h is impregnated, 3h is then dried in vacuo at 110 DEG C obtains catalyst precursor, finally with the hydrogen diluted through 5 times of volume nitrogen
The lower 160 DEG C of reduction 3h filterings of 150ml/min, obtain Pd-Ir-Cu-Pb/C finished catalysts, are analyzed through ICP-AES, in catalyst
Pd contents be that 0.4wt%, Ir content are that 0.02wt%, Cu content are that 2wt% and Pb contents are 0.006wt%, for ease of than
Compared with, by gained catalyst composition be listed in Table 1 below.
Evaluating catalyst：3300ppm p -carboxybenzaldehydes (4-CBA), 5wt%PX crude terephthalic acid 18g, water will be contained
42g and above-mentioned catalyst 2g is fitted into the titanium pressure vessel that capacity is 100ml, is filled with hydrogen 0.5MPa, is reacted at 280 DEG C
10min.Reaction product is analyzed, compared for convenience, analysis result is listed in Table 1 below.Catalyst is applied mechanically 10 times, and
The reaction product analysis result of the 10th time is also shown in Table 1 below.
【Embodiment 13】
The preparation of catalyst：It is that 0.4wt%, Ir content are to be first according to Pd contents in Pd-Ir-Cu-Pb/C catalyst
0.02wt%, Cu content are that 2wt% and Pb contents are the H that 0.01wt% weighs respective quality2PdCl4、IrCl3、CuCl2With
(CH3COO)2Pb simultaneously is dissolved in forming 250ml maceration extracts in 15wt% hydrochloric acid, and gained maceration extract is mixed with 50 grams of activated carbons,
12h is impregnated, 3h is then dried in vacuo at 110 DEG C obtains catalyst precursor, finally with the hydrogen diluted through 5 times of volume nitrogen
The lower 160 DEG C of reduction 3h filterings of 150ml/min, obtain Pd-Ir-Cu-Pb/C finished catalysts, are analyzed through ICP-AES, in catalyst
Pd contents be that 0.4wt%, Ir content are that 0.02wt%, Cu content are that 2wt% and Pb contents are 0.01wt%, for ease of than
Compared with, by gained catalyst composition be listed in Table 1 below.
Evaluating catalyst：3300ppm p -carboxybenzaldehydes (4-CBA), 5wt%PX crude terephthalic acid 18g, water will be contained
42g and above-mentioned catalyst 2g is fitted into the titanium pressure vessel that capacity is 100ml, is filled with hydrogen 0.5MPa, is reacted at 280 DEG C
10min.Reaction product is analyzed, compared for convenience, analysis result is listed in Table 1 below.Catalyst is applied mechanically 10 times, and
The reaction product analysis result of the 10th time is also shown in Table 1 below.
【Embodiment 14】
The preparation of catalyst：It is that 0.4wt%, Ir content are to be first according to Pd contents in Pd-Ir-Cu-Pb/C catalyst
0.02wt%, Cu content are that 2wt% and Pb contents are the H that 0.005wt% weighs respective quality2PdCl4、IrCl3、CuCl2With
(CH3COO)2Pb simultaneously is dissolved in forming 250ml maceration extracts in 15wt% hydrochloric acid, and gained maceration extract is mixed with 50 grams of activated carbons,
12h is impregnated, 3h is then dried in vacuo at 110 DEG C obtains catalyst precursor, finally with the hydrogen diluted through 5 times of volume nitrogen
The lower 160 DEG C of reduction 3h filterings of 150ml/min, obtain Pd-Ir-Cu-Pb/C finished catalysts, are analyzed through ICP-AES, in catalyst
Pd contents be that 0.4wt%, Ir content are that 0.02wt%, Cu content are that 2wt% and Pb contents are 0.005wt%, for ease of than
Compared with, by gained catalyst composition be listed in Table 1 below.
Evaluating catalyst：To contain 3300ppm p -carboxybenzaldehydes (4-CBA) crude terephthalic acid 18g, water 42g and on
State catalyst 2g to be fitted into the titanium pressure vessel that capacity is 100ml, be filled with hydrogen 0.5MPa, react 10min at 280 DEG C.
Reaction product is analyzed, compared for convenience, analysis result is listed in Table 1 below.Catalyst is applied mechanically 10 times, and by the 10th
Secondary reaction product analysis result is also shown in Table 1 below.
【Embodiment 15】
The preparation of catalyst：It is that 0.4wt%, Ir content are to be first according to Pd contents in Pd-Ir-Cu-Pb/C catalyst
0.02wt%, Cu content are that 2wt% and Pb contents are the H that 0.005wt% weighs respective quality2PdCl4、IrCl3、CuCl2With
(CH3COO)2Pb simultaneously is dissolved in forming 250ml maceration extracts in 15wt% hydrochloric acid, and gained maceration extract is mixed with 50 grams of activated carbons,
12h is impregnated, 3h is then dried in vacuo at 110 DEG C obtains catalyst precursor, finally with the hydrogen diluted through 5 times of volume nitrogen
The lower 160 DEG C of reduction 3h filterings of 150ml/min, obtain Pd-Ir-Cu-Pb/C finished catalysts, are analyzed through ICP-AES, in catalyst
Pd contents be that 0.4wt%, Ir content are that 0.02wt%, Cu content are that 2wt% and Pb contents are 0.005wt%, for ease of than
Compared with, by gained catalyst composition be listed in Table 1 below.
Evaluating catalyst：To contain 3300ppm p -carboxybenzaldehydes (4-CBA), 10wt%PX crude terephthalic acid 18g,
Water 42g and above-mentioned catalyst 2g is fitted into the titanium pressure vessel that capacity is 100ml, is filled with hydrogen 0.5MPa, anti-at 280 DEG C
Answer 10min.Reaction product is analyzed, compared for convenience, analysis result is listed in Table 1 below.Catalyst is applied mechanically 10 times,
And the reaction product analysis result of the 10th time is also shown in Table 1 below.
【Embodiment 16】
The preparation of catalyst：It is that 0.4wt%, Ir content are to be first according to Pd contents in Pd-Ir-Cu-Pb/C catalyst
0.02wt%, Cu content are that 2wt% and Pb contents are the H that 0.005wt% weighs respective quality2PdCl4、IrCl3、CuCl2With
(CH3COO)2Pb simultaneously is dissolved in forming 250ml maceration extracts in 15wt% hydrochloric acid, and gained maceration extract is mixed with 50 grams of activated carbons,
12h is impregnated, 3h is then dried in vacuo at 110 DEG C obtains catalyst precursor, finally with the hydrogen diluted through 5 times of volume nitrogen
The lower 160 DEG C of reduction 3h filterings of 150ml/min, obtain Pd-Ir-Cu-Pb/C finished catalysts, are analyzed through ICP-AES, in catalyst
Pd contents be that 0.4wt%, Ir content are that 0.02wt%, Cu content are that 2wt% and Pb contents are 0.005wt%, for ease of than
Compared with, by gained catalyst composition be listed in Table 1 below.
Evaluating catalyst：To contain 3300ppm p -carboxybenzaldehydes (4-CBA), 20wt%PX crude terephthalic acid 18g,
Water 42g and above-mentioned catalyst 2g is fitted into the titanium pressure vessel that capacity is 100ml, is filled with hydrogen 0.5MPa, anti-at 280 DEG C
Answer 10min.Reaction product is analyzed, compared for convenience, analysis result is listed in Table 1 below.Catalyst is applied mechanically 10 times,
And the reaction product analysis result of the 10th time is also shown in Table 1 below.
【Comparative example 1】
Evaluating catalyst：3300ppm p -carboxybenzaldehydes (4-CBA), 5wt%PX crude terephthalic acid 18g, water will be contained
42g and commercialized CTV-IV types palladium carbon catalyst 2g is fitted into the titanium pressure vessel that capacity is 100ml, is filled with hydrogen
0.5MPa, react 10min at 280 DEG C.Reaction product is analyzed, compared for convenience, analysis result is listed in table 1
In.Catalyst is applied mechanically 10 times, and the reaction product analysis result of the 10th time is also shown in Table 1 below.
【Comparative example 2】
The preparation of catalyst：It is that 0.4wt%, Ir content are to be first according to Pd contents in Pd-Ir-Cu/C catalyst
0.02wt% and Cu contents are the H that 2.005wt% weighs respective quality2PdCl4、IrCl3And CuCl2And it is dissolved in 15wt%
250ml maceration extracts are formed in hydrochloric acid, gained maceration extract is mixed with 50 grams of activated carbons, impregnate 12h, then the vacuum at 110 DEG C
Dry 3h and obtain catalyst precursor, finally filtered with the lower 160 DEG C of reduction 3h of the hydrogen 150ml/min diluted through 5 times of volume nitrogen,
Pd-Ir-Cu/C finished catalysts are obtained, are analyzed through ICP-AES, the Pd contents in catalyst are that 0.4wt%, Ir content are
0.02wt% and Cu contents are 2wt%, and for ease of comparing, gained catalyst composition is listed in Table 1 below.
Evaluating catalyst：3300ppm p -carboxybenzaldehydes (4-CBA), 5wt%PX crude terephthalic acid 18g, water will be contained
42g and above-mentioned catalyst 2g is fitted into the titanium pressure vessel that capacity is 100ml, is filled with hydrogen 0.5MPa, is reacted at 280 DEG C
10min.Reaction product is analyzed, compared for convenience, analysis result is listed in Table 1 below.Catalyst is applied mechanically 10 times, and
The reaction product analysis result of the 10th time is also shown in Table 1 below.
【Comparative example 3】
The preparation of catalyst：It is that 0.4wt%, Ir content are to be first according to Pd contents in Pd-Ir-Pb/C catalyst
0.02wt% and Pb contents are the H that 2.005wt% weighs respective quality2PdCl4、IrCl3(CH3COO)2Pb is simultaneously dissolved in
250ml maceration extracts are formed in 15wt% hydrochloric acid, gained maceration extract is mixed with 50 grams of activated carbons, 12h are impregnated, then at 110 DEG C
Lower vacuum drying 3h obtains catalyst precursor, finally with the lower 160 DEG C of reduction of the hydrogen 150ml/min diluted through 5 times of volume nitrogen
3h is filtered, and is obtained Pd-Ir-Cu-Pb/C finished catalysts, is analyzed through ICP-AES, the Pd contents in catalyst are 0.4wt%, Ir
Content is that 0.02wt% and Pb contents are 0.005wt%, and for ease of comparing, gained catalyst composition is listed in Table 1 below.
Evaluating catalyst：3300ppm p -carboxybenzaldehydes (4-CBA), 5wt%PX crude terephthalic acid 18g, water will be contained
42g and above-mentioned catalyst 2g is fitted into the titanium pressure vessel that capacity is 100ml, is filled with hydrogen 0.5MPa, is reacted at 280 DEG C
10min.Reaction product is analyzed, compared for convenience, analysis result is listed in Table 1 below.Catalyst is applied mechanically 10 times, and
The reaction product analysis result of the 10th time is also shown in Table 1 below.
【Comparative example 4】
The preparation of catalyst：It is that 0.42wt%, Cu content are 2wt% to be first according to Pd contents in Pd-Cu-Pb/C catalyst
It is the H that 0.005wt% weighs respective quality with Pb contents2PdCl4、CuCl2(CH3COO)2Pb is simultaneously dissolved in 15wt% salt
250ml maceration extracts are formed in acid, gained maceration extract is mixed with 50 grams of activated carbons, impregnate 12h, then vacuum is done at 110 DEG C
Dry 3h obtains catalyst precursor, finally with the lower 160 DEG C of reduction 3h filterings of the hydrogen 150ml/min diluted through 5 times of volume nitrogen, obtains
To Pd-Ir-Cu-Pb/C finished catalysts, analyzed through ICP-AES, the Pd contents in catalyst are that 0.42wt%, Cu content are
2wt% and Pb contents are 0.005wt%, and for ease of comparing, gained catalyst composition is listed in Table 1 below.
Evaluating catalyst：3300ppm p -carboxybenzaldehydes (4-CBA), 5wt%PX crude terephthalic acid 18g, water will be contained
42g and above-mentioned catalyst 2g is fitted into the titanium pressure vessel that capacity is 100ml, is filled with hydrogen 0.5MPa, is reacted at 280 DEG C
10min.Reaction product is analyzed, compared for convenience, analysis result is listed in Table 1 below.Catalyst is applied mechanically 10 times, and
The reaction product analysis result of the 10th time is also shown in Table 1 below.
【Comparative example 5】
The preparation of catalyst：It is that 0.42wt%, Cu content are 2wt% to be first according to Ir contents in Ir-Cu-Pb/C catalyst
It is the H that 0.005wt% weighs respective quality with Pb contents2PdCl4、IrCl3、CuCl2(CH3COO)2Pb is simultaneously dissolved in
250ml maceration extracts are formed in 15wt% hydrochloric acid, gained maceration extract is mixed with 50 grams of activated carbons, 12h are impregnated, then at 110 DEG C
Lower vacuum drying 3h obtains catalyst precursor, finally with the lower 160 DEG C of reduction of the hydrogen 150ml/min diluted through 5 times of volume nitrogen
3h is filtered, and is obtained Ir-Cu-Pb/C finished catalysts, is analyzed through ICP-AES, Ir contents are 0.42wt%, Cu content in catalyst
It is 0.005wt% for 2wt% and Pb contents, for ease of comparing, gained catalyst composition is listed in Table 1 below.
Evaluating catalyst：3300ppm p -carboxybenzaldehydes (4-CBA), 5wt%PX crude terephthalic acid 18g, water will be contained
42g and above-mentioned catalyst 2g is fitted into the titanium pressure vessel that capacity is 100ml, is filled with hydrogen 0.5MPa, is reacted at 280 DEG C
10min.Reaction product is analyzed, compared for convenience, analysis result is listed in Table 1 below.Catalyst is applied mechanically 10 times, and
The reaction product analysis result of the 10th time is also shown in Table 1 below.
As it can be seen from table 1 the technology achieves good reaction result applied to hydrofining crude terephthalic acid.With
Pd-Ir-Cu-Pb/C is that catalyst can ensure still there is good catalytic activity when handling the crude terephthalic acid containing PX,
So as to which the life-span of catalyst greatly improved, but without positive effect if any of which metallic element is lacked, and when control
Pd contents processed are in 0.3~0.5wt%, and Ir contents are in 0.02~0.03wt%, and Cu contents are in 2~3wt%, and Pb contents are 0.005
~0.006wt%, while when ensureing that PX contents are not higher than 10wt% in crude terephthalic acid, catalyst is kept fine
Activity and the life-span, while also ensure PX do not occur hydrogenation reaction generation Isosorbide-5-Nitrae-dimethyl cyclohexane, so as to avoid PX stream
Lose.
Table 1 (continued)
The (Continued) of table 1
Claims (6)
1. a kind of hydrofining crude terephthalic acid catalyst, using activated carbon as carrier, including Pd, Ir, Cu and Pb are activearm
Point；Pd contents are 0.1~1wt%；Ir contents are 0.01~0.05wt%；Cu contents are 1~5wt%；Pb contents be 0.005~
0.01wt%.
2. the preparation method of catalyst described in claim 1, comprises the following steps：
A) lived with the solution impregnating carrier of the desired amount of compound containing Pd, compound containing Ir, compound containing Cu and the compound containing Pb
Property charcoal；
B) Pd, Ir, Cu and Pb compound are reduced to metal simple-substance with reducing agent.
3. preparation method according to claim 2, it is characterised in that described reducing agent is hydrogen, formaldehyde, sodium formate, water
Close at least one of hydrazine or formic acid.
4. the hydrofinishing process of crude terephthalic acid, in the presence of catalyst described in claim 1, using water as solvent, hydrogen
Gas and crude terephthalic acid react to obtain p-phthalic acid.
5. hydrofinishing process according to claim 4, it is characterised in that contained PX contents are 0 in crude terephthalic acid
~20wt%.
6. hydrofinishing process according to claim 4, it is characterised in that catalyst and crude terephthalic acid inventory
Mass ratio is 1:(1~20).
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1622856A (en) * | 2001-12-21 | 2005-06-01 | 恩格哈德公司 | Catalyst supported on carbon having macroporosity for purification of aromatic acids |
| CN101347737A (en) * | 2007-07-18 | 2009-01-21 | 中国石油化工股份有限公司 | Selective hydrogenation catalyst of aromatic aldehydes for refinement of terephthalic acid |
| 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 |
| CN103285876A (en) * | 2012-02-27 | 2013-09-11 | 清华大学 | Vinyl acetylene hydrogenation catalyst and preparation method and applications thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1622856A (en) * | 2001-12-21 | 2005-06-01 | 恩格哈德公司 | Catalyst supported on carbon having macroporosity for purification of aromatic acids |
| CN101347737A (en) * | 2007-07-18 | 2009-01-21 | 中国石油化工股份有限公司 | Selective hydrogenation catalyst of aromatic aldehydes for refinement of terephthalic acid |
| 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 |
| CN103285876A (en) * | 2012-02-27 | 2013-09-11 | 清华大学 | Vinyl acetylene hydrogenation catalyst and preparation method and applications thereof |
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