CN103721706B - Purification of terephthalic acid palladium carbon catalyst reduction washing methods - Google Patents
Purification of terephthalic acid palladium carbon catalyst reduction washing methods Download PDFInfo
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- CN103721706B CN103721706B CN201210389322.0A CN201210389322A CN103721706B CN 103721706 B CN103721706 B CN 103721706B CN 201210389322 A CN201210389322 A CN 201210389322A CN 103721706 B CN103721706 B CN 103721706B
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Abstract
The present invention relates to a kind of purification of terephthalic acid palladium carbon catalyst reduction washing methods, mainly solving prior art, to there is catalyst insufficient contact with reduction cleaning mixture, and reduction cleaning mixture consumption is big, and wash time of reducing is long, the problem that unit equipment production efficiency is low.The present invention is provided with the container of gas distributor or porous plate by using a) offer；Purification of terephthalic acid palladium carbon catalyst is placed in above gas distributor or porous plate；B) it is passed through reducing solution, makes catalyst described in reducing solution submergence；Being passed through the gas inert to catalyst and reducing solution, described gas is contacted with catalyst by the perforate on gas distributor or porous plate；Reducing solution is made to separate with catalyst after catalyst reduction；C) it is passed through washings, makes the catalyst after washings submergence reduction；Being passed through the gas inert to catalyst, the technical scheme that described gas is contacted with catalyst by the perforate on gas distributor or porous plate preferably solves this problem, can be used in the commercial production of purification of terephthalic acid palladium carbon catalyst reduction washing.
Description
Technical field
The present invention relates to a kind of purification of terephthalic acid palladium carbon catalyst reduction washing methods.
Background technology
Supported palladium/carbon catalyst is mainly used in the selective hydrogenation of unsaturated compounds, it is particularly suited for the refined of crude terephthalic acid, the impurity such as the p-carboxybenzaldehyde (being called for short 4-CBA) in crude terephthalic acid, by being changed into other compound after hydrogenation, the most just can carry out separating-purifying by the method for crystallization.Document CN200610029964.4 discloses the preparation method of a kind of supported palladium/carbon catalyst, comprise the following steps: a) first by the mineral acid pickling 0.5 of activated carbon 0.01～5 mol/L concentration～8 hours, then after being washed with water to neutrality, it is dried 0.5～10 hour under the conditions of 80～150 DEG C, obtains activity carbon carrier；B) with the solution impregnation containing Pd compound and additive or sprinkling activity carbon carrier, make on activated carbon, to obtain catalyst precarsor containing Pd is compound loaded；C) catalyst precarsor reducing agent is carried out reduction treatment, the catalyst of metal Pd must be contained.
At present, known reduction washing facility is rinsing machine, is a steam-heated stainless steel tank of jacketed, the dual manually-operated gate of bottom belt, wherein above one bottom valve band mesh.Only opening following one bottom valve after reduction terminates, after bleeding off reducing solution, material still remains in groove and washs.Material is deposited in middle and lower part in the device, and reduction washing is uneven, reduce, when washing the fluctuation of steam heating-up temperature relatively big, energy consumption is high, it is more difficult to ensure catalyst quality.
Summary of the invention
The technical problem to be solved is to be only to be immersed in by catalyst in reduction cleaning mixture when the reduction of prior art palladium carbon catalyst, washing, there is catalyst insufficient contact with reduction cleaning mixture, reduction cleaning mixture consumption is big, reduction wash time is long, the problem that unit equipment production efficiency is low, it is provided that a kind of new purification of terephthalic acid palladium carbon catalyst reduction washing methods.The method has catalyst and contacts fully with reduction cleaning mixture, and the most fully, washing times is few, the time is short, and cleaning mixture consumption is few, the feature that unit equipment production efficiency is high in reduction.
For solving above-mentioned technical problem, the technical solution used in the present invention is as follows: a kind of purification of terephthalic acid palladium carbon catalyst reduction washing methods, including:
A) offer is provided with the container of gas distributor or porous plate；Purification of terephthalic acid palladium carbon catalyst is placed in above gas distributor or porous plate；
B) it is passed through reducing solution, makes catalyst described in reducing solution submergence；Being passed through the gas inert to catalyst and reducing solution, described gas is contacted with catalyst by the perforate on gas distributor or porous plate；Reducing solution is made to separate with catalyst after catalyst reduction；
C) it is passed through washings, makes the catalyst after washings submergence reduction；Being passed through the gas inert to catalyst, described gas is contacted with catalyst by the perforate on gas distributor or porous plate；Wherein, washing procatalyst sodium ions content, more than 10000ppm, makes catalyst sodium ions content less than 1500ppm after repeated washing；
Wherein, the amount of described inert gas be 0.15～0.35 liter/(minute kg catalyst).
In technique scheme, described inert gas is selected from air, nitrogen or CO2, preferred version is selected from air.The preferred scope of percent opening of gas distributor or porous plate is 10～20%, and the preferred scope of open pore size is 1～3.5 millimeter.Described porous plate preferred version is porous turnover panel.The preferred scope of amount of described inert gas is 0.2～0.3 liter/(minute kg catalyst).Described reducing agent preferred version is is 0.1 selected from concentration expressed in percentage by weight～at least one in the formic acid of 0.5%, sodium formate, formaldehyde, hydrazine hydrate or glucose.The preferred scope of reduction temperature is 80～< 100 DEG C, more preferably scope is 85～< 100 DEG C.Recovery time preferred scope be 0.1～1.5 hour/kg catalyst, more preferably scope be 0.2～1 hour/kg catalyst.The preferred scope of wash temperature is 80～< 100 DEG C.The washing preferred scope of procatalyst sodium ions content is > 10000～15000ppm.The washing preferred scope of rear catalyst sodium ions content is less than 1000ppm.
In the inventive method, described porous plate preferred version is porous turnover panel, can facilitate the discharging of catalyst.
In the inventive method, by the gas sparging bottom increasing, catalyst is fully contacted with reducing solution and cleaning mixture, the most fully, washing times is few, the time is short in reduction, and slurry amount reduces, pure water consumption can be by 400 ton/ton catalyst degradation of prior art to 37 ton/ton catalyst, unit equipment production efficiency is high, and production capacity improves 1 times, achieves preferable technique effect.
Detailed description of the invention
Below by embodiment, the present invention is further elaborated.
[embodiment 1]
Being provided with porous turnover panel in container, purification of terephthalic acid palladium carbon catalyst (butt) 100 kilograms is placed in above porous turnover panel.It is passed through reducing solution, makes catalyst described in reducing solution submergence.Being passed through air, air is contacted with catalyst by the perforate on porous turnover panel.Reducing solution is made to separate with catalyst after catalyst reduction.It is passed through washings, makes the catalyst after washings submergence reduction.Being passed through air, air is contacted with catalyst by the perforate on porous turnover panel.The percent opening of porous turnover panel is 15%, and open pore size is 2 millimeters.
Wherein, be passed through the amount of air be 0.2 liter/(minute kg catalyst).Described reducing solution be concentration expressed in percentage by weight be the sodium formate solution of 0.2%, reduction temperature is 95 DEG C, constant temperature time 30 minutes.Wash temperature is 90 DEG C, washs 3 times, and each 30 minutes, slurry amount 1200 liters, washing procatalyst sodium ions content was 20000ppm, and washing rear catalyst sodium ions content is 925ppm.
[embodiment 2]
Being provided with gas distributor in container, purification of terephthalic acid palladium carbon catalyst (butt) 100 kilograms is placed in above gas distributor.It is passed through reducing solution, makes catalyst described in reducing solution submergence.Being passed through air, air is contacted with catalyst by the perforate on gas distributor.Reducing solution is made to separate with catalyst after catalyst reduction.It is passed through washings, makes the catalyst after washings submergence reduction.Being passed through air, air is contacted with catalyst by the perforate on gas distributor.The percent opening of gas distributor is 12%, and open pore size is 1.8 millimeters.
Wherein, be passed through the amount of air be 0.25 liter/(minute kg catalyst).Described reducing solution be concentration expressed in percentage by weight be the sodium formate solution of 0.25%, reduction temperature is 90 DEG C, constant temperature time 40 minutes.Wash temperature is 95 DEG C, washs 3 times, and each 30 minutes, slurry amount 1000 liters, washing procatalyst sodium ions content was 20000ppm, and washing rear catalyst sodium ions content is 825ppm.
[embodiment 3]
Being provided with porous turnover panel in container, purification of terephthalic acid palladium carbon catalyst (butt) 100 kilograms is placed in above porous turnover panel.It is passed through reducing solution, makes catalyst described in reducing solution submergence.Being passed through nitrogen, nitrogen is contacted with catalyst by the perforate on porous turnover panel.Reducing solution is made to separate with catalyst after catalyst reduction.It is passed through washings, makes the catalyst after washings submergence reduction.Being passed through nitrogen, nitrogen is contacted with catalyst by the perforate on porous turnover panel.The percent opening of porous turnover panel is 15%, and open pore size is 2 millimeters.
Wherein, be passed through the amount of nitrogen be 0.3 liter/(minute kg catalyst).Described reducing solution be concentration expressed in percentage by weight be the sodium formate solution of 0.3%, reduction temperature is 90 DEG C, constant temperature time 35 minutes.Wash temperature is 98 DEG C, washs 3 times, and each 30 minutes, slurry amount 980 liters, washing procatalyst sodium ions content was 20000ppm, and washing rear catalyst sodium ions content is 800ppm.
[comparative example 1]
Phthalic acid refining palladium carbon catalyst (butt) 100 kilograms and impregnated in the sodium formate solution that concentration expressed in percentage by weight is 0.3%, reduction temperature is 90 DEG C, dip time 35 minutes.Reducing solution is separated with catalyst.Washing the catalyst after reduction with water, wash 6 times, each 30 minutes, slurry amount 2400 liters, washing procatalyst sodium ions content was 20000ppm, and washing rear catalyst sodium ions content is 2148ppm.
Claims (6)
1. a purification of terephthalic acid palladium carbon catalyst reduction washing methods, including:
A) offer is provided with gas distributor or percent opening is 10～20%, and open pore size is the container of the porous turnover panel of 1～3.5 millimeter；Purification of terephthalic acid palladium carbon catalyst is placed in above gas distributor or porous plate；
B) being passed through reducing solution, make catalyst described in reducing solution submergence, described reducing agent is 0.1～at least one in the formic acid of 0.5%, sodium formate, formaldehyde, hydrazine hydrate or glucose selected from concentration expressed in percentage by weight；Being passed through the gas inert to catalyst and reducing solution, described gas is contacted with catalyst by the perforate on gas distributor or porous plate；Making reducing solution separate with catalyst after catalyst reduction, reduction temperature is 80～< 100 DEG C；Recovery time is per kilogram catalyst 0.1～1.5 hours；
C) it is passed through washings, makes the catalyst after washings submergence reduction；Being passed through the gas inert to catalyst, described gas is contacted with catalyst by the perforate on gas distributor or porous plate；Wherein, washing procatalyst sodium ions content, more than 10000ppm, makes catalyst sodium ions content less than 1500ppm after repeated washing；
Wherein, the amount of described inert gas be 0.15～0.35 liter/(minute kg catalyst).
Purification of terephthalic acid palladium carbon catalyst the most according to claim 1 reduction washing methods, it is characterised in that described inert gas is selected from air, nitrogen or CO2。
Purification of terephthalic acid palladium carbon catalyst the most according to claim 2 reduction washing methods, it is characterised in that described inert gas is selected from air.
Purification of terephthalic acid palladium carbon catalyst the most according to claim 1 reduction washing methods, it is characterised in that the amount of described inert gas is 0.2～0.3 liter/(minute kg catalyst).
Purification of terephthalic acid palladium carbon catalyst the most according to claim 1 reduction washing methods, it is characterised in that reduction temperature is 85～< 100 DEG C；Recovery time is per kilogram catalyst 0.2～1 hour.
Purification of terephthalic acid palladium carbon catalyst the most according to claim 1 reduction washing methods, it is characterized in that wash temperature is 80～< 100 DEG C, washing procatalyst sodium ions content is that less than or equal to 15000ppm, washing rear catalyst sodium ions content is less than 1000ppm more than 10000ppm.
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Citations (6)
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|---|---|---|---|---|
| US3542863A (en) * | 1965-05-17 | 1970-11-24 | Standard Oil Co | Palladium catalyst treatment with formic acid |
| EP0222499B1 (en) * | 1985-10-07 | 1991-01-02 | Amoco Corporation | Purification of terephthalic acid to relatively low levels of 4-carboxybenzaldehyde and catalyst therefor |
| CN101121127A (en) * | 2006-08-11 | 2008-02-13 | 中国石油化工股份有限公司 | Method for preparing supported palladium/carbon catalyst |
| CN101234291A (en) * | 2007-11-12 | 2008-08-06 | 青岛科技大学 | Photocatalysis fluid bed reactor device for degrading volatile organic matter |
| CN101347728A (en) * | 2007-07-18 | 2009-01-21 | 中国石油化工股份有限公司 | Process for preparing Pd/carbon catalyst of high activity |
| CN101544570A (en) * | 2009-04-17 | 2009-09-30 | 德纳（南京）化工有限公司 | Method for preparing m-phenylene dimethylamine |
-
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3542863A (en) * | 1965-05-17 | 1970-11-24 | Standard Oil Co | Palladium catalyst treatment with formic acid |
| EP0222499B1 (en) * | 1985-10-07 | 1991-01-02 | Amoco Corporation | Purification of terephthalic acid to relatively low levels of 4-carboxybenzaldehyde and catalyst therefor |
| CN101121127A (en) * | 2006-08-11 | 2008-02-13 | 中国石油化工股份有限公司 | Method for preparing supported palladium/carbon catalyst |
| CN101347728A (en) * | 2007-07-18 | 2009-01-21 | 中国石油化工股份有限公司 | Process for preparing Pd/carbon catalyst of high activity |
| CN101234291A (en) * | 2007-11-12 | 2008-08-06 | 青岛科技大学 | Photocatalysis fluid bed reactor device for degrading volatile organic matter |
| CN101544570A (en) * | 2009-04-17 | 2009-09-30 | 德纳（南京）化工有限公司 | Method for preparing m-phenylene dimethylamine |
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