CN103721706A - Method for reduction washing of palladium carbon catalyst for terephthalic acid refining - Google Patents
Method for reduction washing of palladium carbon catalyst for terephthalic acid refining Download PDFInfo
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- CN103721706A CN103721706A CN201210389322.0A CN201210389322A CN103721706A CN 103721706 A CN103721706 A CN 103721706A CN 201210389322 A CN201210389322 A CN 201210389322A CN 103721706 A CN103721706 A CN 103721706A
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Abstract
The invention relates to a method for reduction washing of a palladium carbon catalyst for terephthalic acid refining, and mainly solves the problems in the prior art of inadequate contact of catalysts with reduction washing liquid, large using amount of reduction washing liquid, long reduction washing time, and low production efficiency per unit equipment. The method of the invention well solves the problems by the technical scheme of: a) providing a container with a gas distributor or a porous plate; putting a palladium carbon catalyst for terephthalic acid refining on the gas distributor or the porous plate; b) introducing a reducing solution, soaking the catalyst with the reducing solution; introducing gas being inert to the catalyst and the reducing solution, allowing the gas to contact the catalyst through pores on the gas distributor or the porous plate; reducing the catalyst, separating the reducing solution from the catalyst; c) introducing washing water, soaking the reduced catalyst with the washing water; introducing gas being inert to the catalyst, and allowing the gas to contact the catalyst through pores on the gas distributor or the porous plate. The method can be used in industrial production for reduction washing of palladium carbon catalysts for terephthalic acid refining.
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, be particularly useful for the refining of crude terephthalic acid, the compound that the impurity such as carboxyl benzaldehyde (be called for short 4-CBA) is changed into other after by hydrogenation in crude terephthalic acid, just can carry out separating-purifying by the method for crystallization subsequently.Document CN200610029964.4 discloses a kind of preparation method of supported palladium/carbon catalyst, comprise the following steps: a) first by the inorganic acid pickling of activated carbon 0.01～5 mol/L concentration 0.5～8 hour, then be washed with water to after neutrality, under 80～150 ℃ of conditions, be dried 0.5～10 hour, obtain activity carbon carrier; B) with the solution impregnation containing Pd compound and additive or sprinkling activity carbon carrier, make containing the compound loaded catalyst precarsor that obtains on activated carbon of Pd; C) catalyst precarsor is reduced to processing with reducing agent, obtain the catalyst of containing metal Pd.
At present, known reduction washing facility is rinsing machine, is a steam-heated stainless steel tank of jacketed, and dual manually-operated gate is with in bottom, wherein one bottom valve band mesh above.One bottom valve below only opening after reduction finishes, bleed off reducing solution after material still stay in groove and wash.Material is deposited in middle and lower part in this equipment, and reduction washing is inhomogeneous, when reduction, washing Steam Heating temperature fluctuation larger, energy consumption is high, is difficult to ensure card catalyst quality.
Summary of the invention
Technical problem to be solved by this invention while being prior art palladium carbon catalyst reduction, washing, be only by catalyst soakage in reduction cleaning solution, exist catalyst to contact insufficient with reduction cleaning solution, reduction cleaning solution consumption is large, reduction wash time is long, the problem that unit equipment production efficiency is low, provides a kind of new purification of terephthalic acid palladium carbon catalyst reduction washing methods.The method has catalyst and contacts fully with reduction cleaning solution, and evenly fully, washing times is few, the time is short in reduction, and cleaning solution consumption is few, the feature that unit equipment production efficiency is high.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of purification of terephthalic acid palladium carbon catalyst reduction washing methods, comprising:
A) provide the container that is provided with gas distributor or porous plate; Purification of terephthalic acid palladium carbon catalyst be placed in gas distributor or porous plate above;
B) pass into reducing solution, make catalyst described in reducing solution submergence; Pass into the gas that catalyst and reducing solution is to inertia, described gas contacts with catalyst by the perforate on gas distributor or porous plate; After catalyst reduction, make reducing solution and catalyst separation;
C) pass into washings, make the catalyst after washings submergence reduction; Pass into the gas that catalyst is to inertia, described gas contacts with catalyst by the perforate on gas distributor or porous plate; Wherein, washing procatalyst sodium ions content is greater than 10000ppm, makes catalyst sodium ions content be less than 1500ppm after repeated washing;
Wherein, the amount that is the gas of inertia described in be 0.15～0.35 liter/(minute kilogram catalyst).
In technique scheme, described in be inertia gas be selected from air, nitrogen or CO
2, preferred version is for being selected from air.The percent opening preferable range of gas distributor or porous plate is 10～20%, and perforate aperture preferable range is 1～3.5 millimeter.Described porous plate preferred version is porous turnover panel.The amount preferable range of the described gas that is inertia be 0.2～0.3 liter/(minute kilogram catalyst).Described reducing agent preferred version is that to be selected from concentration expressed in percentage by weight be at least one in 0.1～0.5% formic acid, sodium formate, formaldehyde, hydrazine hydrate or glucose.Reduction temperature preferable range is 80～<100 ℃, and more preferably scope is 85～<100 ℃.Recovery time preferable range is 0.1～1.5 hour/kilogram of catalyst, and more preferably scope is 0.2～1 hour/kilogram of catalyst.Wash temperature preferable range is 80～<100 ℃.Washing procatalyst sodium ions content preferable range is >10000～15000ppm.Washing rear catalyst sodium ions content preferable range is for being 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 increasing the gas sparging of bottom, make catalyst carry out fully contacting with reducing solution and cleaning solution, evenly fully, washing times is few, the time is short in reduction, and slurry amount reduces, pure water consumption can be by 400 of prior art ton of/ton of Catalysts for Reducing to 37 ton of/ton of catalyst, unit equipment production efficiency is high, and production capacity improves 1 times, has obtained good technique effect.
The specific embodiment
Below by embodiment, the present invention is further elaborated.
[embodiment 1]
In container, be provided with porous turnover panel, 100 kilograms of purification of terephthalic acid palladium carbon catalysts (butt) are placed in above porous turnover panel.Pass into reducing solution, make catalyst described in reducing solution submergence.Pass into air, air contacts with catalyst by the perforate on porous turnover panel.After catalyst reduction, make reducing solution and catalyst separation.Pass into washings, make the catalyst after washings submergence reduction.Pass into air, air contacts with catalyst by the perforate on porous turnover panel.The percent opening of porous turnover panel is 15%, and perforate aperture is 2 millimeters.
Wherein, the amount that passes into air be 0.2 liter/(minute kilogram catalyst).Described reducing solution is that concentration expressed in percentage by weight is 0.2% sodium formate solution, and reduction temperature is 95 ℃, constant temperature time 30 minutes.Wash temperature is 90 ℃, washs 3 times, and each 30 minutes, 1200 liters of slurry amounts, washing procatalyst sodium ions content is 20000ppm, washing rear catalyst sodium ions content is 925ppm.
[embodiment 2]
In container, be provided with gas distributor, 100 kilograms of purification of terephthalic acid palladium carbon catalysts (butt) are placed in above gas distributor.Pass into reducing solution, make catalyst described in reducing solution submergence.Pass into air, air contacts with catalyst by the perforate on gas distributor.After catalyst reduction, make reducing solution and catalyst separation.Pass into washings, make the catalyst after washings submergence reduction.Pass into air, air contacts with catalyst by the perforate on gas distributor.The percent opening of gas distributor is 12%, and perforate aperture is 1.8 millimeters.
Wherein, the amount that passes into air be 0.25 liter/(minute kilogram catalyst).Described reducing solution is that concentration expressed in percentage by weight is 0.25% sodium formate solution, and reduction temperature is 90 ℃, constant temperature time 40 minutes.Wash temperature is 95 ℃, washs 3 times, and each 30 minutes, 1000 liters of slurry amounts, washing procatalyst sodium ions content is 20000ppm, washing rear catalyst sodium ions content is 825ppm.
[embodiment 3]
In container, be provided with porous turnover panel, 100 kilograms of purification of terephthalic acid palladium carbon catalysts (butt) are placed in above porous turnover panel.Pass into reducing solution, make catalyst described in reducing solution submergence.Pass into nitrogen, nitrogen contacts with catalyst by the perforate on porous turnover panel.After catalyst reduction, make reducing solution and catalyst separation.Pass into washings, make the catalyst after washings submergence reduction.Pass into nitrogen, nitrogen contacts with catalyst by the perforate on porous turnover panel.The percent opening of porous turnover panel is 15%, and perforate aperture is 2 millimeters.
Wherein, the amount that passes into nitrogen be 0.3 liter/(minute kilogram catalyst).Described reducing solution is that concentration expressed in percentage by weight is 0.3% sodium formate solution, and reduction temperature is 90 ℃, constant temperature time 35 minutes.Wash temperature is 98 ℃, washs 3 times, and each 30 minutes, 980 liters of slurry amounts, washing procatalyst sodium ions content is 20000ppm, washing rear catalyst sodium ions content is 800ppm.
[comparative example 1]
It is that in 0.3% sodium formate solution, reduction temperature is 90 ℃, dip time 35 minutes that 100 kilograms of refining phthalic acid palladium carbon catalysts (butt) be impregnated in to concentration expressed in percentage by weight.By reducing solution and catalyst separation.Wash the catalyst after reduction with water, wash 6 times, each 30 minutes, 2400 liters of slurry amounts, washing procatalyst sodium ions content is 20000ppm, washing rear catalyst sodium ions content is 2148ppm.
Claims (9)
1. a purification of terephthalic acid palladium carbon catalyst reduction washing methods, comprising:
A) provide the container that is provided with gas distributor or porous plate; Purification of terephthalic acid palladium carbon catalyst be placed in gas distributor or porous plate above;
B) pass into reducing solution, make catalyst described in reducing solution submergence; Pass into the gas that catalyst and reducing solution is to inertia, described gas contacts with catalyst by the perforate on gas distributor or porous plate; After catalyst reduction, make reducing solution and catalyst separation;
C) pass into washings, make the catalyst after washings submergence reduction; Pass into the gas that catalyst is to inertia, described gas contacts with catalyst by the perforate on gas distributor or porous plate; Wherein, washing procatalyst sodium ions content is greater than 10000ppm, makes catalyst sodium ions content be less than 1500ppm after repeated washing;
Wherein, the amount that is the gas of inertia described in be 0.15～0.35 liter/(minute kilogram catalyst).
2. purification of terephthalic acid palladium carbon catalyst reduction washing methods according to claim 1, the gas that is inertia described in it is characterized in that is selected from air, nitrogen or CO
2.
3. purification of terephthalic acid palladium carbon catalyst reduction washing methods according to claim 2, the gas that is inertia described in it is characterized in that is selected from air.
4. purification of terephthalic acid palladium carbon catalyst reduction washing methods according to claim 1, the percent opening that it is characterized in that gas distributor or porous plate is 10～20%, perforate aperture is 1～3.5 millimeter.
5. purification of terephthalic acid palladium carbon catalyst reduction washing methods according to claim 1, is characterized in that described porous plate is porous turnover panel.
6. purification of terephthalic acid palladium carbon catalyst according to claim 1 reduction washing methods, the amount that is the gas of inertia described in it is characterized in that be 0.2～0.3 liter/(minute kilogram catalyst).
7. purification of terephthalic acid palladium carbon catalyst according to claim 1 reduction washing methods, is characterized in that it is at least one in 0.1～0.5% formic acid, sodium formate, formaldehyde, hydrazine hydrate or glucose that described reducing agent is selected from concentration expressed in percentage by weight; Reduction temperature is 80～<100 ℃; Recovery time is 0.1～1.5 hour/kilogram of catalyst.
8. purification of terephthalic acid palladium carbon catalyst reduction washing methods according to claim 7, is characterized in that reduction temperature is 85～<100 ℃; Recovery time is 0.2～1 hour/kilogram of catalyst.
9. purification of terephthalic acid palladium carbon catalyst reduction washing methods according to claim 1, is characterized in that wash temperature is 80～<100 ℃
Purification of terephthalic acid palladium carbon catalyst reduction washing methods according to claim 1, it is characterized in that washing procatalyst sodium ions content is >10000～15000ppm, washing rear catalyst sodium ions content is less than 1000ppm.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107486252A (en) * | 2016-06-13 | 2017-12-19 | 中国石油化工股份有限公司 | A kind of catalyst reduction device and restoring method |
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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 |
-
2012
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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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107486252A (en) * | 2016-06-13 | 2017-12-19 | 中国石油化工股份有限公司 | A kind of catalyst reduction device and restoring method |
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