CN102397787A - Method and apparatus for preparing palladium carbon catalyst - Google Patents
Method and apparatus for preparing palladium carbon catalyst Download PDFInfo
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- CN102397787A CN102397787A CN2010102799152A CN201010279915A CN102397787A CN 102397787 A CN102397787 A CN 102397787A CN 2010102799152 A CN2010102799152 A CN 2010102799152A CN 201010279915 A CN201010279915 A CN 201010279915A CN 102397787 A CN102397787 A CN 102397787A
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Abstract
The invention provides a method and an apparatus for preparing a palladium carbon catalyst. The apparatus comprises a palladium chloride dissolving reactor, an active carbon slurry preparing reactor, a hydrogenation reactor, a catalyst storage tank and a catalyst scrubber. The catalyst scrubber is provided with a top nitrogen inlet and a middle nitrogen inlet, and a filtering segment at a middle section. The preparation method comprises steps of: preparing a palladium chloride solution; adding water to prepare a active carbon slurry; adsorbing palladium chloride to active carbon; adding alkali to prepare palladium hydroxide; hydrogenating to reduce into a metal target; and preparing into a crude catalyst; washing the crude catalyst in the catalyst scrubber with stirring by nitrogen; filtering until a chloride ion content in a filtrate is qualified; sending the slurry to a storage tank for preservation. The invention increases catalyst activity by 0.2-0.3(Z0), reduces catalyst loss, lowers production cost, increases economic benefit and reduces labor intensity during catalyst preparation.
Description
Technical field
The invention belongs to chemical production technical field, relate to preparation method and the equipment of a kind of hydrogenation, be specially the improvement of benzoic acid hydrogenation with palladium-carbon catalyst preparation method and device with metallic catalyst.
Background technology
Benzoic acid hydrogenation is the pilot process that the SNIA method is produced caprolactam, and this reaction is raw material with the benzoic acid, is Catalyst Production intermediate product cyclohexane-carboxylic acid at the precious metal palladium, and the activity of palladium-carbon catalyst is the key factor that influences the benzoic acid hydrogenation effect.Palladium-carbon catalyst is an active component with the palladium, is carrier with the active carbon, and the preparation process mainly may further comprise the steps:
(1) palladium bichloride is adsorbed on the active carbon.
PdCl
2(solvate)+active carbon C (catalyst carrier) → (PdCl
2)/active carbon C
(2) adding NaOH makes the absorption palladium bichloride be converted into palladium dydroxide.
PdCl
2+2NaOH→Pd(OH)
2+2NaCl
(3) hydrogenation makes palladium dydroxide be reduced to Metal Palladium, processes thick palladium-carbon catalyst.
Pd(OH)
2+H
2→Pd+2H
2O
(4) remove chlorion in the catalyst, process the catalyst finished product.
Palladium carbon catalyst prepares in the process, need wash thick catalyst, and the chlorion of removing in the thick catalyst is processed finished catalyst.The thick catalyst detergent of prior art carries out in centrifuge, mainly comprises charging, washes material, step such as drying, discharging, barrelling.The finished catalyst water content is 40～60% leather hard, adds the device reaction system to and uses.The deficiency of prior art is: (1) palladium-carbon catalyst is poisoned in air easily, reduces catalyst activity, and test shows that the catalyst oven dry back activity of leather hard has 1.3 to reduce to below 0.5.So the catalyst after centrifugal washing and the drying, waiting operation and leaving the easy inactivation of part that the interior storage of bucket is exposed to air in of half-dried catalyst barrelling reduces the quality of fresh finished catalyst.(2) there is potential safety hazard in complicated operating process, in charging, wash in the material process centrifuge vibrations and cause the machine positioning greatly.(3) the material system of scraping of centrifuge scrapes material and leaves one deck catalyst on the filter cloth afterwards, scrapes automatically after the material shutdown, needs operating personnel to get into machine and scrapes material, wastes time and energy, and causes the loss of catalyst again easily.(4) artificial barrelling and add catalyst to reaction system, intermittently operated, labour intensity is high.(5) catalyst exposure causes the environmental pollution ring outside.
Summary of the invention
For overcoming the deficiency of above-mentioned prior art; The present invention provides a kind of method for preparing palladium-carbon catalyst, and the thick catalyst behind the hydrogenation is washed in closed container, deposits and carries to reaction system with slurry condition; Optimize catalyst preparation process; It is active to improve finished catalyst, reduces the loss, and reduces labour intensity.Another object of the present invention provides a kind of device of realizing above-mentioned preparation palladium-carbon catalyst method.
Preparation palladium-carbon catalyst method provided by the invention, step comprises: 1. palladium bichloride adds water and is prepared into PdCl
2The palladium chloride solution of content 5～15% (weight).2. activated carbon adds water and acid to process solid content is that 5～15% (weight) pH value is 1～5 active carbon slurries.3. step palladium chloride solution is 1. joined in the step activated carbon slurries 2., palladium bichloride evenly is adsorbed on the activated carbon of slurries, the addition of palladium chloride solution is a palladium content 3～10% (weight) on the catalyst.4. add alkali lye and make the palladium bichloride of absorption be converted into palladium dydroxide, control slurries pH value is 10.5～11.5.5. hydrogenation makes the palladium dydroxide that is adsorbed on the activated carbon be reduced into palladium, and hydrogenation pressure 30～100KPa generates thick palladium-carbon catalyst.6. thick catalyst washs, filters under nitrogen stirs in the catalyst detergent device, and the chloride ion content in washing to the filtrating is less than 0.2 ± 0.05% (weight), and washer pressure is 300～1000KPa.7. it is subsequent use that the catalyst after washing is delivered to the catalyst storage tank stores with slurry condition.
The alkali of step in 4. is NaOH, KOH or Na
2CO
3, concentration of lye is 20～40%.The acid of step in 2. is hydrochloric acid or sulfuric acid, and water is desalted water or distilled water.1., 2., 3., 4. and 5. step carries out under stirring.The palladium content of slurry condition finished product palladium-carbon catalyst is 5 ± 0.2% (weight), and water content is 75～90% (weight), and palladium content is dry weight, i.e. percetage by weight after 105 ℃ of oven dry.The process that palladium bichloride dissolving, active carbon slurry preparation and palladium bichloride are converted into palladium dydroxide is a normal pressure, and whole catalyst preparation process is a normal-temperature operation.
A kind of realization prepares the palladium-carbon catalyst device, mainly comprises: palladium bichloride dissolution reactor, active carbon slurry preparation reactor, hydrogenation reactor and catalyst storage tank.Palladium bichloride dissolution reactor, active carbon slurry preparation reactor and hydrogenation reactor are provided with agitator.The material outlet of palladium bichloride dissolution reactor is connected to the inlet of active carbon slurry preparation reactor, and the material outlet of active carbon slurry preparation reactor is connected to the inlet of hydrogenation reactor.Device also is provided with the catalyst detergent device, and the material inlet of catalyst detergent device is connected with the material outlet of hydrogenation reactor, and outlet is connected with the catalyst storage tank.The catalyst detergent device is provided with top nitrogen inlet and middle part nitrogen inlet, and the middle part is provided with fillter section.
The fillter section of catalyst detergent device comprises filter course, baffle and gripper shoe.Stating filter course is filter cloth or filter screen.Be provided with siphon pipe in the said active carbon slurry preparation reactor, the siphon pipe outlet is connected to catalyst hydrogenation reactor feed mouth.Palladium bichloride dissolution reactor, active carbon slurry preparation reactor are equipped with the acid and alkali resistance lining, and the material of acid and alkali-resistance lining is pottery or resin.Hydrogenation reactor is provided with the hydrogen distributor, and the hydrogen distributor pipe is connected with hydrogen pipeline.Catalyst detergent device middle part is provided with the nitrogen distributor, and the nitrogen distributor is connected with the middle part nitrogen inlet.
After the embodiment of the present invention, the fresh catalyst of production is carried with slurry condition and is deposited, and avoids contacting poisoning with air, has improved about 0.2～0.3 (the catalyst activity sex index Z of catalyst activity
0).Wash under the catalyst air-tight state and carry, avoided centrifuge to scrape the loss that material, barrelling process cause catalyst, production practices are practiced thrift 24.73% precious metal palladium after showing embodiment of the present invention, have improved the Catalyst Production quality of stability simultaneously.The catalyst detergent process is carried out continuously, has reduced barrelling, process for preparation, has reduced labour intensity.The technological operation of washer washing chlorion is simple and easy, safety, device load are big, production cost obviously reduces.
Description of drawings
Fig. 1 prepares the flow chart of palladium-carbon catalyst device for the present invention;
Fig. 2 is a catalyst detergent device structure chart.
Wherein:
1-palladium bichloride dissolution reactor, 2-agitator, 3-valve, 4-active carbon slurry preparation reactor, 5-hydrogenation reactor, 6-catalyst detergent device, 7-catalyst storage tank, 8-pump, 9-safety valve, 10-atmospheric valve, 11-washer charging aperture, 12-top nitrogen inlet, 13-middle part nitrogen inlet, 14-filter cloth baffle, 15-filter course, 16-filter cloth gripper shoe, 17-fillter section, 18-discharging opening, 19-siphon pipe, 20-hydrogen distributor, 21-nitrogen distributor, 22-active carbon add inlet, the outlet of 23-cleaning solution.
The specific embodiment
Below in conjunction with accompanying drawing the present invention is further described.
The present invention prepares the palladium-carbon catalyst device; As shown in Figure 1; Mainly be made up of palladium bichloride dissolution reactor 1, active carbon slurry preparation reactor 4, hydrogenation reactor 5, catalyst detergent device 6, catalyst storage tank 7 and supporting pipeline, pump 8 and valve 3, said palladium bichloride dissolution reactor, active carbon slurry preparation reactor and hydrogenation reactor are provided with agitator 2.The material outlet of palladium bichloride dissolution reactor is connected to the palladium chloride solution inlet of active carbon slurry preparation reactor.Active carbon slurry preparation reactor is provided with active carbon charge door 22 and alkali liquor inlet.Be provided with siphon pipe 19 in the active carbon slurry preparation reactor, siphon pipe is inserted into the bottom of active carbon slurry preparation reactor, and outlet is connected to catalyst hydrogenation reactor feed mouth.The catalyst hydrogenation reactor is provided with hydrogen inlet and nitrogen inlet, and the bottom is provided with hydrogen distributor 20, and the hydrogen distributor is connected with hydrogen inlet.The material outlet of catalyst hydrogenation reactor is connected to the washer charging aperture at catalyst detergent device top through pipeline and pump 8.As shown in Figure 2, the catalyst detergent device is provided with the top and is provided with safety valve 9, atmospheric valve 10, washer charging aperture 11 and top nitrogen inlet 12, and the centre is provided with middle part nitrogen inlet 13 and is provided with cleaning solution outlet 23 with discharging opening 18 bottoms.Catalyst detergent device bosom is provided with fillter section 17 and nitrogen distributor 21.Fillter section is by filter course 15, and the filter cloth baffle 14 on top and the filter cloth gripper shoe of bottom 16 are formed, and filter course is a filter cloth.The middle part nitrogen inlet be positioned at fillter section on, be connected with nitrogen distributor 21.Discharging opening is positioned at fillter section top, and discharging opening 18 is connected to catalyst storage tank 7 through pipeline and pump.The desalted water pipeline is connected to palladium bichloride dissolution reactor, active carbon slurry preparation reactor, hydrogenation reactor and catalyst detergent device.Palladium bichloride dissolution reactor, active carbon slurry preparation reactor are equipped with ceramic lined.
The preparation process of palladium-carbon catalyst of the present invention is: 1. add to palladium bichloride dissolution reactor 1 and contain palladium bichloride 20% (weight) commodity palladium chloride solution, press PdCl
2The amount of water of content 8% (weight) adds desalted water, starts agitator 2 and stirs the palladium chloride solution that was prepared in 1 hour.2. in active carbon slurry preparation reactor 4 by the metering desalted water of packing into, add hydrochloric acid, active carbon activated carbon, stirred 1 hour, processing solid content is that 10% (weight), pH value are 2 active carbon slurries.3. with the mode that drips step palladium chloride solution is 1. joined in the step activated carbon slurries 2.; Control rate of addition make palladium bichloride in the activated carbon slurries all with the distribution; The addition of palladium chloride solution is a palladium content 5% (weight) on the catalyst; Stirred 5 hours, ageing 3 hours is adsorbed on the active carbon palladium bichloride equably.30% (weight) NaOH solution that 4. in active carbon slurry preparation reactor, will prepare slowly splashes into and carries out ion exchange in the slurries; Stir simultaneously; Make and be adsorbed on that palladium bichloride is converted into palladium dydroxide on the active carbon; Dripped 10 hours, stirred after dripping 1 hour again, the control pH value is 10.5～11.5.5. through siphon pipe 19 with the mass transport of active carbon slurry preparation reactor bottom in catalyst hydrogenation reactor 5.Open nitrogen inlet, feed nitrogen and catch up with air, feed hydrogen then and carry out hydrogenation reaction, make that palladium dydroxide is reduced into Metal Palladium on the catalyst.Start agitator and stir, hydrogenation pressure is 50KPa, keeps hydrogenation time 8 hours, processes thick catalyst.Hydrogenation finishes back emptying hydrogen, with hydrogen remaining in the nitrogen replacement hydrogenation reactor, guarantees safety.6. the thick catalyst in the hydrogenation reactor is transported to catalyst detergent device 6 through pipeline, pump 8 and washer charging aperture 11.Feed desalted water and wash, washer pressure is 500KPa, opens top nitrogen inlet 12, presses down washings.Filter course is in order to forming the catalyst filter cake, on the desalted water and down by the tower inner catalyst is washed continuously, take away chlorion in the catalyst.Nitrogen inlet 13 feeds and stirs from the middle part, and inspection stops washing when analyzing cleaning solution rate ion concentration less than 0.2% (weight), stirs 1 hour again, makes catalyst be the slurries shape, and washing finishes and is finished catalyst.7. finished catalyst is transported to catalyst storage tank 7 through discharging opening 18, connecting line and pump.It is normal pressure that palladium bichloride dissolving, active carbon slurry preparation and palladium bichloride are converted into palladium dydroxide, and whole catalyst preparation process is a normal-temperature operation.From catalyst storage tank sample analysis, the finished product palladium-carbon catalyst be content 4.88% (weight), water content 85.25% (weight), catalyst activity Z
0=1.35.
Z
0Be the characterization value of the activity of palladium-carbon catalyst, Z
0Big more, the expression catalyst hydrogenation activity is high more, the active Z of fresh catalyst
0Be generally 1.0～1.50, Z
0Assay method ask for an interview chemical fibre division department of Shijiazhuang branch company of China Petrochemical Corp. " caprolactam analyzed handbook.The finished catalyst average activity of prior art centrifuge washing is 1.0～1.20, and embodiment of the present invention rear catalyst activity is 1.25～1.50.Not only improve the activity and the benzoic acid hydrogenation performance of palladium-carbon catalyst after the embodiment of the present invention, also reduced production cost, improved economic benefit.
Claims (10)
1. one kind preparation palladium-carbon catalyst method, step comprises: 1. palladium bichloride adds water and is prepared into PdCl
2Content is the palladium chloride solution of 5～15% (weight); 2. activated carbon adds water and acid to process solid content is that 5～15% (weight), pH value are 1～5 active carbon slurries; 3. step palladium chloride solution is 1. joined in the step activated carbon slurries 2., palladium bichloride evenly is adsorbed on the activated carbon of slurries, the addition of palladium chloride solution is a palladium content 3～10% (weight) on the catalyst; 4. add alkali lye and make the palladium bichloride of absorption be converted into palladium dydroxide, control slurries pH value is 10.5～11.5; 5. hydrogenation makes the palladium dydroxide that is adsorbed on the activated carbon be reduced into palladium, and hydrogenation pressure 30～100KPa generates thick palladium-carbon catalyst; It is characterized in that: 6. said thick catalyst is washing under the nitrogen stirring, filtration in catalyst detergent device (6), and the chloride ion content during washing is extremely filtrated is less than 0.2 ± 0.05% (weight), and washer pressure is 300～1000KPa; 7. to deliver to catalyst storage tank (7) with slurry condition subsequent use for washing back finished catalyst.
2. according to the said method for preparing palladium-carbon catalyst of claim 1, it is characterized in that: the step 4. alkali of said alkali lye is NaOH, KOH or Na
2CO
3, concentration of lye is 20～40% (weight); The 2. described acid of step is hydrochloric acid or sulfuric acid; Described water is desalted water or distilled water.
3. according to the said method for preparing palladium-carbon catalyst of claim 1, it is characterized in that: the palladium content of said slurry condition finished product palladium-carbon catalyst is 5 ± 0.5% (weight, dry weights), and water content is 75～90% (weight).
4. according to the said method for preparing palladium-carbon catalyst of claim 1, it is characterized in that: 1., 2., 3., 4. and 5. said step carries out under stirring.
5. device of realizing preparing palladium-carbon catalyst; Mainly comprise: palladium bichloride dissolution reactor (1), active carbon slurry preparation reactor (4), hydrogenation reactor (5) and catalyst storage tank (7); Said palladium bichloride dissolution reactor, active carbon slurry preparation reactor and hydrogenation reactor are provided with agitator; The material outlet of palladium bichloride dissolution reactor is connected to the inlet of active carbon slurry preparation reactor, and the material outlet of active carbon slurry preparation reactor is connected to the inlet of hydrogenation reactor, and it is characterized in that: said device also is provided with the catalyst detergent device; The material inlet of said catalyst detergent device is connected with the material outlet of hydrogenation reactor; Outlet is connected with the catalyst storage tank, and said catalyst detergent device is provided with top nitrogen inlet (12) and middle part nitrogen inlet (13), and the middle part is provided with fillter section (17).
6. according to the device of the said preparation palladium-carbon catalyst of claim 5, it is characterized in that: the fillter section of said catalyst detergent device comprises filter course (15), baffle (14) and gripper shoe (16).
7. according to the device of the said preparation palladium-carbon catalyst of claim 6, it is characterized in that: said filter course is filter cloth or filter screen.
8. according to the device of the said preparation palladium-carbon catalyst of claim 5, it is characterized in that: (4) are provided with siphon pipe in the said active carbon slurry preparation reactor, and the siphon pipe outlet is connected to catalyst hydrogenation reactor feed mouth.
9. according to the device of the said preparation palladium-carbon catalyst of claim 5, it is characterized in that: said palladium bichloride dissolution reactor, active carbon slurry preparation reactor are equipped with the acid and alkali resistance lining, and the material of said acid and alkali-resistance lining is pottery or resin.
10. according to the device of the said preparation palladium-carbon catalyst of claim 5, it is characterized in that: said hydrogenation reactor is provided with hydrogen distributor (20), and the hydrogen distributor is connected with hydrogen pipeline; Said catalyst detergent device middle part is provided with nitrogen distributor (21), and the nitrogen distributor is connected with the middle part nitrogen inlet.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103041805A (en) * | 2012-12-07 | 2013-04-17 | 贵研铂业股份有限公司 | Preparation method of high-activity palladium-carbon catalyst for synthesis of imipenem antibiotics |
| CN103933974A (en) * | 2014-05-05 | 2014-07-23 | 中国石油大学(华东) | Preparation method for supported type palladium catalyst |
| CN104399455A (en) * | 2014-12-18 | 2015-03-11 | 陕西瑞科新材料股份有限公司 | Preparation method of palladium-carbon catalyst |
| CN105854916A (en) * | 2016-05-05 | 2016-08-17 | 广州合成材料研究院有限公司 | Palladium catalyst wrapped with calcium carbonate and preparing technology of palladium catalyst |
| CN107826358A (en) * | 2017-10-24 | 2018-03-23 | 南京工业大学 | A kind of storage method after phenol hydrogenation Pd@CN catalyst uses |
| CN108855055A (en) * | 2018-05-31 | 2018-11-23 | 南京东焱氢能源科技有限公司 | A kind of preparation method of the high activity hydroxide palladium carbon based on microreactor |
| CN110918004A (en) * | 2019-12-20 | 2020-03-27 | 湖南双阳高科化工有限公司 | Palladium-carbon filtering and recycling system and method |
| CN113600182A (en) * | 2021-08-30 | 2021-11-05 | 重庆工商大学 | Catalyst for synthesizing dimethyl carbonate and preparation method and equipment thereof |
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| CN1376537A (en) * | 2001-09-29 | 2002-10-30 | 曹峻清 | Superfine-grain charred palladium as hydrocatalyst for preparing caprolactam and its preparing process |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103041805A (en) * | 2012-12-07 | 2013-04-17 | 贵研铂业股份有限公司 | Preparation method of high-activity palladium-carbon catalyst for synthesis of imipenem antibiotics |
| CN103933974A (en) * | 2014-05-05 | 2014-07-23 | 中国石油大学(华东) | Preparation method for supported type palladium catalyst |
| CN103933974B (en) * | 2014-05-05 | 2015-05-20 | 中国石油大学(华东) | Preparation method for supported type palladium catalyst |
| CN104399455A (en) * | 2014-12-18 | 2015-03-11 | 陕西瑞科新材料股份有限公司 | Preparation method of palladium-carbon catalyst |
| CN105854916A (en) * | 2016-05-05 | 2016-08-17 | 广州合成材料研究院有限公司 | Palladium catalyst wrapped with calcium carbonate and preparing technology of palladium catalyst |
| CN107826358A (en) * | 2017-10-24 | 2018-03-23 | 南京工业大学 | A kind of storage method after phenol hydrogenation Pd@CN catalyst uses |
| CN108855055A (en) * | 2018-05-31 | 2018-11-23 | 南京东焱氢能源科技有限公司 | A kind of preparation method of the high activity hydroxide palladium carbon based on microreactor |
| CN110918004A (en) * | 2019-12-20 | 2020-03-27 | 湖南双阳高科化工有限公司 | Palladium-carbon filtering and recycling system and method |
| CN110918004B (en) * | 2019-12-20 | 2024-04-12 | 湖南双阳高科化工有限公司 | Palladium-carbon filtering and recycling system and recycling method |
| CN113600182A (en) * | 2021-08-30 | 2021-11-05 | 重庆工商大学 | Catalyst for synthesizing dimethyl carbonate and preparation method and equipment thereof |
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Application publication date: 20120404 |