CN105195136A - Method for improving catalytic activity of palladium-carbon catalyst - Google Patents

Abstract

The invention belongs to the technical field of catalyst preparation and discloses a method for improving catalytic activity of a palladium-carbon catalyst. The method includes: carbonizing and grinding peanut shells, soaking in egg white, adding papain to generate amino acid, adding palladium chloride and sodium hydroxide in a container to generate precipitates, enabling pores in carbon surface to be uniformly distributed by means of microbiological degradation, and adopting formaldehyde for reduction to generate palladium loaded on carbon, so that catalytic activity of the palladium-carbon catalyst is improved. According to examples, the method is simple and feasible and not only enables dispersion uniformity of carbon specific surface area and increase of surface pore size but also gives full play to reaction activity of the palladium-carbon catalyst, and catalytic activity of the palladium-carbon catalyst is improved to more than 95%.

Description

A kind of method improving palladium carbon catalyst catalytic activity

Technical field

The invention discloses a kind of method improving palladium carbon catalyst catalytic activity, belong to catalyst preparation technical field.

Background technology

Palladium carbon catalyst Metal Palladium is loaded in active carbon to form load hydrogenation catalyst for refining, for refinement treatment terephthaldehyde acid starting material, and production purified terephthalic.

Palladium carbon catalyst catalytic activity is high, selective good, in petrochemical industry, pharmacy, fine chemistry industry and organic synthesis, occupy very important status.Find that since 1872 palladium charcoal has beyond catalytic action to the nitro hydrogenation reduction reaction on phenyl ring, palladium carbon catalyst hydrogenation, with its flow process letter, the advantage such as conversion ratio is high, productive rate is high and the three wastes are few, causes and pays close attention to greatly both at home and abroad.

In the Industrial Catalysis reactions such as oil refining, pharmacy, petrochemical industry now, there is a lot of palladium-catalyzed reaction, especially the selec-tive hydrogenation in hydrogenation, and in oxidation reaction, selective oxidation production acetaldehyde, vinyl acetate, methacrylic acid formaldehyde all extensively adopt palladium catalyst; In addition, petroleum reforming is reacted, palladium is also one of catalytic component often chosen, but still there is many defects in palladium carbon catalyst at that time, such as, the impact that aperture that is uneven by product specific area, pore structure is smaller, surface chemical property is unstable etc., the reaction vigor of palladium carbon catalyst can not give full play of.

Summary of the invention

The technical problem that the present invention mainly solves: although for current palladium carbon catalyst in petrochemical industry, pharmacy, very important status is occupied in fine chemistry industry and organic synthesis, but it is uneven still to there is specific area dispersion, carbon surface aperture is smaller, the problem that surface chemical property is unstable and reaction vigor can not give full play in course of reaction, provide a kind of method improving palladium carbon catalyst catalytic activity, first peanut shell carbonizes by the method, put into egg white after pulverizing to soak, after add papain generate amino acid, add palladium bichloride and NaOH generation precipitation afterwards in a reservoir, pass through microbial degradation subsequently, make carbon surface even pore distribution, finally utilize formaldehyde to reduce and generate palladium load on charcoal, thus improve palladium carbon catalyst catalytic activity.This method not only makes charcoal specific area be uniformly dispersed, and surface apertures expands, and makes the palladium carbon catalyst vigor that reacts obtain and give full play to, and improves more than catalytic activity to 95%.

In order to solve the problems of the technologies described above, the technical solution adopted in the present invention is:

(1) get peanut shell clear water to clean, put into container, add wherein mass fraction be 6 ~ 11% sodium hydroxide solution flood peanut shell 5 ~ 6cm, add the sodium abietate of peanut shell quality 0.15 ~ 0.25% more respectively, the sodium chromate of peanut shell quality 0.1 ~ 0.3% and the methyl diethanolamine of sodium hydroxide solution volume 22 ~ 32%, agitating heating 1 ~ 2h, temperature is set as 85 ~ 95 DEG C, and speed setting is 350 ~ 450r/min;

(2) after above-mentioned heating terminates, filter while hot, the peanut shell of gained is put into extruder and is squeezed into block, then put it into 1 ~ 3h in retort, temperature is set as 750 ~ 850 DEG C, after charing terminates, charing block is cooled to room temperature, puts into pulverizer, be ground into 95 ~ 115 order particles;

(3) particle after pulverizing is put into container, add egg white and soak particle, stir, get the papain of granular mass 5 ~ 10% afterwards, regulate temperature be 35 ~ 50 DEG C, service property (quality) concentration be 5% sodium hydroxide solution regulate pH be 7 ~ 7.5, stir 1 ~ 2h;

(4) after above-mentioned stirring terminates, by palladium bichloride and NaOH mol ratio 1:2, get palladium bichloride and mass fraction be 70% sodium hydroxide solution add in said vesse, being stirred to and producing without precipitation, continuing afterwards to stir, to precipitating disappearance, then filter, get particle;

(5) the above-mentioned particle obtained is put into container, the rumen fluid adding sheep wherein soaks particle, then adds beef extract wherein, and addition is 10 ~ 15% of particle quality, is adjusted to temperature 30 ~ 35 DEG C, sealing stirring 1 ~ 2 day;

(6) after above-mentioned stirring terminates, mixture in said vesse is put into centrifuge, centrifugation 15 ~ 20min under rotating speed is 10000 ~ 15000r/min, get centrifugal rear solid, afterwards the solid of gained is put into container, add formaldehyde wherein and soak solid, abundant stirring 35 ~ 60min, filter after leaving standstill 1 ~ 2h again, the filtrate of gained put into baking oven and dries.

Application process of the present invention is: the palladium carbon catalyst obtained by the present invention getting reaction raw materials gross mass 5 ~ 10%, hydrodehalogenation is carried out to parachlorophenol, after 15 ~ 25min, the conversion ratio up to more than 90% can be obtained, keep selective preferably simultaneously, the palladium carbon catalyst vigor that reacts is obtained fully play, catalytic activity is up to more than 95%.

The invention has the beneficial effects as follows:

(1) preparation is simple in the present invention, and charcoal specific area is uniformly dispersed, and surface apertures expands;

(2) the invention enables the palladium carbon catalyst vigor that reacts to obtain to give full play to, improve more than catalytic activity to 95%.

Detailed description of the invention

First get peanut shell clear water to clean, put into container, add wherein mass fraction be 6 ~ 11% sodium hydroxide solution flood peanut shell 5 ~ 6cm, add the sodium abietate of peanut shell quality 0.15 ~ 0.25% more respectively, the sodium chromate of peanut shell quality 0.1 ~ 0.3% and the methyl diethanolamine of sodium hydroxide solution volume 22 ~ 32%, agitating heating 1 ~ 2h, temperature is set as 85 ~ 95 DEG C, and speed setting is 350 ~ 450r/min; Afterwards after above-mentioned heating terminates, filter while hot, the peanut shell of gained is put into extruder and is squeezed into block, then put it into 1 ~ 3h in retort, temperature is set as 750 ~ 850 DEG C, after charing terminates, charing block is cooled to room temperature, puts into pulverizer, be ground into 95 ~ 115 order particles; Particle after pulverizing is put into container, adds egg white and soak particle, stir, get the papain of granular mass 5 ~ 10% afterwards, regulate temperature be 35 ~ 50 DEG C, service property (quality) concentration be 5% sodium hydroxide solution regulate pH be 7 ~ 7.5, stir 1 ~ 2h; Subsequently after above-mentioned stirring terminates, by palladium bichloride and NaOH mol ratio 1:2, get palladium bichloride and mass fraction be 70% sodium hydroxide solution add in said vesse, being stirred to and producing without precipitation, continuing afterwards to stir, to precipitating disappearance, then filter, get particle; Again the above-mentioned particle obtained is put into container, the rumen fluid adding sheep wherein soaks particle, then adds beef extract wherein, and addition is 10 ~ 15% of particle quality, is adjusted to temperature 30 ~ 35 DEG C, sealing stirring 1 ~ 2 day; Finally after above-mentioned stirring terminates, mixture in said vesse is put into centrifuge, centrifugation 15 ~ 20min under rotating speed is 10000 ~ 15000r/min, get centrifugal rear solid, afterwards the solid of gained is put into container, add formaldehyde wherein and soak solid, abundant stirring 35 ~ 60min, filter after leaving standstill 1 ~ 2h again, the filtrate of gained put into baking oven and dries.

Example 1

First get peanut shell clear water to clean, put into container, add wherein mass fraction be 6% sodium hydroxide solution flood peanut shell 5cm, add the sodium abietate of peanut shell quality 0.15% more respectively, the sodium chromate of peanut shell quality 0.1% and the methyl diethanolamine of sodium hydroxide solution volume 22%, agitating heating 1h, temperature is set as 85 DEG C, and speed setting is 350r/min; Afterwards after above-mentioned heating terminates, filter while hot, the peanut shell of gained is put into extruder and is squeezed into block, then put it into 1h in retort, temperature is set as 750 DEG C, after charing terminates, charing block is cooled to room temperature, puts into pulverizer, be ground into 95 order particles; By pulverize after particle put into container, add egg white soak particle, stir, get the papain of granular mass 5% afterwards, regulate temperature be 35 DEG C, service property (quality) concentration be 5% sodium hydroxide solution regulate pH be 7, stir 1h; Subsequently after above-mentioned stirring terminates, by palladium bichloride and NaOH mol ratio 1:2, get palladium bichloride and mass fraction be 70% sodium hydroxide solution add in said vesse, being stirred to and producing without precipitation, continuing afterwards to stir, to precipitating disappearance, then filter, get particle; Again the above-mentioned particle obtained is put into container, the rumen fluid adding sheep wherein soaks particle, then adds beef extract wherein, and addition is 10% of particle quality, is adjusted to temperature 30 DEG C, sealing stirring 1 day; Finally after above-mentioned stirring terminates, mixture in said vesse is put into centrifuge, centrifugation 15min under rotating speed is 10000r/min, get centrifugal rear solid, afterwards the solid of gained is put into container, add formaldehyde wherein and soak solid, abundant stirring 35min, filter after leaving standstill 1h again, the filtrate of gained put into baking oven and dries.

This example operation is simple, in use, get the palladium carbon catalyst obtained by the present invention of reaction raw materials gross mass 5%, hydrodehalogenation is carried out to parachlorophenol, after 15min, the conversion ratio up to 90% can be obtained, keep selective preferably simultaneously, the palladium carbon catalyst vigor that reacts is obtained fully play, catalytic activity is up to 95%.

Example 2

First get peanut shell clear water to clean, put into container, add wherein mass fraction be 9% sodium hydroxide solution flood peanut shell 5.5cm, add the sodium abietate of peanut shell quality 0.2% more respectively, the sodium chromate of peanut shell quality 0.2% and the methyl diethanolamine of sodium hydroxide solution volume 28%, agitating heating 1.5h, temperature is set as 90 DEG C, and speed setting is 400r/min; Afterwards after above-mentioned heating terminates, filter while hot, the peanut shell of gained is put into extruder and is squeezed into block, then put it into 2h in retort, temperature is set as 800 DEG C, after charing terminates, charing block is cooled to room temperature, puts into pulverizer, be ground into 105 order particles; By pulverize after particle put into container, add egg white soak particle, stir, get the papain of granular mass 8% afterwards, regulate temperature be 45 DEG C, service property (quality) concentration be 5% sodium hydroxide solution regulate pH be 7.2, stir 1.5h; Subsequently after above-mentioned stirring terminates, by palladium bichloride and NaOH mol ratio 1:2, get palladium bichloride and mass fraction be 70% sodium hydroxide solution add in said vesse, being stirred to and producing without precipitation, continuing afterwards to stir, to precipitating disappearance, then filter, get particle; Again the above-mentioned particle obtained is put into container, the rumen fluid adding sheep wherein soaks particle, then adds beef extract wherein, and addition is 13% of particle quality, is adjusted to temperature 32 DEG C, sealing stirring 1.5 days; Finally after above-mentioned stirring terminates, mixture in said vesse is put into centrifuge, centrifugation 18min under rotating speed is 13500r/min, get centrifugal rear solid, afterwards the solid of gained is put into container, add formaldehyde wherein and soak solid, abundant stirring 45min, filter after leaving standstill 1.5h again, the filtrate of gained put into baking oven and dries.

This example operation is simple, in use, get the palladium carbon catalyst obtained by the present invention of reaction raw materials gross mass 8%, hydrodehalogenation is carried out to parachlorophenol, after 20min, the conversion ratio up to 92% can be obtained, keep selective preferably simultaneously, the palladium carbon catalyst vigor that reacts is obtained fully play, catalytic activity is up to 96%.

Example 3

First get peanut shell clear water to clean, put into container, add wherein mass fraction be 11% sodium hydroxide solution flood peanut shell 6cm, add the sodium abietate of peanut shell quality 0.25% more respectively, the sodium chromate of peanut shell quality 0.3% and the methyl diethanolamine of sodium hydroxide solution volume 32%, agitating heating 2h, temperature is set as 95 DEG C, and speed setting is 450r/min; Afterwards after above-mentioned heating terminates, filter while hot, the peanut shell of gained is put into extruder and is squeezed into block, then put it into 3h in retort, temperature is set as 850 DEG C, after charing terminates, charing block is cooled to room temperature, puts into pulverizer, be ground into 115 order particles; By pulverize after particle put into container, add egg white soak particle, stir, get the papain of granular mass 10% afterwards, regulate temperature be 50 DEG C, service property (quality) concentration be 5% sodium hydroxide solution regulate pH be 7.5, stir 2h; Subsequently after above-mentioned stirring terminates, by palladium bichloride and NaOH mol ratio 1:2, get palladium bichloride and mass fraction be 70% sodium hydroxide solution add in said vesse, being stirred to and producing without precipitation, continuing afterwards to stir, to precipitating disappearance, then filter, get particle; Again the above-mentioned particle obtained is put into container, the rumen fluid adding sheep wherein soaks particle, then adds beef extract wherein, and addition is 15% of particle quality, is adjusted to temperature 35 DEG C, sealing stirring 2 days; Finally after above-mentioned stirring terminates, mixture in said vesse is put into centrifuge, centrifugation 20min under rotating speed is 15000r/min, get centrifugal rear solid, afterwards the solid of gained is put into container, add formaldehyde wherein and soak solid, abundant stirring 60min, filter after leaving standstill 2h again, the filtrate of gained put into baking oven and dries.

This example operation is simple, in use, get the palladium carbon catalyst obtained by the present invention of reaction raw materials gross mass 10%, hydrodehalogenation is carried out to parachlorophenol, after 25min, the conversion ratio up to 94% can be obtained, keep selective preferably simultaneously, the palladium carbon catalyst vigor that reacts is obtained fully play, catalytic activity is up to 97%.

Claims (1)

1. improve a method for palladium carbon catalyst catalytic activity, it is characterized in that concrete operation step is:

(1) get peanut shell clear water to clean, put into container, add wherein mass fraction be 6 ~ 11% sodium hydroxide solution flood peanut shell 5 ~ 6cm, add the sodium abietate of peanut shell quality 0.15 ~ 0.25% more respectively, the sodium chromate of peanut shell quality 0.1 ~ 0.3% and the methyl diethanolamine of sodium hydroxide solution volume 22 ~ 32%, agitating heating 1 ~ 2h, temperature is set as 85 ~ 95 DEG C, and speed setting is 350 ~ 450r/min;

(2) after above-mentioned heating terminates, filter while hot, the peanut shell of gained is put into extruder and is squeezed into block, then put it into 1 ~ 3h in retort, temperature is set as 750 ~ 850 DEG C, after charing terminates, charing block is cooled to room temperature, puts into pulverizer, be ground into 95 ~ 115 order particles;

(3) particle after pulverizing is put into container, add egg white and soak particle, stir, get the papain of granular mass 5 ~ 10% afterwards, regulate temperature be 35 ~ 50 DEG C, service property (quality) concentration be 5% sodium hydroxide solution regulate pH be 7 ~ 7.5, stir 1 ~ 2h;

(4) after above-mentioned stirring terminates, by palladium bichloride and NaOH mol ratio 1:2, get palladium bichloride and mass fraction be 70% sodium hydroxide solution add in said vesse, being stirred to and producing without precipitation, continuing afterwards to stir, to precipitating disappearance, then filter, get particle;

(5) the above-mentioned particle obtained is put into container, the rumen fluid adding sheep wherein soaks particle, then adds beef extract wherein, and addition is 10 ~ 15% of particle quality, is adjusted to temperature 30 ~ 35 DEG C, sealing stirring 1 ~ 2 day;

(6) after above-mentioned stirring terminates, mixture in said vesse is put into centrifuge, centrifugation 15 ~ 20min under rotating speed is 10000 ~ 15000r/min, get centrifugal rear solid, afterwards the solid of gained is put into container, add formaldehyde wherein and soak solid, abundant stirring 35 ~ 60min, filter after leaving standstill 1 ~ 2h again, the filtrate of gained put into baking oven and dries.