CN114192140B - Catalyst for synthesizing 2, 3-dichloropyridine and preparation method thereof - Google Patents

Catalyst for synthesizing 2, 3-dichloropyridine and preparation method thereof Download PDF

Info

Publication number
CN114192140B
CN114192140B CN202111669247.9A CN202111669247A CN114192140B CN 114192140 B CN114192140 B CN 114192140B CN 202111669247 A CN202111669247 A CN 202111669247A CN 114192140 B CN114192140 B CN 114192140B
Authority
CN
China
Prior art keywords
catalyst
metal
palladium
activated carbon
solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202111669247.9A
Other languages
Chinese (zh)
Other versions
CN114192140A (en
Inventor
张洁兰
陈丹
颜攀敦
李岳锋
赵雯宁
张彬雁
王昭文
张鹏
闫江梅
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kaili Catalyst New Materials Co Ltd
Original Assignee
Kaili Catalyst New Materials Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kaili Catalyst New Materials Co Ltd filed Critical Kaili Catalyst New Materials Co Ltd
Priority to CN202111669247.9A priority Critical patent/CN114192140B/en
Publication of CN114192140A publication Critical patent/CN114192140A/en
Application granted granted Critical
Publication of CN114192140B publication Critical patent/CN114192140B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8906—Iron and noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/60—Platinum group metals with zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/892—Nickel and noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8926—Copper and noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8953—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/617—500-1000 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/618—Surface area more than 1000 m2/g
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/61—Halogen atoms or nitro radicals

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a catalyst for synthesizing 2, 3-dichloropyridine, which comprises a flaky active carbon carrier and a metal component loaded on the carrier, wherein the metal component comprises 0.01-0.2% of palladium and 0.005-0.05% of auxiliary metal by mass percent. In addition, the invention also discloses a preparation method of the catalyst. The catalyst has the advantages of greatly reduced metal content, greatly reduced cost, high catalytic efficiency, low noble metal palladium content, stable performance, stable use for more than 90 days, 100% of product conversion rate and more than 95% of selectivity when being used for synthesizing 2.3-dichloropyridine.

Description

Catalyst for synthesizing 2, 3-dichloropyridine and preparation method thereof
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a catalyst for synthesizing 2, 3-dichloropyridine and a preparation method thereof.
Background
2, 3-Dichloropyridine is a key intermediate of novel insecticide chlorantraniliprole, and market demand is increasing year by year.
Chinese patent CN 112142652A discloses a method and apparatus for producing 2, 3-dichloropyridine, firstly, activating catalyst in tubular reaction tube under 500 deg.c and nitrogen, then cooling to reaction temperature (70-100 deg.c), adding 2,3, 6-trichloropyridine and acid-binding agent, and reacting under hydrogen. The service life of the catalyst is more than 60 hours, the selectivity of the product is more than 98 percent, and the conversion rate is 100 percent. The patent adopts M-N/APO-5 as a catalyst, wherein M represents Pt/Pd/Zn/Ni; n represents Co, mg and Ca, the content of M is 0.5-10%, the content of N is 0.5-10%, and the specific catalyst preparation method is not shown. The catalyst in the patent has high metal content, high price, low service life and more than 60 hours.
Chinese patent CN 112194617A discloses a method and a device for synthesizing 2, 3-dichloropyridine, firstly, activating a catalyst in a tubular reaction tube at 400 ℃ under nitrogen, then cooling to the reaction temperature (100-250 ℃), adding an organic solvent solution of 2,3, 6-trichloropyridine, reacting under hydrogen, wherein the service life of the catalyst is more than 60 hours, the selectivity of the product is more than 98%, and the conversion rate is 100%. The patent adopts M/MCM-41 molecular sieve as catalyst, M represents Pt/Pd/Zn/Ni, the content of M is 0.5% -10%, and the specific catalyst preparation method is not shown. The catalyst in the patent has high metal content, high price, low service life and more than 60 hours.
Chinese patent CN201910665611.0 discloses a catalyst for synthesizing 2, 3-dichloropyridine, wherein Pd and Pt loaded powder gamma-alumina is used as catalyst to catalyze 2,3, 6-trichloropyridine to synthesize 2, 3-dichloropyridine, the conversion rate of raw material is 100%, and the selectivity is about 95%. The catalyst adopts palladium-platinum bimetallic, the mass percentage of Pd is 2.5% -4.5%, and the mass percentage of Pt is 0.5% -2.5%. The catalyst has more noble metals, the catalyst has higher price, palladium and platinum need to be reduced respectively, and the preparation process is more complex. The invention needs intermittent reaction, which has low reaction efficiency, high pressure and high equipment requirement, and is unfavorable for industrial production.
Disclosure of Invention
The invention aims to solve the technical problem of providing a catalyst for synthesizing 2, 3-dichloropyridine and a preparation method thereof aiming at the defects in the prior art. The catalyst is used in the synthesis of 2, 3-dichloropyridine in a fixed bed reaction, can be stably used for more than 90 days, has 100% of product conversion rate and more than 95% of selectivity, and has the advantages of high catalytic efficiency, low noble metal content, stable performance and the like.
In order to solve the technical problems, the invention adopts the following technical scheme: the catalyst for synthesizing the 2, 3-dichloropyridine is characterized by comprising a flaky active carbon carrier and a metal component loaded on the carrier, wherein the metal component is palladium and an auxiliary metal, the mass percent of the palladium in the catalyst is 0.01-0.2%, the mass percent of the auxiliary metal is 0.005-0.05%, and the auxiliary metal is one or more of iron, nickel, zinc and copper.
The catalyst for synthesizing the 2, 3-dichloropyridine is characterized in that the specific surface area of the flaky active carbon carrier is 900m 2/g～1500m2/g, and the particle size is 20-30 meshes.
The catalyst for synthesizing the 2, 3-dichloropyridine is characterized in that the mass percentage of palladium in the catalyst is 0.05-0.2%, and the mass percentage of additive metal is 0.01-0.05%.
The catalyst for synthesizing the 2, 3-dichloropyridine is characterized in that the mass percentage of palladium in the catalyst is 0.1%, and the mass percentage of additive metal is 0.02%.
In addition, the invention also provides a method for preparing the catalyst, which is characterized by comprising the following steps:
step one, adding activated carbon into a tubular furnace, treating for 3 to 6 hours at 500 to 1000 ℃ in an ammonia gas atmosphere, then washing until the pH value of the activated carbon is 7 to 8, and drying the washed activated carbon to constant weight to obtain a pretreated activated carbon carrier;
Step two, uniformly mixing the dispersing agent A and the water solution of the soluble salt of the auxiliary metal to obtain an auxiliary metal solution;
Step three, adding the pretreated activated carbon carrier in the step one into the auxiliary metal solution in the step two, dipping for 4-10 hours, regulating the pH value of a dipping system to 8-10 by using sodium hydroxide solution, continuously dipping for 2 hours, filtering, and drying to constant weight to obtain the activated carbon loaded with auxiliary metal;
step four, ammonia water is used for adjusting the pH value of the dichloro tetra-ammonia palladium solution to 8.5, a dispersing agent B is added into the dichloro tetra-ammonia palladium solution with the pH value adjusted, and the mixture is stirred uniformly to obtain a palladium precursor solution;
step five, adding the activated carbon loaded with the auxiliary metal in the step three into the palladium precursor solution in the step four, uniformly stirring, soaking for 24 hours, filtering, and drying to constant weight;
And step six, reducing the dried product in the step five in hydrogen atmosphere at 150-250 ℃ for 2-4 hours to obtain the catalyst for synthesizing the 2, 3-dichloropyridine.
The method is characterized in that in the second step, the dispersing agent A is polyethylene glycol-400, polyvinylpyrrolidone or sodium polyacrylate, and the mass of the dispersing agent A is 1-5 times of the mass of the auxiliary agent metal.
The method is characterized in that the soluble salt of the auxiliary metal in the second step is nitrate.
The method is characterized in that in the fourth step, the dispersing agent B is hexamethylphosphoric triamide or 1-hydroxyethylene-1, 1-diphosphonic acid, and the molar quantity of the dispersing agent B is 0.5-4 times of the molar quantity of palladium.
Compared with the prior art, the invention has the following advantages:
1. The invention adopts ammonia gas high temperature treatment to pretreat the activated carbon, and washes the activated carbon to make the pH value of the activated carbon 7-8, and dries the activated carbon in an oven to constant weight at 120 ℃ to obtain the pretreated activated carbon. Can realize uniform nitrogen doping of the activated carbon, and can remove redundant ammonia adsorbed by the activated carbon in the subsequent washing process.
2. The mass percentage of palladium in the catalyst is 0.01-0.2%, and the mass percentage of additive metal is 0.005-0.05%. The metal content is greatly reduced, and the cost of the catalyst is greatly reduced.
3. According to the invention, the auxiliary metal and the noble metal palladium are respectively adsorbed, and matched dispersing agents are added in the two adsorption processes, so that the metal is uniformly dispersed, and the metal utilization rate is high.
4. The catalyst disclosed by the invention is simple in preparation method and good in repeatability, and the prepared metal particles are small and can be highly dispersed on a carrier, so that the service life of the catalyst is greatly prolonged.
5. The catalyst of the invention is used in the fixed bed reaction 2, 3-dichloropyridine synthesis, can be stably used for more than 90 days, has 100% of product conversion rate and more than 95% of selectivity, and has the advantages of high catalytic efficiency, low noble metal content, stable performance and the like.
The technical scheme of the invention is further described in detail through examples.
Detailed Description
Example 1
The catalyst of the embodiment comprises a flaky active carbon carrier and a metal component loaded on the carrier, wherein the metal component is palladium and auxiliary metal, the mass percentage of the palladium in the catalyst is 0.2%, the mass percentage of the auxiliary metal is 0.05%, and the auxiliary metal is iron. The specific surface area of the flaky active carbon carrier is 900m 2/g～1500m2/g, and the particle size is 20-30 meshes.
The preparation method of the catalyst of the embodiment comprises the following steps:
Step one, adding 80g of activated carbon into a tube furnace, treating for 5 hours at 500 ℃ in an ammonia gas atmosphere, then washing until the pH value of the activated carbon is 7-8, and drying the washed activated carbon to constant weight at 120 ℃ to obtain a pretreated activated carbon carrier;
Step two, 0.1809g of Fe (NO 3)3·9H2 O is dissolved in 80mL of deionized water, then 0.05g of polyethylene glycol-400 is added, and the mixture is uniformly mixed to obtain an auxiliary metal solution;
Step three, adding 50g of the pretreated active carbon carrier in the step one into the auxiliary metal solution in the step two, soaking for 5 hours, regulating the pH value of a soaking system to 8 by using a 2% sodium hydroxide solution, continuously soaking for 2 hours, filtering, and drying in an oven at 120 ℃ to constant weight to obtain the active carbon loaded with auxiliary metal;
Taking 0.2306g of tetra-ammine palladium dichloride to be dissolved in 80mL of deionized water, regulating the pH value of the tetra-ammine palladium dichloride solution to be 8.5 by ammonia water, adding 0.0842g of hexamethylphosphoric triamide into the tetra-ammine palladium dichloride solution with the pH value regulated, and uniformly stirring to obtain a palladium precursor solution;
Step five, adding the activated carbon loaded with the auxiliary metal in the step three into the palladium precursor solution in the step four, uniformly stirring, soaking for 24 hours, filtering, and drying in an oven at 120 ℃ to constant weight;
And step six, reducing the dried product in the step five in a hydrogen atmosphere at 150 ℃ for 4 hours to obtain the catalyst for synthesizing the 2, 3-dichloropyridine.
Comparative example 1
This comparative example differs from example 1 in that: and (3) without the carrier pretreatment process of ammonia gas in the step one, directly washing the activated carbon by deionized water to enable the pH value to be 7-8, and drying in an oven at 120 ℃ to constant weight to obtain the pretreated activated carbon.
Example 2
The catalyst of the embodiment comprises a flaky active carbon carrier and a metal component loaded on the carrier, wherein the metal component is palladium and auxiliary metal, the mass percentage of the palladium in the catalyst is 0.05%, the mass percentage of the auxiliary metal is 0.01%, and the auxiliary metal is nickel. The specific surface area of the flaky active carbon carrier is 900m 2/g～1500m2/g, and the particle size is 20-30 meshes.
The preparation method of the catalyst of the embodiment comprises the following steps:
Step one, adding 80g of activated carbon into a tube furnace, treating for 3 hours at 800 ℃ in an ammonia gas atmosphere, then washing until the pH value of the activated carbon is 7-8, and drying the washed activated carbon to constant weight at 120 ℃ to obtain a pretreated activated carbon carrier;
taking 0.0248g of Ni (NO 3)2·6H2 O is dissolved in 80mL of deionized water, then adding 0.02g of polyvinylpyrrolidone, and uniformly mixing to obtain an auxiliary agent metal solution;
Step three, adding 50g of the pretreated active carbon carrier in the step one into the auxiliary metal solution in the step two, soaking for 5 hours, regulating the pH value of a soaking system to be 10 by using a 2% sodium hydroxide solution, continuously soaking for 2 hours, filtering, and drying in an oven at 120 ℃ to constant weight to obtain the active carbon loaded with auxiliary metal;
step four, 0.0577g of dichlorotetraamminepalladium is taken and dissolved in 80mL of deionized water, the pH value of the dichlorotetraamminepalladium solution is regulated to 8.5 by ammonia water, 0.0536g of 1-hydroxyethylidene-1, 1-diphosphonic acid is added into the dichlorotetraamminepalladium solution with the pH value regulated, and the solution is stirred uniformly to obtain a palladium precursor solution;
Step five, adding the activated carbon loaded with the auxiliary metal in the step three into the palladium precursor solution in the step four, uniformly stirring, soaking for 24 hours, filtering, and drying in an oven at 120 ℃ to constant weight;
And step six, reducing the dried product in the step five in a hydrogen atmosphere at 250 ℃ for 2 hours to obtain the catalyst for synthesizing the 2, 3-dichloropyridine.
Comparative example 2
This comparative example differs from example 2in that: no step II is provided, and no auxiliary agent metal salt nickel nitrate hexahydrate and dispersing agent polyvinylpyrrolidone are added.
Example 3
The catalyst of the embodiment comprises a flaky active carbon carrier and a metal component loaded on the carrier, wherein the metal component is palladium and auxiliary metal, the mass percentage of the palladium in the catalyst is 0.175%, the mass percentage of the auxiliary metal is 0.04%, and the auxiliary metal is zinc. The specific surface area of the flaky active carbon carrier is 900m 2/g～1500m2/g, and the particle size is 20-30 meshes.
The preparation method of the catalyst of the embodiment comprises the following steps:
Step one, adding 80g of activated carbon into a tube furnace, treating for 4.5 hours at 600 ℃ in an ammonia gas atmosphere, then washing until the pH value of the activated carbon is 7-8, and drying the washed activated carbon to constant weight at 120 ℃ to obtain a pretreated activated carbon carrier;
Step two, 0.0909Zn (NO 3)2·6H2 O is dissolved in 80mL of deionized water, then 0.05g of sodium polyacrylate is added, and the mixture is uniformly mixed to obtain an auxiliary agent metal solution;
Step three, adding 50g of the pretreated active carbon carrier in the step one into the auxiliary metal solution in the step two, soaking for 5 hours, regulating the pH value of a soaking system to 9 by using a 2% sodium hydroxide solution, continuously soaking for 2 hours, filtering, and drying in an oven at 120 ℃ to constant weight to obtain the active carbon loaded with auxiliary metal;
taking 0.1845g of tetra-ammine palladium dichloride to be dissolved in 80mL of deionized water, regulating the pH value of the tetra-ammine palladium dichloride solution to be 8.5 by ammonia water, adding 0.1347g of hexamethylphosphoric triamide into the tetra-ammine palladium dichloride solution with the pH value regulated, and uniformly stirring to obtain a palladium precursor solution;
Step five, adding the activated carbon loaded with the auxiliary metal in the step three into the palladium precursor solution in the step four, uniformly stirring, soaking for 24 hours, filtering, and drying in an oven at 120 ℃ to constant weight;
And step six, reducing the dried product in the step five in a hydrogen atmosphere at 200 ℃ for 3 hours to obtain the catalyst for synthesizing the 2, 3-dichloropyridine.
Comparative example 3
The comparative example differs from example 3 in that: 0.1845g of palladium tetra-ammine dichloride in the fourth step is changed into 0.1458g of palladium chloride, and no step of adjusting the pH value to 8.5 by ammonia water is adopted.
Example 4
The catalyst of the embodiment comprises a flaky active carbon carrier and a metal component loaded on the carrier, wherein the metal component is palladium and auxiliary metal, the mass percentage of the palladium in the catalyst is 0.1%, the mass percentage of the auxiliary metal is 0.02%, and the auxiliary metal is copper. The specific surface area of the flaky active carbon carrier is 900m 2/g～1500m2/g, and the particle size is 20-30 meshes.
The preparation method of the catalyst of the embodiment comprises the following steps:
step one, adding 80g of activated carbon into a tube furnace, treating for 4 hours at 700 ℃ in an ammonia gas atmosphere, then washing until the pH value of the activated carbon is 7-8, and drying the washed activated carbon to constant weight at 120 ℃ to obtain a pretreated activated carbon carrier;
step two, 0.038g of Cu (NO 3)2·9H2 O is dissolved in 80mL of deionized water, then 0.03g of polyvinylpyrrolidone is added, and the mixture is uniformly mixed to obtain an auxiliary metal solution;
Step three, adding 50g of the pretreated activated carbon carrier in the step one into the auxiliary metal solution in the step two, soaking for 5 hours, regulating the pH value of a soaking system to 8.5 by using a 2% sodium hydroxide solution, continuously soaking for 2 hours, filtering, and drying in an oven at 120 ℃ to constant weight to obtain the activated carbon loaded with the auxiliary metal;
Taking 0.1153g of dichlorotetraammine palladium to be dissolved in 80mL of deionized water, regulating the pH value of the dichlorotetraammine palladium solution to 8.5 by ammonia water, adding 0.0857g of 1-hydroxyethylidene-1, 1-diphosphonic acid into the dichlorotetraammine palladium solution with the pH value regulated, and uniformly stirring to obtain a palladium precursor solution;
Step five, adding the activated carbon loaded with the auxiliary metal in the step three into the palladium precursor solution in the step four, uniformly stirring, soaking for 24 hours, filtering, and drying in an oven at 120 ℃ to constant weight;
And step six, reducing the dried product in the step five in a hydrogen atmosphere at 220 ℃ for 2.5 hours to obtain the catalyst for synthesizing the 2, 3-dichloropyridine.
Comparative example 4
This comparative example differs from example 4 in that: in the fourth step, 1-hydroxyethylidene-1, 1-diphosphonic acid is not added.
Example 5
The catalyst of the embodiment comprises a flaky active carbon carrier and a metal component loaded on the carrier, wherein the metal component is palladium, auxiliary metal iron and nickel, the mass percentage of the palladium in the catalyst is 0.01%, and the mass percentage of the auxiliary metal is 0.005% (iron 0.002% and nickel 0.003%). The specific surface area of the flaky active carbon carrier is 900m 2/g～1500m2/g, and the particle size is 20-30 meshes.
The preparation method of the catalyst of the embodiment comprises the following steps:
Step one, adding 80g of activated carbon into a tube furnace, treating for 3 hours at 1000 ℃ in an ammonia gas atmosphere, then washing until the pH value of the activated carbon is 7-8, and drying the washed activated carbon to constant weight at 120 ℃ to obtain a pretreated activated carbon carrier;
step two, taking 0.0073g of Fe (NO 3)3·9H2 O and 0.0068g of Ni (NO 3)2·6H2 O are dissolved in 80mL of deionized water, then adding 0.0125g of polyvinylpyrrolidone, and uniformly mixing to obtain an auxiliary metal solution;
Step three, adding 50g of the pretreated activated carbon carrier in the step one into the auxiliary metal solution in the step two, soaking for 10 hours, regulating the pH value of a soaking system to 8.5 by using a 2% sodium hydroxide solution, continuously soaking for 2 hours, filtering, and drying in an oven at 120 ℃ to constant weight to obtain the activated carbon loaded with the auxiliary metal;
Step four, 0.0115g of tetra-ammine palladium dichloride is taken and dissolved in 80mL of deionized water, the pH value of the tetra-ammine palladium dichloride solution is regulated to 8.5 by ammonia water, 0.0337g of hexamethylphosphoric triamide is added into the tetra-ammine palladium dichloride solution with the pH value regulated, and the palladium precursor solution is obtained by stirring uniformly;
Step five, adding the activated carbon loaded with the auxiliary metal in the step three into the palladium precursor solution in the step four, uniformly stirring, soaking for 24 hours, filtering, and drying in an oven at 120 ℃ to constant weight;
And step six, reducing the dried product in the step five in a hydrogen atmosphere at 220 ℃ for 2.5 hours to obtain the catalyst for synthesizing the 2, 3-dichloropyridine.
Example 6
The catalyst of the embodiment comprises a flaky active carbon carrier and metal components loaded on the carrier, wherein the metal components are palladium, auxiliary metals such as iron, nickel, zinc and copper, the mass percentage of the palladium in the catalyst is 0.1%, the mass percentage of the auxiliary metals in the catalyst is 0.02% (iron 0.005%, nickel 0.005%, zinc 0.005% and copper 0.005%), the specific surface area of the flaky active carbon carrier is 900m 2/g～1500m2/g, and the particle size is 20-30 meshes.
The preparation method of the catalyst of the embodiment comprises the following steps:
step one, adding 80g of activated carbon into a tube furnace, treating for 6 hours at 500 ℃ in an ammonia gas atmosphere, then washing until the pH value of the activated carbon is 7-8, and drying the washed activated carbon to constant weight at 120 ℃ to obtain a pretreated activated carbon carrier;
Step two, 0.0181g Fe(NO3)3·9H2O,0.0124g Ni(NO3)2·6H2O,0.0114Zn(NO3)2·6H2O,0.0095g Cu(NO3)2·9H2O is taken and dissolved in 80mL of deionized water, then 0.01g of sodium polyacrylate is added, and the mixture is uniformly mixed to obtain an auxiliary agent metal solution;
Step three, adding 50g of the pretreated activated carbon carrier in the step one into the auxiliary metal solution in the step two, soaking for 4 hours, regulating the pH value of a soaking system to 8.5 by using a 2% sodium hydroxide solution, continuously soaking for 2 hours, filtering, and drying in an oven at 120 ℃ to constant weight to obtain the activated carbon loaded with the auxiliary metal;
Taking 0.1153g of tetra-ammine palladium dichloride to be dissolved in 80mL of deionized water, regulating the pH value of the tetra-ammine palladium dichloride solution to be 8.5 by ammonia water, adding 0.1944g of 1-hydroxyethylidene-1, 1-diphosphonic acid into the tetra-ammine palladium dichloride solution with the pH value regulated, and uniformly stirring to obtain a palladium precursor solution;
Step five, adding the activated carbon loaded with the auxiliary metal in the step three into the palladium precursor solution in the step four, uniformly stirring, soaking for 24 hours, filtering, and drying in an oven at 120 ℃ to constant weight;
And step six, reducing the dried product in the step five in a hydrogen atmosphere at 220 ℃ for 2.5 hours to obtain the catalyst for synthesizing the 2, 3-dichloropyridine.
Example 7
The method for synthesizing 2, 3-dichloropyridine by catalyzing 2.3.6-trichloropyridine through hydrogenation by using the catalyst comprises the following steps: 10g of catalyst sample is weighed and filled on normal pressure fixed bed catalyst performance evaluation equipment, nitrogen is firstly introduced to replace air in a reactor, then hydrogen is changed into the catalyst, and the hydrogen is introduced, wherein the gas flow is 100ml/min. The reaction tube temperature was raised to 200 ℃ at a rate of 2 ℃/min for 30min and then lowered to the reaction temperature. 2.3.6-trichloropyridine is dissolved into methanol solution to prepare 2.3.6-trichloropyridine solution, the solution of 2,3, 6-trichloropyridine is conveyed into a fixed bed reactor through a metering pump, contacts with hydrogen to perform dechlorination reaction on a catalyst, materials after the reaction flow out of the bottom of a reaction tube, after condensation and gas-liquid separation, the redundant hydrogen is discharged out of the reactor, liquid phase products are collected, and sampling and gas chromatography analysis are performed. The mass space velocity of 2.3.6-trichloropyridine is 0.2h -1.
Results and discussion
The catalysts of examples 1,2, 3, 4,5 and comparative examples 1,2, 3, 4 were used to catalyze the hydrogenation of 2,3, 6-trichloropyridine to 2, 3-dichloropyridine according to the method of example 6, respectively, and the reaction results are shown in the following table.
TABLE 1 catalytic Effect of catalyst for hydrogenation of 2,3, 6-trichloropyridine to 2, 3-dichloropyridine
As can be seen from Table 1, the catalyst prepared by the invention is suitable for the reaction of catalyzing 2.3.6-trichloropyridine to synthesize 2.3-dichloropyridine, and has the advantages of higher conversion rate and selectivity, 100% of product conversion rate, more than 95% of selectivity and high catalytic efficiency due to doping modification of active carbon, addition of additive metal and auxiliary metal adaptive dispersing agent, use of tetraaminopalladium dichloride and use of active metal palladium adaptive dispersing agent.
Using the catalyst prepared in example 1 as an example, the reaction was carried out under the reaction conditions of example 7, and the reaction results were shown in the following table for 90 days.
TABLE 2 catalytic Effect of the catalyst of example 1 on the hydrogenation of 2,3, 6-trichloropyridine to 2, 3-dichloropyridine for 90 days
As can be seen from Table 2, the catalyst of the invention can be stably used for more than 90 days, the conversion rate of the product is 100%, the selectivity is maintained at more than 95%, and the catalyst has the advantages of high catalytic efficiency, low noble metal content, stable performance and the like.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modification, variation and equivalent variation of the above embodiment according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.

Claims (4)

1. The application of the catalyst in catalyzing 2,3, 6-trichloropyridine to synthesize 2, 3-dichloropyridine is characterized in that the catalyst comprises a flaky active carbon carrier and a metal component loaded on the carrier, wherein the metal component comprises 0.01-0.2% of palladium and 0.005-0.05% of auxiliary metal by mass percent, and the auxiliary metal is one or more of iron, nickel, zinc and copper; the specific surface area of the flaky active carbon carrier is 900m 2/g～1500m2/g, and the particle size is 20-30 meshes;
the preparation method of the catalyst comprises the following steps:
step one, adding activated carbon into a tubular furnace, treating for 3 to 6 hours at 500 to 1000 ℃ in an ammonia gas atmosphere, then washing until the pH value of the activated carbon is 7 to 8, and drying the washed activated carbon to constant weight to obtain a pretreated activated carbon carrier;
Step two, uniformly mixing the dispersing agent A and the water solution of the soluble salt of the auxiliary metal to obtain an auxiliary metal solution; the dispersing agent A is polyethylene glycol-400, polyvinylpyrrolidone or sodium polyacrylate, and the mass of the dispersing agent A is 1-5 times of the mass of the auxiliary agent metal;
Step three, adding the pretreated activated carbon carrier in the step one into the auxiliary metal solution in the step two, dipping for 4-10 hours, regulating the pH value of a dipping system to 8-10 by using sodium hydroxide solution, continuously dipping for 2 hours, filtering, and drying to constant weight to obtain the activated carbon loaded with auxiliary metal;
Step four, ammonia water is used for adjusting the pH value of the dichloro tetra-ammonia palladium solution to 8.5, a dispersing agent B is added into the dichloro tetra-ammonia palladium solution with the pH value adjusted, and the mixture is stirred uniformly to obtain a palladium precursor solution; the dispersing agent B is hexamethylphosphoric triamide or 1-hydroxyethylene-1, 1-diphosphonic acid, and the molar quantity of the dispersing agent B is 0.5-4 times of the molar quantity of palladium;
step five, adding the activated carbon loaded with the auxiliary metal in the step three into the palladium precursor solution in the step four, uniformly stirring, soaking for 24 hours, filtering, and drying to constant weight;
And step six, reducing the dried product in the step five in hydrogen atmosphere at 150-250 ℃ for 2-4 hours to obtain the catalyst for synthesizing the 2, 3-dichloropyridine.
2. The application of the catalyst according to claim 1 in catalyzing 2,3, 6-trichloropyridine to synthesize 2, 3-dichloropyridine, wherein the mass percentage of palladium in the catalyst is 0.05-0.2%, and the mass percentage of additive metal is 0.01-0.05%.
3. The use of a catalyst according to claim 2 for catalyzing the hydrogenation of 2,3, 6-trichloropyridine to synthesize 2, 3-dichloropyridine, wherein the mass percentage of palladium in the catalyst is 0.1%, and the mass percentage of additive metal is 0.02%.
4. The use of a catalyst according to claim 1 for catalyzing the hydrogenation of 2,3, 6-trichloropyridine to 2, 3-dichloropyridine, wherein the soluble salt of the promoter metal in step two is a nitrate.
CN202111669247.9A 2021-12-30 2021-12-30 Catalyst for synthesizing 2, 3-dichloropyridine and preparation method thereof Active CN114192140B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111669247.9A CN114192140B (en) 2021-12-30 2021-12-30 Catalyst for synthesizing 2, 3-dichloropyridine and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111669247.9A CN114192140B (en) 2021-12-30 2021-12-30 Catalyst for synthesizing 2, 3-dichloropyridine and preparation method thereof

Publications (2)

Publication Number Publication Date
CN114192140A CN114192140A (en) 2022-03-18
CN114192140B true CN114192140B (en) 2024-06-25

Family

ID=80657723

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111669247.9A Active CN114192140B (en) 2021-12-30 2021-12-30 Catalyst for synthesizing 2, 3-dichloropyridine and preparation method thereof

Country Status (1)

Country Link
CN (1) CN114192140B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115400750B (en) * 2022-09-29 2024-06-07 西安凯立新材料股份有限公司 Catalyst for preparing saturated ketone by hydrogenating multi-double bond unsaturated ketone, and preparation method and application thereof
CN116351412B (en) * 2023-01-17 2024-05-28 西安凯立新材料股份有限公司 Supported bimetallic catalyst for antioxidant 44PD synthesis and catalytic method thereof
CN116059998A (en) * 2023-01-19 2023-05-05 利尔化学股份有限公司 Bimetallic catalyst and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109535173A (en) * 2018-12-10 2019-03-29 西安凯立新材料股份有限公司 A kind of high method applied active palladium carbon catalyst and catalyze and synthesize biotin
CN110961110A (en) * 2019-12-23 2020-04-07 上海华谊（集团）公司 Catalyst and application thereof in hydrodechlorination of 2,3, 6-trichloropyridine

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2523753B2 (en) * 1988-01-27 1996-08-14 ダイセル化学工業株式会社 Method for producing 2,3-dichloropyridine
CN102153507B (en) * 2011-03-13 2012-11-21 联化科技股份有限公司 Preparation method of 2,3-dichloropyridine
CN109453786B (en) * 2018-12-03 2020-10-09 西安凯立新材料股份有限公司 Catalyst for preparing 2, 3-dichloropyridine and preparation method and application thereof
CN110280239B (en) * 2019-07-23 2022-05-03 西安凯立新材料股份有限公司 Catalyst for synthesizing 2, 3-dichloropyridine and preparation method and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109535173A (en) * 2018-12-10 2019-03-29 西安凯立新材料股份有限公司 A kind of high method applied active palladium carbon catalyst and catalyze and synthesize biotin
CN110961110A (en) * 2019-12-23 2020-04-07 上海华谊（集团）公司 Catalyst and application thereof in hydrodechlorination of 2,3, 6-trichloropyridine

Also Published As

Publication number Publication date
CN114192140A (en) 2022-03-18

Similar Documents

Publication Publication Date Title
CN114192140B (en) Catalyst for synthesizing 2, 3-dichloropyridine and preparation method thereof
CN113019414B (en) Hydrogenation catalyst, preparation method and application thereof
CN101502802B (en) Preparation method of catalyst for continuous production of succinic anhydride from hydrogenation of maleic anhydride
CN110280239B (en) Catalyst for synthesizing 2, 3-dichloropyridine and preparation method and application thereof
CN111185237B (en) Selective hydrogenation catalyst, preparation method and application thereof
CN112371173B (en) Platinum-carbon catalyst applied to hydrogenation of m-nitrobenzenesulfonic acid and preparation method thereof
CN110270375B (en) Unsaturated carbon-carbon triple bond selective hydrogenation catalyst and preparation method thereof
CN112570015B (en) Molecular sieve catalyst for packaging Pd-based alloy and preparation method and application thereof
CN111715268A (en) Catalyst with nitrogen-doped carbon material as carrier and preparation method thereof
CN111153768A (en) Synthetic method of isohexide
CN114160145A (en) Catalyst for preparing ethanol by acetic acid hydrogenation and preparation method thereof
CN113731465A (en) Pd/N-CNTs catalyst, and preparation method and application thereof
CN113600181B (en) Preparation method of nano palladium supported catalyst
CN109453762A (en) A kind of preparation method and application of modified clay mine loaded palladium catalyst
CN113713841B (en) Acetylene copper chloride-based catalyst and preparation method and application thereof
CN110841635A (en) High-dispersion Pd-Ag supported acetylene hydrogenation catalyst and preparation method thereof
CN110508277A (en) High-dispersion palladium nanoparticle catalyst and preparation method and application thereof
CN105749913B (en) The catalyst and acetate preparation of ethanol through hydrogenation method of acetate preparation of ethanol through hydrogenation
CN109012751B (en) Catalyst with carbene-palladium structure and application thereof in selective hydrogenation reaction of acetylene
CN111167444A (en) Supported Pd-based catalyst and preparation method and application thereof
CN112371170B (en) Heterojunction nano composite catalyst and preparation method and application thereof
CN114100653B (en) Nitride supported palladium catalyst and preparation method and application thereof
CN112973791B (en) Preparation method of Schiff base modified cellulose supported palladium catalyst
CN110624571B (en) Catalyst for synthesizing 3, 5-dichloroaniline and preparation method and application thereof
CN114345336A (en) Transition metal molybdenum modified palladium silver-alumina catalyst, and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant