CN104174394A - Catalyst for preparing 2(p)-cyanobenzylchloride by selective dechlorination and catalytic method - Google Patents

Catalyst for preparing 2(p)-cyanobenzylchloride by selective dechlorination and catalytic method Download PDF

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CN104174394A
CN104174394A CN201410394623.1A CN201410394623A CN104174394A CN 104174394 A CN104174394 A CN 104174394A CN 201410394623 A CN201410394623 A CN 201410394623A CN 104174394 A CN104174394 A CN 104174394A
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catalyst
metal
cyano group
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solid material
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CN104174394B (en
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万克柔
林涛
程杰
张之翔
曾永康
高武
陈伟
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XI'AN CATALYST CHEMICAL CO Ltd
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XI'AN CATALYST CHEMICAL CO Ltd
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Abstract

The invention discloses a catalyst for preparing 2(p)-cyanobenzylchloride by selective dechlorination, which comprises an Al2O3 carrier, Pd, a metal M1 and a metal M2, wherein the Pd is loaded on the Al2O3 carrier, the content of the Pd in the catalyst is 0.1-1% by mass, the content of the metal M1 is 0.05-3% by mass, and the content of the metal M2 is 0.05-2% by mass; and the metal M1 is Pt or Sn; and the metal M2 is K, Zn or Ce. In addition, the invention also discloses a method for preparing 2(p)-cyanobenzylchloride by selective catalytic dechlorination through using the catalyst. The catalyst disclosed by the invention has high catalytic activity and selectivity, and can selectively catalytically produce 2(p)-cyan benzal chloride in a waste liquid produced by 2(p)-cyanobenzylchloride, the conversion rate of 2(p)-cyan benzal chloride is greater than 98%, and the selectivity of products 2(p)-cyanobenzylchloride is greater than 98%.

Description

Selective dechlorination preparation adjacent (to) catalyst and the catalysis process of cyano group benzyl chloride
Technical field
The invention belongs to catalysis dechlorination technology field, be specifically related to a kind of selective dechlorination preparation adjacent (to) catalyst and the catalysis process of cyano group benzyl chloride.
Background technology
Adjacent (to) cyano group benzyl chloride is synthetic fluorescent whitening agent ER, OB-1,4, the important source material of 4 '-bis-benzoxazoles talan, be also synthetic adjacent (to) intermediate of the fine chemicals such as cyano group benzylamine.Adjacent (to) cyano group benzyl chloride normally taking adjacent (to) cyano group toluene is as raw material, under the condition of illumination, prepare with chlorine generation optical chlorinating reaction; Due to adjacent (to) chlorination reaction of cyano group toluene is typical consecutive reaction, so an introduce chlorine gas to make reaction, adjacent (to) the highest yield of cyano group benzyl chloride is no more than 78%.Adjacent (to) cyano group benzal chloride be produce adjacent (to) Main By product of cyano group benzyl chloride, due to adjacent (to) cyano group benzyl chloride and neighbour (to) cyano group benzal chloride can form eutectic, when adjacent in chlorated liquid (to) cyano group benzyl chloride content is lower than 30% time, adjacent (to) cyano group benzyl chloride is not with regard to crystallization out, both boiling points are high, separated is had any problem, adjacent (to) cyano group benzal chloride also do not have Application and Development, so can produce a large amount of waste reaction solutions, the chief component of waste liquid be adjacent (to) cyano group benzyl chloride, adjacent (to) cyano group toluene and neighbour (to) cyano group benzal chloride.
The present invention is directed to above-mentioned waste liquid, selective dechlorination technology has been proposed, make neighbour in waste liquid (to) dechlorination of cyano group benzal chloride generates corresponding cyano group benzyl chloride, waste liquid become neighbour (to) cyano group benzyl chloride and neighbour (to) cyano group toluene two components, adjacent (to) the easy Crystallization Separation of cyano group benzyl chloride, adjacent (to) cyano group toluene is reused as raw material.This technique to high-efficiency environmental protection, energy consumption is low, make neighbour (to) production efficiency and the cost of cyano group benzyl chloride decrease, and turns waste into wealth, solved the processing problem of waste liquid, and produced considerable economic worth.
Summary of the invention
Technical problem to be solved by this invention is for above-mentioned the deficiencies in the prior art, provide a kind of selective dechlorination preparation adjacent (to) catalyst of cyano group benzyl chloride.This catalyst has higher catalytic activity and selective, adjacent (to) conversion ratio of cyano group benzal chloride is greater than 98%, product neighbour (to) cyano group benzyl chloride be selectively greater than 98%, the catalyst single life-span is not less than 1500 hours, catalyst is renewable, regenerates and still has higher catalytic activity and selective after 5 times.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of selective dechlorination preparation adjacent (to) catalyst of cyano group benzyl chloride, it is characterized in that, comprise Al 2o 3carrier, is carried on Al 2o 3pd on carrier, metal M 1and metal M 2; In described catalyst, the quality percentage composition of Pd is 0.1%～1%, metal M 1quality percentage composition be 0.05%～3%, metal M 2quality percentage composition be 0.05%～2%; Described metal M 1for Pt or Sn; Described metal M 2for K, Zn or Ce.
Above-mentioned selective dechlorination preparation adjacent (to) catalyst of cyano group benzyl chloride, it is characterized in that, in described catalyst, the quality percentage composition of Pd is 0.3%～0.8%, metal M 1quality percentage composition be 0.5%～2%, metal M 2quality percentage composition be 0.2%～1%.
Above-mentioned selective dechlorination preparation adjacent (to) catalyst of cyano group benzyl chloride, it is characterized in that, in described catalyst, the quality percentage composition of Pd is 0.5%, metal M 1quality percentage composition be 1%, metal M 2quality percentage composition be 0.5%.
Above-mentioned selective dechlorination preparation adjacent (to) catalyst of cyano group benzyl chloride, it is characterized in that described Al 2o 3carrier is γ-Al 2o 3, Al 2o 3the average grain diameter of carrier is 1mm～2mm, and specific area is 150m 2/ g～250m 2/ g.
Above-mentioned selective dechlorination preparation adjacent (to) catalyst of cyano group benzyl chloride, it is characterized in that, the preparation method of described catalyst is:
Step 1, the presoma of Pd is dissolved in rare nitric acid, obtains solution A, then aluminium oxide is immersed in solution A, stir 1h～2h after having the solution A of aluminium oxide to be heated to 60 DEG C～65 DEG C submergence, filter and obtain solid material A; The presoma of described Pd is the hydrochloride of Pd or the nitrate of Pd;
Step 2, the A of solid material described in step 1 is dried, then, by the solid material A roasting 3h～5h at 550 DEG C～600 DEG C after drying, obtaining load after cooling has the catalyst precursor of Pd;
Step 3, by metal M 1presoma be dissolved in rare nitric acid, obtain solution B, then there is the catalyst precursor of Pd to be immersed in solution B load described in step 2, stir 1h～2h after having load to have the solution B of the catalyst precursor of Pd to be heated to 60 DEG C～65 DEG C submergence, filter and obtain solid material B; Described metal M 1presoma be metal M 1hydrochloride or metal M 1nitrate;
Step 4, the B of solid material described in step 3 is dried, then, by the solid material B roasting 3h～5h at 550 DEG C～600 DEG C after drying, obtaining load after cooling has Pd and metal M 1catalyst precursor;
Step 5, by metal M 2presoma be dissolved in rare nitric acid, obtain solution C, then load described in step 4 is had to Pd and metal M 1catalyst precursor be immersed in solution C, have load to have Pd and metal M submergence 1the solution C of catalyst precursor stir 1h～2h after being heated to 60 DEG C～65 DEG C, filter and obtain solid material C; Described metal M 2presoma be metal M 2hydrochloride or metal M 2nitrate;
Step 6, the C of solid material described in step 5 is dried, then, by the solid material C roasting 3h～5h at 550 DEG C～600 DEG C after drying, obtain catalyst precursor after cooling;
Step 7, adopt hydrogen to reduce processing to catalyst precursor described in step 6, obtain the catalyst of o-fluoronitrobenzene Hydrogenation for adjacent fluoroaniline.
Above-mentioned selective dechlorination preparation adjacent (to) catalyst of cyano group benzyl chloride, it is characterized in that, described in step 1, step 3 and step 5, the mass concentration of rare nitric acid is 1%～2%.
In addition, the present invention also provide the above-mentioned catalyst selectivity catalysis dechlorination of a kind of employing prepare neighbour (to) method of cyano group benzyl chloride, it is characterized in that, the method comprises the following steps:
Step 1, by Catalyst packing in fixed bed reactors, at room temperature in the fixed bed reactors of catalyst, pass into nitrogen to the air emptying in fixed bed reactors to being filled with, then to the hydrogen that passes into nitrogen dilution in fixed bed reactors, with the heating rate of 0.1 DEG C/min～1 DEG C/min, the temperature of fixed bed reactors is risen to 200 DEG C～280 DEG C; In the reducibility gas of nitrogen dilution, the volumn concentration of reducibility gas is 15%～20%; The flow of the reducibility gas of nitrogen dilution and the mass ratio of catalyst are (10～20): 1, and wherein the unit of flow is mL/min, the unit of quality is g;
Step 2, will produce adjacent (to) waste liquid that produces of cyano group benzyl chloride is as material liquid, treat that in step 1, the temperature of fixed bed reactors is down to reaction temperature, stablize to pass in the backward fixed bed reactors of 30min～60min and be preheated to the hydrogen of 75 DEG C～125 DEG C and be preheated to the material liquid of 75 DEG C～125 DEG C, under reaction temperature and under the effect of catalyst to the neighbour in material liquid (to) cyano group benzal chloride carries out catalysis dechlorination reaction; 80 DEG C～130 DEG C of described reaction temperatures;
Step 3, reacted catalysis dechlorination in step 2 material is sent into condensation in condenser, then condensed material is carried out to Separation of Solid and Liquid, obtain solid neighbour (to) cyano group benzyl chloride.
Above-mentioned method, is characterized in that, neighbour in hydrogen described in step 2 and material liquid (to) mol ratio of cyano group benzal chloride is (10～60): 1.
Above-mentioned method, is characterized in that, the volume space velocity of material liquid described in step 2 is 0.01mL/gcat/hr～0.5mL/gcat/hr.
Above-mentioned method, is characterized in that, the condensation temperature of condenser described in step 3 is 5 DEG C～8 DEG C.
The present invention compared with prior art has the following advantages:
1, catalyst of the present invention has higher catalytic activity and selective, optionally catalytic production neighbour (to) cyano group benzyl chloride produce waste liquid in neighbour (to) cyano group benzal chloride, adjacent (to) conversion ratio of cyano group benzal chloride is greater than 98%, product neighbour (to) cyano group benzyl chloride be selectively greater than 98%, the catalyst single life-span is not less than 1500 hours, catalyst is renewable, regenerates and still has higher catalytic activity and selective after 5 times.
2, catalysis process of the present invention adopts fixed bed reactors, can be continuous adjacent to producing in industry (to) waste liquid that produces of cyano group benzyl chloride carry out selective dechlorination neighbour processed (to) cyano group benzyl chloride, reaction condition gentleness, easily controls.
3, adopt the selective dechlorination of the inventive method neighbour processed (to) cyano group benzyl chloride, treating capacity is large, simple to operate, safety and environmental protection, energy consumption is low, any murder by poisoning ion undopes in product.
4, adopt the selective dechlorination of method of the present invention neighbour processed (to) cyano group benzyl chloride, the byproduct hydrogen chloride of reaction can, through ammonia absorption, obtain ammonium chloride, can reach the zero-emission of pollutant.
5, method of the present invention be one efficient process adjacent (to) friendly process of cyano group benzal chloride, make to produce in industry adjacent (to) waste liquid that produces of cyano group benzyl chloride well utilized, and produces economic worth.
Below by embodiment, technical solution of the present invention is described in further detail.
Detailed description of the invention
Catalysts and its preparation method of the present invention is described by following examples 1 to embodiment 8:
Embodiment 1
The catalyst of the present embodiment comprises Al 2o 3carrier, is carried on Al 2o 3pd, Sn and Zn on carrier; The quality percentage composition that the quality percentage composition that in described catalyst, the quality percentage composition of Pd is 0.3%, Sn is 0.9%, Zn is 0.9%; Described Al 2o 3carrier is γ-Al 2o 3, Al 2o 3the average grain diameter of carrier is 1mm, and specific area is 150m 2/ g.
The preparation method of the catalyst of the present embodiment is:
Step 1, be in rare nitric acid of 1% by be dissolved in mass concentration containing the palladium bichloride of 0.3g palladium, obtain solution A, then by 97.9g γ-Al 2o 3be immersed in solution A, submergence is had to γ-Al 2o 3solution A stir 2h after being heated to 60 DEG C, filter and obtain solid material A;
Step 2, the A of solid material described in step 1 is dried to 4h at 120 DEG C, then by the solid material A roasting 4h at 580 DEG C after drying, obtaining load after cooling has the catalyst precursor of Pd;
Step 3, be in rare nitric acid of 1% by be dissolved in mass concentration containing the stannous chloride of 0.9g tin, obtain solution B, then there is the catalyst precursor of Pd to be immersed in solution B load described in step 2, after having load to have the solution B of the catalyst precursor of Pd to be heated to 60 DEG C submergence, stir 2h, filter and obtain solid material B;
Step 4, the B of solid material described in step 3 is dried to 4h at 120 DEG C, then by the solid material B roasting 4h at 580 DEG C after drying, obtaining load after cooling has the catalyst precursor of Pd and Sn;
Step 5, be in rare nitric acid of 1% by be dissolved in mass concentration containing the zinc nitrate of 0.9g zinc, obtain solution C, then there is the catalyst precursor of Pd and Sn to be immersed in solution C load described in step 4, after having load to have the solution C of the catalyst precursor of Pd and Sn to be heated to 60 DEG C submergence, stir 2h, filter and obtain solid material C;
Step 6, the C of solid material described in step 5 is dried to 4h at 120 DEG C, then by the solid material C roasting 4h at 580 DEG C after drying, obtain catalyst precursor after cooling;
Step 7, adopt hydrogen to reduce processing to catalyst precursor described in step 6, obtain the catalyst of o-fluoronitrobenzene Hydrogenation for adjacent fluoroaniline; The temperature of described reduction processing is 200 DEG C, and the time is 3h.
Embodiment 2
The catalyst of the present embodiment comprises Al 2o 3carrier, is carried on Al 2o 3pd, Pt and K on carrier; The quality percentage composition that the quality percentage composition that in described catalyst, the quality percentage composition of Pd is 0.5%, Pt is 0.5%, K is 2.0%; Described Al 2o 3carrier is γ-Al 2o 3, Al 2o 3the average grain diameter of carrier is 1mm, and specific area is 200m 2/ g.
The preparation method of the catalyst of the present embodiment is:
Step 1, be in rare nitric acid of 2% by be dissolved in mass concentration containing the palladium bichloride of 0.5g palladium, obtain solution A, then by 97g γ-Al 2o 3be immersed in solution A, submergence is had to γ-Al 2o 3solution A stir 1h after being heated to 65 DEG C, filter and obtain solid material A;
Step 2, the A of solid material described in step 1 is dried to 6h at 120 DEG C, then by the solid material A roasting 5h at 550 DEG C after drying, obtaining load after cooling has the catalyst precursor of Pd;
Step 3, be in rare nitric acid of 2% by be dissolved in mass concentration containing the platinum nitrate of 0.5g platinum, obtain solution B, then there is the catalyst precursor of Pd to be immersed in solution B load described in step 2, after having load to have the solution B of the catalyst precursor of Pd to be heated to 65 DEG C submergence, stir 1h, filter and obtain solid material B;
Step 4, the B of solid material described in step 3 is dried to 6h at 120 DEG C, then by the solid material B roasting 5h at 550 DEG C after drying, obtaining load after cooling has the catalyst precursor of Pd and Pt;
Step 5, be in rare nitric acid of 2% by be dissolved in mass concentration containing the potassium chloride of 2.0g potassium, obtain solution C, then there is the catalyst precursor of Pd and Pt to be immersed in solution C load described in step 4, after having load to have the solution C of the catalyst precursor of Pd and Pt to be heated to 65 DEG C submergence, stir 1h, filter and obtain solid material C;
Step 6, the C of solid material described in step 5 is dried to 6h at 120 DEG C, then by the solid material C roasting 5h at 550 DEG C after drying, obtain catalyst precursor after cooling;
Step 7, adopt hydrogen to reduce processing to catalyst precursor described in step 6, obtain the catalyst of o-fluoronitrobenzene Hydrogenation for adjacent fluoroaniline; The temperature of described reduction processing is 280 DEG C, and the time is 2h.
Embodiment 3
The catalyst of the present embodiment comprises Al 2o 3carrier, is carried on Al 2o 3pd, Pt and K on carrier; The quality percentage composition that the quality percentage composition that in described catalyst, the quality percentage composition of Pd is 0.8%, Pt is 0.5%, K is 1%; Described Al 2o 3carrier is γ-Al 2o 3, Al 2o 3the average grain diameter of carrier is 1.5mm, and specific area is 250m 2/ g.
The preparation method of the catalyst of the present embodiment is:
Step 1, be in rare nitric acid of 1.5% by be dissolved in mass concentration containing the palladium bichloride of 0.8g palladium, obtain solution A, then by 97.7g γ-Al 2o 3be immersed in solution A, submergence is had to γ-Al 2o 3solution A stir 1.5h after being heated to 62 DEG C, filter and obtain solid material A;
Step 2, the A of solid material described in step 1 is dried to 5h at 120 DEG C, then by the solid material A roasting 5h at 550 DEG C after drying, obtaining load after cooling has the catalyst precursor of Pd;
Step 3, be in rare nitric acid of 2% by be dissolved in mass concentration containing the platinum nitrate of 0.5g platinum, obtain solution B, then there is the catalyst precursor of Pd to be immersed in solution B load described in step 2, after having load to have the solution B of the catalyst precursor of Pd to be heated to 62 DEG C submergence, stir 1.5h, filter and obtain solid material B;
Step 4, the B of solid material described in step 3 is dried to 5h at 120 DEG C, then by the solid material B roasting 3h at 600 DEG C after drying, obtaining load after cooling has the catalyst precursor of Pd and Pt;
Step 5, be in rare nitric acid of 2% by be dissolved in mass concentration containing the potassium nitrate of 1.0g potassium, obtain solution C, then there is the catalyst precursor of Pd and Pt to be immersed in solution C load described in step 4, after having load to have the solution C of the catalyst precursor of Pd and Pt to be heated to 62 DEG C submergence, stir 1.5h, filter and obtain solid material C;
Step 6, the C of solid material described in step 5 is dried to 5h at 120 DEG C, then by the solid material C roasting 3h at 600 DEG C after drying, obtain catalyst precursor after cooling;
Step 7, adopt hydrogen to reduce processing to catalyst precursor described in step 6, obtain the catalyst of o-fluoronitrobenzene Hydrogenation for adjacent fluoroaniline; The temperature of described reduction processing is 250 DEG C, and the time is 2.5h.
Embodiment 4
The catalyst of the present embodiment comprises Al 2o 3carrier, is carried on Al 2o 3pd, Sn and Zn on carrier; The quality percentage composition that the quality percentage composition that in described catalyst, the quality percentage composition of Pd is 1.0%, Sn is 3.0%, Zn is 2.0%; Described Al 2o 3carrier is γ-Al 2o 3, Al 2o 3the average grain diameter of carrier is 2mm, and specific area is 250m 2/ g.
The preparation method of the catalyst of the present embodiment is:
Step 1, be in rare nitric acid of 1.5% by be dissolved in mass concentration containing the palladium nitrate of 1.0g palladium, obtain solution A, then by 94.0g γ-Al 2o 3be immersed in solution A, submergence is had to γ-Al 2o 3solution A stir 1h after being heated to 65 DEG C, filter and obtain solid material A;
Step 2, the A of solid material described in step 1 is dried to 5h at 120 DEG C, then by the solid material A roasting 3h at 600 DEG C after drying, obtaining load after cooling has the catalyst precursor of Pd;
Step 3, be in rare nitric acid of 1.5% by be dissolved in mass concentration containing the stannous chloride of 3.0g tin, obtain solution B, then there is the catalyst precursor of Pd to be immersed in solution B load described in step 2, after having load to have the solution B of the catalyst precursor of Pd to be heated to 62 DEG C submergence, stir 1.5h, filter and obtain solid material B;
Step 4, the B of solid material described in step 3 is dried to 5h at 120 DEG C, then by the solid material B roasting 3h at 600 DEG C after drying, obtaining load after cooling has the catalyst precursor of Pd and Sn;
Step 5, be in rare nitric acid of 1.5% by be dissolved in mass concentration containing the zinc chloride of 2.0g zinc, obtain solution C, then there is the catalyst precursor of Pd and Sn to be immersed in solution C load described in step 4, after having load to have the solution C of the catalyst precursor of Pd and Sn to be heated to 62 DEG C submergence, stir 1.5h, filter and obtain solid material C;
Step 6, the C of solid material described in step 5 is dried to 5h at 120 DEG C, then by the solid material C roasting 3h at 600 DEG C after drying, obtain catalyst precursor after cooling;
Step 7, adopt hydrogen to reduce processing to catalyst precursor described in step 6, obtain the catalyst of o-fluoronitrobenzene Hydrogenation for adjacent fluoroaniline; The temperature of described reduction processing is 260 DEG C, and the time is 2h.
Embodiment 5
The catalyst of the present embodiment comprises Al 2o 3carrier, is carried on Al 2o 3pd, Pt and Ce on carrier; The quality percentage composition that the quality percentage composition that in described catalyst, the quality percentage composition of Pd is 0.5%, Pt is 2.0%, Ce is 0.2%; Described Al 2o 3carrier is γ-Al 2o 3, Al 2o 3the average grain diameter of carrier is 1mm, and specific area is 200m 2/ g.
The preparation method of the catalyst of the present embodiment is:
Step 1, be in rare nitric acid of 2% by be dissolved in mass concentration containing the palladium bichloride of 0.5g palladium, obtain solution A, then by 97.3g γ-Al 2o 3be immersed in solution A, submergence is had to γ-Al 2o 3solution A stir 1h after being heated to 65 DEG C, filter and obtain solid material A;
Step 2, the A of solid material described in step 1 is dried to 6h at 120 DEG C, then by the solid material A roasting 5h at 550 DEG C after drying, obtaining load after cooling has the catalyst precursor of Pd;
Step 3, be in rare nitric acid of 2% by be dissolved in mass concentration containing the platinum nitrate of 2.0g platinum, obtain solution B, then there is the catalyst precursor of Pd to be immersed in solution B load described in step 2, after having load to have the solution B of the catalyst precursor of Pd to be heated to 65 DEG C submergence, stir 1h, filter and obtain solid material B;
Step 4, the B of solid material described in step 3 is dried to 6h at 120 DEG C, then by the solid material B roasting 5h at 550 DEG C after drying, obtaining load after cooling has the catalyst precursor of Pd and Pt;
Step 5, be in rare nitric acid of 2% by be dissolved in mass concentration containing the cerous nitrate of 0.2g cerium, obtain solution C, then there is the catalyst precursor of Pd and Pt to be immersed in solution C load described in step 4, after having load to have the solution C of the catalyst precursor of Pd and Pt to be heated to 65 DEG C submergence, stir 1h, filter and obtain solid material C;
Step 6, the C of solid material described in step 5 is dried to 6h at 120 DEG C, then by the solid material C roasting 5h at 550 DEG C after drying, obtain catalyst precursor after cooling;
Step 7, adopt hydrogen to reduce processing to catalyst precursor described in step 6, obtain the catalyst of o-fluoronitrobenzene Hydrogenation for adjacent fluoroaniline; The temperature of described reduction processing is 220 DEG C, and the time is 3h.
Embodiment 6
The catalyst of the present embodiment comprises Al 2o 3carrier, is carried on Al 2o 3pd, Sn and Ce on carrier; The quality percentage composition that the quality percentage composition that in described catalyst, the quality percentage composition of Pd is 0.1%, Sn is 0.05%, Ce is 0.05%; Described Al 2o 3carrier is γ-Al 2o 3, Al 2o 3the average grain diameter of carrier is 1mm, and specific area is 150m 2/ g.
The preparation method of the catalyst of the present embodiment is:
Step 1, be in rare nitric acid of 1% by be dissolved in mass concentration containing the palladium nitrate of 0.1g palladium, obtain solution A, then by 99.8g γ-Al 2o 3be immersed in solution A, submergence is had to γ-Al 2o 3solution A stir 2h after being heated to 60 DEG C, filter and obtain solid material A;
Step 2, the A of solid material described in step 1 is dried to 4h at 120 DEG C, then by the solid material A roasting 4h at 580 DEG C after drying, obtaining load after cooling has the catalyst precursor of Pd;
Step 3, be in rare nitric acid of 1% by be dissolved in mass concentration containing the stannous chloride of 0.05g tin, obtain solution B, then there is the catalyst precursor of Pd to be immersed in solution B load described in step 2, after having load to have the solution B of the catalyst precursor of Pd to be heated to 60 DEG C submergence, stir 2h, filter and obtain solid material B;
Step 4, the B of solid material described in step 3 is dried to 4h at 120 DEG C, then by the solid material B roasting 4h at 580 DEG C after drying, obtaining load after cooling has the catalyst precursor of Pd and Sn;
Step 5, be in rare nitric acid of 1% by be dissolved in mass concentration containing the cerous nitrate of 0.05g cerium, obtain solution C, then there is the catalyst precursor of Pd and Sn to be immersed in solution C load described in step 4, after having load to have the solution C of the catalyst precursor of Pd and Sn to be heated to 60 DEG C submergence, stir 2h, filter and obtain solid material C;
Step 6, the C of solid material described in step 5 is dried to 4h at 120 DEG C, then by the solid material C roasting 4h at 580 DEG C after drying, obtain catalyst precursor after cooling;
Step 7, adopt hydrogen to reduce processing to catalyst precursor described in step 6, obtain the catalyst of o-fluoronitrobenzene Hydrogenation for adjacent fluoroaniline; The temperature of described reduction processing is 200 DEG C, and the time is 3h.
Embodiment 7
The catalyst of the present embodiment comprises Al 2o 3carrier, is carried on Al 2o 3pd, Pt and Zn on carrier; The quality percentage composition that the quality percentage composition that in described catalyst, the quality percentage composition of Pd is 0.5%, Pt is 1.0%, Zn is 0.5%; Described Al 2o 3carrier is γ-Al 2o 3, Al 2o 3the average grain diameter of carrier is 1mm, and specific area is 200m 2/ g.
The preparation method of the catalyst of the present embodiment is:
Step 1, be in rare nitric acid of 2% by be dissolved in mass concentration containing the palladium bichloride of 0.5g palladium, obtain solution A, then by 98.0g γ-Al 2o 3be immersed in solution A, submergence is had to γ-Al 2o 3solution A stir 1h after being heated to 65 DEG C, filter and obtain solid material A;
Step 2, the A of solid material described in step 1 is dried to 6h at 120 DEG C, then by the solid material A roasting 5h at 550 DEG C after drying, obtaining load after cooling has the catalyst precursor of Pd;
Step 3, be in rare nitric acid of 2% by be dissolved in mass concentration containing the platinum nitrate of 1.0g platinum, obtain solution B, then there is the catalyst precursor of Pd to be immersed in solution B load described in step 2, after having load to have the solution B of the catalyst precursor of Pd to be heated to 65 DEG C submergence, stir 1h, filter and obtain solid material B;
Step 4, the B of solid material described in step 3 is dried to 6h at 120 DEG C, then by the solid material B roasting 5h at 550 DEG C after drying, obtaining load after cooling has the catalyst precursor of Pd and Pt;
Step 5, be in rare nitric acid of 2% by be dissolved in mass concentration containing the zinc nitrate of 0.5g zinc, obtain solution C, then there is the catalyst precursor of Pd and Pt to be immersed in solution C load described in step 4, after having load to have the solution C of the catalyst precursor of Pd and Pt to be heated to 65 DEG C submergence, stir 1h, filter and obtain solid material C;
Step 6, the C of solid material described in step 5 is dried to 6h at 120 DEG C, then by the solid material C roasting 5h at 550 DEG C after drying, obtain catalyst precursor after cooling;
Step 7, adopt hydrogen to reduce processing to catalyst precursor described in step 6, obtain the catalyst of o-fluoronitrobenzene Hydrogenation for adjacent fluoroaniline; The temperature of described reduction processing is 280 DEG C, and the time is 2h.
Embodiment 8
The catalyst of the present embodiment comprises Al 2o 3carrier, is carried on Al 2o 3pd, Sn and Zn on carrier; The quality percentage composition that the quality percentage composition that in described catalyst, the quality percentage composition of Pd is 0.5%, Sn is 1.0%, Zn is 0.5%; Described Al 2o 3carrier is γ-Al 2o 3, Al 2o 3the average grain diameter of carrier is 1mm, and specific area is 200m 2/ g.
The preparation method of the catalyst of the present embodiment is:
Step 1, be in rare nitric acid of 2% by be dissolved in mass concentration containing the palladium bichloride of 0.5g palladium, obtain solution A, then by 98.0g γ-Al 2o 3be immersed in solution A, submergence is had to γ-Al 2o 3solution A stir 1h after being heated to 65 DEG C, filter and obtain solid material A;
Step 2, the A of solid material described in step 1 is dried to 6h at 120 DEG C, then by the solid material A roasting 4h at 580 DEG C after drying, obtaining load after cooling has the catalyst precursor of Pd;
Step 3, be in rare nitric acid of 2% by be dissolved in mass concentration containing the stannous chloride of 1.0g tin, obtain solution B, then there is the catalyst precursor of Pd to be immersed in solution B load described in step 2, after having load to have the solution B of the catalyst precursor of Pd to be heated to 65 DEG C submergence, stir 1h, filter and obtain solid material B;
Step 4, the B of solid material described in step 3 is dried to 6h at 120 DEG C, then by the solid material B roasting 4h at 580 DEG C after drying, obtaining load after cooling has the catalyst precursor of Pd and Pt;
Step 5, be in rare nitric acid of 2% by be dissolved in mass concentration containing the zinc nitrate of 0.5g zinc, obtain solution C, then there is the catalyst precursor of Pd and Sn to be immersed in solution C load described in step 4, after having load to have the solution C of the catalyst precursor of Pd and Sn to be heated to 65 DEG C submergence, stir 1h, filter and obtain solid material C;
Step 6, the C of solid material described in step 5 is dried to 6h at 120 DEG C, then by the solid material C roasting 4h at 580 DEG C after drying, obtain catalyst precursor after cooling;
Step 7, adopt hydrogen to reduce processing to catalyst precursor described in step 6, obtain the catalyst of o-fluoronitrobenzene Hydrogenation for adjacent fluoroaniline; The temperature of described reduction processing is 250 DEG C, and the time is 3h.
Prepared by catalyst selectivity catalysis dechlorination of the present invention adjacent (to) method of cyano group benzyl chloride is described by following examples 9 to embodiment 11:
Embodiment 9
The catalyst that the present embodiment adopts is the catalyst of embodiment 1,2 or 3 preparations, and selective dechlorination method is as follows:
Step 1, by 8g Catalyst packing in fixed bed reactors, at room temperature in the fixed bed reactors of catalyst, pass into nitrogen to the air emptying in fixed bed reactors to being filled with, then to the hydrogen that passes into nitrogen dilution in fixed bed reactors, with the heating rate of 0.5 DEG C/min, the temperature of fixed bed reactors is risen to 250 DEG C; In the reducibility gas of nitrogen dilution, the volumn concentration of reducibility gas is 15%; The flow of the reducibility gas of nitrogen dilution is 80mL/min;
Step 2, will produce adjacent cyano group benzyl chloride (or to cyano group benzyl chloride) produce waste liquid as material liquid, treat that in step 1, the temperature of fixed bed reactors is down to 80 DEG C, stablize in the backward fixed bed reactors of 30min and pass into and be preheated to the hydrogen of 75 DEG C and be preheated to the material liquid of 75 DEG C, at 80 DEG C, under the effect of catalyst, the adjacent cyano group benzal chloride (or to cyano group benzal chloride) in material liquid is carried out to catalysis dechlorination reaction; The mol ratio of the adjacent cyano group benzal chloride (or to cyano group benzal chloride) in described hydrogen and material liquid is 15:1; The volume space velocity of described material liquid is 0.2mL/gcat/hr;
Step 3, reacted catalysis dechlorination in step 2 material is sent into condensation at 5 DEG C in condenser, then condensed material is carried out to Separation of Solid and Liquid, obtain the adjacent cyano group benzyl chloride of solid (or to cyano group benzyl chloride).
The selective dechlorination result of table 1 embodiment 9
Reusability after the catalyst regeneration that the present embodiment is adopted, the catalytic degradation after 5 times of regenerating the results are shown in Table 2.The renovation process of catalyst is: after above-mentioned reaction finishes, at ambient temperature to the mist (wherein volume of air percentage is 5%～10%) that passes into air and nitrogen in fixed bed reactors, the flow (mL/min) of the mist of air and nitrogen is (10～20) with the ratio of loaded catalyst (g): 1, speed with 0.5 DEG C/min～5 DEG C/min is warming up to 550 DEG C～600 DEG C, keep 3h～5h, then be down to room temperature, complete the regeneration of catalyst.
Selective dechlorination result after table 2 catalyst regeneration 5 times
Embodiment 10
The catalyst that the present embodiment adopts is the catalyst of embodiment 4,5 or 6 preparations, and selective dechlorination method is as follows:
Step 1, by 8g Catalyst packing in fixed bed reactors, at room temperature in the fixed bed reactors of catalyst, pass into nitrogen to the air emptying in fixed bed reactors to being filled with, then to the hydrogen that passes into nitrogen dilution in fixed bed reactors, with the heating rate of 0.1 DEG C/min, the temperature of fixed bed reactors is risen to 200 DEG C; In the reducibility gas of nitrogen dilution, the volumn concentration of reducibility gas is 20%; The flow of the reducibility gas of nitrogen dilution is 160mL/min;
Step 2, will produce adjacent cyano group benzyl chloride (or to cyano group benzyl chloride) produce waste liquid as material liquid, treat that in step 1, the temperature of fixed bed reactors is down to 130 DEG C, stablize in the backward fixed bed reactors of 60min and pass into and be preheated to the hydrogen of 125 DEG C and be preheated to the material liquid of 125 DEG C, at 130 DEG C, under the effect of catalyst, the adjacent cyano group benzal chloride (or to cyano group benzal chloride) in material liquid is carried out to catalysis dechlorination reaction; The mol ratio of the adjacent cyano group benzal chloride (or to cyano group benzal chloride) in described hydrogen and material liquid is 10:1; The volume space velocity of described material liquid is 0.01mL/gcat/hr;
Step 3, reacted catalysis dechlorination in step 2 material is sent into condensation at 8 DEG C in condenser, then condensed material is carried out to Separation of Solid and Liquid, obtain the adjacent cyano group benzyl chloride of solid (or to cyano group benzyl chloride).
The selective dechlorination result of table 3 embodiment 10
Reusability after the catalyst regeneration that the present embodiment is adopted, the catalytic degradation after 5 times of regenerating the results are shown in Table 4.Catalyst is regenerated according to renovation process described in embodiment 9.
Selective dechlorination result after table 4 catalyst regeneration 5 times
Embodiment 11
The catalyst that the present embodiment adopts is the catalyst of embodiment 7 or 8 preparations, and selective dechlorination method is as follows:
Step 1, by 8g Catalyst packing in fixed bed reactors, at room temperature in the fixed bed reactors of catalyst, pass into nitrogen to the air emptying in fixed bed reactors to being filled with, then to the hydrogen that passes into nitrogen dilution in fixed bed reactors, with the heating rate of 1 DEG C/min, the temperature of fixed bed reactors is risen to 280 DEG C; In the reducibility gas of nitrogen dilution, the volumn concentration of reducibility gas is 18%; The flow of the reducibility gas of nitrogen dilution is 120mL/min;
Step 2, will produce adjacent cyano group benzyl chloride (or to cyano group benzyl chloride) produce waste liquid as material liquid, treat that in step 1, the temperature of fixed bed reactors is down to 100 DEG C, stablize in the backward fixed bed reactors of 50min and pass into and be preheated to the hydrogen of 95 DEG C and be preheated to the material liquid of 95 DEG C, at 100 DEG C, under the effect of catalyst, the adjacent cyano group benzal chloride (or to cyano group benzal chloride) in material liquid is carried out to catalysis dechlorination reaction; The mol ratio of the adjacent cyano group benzal chloride (or to cyano group benzal chloride) in described hydrogen and material liquid is 60:1; The volume space velocity of described material liquid is 0.5mL/gcat/hr;
Step 3, reacted catalysis dechlorination in step 2 material is sent into condensation at 6 DEG C in condenser, then condensed material is carried out to Separation of Solid and Liquid, obtain the adjacent cyano group benzyl chloride of solid (or to cyano group benzyl chloride).
The selective dechlorination result of table 5 embodiment 11
Reusability after the catalyst regeneration that the present embodiment is adopted, the catalytic degradation after 5 times of regenerating the results are shown in Table 6.Catalyst is regenerated according to renovation process described in embodiment 9.
Selective dechlorination result after table 6 catalyst regeneration 5 times
The above; it is only preferred embodiment of the present invention; not the present invention is done to any restriction, every any simple modification of above embodiment being done according to invention technical spirit, change and equivalent structure change, and all still belong in the protection domain of technical solution of the present invention.

Claims (10)

  1. Selective dechlorination preparation adjacent (to) catalyst of cyano group benzyl chloride, it is characterized in that, comprise Al 2o 3carrier, is carried on Al 2o 3pd on carrier, metal M 1and metal M 2; In described catalyst, the quality percentage composition of Pd is 0.1%～1%, metal M 1quality percentage composition be 0.05%～3%, metal M 2quality percentage composition be 0.05%～2%; Described metal M 1for Pt or Sn; Described metal M 2for K, Zn or Ce.
  2. Selective dechlorination preparation according to claim 1 adjacent (to) catalyst of cyano group benzyl chloride, it is characterized in that, in described catalyst, the quality percentage composition of Pd is 0.3%～0.8%, metal M 1quality percentage composition be 0.5%～2%, metal M 2quality percentage composition be 0.2%～1%.
  3. Selective dechlorination preparation according to claim 2 adjacent (to) catalyst of cyano group benzyl chloride, it is characterized in that, in described catalyst, the quality percentage composition of Pd is 0.5%, metal M 1quality percentage composition be 1%, metal M 2quality percentage composition be 0.5%.
  4. According to the selective dechlorination preparation described in claim 1,2 or 3 adjacent (to) catalyst of cyano group benzyl chloride, it is characterized in that described Al 2o 3carrier is γ-Al 2o 3, Al 2o 3the average grain diameter of carrier is 1mm～2mm, and specific area is 150m 2/ g～250m 2/ g.
  5. According to the selective dechlorination preparation described in claim 1,2 or 3 adjacent (to) catalyst of cyano group benzyl chloride, it is characterized in that, the preparation method of described catalyst is:
    Step 1, the presoma of Pd is dissolved in rare nitric acid, obtains solution A, then aluminium oxide is immersed in solution A, stir 1h～2h after having the solution A of aluminium oxide to be heated to 60 DEG C～65 DEG C submergence, filter and obtain solid material A; The presoma of described Pd is the hydrochloride of Pd or the nitrate of Pd;
    Step 2, the A of solid material described in step 1 is dried, then, by the solid material A roasting 3h～5h at 550 DEG C～600 DEG C after drying, obtaining load after cooling has the catalyst precursor of Pd;
    Step 3, by metal M 1presoma be dissolved in rare nitric acid, obtain solution B, then there is the catalyst precursor of Pd to be immersed in solution B load described in step 2, stir 1h～2h after having load to have the solution B of the catalyst precursor of Pd to be heated to 60 DEG C～65 DEG C submergence, filter and obtain solid material B; Described metal M 1presoma be metal M 1hydrochloride or metal M 1nitrate;
    Step 4, the B of solid material described in step 3 is dried, then, by the solid material B roasting 3h～5h at 550 DEG C～600 DEG C after drying, obtaining load after cooling has Pd and metal M 1catalyst precursor;
    Step 5, by metal M 2presoma be dissolved in rare nitric acid, obtain solution C, then load described in step 4 is had to Pd and metal M 1catalyst precursor be immersed in solution C, have load to have Pd and metal M submergence 1the solution C of catalyst precursor stir 1h～2h after being heated to 60 DEG C～65 DEG C, filter and obtain solid material C; Described metal M 2presoma be metal M 2hydrochloride or metal M 2nitrate;
    Step 6, the C of solid material described in step 5 is dried, then, by the solid material C roasting 3h～5h at 550 DEG C～600 DEG C after drying, obtain catalyst precursor after cooling;
    Step 7, adopt hydrogen to reduce processing to catalyst precursor described in step 6, obtain the catalyst of o-fluoronitrobenzene Hydrogenation for adjacent fluoroaniline.
  6. Selective dechlorination preparation according to claim 5 adjacent (to) catalyst of cyano group benzyl chloride, it is characterized in that, described in step 1, step 3 and step 5, the mass concentration of rare nitric acid is 1%～2%.
  7. Employing catalyst selectivity catalysis dechlorination as described in claim 1,2 or 3 prepare adjacent (to) method of cyano group benzyl chloride, it is characterized in that, the method comprises the following steps:
    Step 1, by Catalyst packing in fixed bed reactors, at room temperature in the fixed bed reactors of catalyst, pass into nitrogen to the air emptying in fixed bed reactors to being filled with, then to the hydrogen that passes into nitrogen dilution in fixed bed reactors, with the heating rate of 0.1 DEG C/min～1 DEG C/min, the temperature of fixed bed reactors is risen to 200 DEG C～280 DEG C; In the reducibility gas of nitrogen dilution, the volumn concentration of reducibility gas is 15%～20%; The flow of the reducibility gas of nitrogen dilution and the mass ratio of catalyst are (10～20): 1, and wherein the unit of flow is mL/min, the unit of quality is g;
    Step 2, will produce adjacent (to) waste liquid that produces of cyano group benzyl chloride is as material liquid, treat that in step 1, the temperature of fixed bed reactors is down to reaction temperature, stablize to pass in the backward fixed bed reactors of 30min～60min and be preheated to the hydrogen of 75 DEG C～125 DEG C and be preheated to the material liquid of 75 DEG C～125 DEG C, under reaction temperature and under the effect of catalyst to the neighbour in material liquid (to) cyano group benzal chloride carries out catalysis dechlorination reaction; 80 DEG C～130 DEG C of described reaction temperatures;
    Step 3, reacted catalysis dechlorination in step 2 material is sent into condensation in condenser, then condensed material is carried out to Separation of Solid and Liquid, obtain solid neighbour (to) cyano group benzyl chloride.
  8. 8. method according to claim 7, is characterized in that, neighbour in hydrogen described in step 2 and material liquid (to) mol ratio of cyano group benzal chloride is (10～60): 1.
  9. 9. method according to claim 7, is characterized in that, the volume space velocity of material liquid described in step 2 is 0.01mL/gcat/hr～0.5mL/gcat/hr.
  10. 10. method according to claim 7, is characterized in that, the condensation temperature of condenser described in step 3 is 5 DEG C～8 DEG C.
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