CN105562048B - Catalyst for electrolytic silver that a kind of caesium, rhenium, phosphorus are modified and its preparation method and application - Google Patents
Catalyst for electrolytic silver that a kind of caesium, rhenium, phosphorus are modified and its preparation method and application Download PDFInfo
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- CN105562048B CN105562048B CN201510937524.8A CN201510937524A CN105562048B CN 105562048 B CN105562048 B CN 105562048B CN 201510937524 A CN201510937524 A CN 201510937524A CN 105562048 B CN105562048 B CN 105562048B
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/187—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/38—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/313—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of doubly bound oxygen containing functional groups, e.g. carboxyl groups
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Abstract
The invention belongs to technical field of chemical engineering catalysts, catalyst for electrolytic silver that specially a kind of caesium, rhenium, phosphorus are modified and its preparation method and application.In the present invention, carrier silver is using the electrolytic silver of electrolysis preparation, and after water vapour is heat-treated, crystal face reconstruct occurs for electrolytic silver, and surface becomes rough by smooth；Dip loading caesium, rhenium, phosphorus compound in electrolytic silver after treatment, are calcined after drying, then are heat-treated by a vapor, that is, caesium, rhenium, the catalyst for electrolytic silver of phosphorus modification is made.Caesium, rhenium, the catalyst for electrolytic silver of phosphorus modification can be used for fatty alcohol or the step of aromatic alcohol catalysis oxidation one to generate corresponding aldehydes or ketones, compared with the catalyst for electrolytic silver of current commercial Application, caesium, rhenium, the catalyst for electrolytic silver of phosphorus modification have good iron-resistant poisoning performance.
Description
Technical field
The invention belongs to technical field of chemical engineering catalysts, and in particular to a kind of caesium, rhenium, phosphorus modification catalyst for electrolytic silver and
Its preparation method and application.
Background technology
The catalyst that electrolytic silver synthesizes corresponding aldehydes or ketones as alcohol gaseous oxidation has applied many years, at present in first
Alcohol air oxidation produces and uses catalyst for electrolytic silver on formaldehyde and ethylene glycol air oxidation synthesizing biformyl process units.Electrolysis
Silver catalyst directly can be bought from the market, easily can also be made by electrolysis, such as United States Patent (USP) US 5,135,
624 describe using 5~100g/L silver nitrate as electrolyte, pH1~4,10~80 DEG C of electrolysis temperature, current density be 100~
3000A/m2Under the conditions of prepare the method for electrolytic crystalline silver catalyst；German patent DE 2,129,776 describe current density 30~
300 A/m2, using the method for rotating cathode legal system electrolytic silver.
Crystal silver catalyst is used for the particle that certain diameter is made when the corresponding aldehyde of gaseous oxidation alcohol system and ketone（0.1~
2.5mm）, react in 500~650 DEG C of progress（JP 59933/1983, JP 54011/1986, US 4,555,583）.Surface
The electrolytic silver of cleaning has good catalytic performance, but ferro element is very easy to make catalyst poisoning, when catalyst surface is several
After individual ppm iron pollution, catalytic performance can be received and had a strong impact on.In industrialized production, inevitably have a small amount of iron from
Silver catalyst surface, the micro iron in silver catalyst surface, such as 10ppm are brought into by reacting gas in raw material or process units
Iron, may result in reaction selectivity degradation, and catalyst service life significantly reduces.Poison the iron of catalyst for electrolytic silver with oxygen
Compound form is present, using ferrous oxide as dominant species when content is low, using di-iron trioxide as dominant species when content is high, these
The oxide of iron enhances the reactivity of surface adsorbed oxygen, exacerbates the deep oxidation of alcohol, meanwhile, the presence of ferriferous oxide,
The reaction path of alcohol oxidation can also be changed, be allowed to be easier to be completely oxidized to carbon dioxide.Both effects, have had a strong impact on electricity
Solve selectivity and the life-span of silver catalyst.
In order that silver catalyst has more preferable iron-resistant poisoning capability, researcher is using phosphorus modification electrolytic silver, in laboratory
When having good effect during research, but applying to production, then the difficulty for being difficult to overcome be present.Because although phosphorus modification can suppress
The activity of iron, so as to play a part of iron-resistant poisoning, but also suppress the activity of electrolytic silver simultaneously.Therefore, phosphorus modification amount is low can not
Suppress the poisoning of iron very well, and modification amount is big, also serious to the activity of electrolytic silver to suppress during such as larger than 80ppm, leads to not
Initiation reaction.
Caesium and rhenium are the auxiliary agents of two kinds of modification carried silver catalysts, have good effect in ethane epoxyization reaction, but
When using it for modifying electrolytic silver, selectivity reduces, therefore both elements are not used to improve the performance of catalyst for electrolytic silver.
The content of the invention
It is an object of the invention to provide catalyst for electrolytic silver that a kind of selectivity is high, catalytic performance is good and preparation method thereof and
Using.
Catalyst for electrolytic silver provided by the invention, it is three kinds of element caesiums, rhenium, the catalyst for electrolytic silver of phosphorus modification.Specifically
Say it is that three kinds of caesium, rhenium, phosphorus elements are loaded in the heat treated electrolytic silver of vapor, then carry out vapor heat to catalyst again
Catalyst obtained from processing.The modification amount of each element is respectively：Caesium 10-1500ppm, rhenium 100-800ppm, phosphorus 80-
100ppm。
First, catalyst for electrolytic silver has loaded the phosphorus of higher concentration, so as to have good iron-resistant poisoning capability；Secondly,
The vapor heat treatment carried out after the addition of caesium and rhenium, and load, can effectively alleviate suppression of the phosphorus to electrolytic silver activity, from
And make catalyst that there is enough reactivities, the electrolytic silver after caesium, rhenium, phosphorus modification is smoothly triggered under production status
Reaction.This caesium, rhenium, the catalyst for electrolytic silver macrostate of phosphorus modification are identical with electrolytic silver, and electrolytic silver uses same side
Method is used and regenerated, and can easily be substituted electrolytic silver and be carried out commercial Application.
Above-mentioned caesium provided by the invention, rhenium, phosphorus modification catalyst for electrolytic silver preparation method, concretely comprise the following steps：
（1）Catalyst for electrolytic silver is subjected to water vapour heat treatment
Heat treatment is carried out in fixed bed reactors or tube furnace, and electrolytic silver is seated in conversion zone, distilled water measuring pump
Gasifier is squeezed into, is mixed with the air after preheating, then is pre-processed after overheat into conversion zone, the liquid hourly space velocity (LHSV) of distilled water
It is 10-50hr-1, air mass flow is every gram of electrolytic silver 0.002-0.011M3/ h, 300-600 DEG C of pretreatment temperature, processing time 8-
36 hours, then stop steam, processing terminate after under air stream cool drying；
（2）Caesium, rhenium, P elements are modified on catalyst for electrolytic silver
Modification can use infusion process, i.e., be dissolved in distilled water and be made into maceration extract the soluble compound of caesium, rhenium, phosphorus, will be through
Step（1）The electrolytic silver of heat treatment is placed in maceration extract, small then at 100-120 DEG C of drying 2-5 in 40-60 DEG C of drying under agitation
When, then in 500-550 DEG C of Muffle furnace roasting 3-4 hours, that is, obtain loading caesium, rhenium, the electrolytic silver of phosphorus.The modification amount of each element
Respectively：Caesium 10-1500ppm；Rhenium 100-800ppm；Phosphorus 80-100ppm；
（3）By step（2）Obtained load caesium, rhenium, the electrolytic silver of phosphorus carry out a vapor heat treatment again, that is, obtain
Caesium, rhenium, the catalyst for electrolytic silver of phosphorus modification.Here vapor heat treatment process and step（1）Vapor heat treatment process phase
Together.
In the present invention, the soluble compound of caesium used is cesium nitrate, cesium sulfate or perrhenic acid caesium；The solubilityization of rhenium
Compound is perrhenic acid, ammonium perrhenate or perrhenic acid caesium；The soluble compound of phosphorus is phosphoric acid or phosphate.
In the present invention, electrolytic silver used can be the commodity catalyst for electrolytic silver of purchase or use numerous texts
Described electrolytic silver preparation method is offered to be prepared.
Electrolytic silver is that a kind of surface is smooth, and the crystallization very smaller than surface silver, itself is not appropriate for as carrier.Electrolytic silver
After vapor high-temperature process, crystal face reconstruct can occur for its surface, and smooth surface becomes rugged, rough table
Face, it can preferably load auxiliary agent.
Caesium prepared by the present invention, rhenium, the catalyst for electrolytic silver of phosphorus modification can be used for catalytic gas phase oxidation fatty alcohol and fragrance
The corresponding aldehyde of alcohol system and ketone, such as propane diols gaseous oxidation synthesizing pyruvaldehyde, ethylene glycol gaseous oxidation synthesizing biformyl, ethyl lactate
Gaseous oxidation synthesizes ethyl pyruvate, gas phase oxidizing and synthesizing phenylacetaldehyde from phenyl ethyl alcohol etc., has good anti-poisoning function to iron.
When iron content reaches 10ppm on catalyst, still there is selectivity and service life better than cleaning catalyst for electrolytic silver.
Caesium prepared by the present invention, rhenium, the catalyst for electrolytic silver of phosphorus modification are used for catalytic gas phase oxidation fatty alcohol and aromatic alcohol
When making corresponding aldehyde and ketone, reaction mass is alcohol, water vapour, air composition gas phase compounds, and oxidation reaction is in fixed bed adiabatic
Carried out on reactor, reaction product chilling；Alcohol, the water of gasification continuously enter catalytic bed and carry out oxidation reaction after being mixed with air,
Its reaction condition is as follows：
（1）The mol ratio of oxygen and alcohol is 0.6-2.0 in air；
（2）The weight proportion of alcohol and water is alcohol 70-90% (wt%), water 10-30% (wt%)；
（3）The liquid hourly space velocity (LHSV) of alcohol charging is 6-60 hr-1；
（4）Oxidizing reaction temperature is 450-550 DEG C.
Specific operation process is：Alcohol squeezes into gasifier with measuring pump, and raw material is heated into more than boiling point gasification or low
The Bubbler vaporizer under boiling conditions；Water vapour can directly use steam, also will be water in gasifier；Alcohol, water vapour, air mix
Enter the catalytic bed reaction for electrolytic crystalline silver catalyst of mating formation after conjunction.The mol ratio oxygen-methanol ratio of oxygen and ethylene glycol is to reaction in unstripped gas
Have a great influence, the mol ratio of oxygen and ethylene glycol is 0.6-2.0 in air when the present invention is fed, and reaction has optimum activity.Alcohol and water
Weight proportion be alcohol 70-90%（Wt%）, water content is 10-30%（Wt%）, water distribution quantity is too high to cause production concentration too
It is low, commodity can not be directly prepared into, water distribution quantity is too low to influence catalyst activity.The liquid hourly space velocity (LHSV) of charging is 6-60hr-1（During liquid
Air speed is the liquid bulk product of the raw alcohol passed through per hour in per volume of catalyst）, liquid hourly space velocity (LHSV) is too small to influence product
The selectivity of aldehydes or ketones, liquid hourly space velocity (LHSV) too conference influence the conversion ratio of alcohol.Reaction is carried out continuously at 450-550 DEG C.Product is anxious
Spray-absorption after cold, commodity aldehyde can be obtained by adjusting the rate of water make-up of spray.
Using the catalyst of the present invention, after 10ppm iron is introduced, catalyst still has good performance, and alcohol turns
Rate is up to 100%, and for the selectivity of aldehydes or ketones up to 83%, catalyst service life is better than the cleaning electrolytic silver without iron poisoning
Catalyst.And the half of the service life deficiency cleaning electrolytic silver of the catalyst for electrolytic silver through 10ppm iron poisonings.
Embodiment
The invention is further illustrated by the following examples.
Embodiment 1. is pre-processed to catalyst for electrolytic silver first, and 5 grams of electrolytic crystalline silver catalyst are loaded into a diameter
In 14mm stainless steel reactor, distilled water to be squeezed into gasifier with measuring pump and vaporized, is mixed with the air after preheating, then pass through
Electrolytic silver is pre-processed into conversion zone after overheat, the liquid hourly space velocity (LHSV) of distilled water is 20hr-1, air mass flow 0.035M3/
H, 600 DEG C of pretreatment temperature, stop steam after 8 hours processing times, the cool drying under air stream.
Cesium nitrate, perrhenic acid and phosphoric acid are dissolved in distilled water and are made into maceration extract, the modification amount of three kinds of elements is respectively：Caesium
10ppm；Rhenium 800ppm；Phosphorus 80ppm.The electrolytic silver being previously obtained is placed in maceration extract, in 40 DEG C of dryings under agitation, then at
100 DEG C dry 5 hours, then obtain loading the electrolytic silver of caesium, rhenium, phosphorus in the roasting 4 hours of 500 DEG C of Muffle furnace.
The electrolytic silver for loading modification element is subjected to a vapor heat treatment again, that is, obtains caesium, rhenium, the electricity of phosphorus modification
Solve silver catalyst #1.
Catalyst #1 made from 5 grams is taken, carries out poisoning processing with 10ppm iron, the stainless steel for loading a diameter of 14mm is anti-
Answer in device, 1,2-PD is squeezed into gasifier gasification with measuring pump, mixed with the air after preheating, vapor, then through overheat
Reacted afterwards into catalytic bed, the liquid hourly space velocity (LHSV) of 1,2-PD is 20hr-1, alcohol water weight ratio is 70:30, air feed
Flow is 0.055M3/ h, 450 DEG C of reaction temperature, spray-absorption after product chilling, the amount of makeup water of spray is controlled, obtains 40%
Pyroracemic aldehyde product, 1,2-PD conversion ratio 100%, the selectivity of pyroracemic aldehyde is 78.5%, catalyst service life 60
My god.
To clean electrolytic silver as comparative example, using same 1,2-PD liquid hourly space velocity (LHSV), under same reaction condition,
1,2-PD conversion ratio 100%, the selectivity of pyroracemic aldehyde is 75.2%, catalyst service life 45 days.
Using 10ppm iron poisonings electrolytic silver as comparative example, using same 1,2-PD liquid hourly space velocity (LHSV), equally reacting
Under the conditions of, 1,2-PD conversion ratio 100%, the selectivity of pyroracemic aldehyde is 63.5%, catalyst service life 28 days.
Embodiment 2. is pre-processed using method similar to Example 1 to electrolytic silver, and the liquid hourly space velocity (LHSV) of distilled water is
10hr-1, air mass flow 0.020M3/ h, 300 DEG C of pretreatment temperature, stop steam after 36 hours processing times, it is cold under air stream
But dry.
Cesium sulfate, ammonium perrhenate and etherophosphoric acid are dissolved in distilled water and are made into maceration extract, the modification amount difference of three kinds of elements
For：Caesium 1500ppm；Rhenium 100ppm；Phosphorus 100ppm.The electrolytic silver being previously obtained is placed in maceration extract, it is dry at 60 DEG C under agitation
It is dry, dried then at 120 DEG C 2 hours, then obtain loading the electrolytic silver of caesium, rhenium, phosphorus in the roasting 3 hours of 550 DEG C of Muffle furnace.
The electrolytic silver for loading modification element is subjected to a vapor heat treatment again, that is, obtains caesium, rhenium, the electricity of phosphorus modification
Solve silver catalyst #2.
Catalyst #2 made from 5 grams is taken, carries out poisoning processing with 10ppm iron, the stainless steel for loading a diameter of 14mm is anti-
Answer in device, 1,2-PD is squeezed into gasifier gasification with measuring pump, mixed with the air after preheating, steam, then after overheat
Reacted into catalytic bed, the liquid hourly space velocity (LHSV) of 1,2-PD is 30hr-1, alcohol water weight ratio is 80:20 air feed rates
For 0.055M3/ h, 550 DEG C of reaction temperature, spray-absorption after product chilling, the amount of makeup water of spray is controlled, obtains the third of 40%
Keto-aldehyde product, 1,2-PD conversion ratio 100%, the selectivity of pyroracemic aldehyde is 76.3%, catalyst service life 110 days.
To clean electrolytic silver as comparative example, using same 1,2-PD liquid hourly space velocity (LHSV), under same reaction condition,
1,2-PD conversion ratio 100%, the selectivity of pyroracemic aldehyde is 73.9%, catalyst service life 102 days.
Using 10ppm iron poisonings electrolytic silver as comparative example, using same 1,2-PD liquid hourly space velocity (LHSV), equally reacting
Under the conditions of, 1,2-PD conversion ratio 100%, the selectivity of pyroracemic aldehyde is 61.1%, catalyst service life 47 days.
Embodiment 3. is pre-processed using method similar to Example 1 to electrolytic silver, and the liquid hourly space velocity (LHSV) of distilled water is
50hr-1, air mass flow 0.055M3/ h, 500 DEG C of pretreatment temperature, stop steam after 12 hours processing times, it is cold under air stream
But dry.
Perrhenic acid caesium and etherophosphoric acid are dissolved in distilled water and are made into maceration extract, the modification amount of three kinds of elements is respectively：Caesium
500ppm；Rhenium 500ppm；Phosphorus 90ppm.The electrolytic silver being previously obtained is placed in maceration extract, in 50 DEG C of dryings under agitation, then
Dried in 110 DEG C 4 hours, then obtain loading the electrolytic silver of caesium, rhenium, phosphorus in the roasting 3 hours of 530 DEG C of Muffle furnace.
The electrolytic silver for loading modification element is subjected to a vapor heat treatment again, that is, obtains caesium, rhenium, the electricity of phosphorus modification
Solve silver catalyst #3.
Catalyst #3 made from 5 grams is taken, carries out poisoning processing with 10ppm iron, the stainless steel for loading a diameter of 14mm is anti-
Answer in device, ethylene glycol is squeezed into gasifier gasification with measuring pump, with the air after preheating, enter after water vapour mixing into catalytic bed
Row reaction, the liquid hourly space velocity (LHSV) of ethylene glycol is 50hr-1, alcohol water weight ratio is 80:20, air feed rate 0.055M3/ h, reaction
450 DEG C of temperature, ethylene glycol reforming rate 100%, the selectivity of glyoxal is 83.0%, catalyst service life 70 days.
To clean electrolytic silver as comparative example, using same ethylene glycol liquid hourly space velocity (LHSV), under same reaction condition, ethylene glycol
Conversion ratio 100%, the selectivity of glyoxal is 75.2%, catalyst service life 50 days.
Using 10ppm iron poisonings electrolytic silver as comparative example, using same ethylene glycol liquid hourly space velocity (LHSV), in same reaction condition
Under, ethylene glycol reforming rate 100%, the selectivity of glyoxal is 63.7%, catalyst service life 30 days.
Embodiment 4. is pre-processed using method similar to Example 1 to electrolytic silver, and the liquid hourly space velocity (LHSV) of distilled water is
30hr-1, air mass flow 0.010M3/ h, 400 DEG C of pretreatment temperature, stop steam after 24 hours processing times, it is cold under air stream
But dry.
Cesium nitrate, perrhenic acid and phosphoric acid are dissolved in distilled water and are made into maceration extract, the modification amount of three kinds of elements is respectively：Caesium
1000ppm；Rhenium 400ppm；Phosphorus 90ppm.The electrolytic silver being previously obtained is placed in maceration extract, in 50 DEG C of dryings under agitation, then
Dried in 100 DEG C 5 hours, then obtain loading the electrolytic silver of caesium, rhenium, phosphorus in the roasting 3 hours of 550 DEG C of Muffle furnace.
The electrolytic silver for loading modification element is subjected to a vapor heat treatment again, that is, obtains caesium, rhenium, the electricity of phosphorus modification
Solve silver catalyst #4.
Catalyst #4 made from 5 grams is taken, carries out poisoning processing with 10ppm iron, the stainless steel for loading a diameter of 14mm is anti-
Answer in device, benzyl carbinol is squeezed into gasifier gasification with measuring pump, with the air after preheating, enter after water vapour mixing into catalytic bed
Row reaction, the liquid hourly space velocity (LHSV) of benzyl carbinol is 10hr-1, alcohol water weight ratio is 90:10, air feed rate 0.015M3/ h, reaction
350 DEG C of temperature, benzyl carbinol conversion ratio 98%, the selectivity of phenylacetaldehyde is 73.1%, catalyst life 65 days.
To clean electrolytic silver as comparative example, using same benzyl carbinol liquid hourly space velocity (LHSV), under same reaction condition, benzyl carbinol
Conversion ratio 100%, the selectivity of phenylacetaldehyde is 70.5%, catalyst service life 60 days.
Using 10ppm iron poisonings electrolytic silver as comparative example, using same benzyl carbinol liquid hourly space velocity (LHSV), in same reaction condition
Under, benzyl carbinol conversion ratio 100%, the selectivity of phenylacetaldehyde is 59.7%, catalyst service life 25 days.
Embodiment 5. is pre-processed using method similar to Example 1 to electrolytic silver, and the liquid hourly space velocity (LHSV) of distilled water is
20hr-1, air mass flow 0.055M3/ h, 550 DEG C of pretreatment temperature, stop steam after 12 hours processing times, it is cold under air stream
But dry.
Cesium nitrate, perrhenic acid and phosphoric acid are dissolved in distilled water and are made into maceration extract, the modification amount of three kinds of elements is respectively：Caesium
700ppm；Rhenium 200ppm；Phosphorus 100ppm.The electrolytic silver being previously obtained is placed in maceration extract, in 50 DEG C of dryings under agitation, then
Dried in 100 DEG C 5 hours, then obtain loading the electrolytic silver of caesium, rhenium, phosphorus in the roasting 3 hours of 550 DEG C of Muffle furnace.
The electrolytic silver for loading modification element is subjected to a vapor heat treatment again, that is, obtains caesium, rhenium, the electricity of phosphorus modification
Solve silver catalyst #5.
Catalyst #5 made from 5 grams is taken, carries out poisoning processing with 10ppm iron, the stainless steel for loading a diameter of 14mm is anti-
Answer in device, the ethyl lactate aqueous solution is squeezed into gasifier gasification with measuring pump, mixed with the air after preheating, then it is laggard through overheating
Enter catalytic bed to be reacted, the liquid hourly space velocity (LHSV) of ethyl lactate is 45hr-1, alcohol water weight ratio is 80:20, air feed rate is
0.070M3/ h, 400 DEG C of reaction temperature, ethyl lactate conversion ratio 100%, the selectivity of ethyl pyruvate is 74.5%.Catalyst
Service life 60 days.
To clean electrolytic silver as comparative example, using same ethyl lactate liquid hourly space velocity (LHSV), under its optimum reaction condition, breast
Acetoacetic ester conversion ratio 100%, the selectivity of ethyl pyruvate is 72.1%, catalyst service life 50 days.
Using 10ppm iron poisonings electrolytic silver as comparative example, using same ethyl lactate liquid hourly space velocity (LHSV), in same reaction condition
Under, ethyl lactate conversion ratio 100%, the selectivity of ethyl pyruvate is 53.9%, catalyst service life 20 days.
Claims (5)
1. the catalyst for electrolytic silver of a kind of caesium, rhenium, phosphorus modification, it is characterised in that be on through the heat treated electrolytic silver of vapor
Load caesium, rhenium, three kinds of elements of phosphorus, then again to load caesium, rhenium, phosphorus electrolytic silver carry out vapor heat treatment and obtain；Three kinds
The modification amount of element is respectively：Caesium 10-1500ppm, rhenium 100-800ppm, phosphorus 80-100ppm.
2. the preparation method of the catalyst for electrolytic silver of a kind of caesium, rhenium, phosphorus modification, it is characterised in that concretely comprise the following steps：
（1）Catalyst for electrolytic silver is subjected to water vapour heat treatment
Heat treatment is carried out in fixed bed reactors or tube furnace, and electrolytic silver is seated in conversion zone, and distilled water is squeezed into measuring pump
Gasifier, mix with the air after preheating, then pre-processed after overheat into conversion zone, the liquid hourly space velocity (LHSV) of distilled water is
10-50hr-1, air mass flow is every gram of electrolytic silver 0.002-0.011m3/ h, 300-600 DEG C of pretreatment temperature, processing time 8-36
Hour, then stop steam, processing terminate after under air stream cool drying；
（2）Caesium, rhenium, P elements are modified on catalyst for electrolytic silver
Modification uses infusion process, i.e., is dissolved in distilled water and is made into maceration extract the soluble compound of caesium, rhenium, phosphorus, will be through step（1）
The electrolytic silver of heat treatment is placed in maceration extract, in 40-60 DEG C of drying under agitation, dries 2-5 hours then at 100-120 DEG C, then
In 500-550 DEG C of roasting 3-4 hour of Muffle furnace, that is, obtain loading caesium, rhenium, the electrolytic silver of phosphorus；The modification amount of each element is respectively：
Caesium 10-1500ppm, rhenium 100-800ppm, phosphorus 80-100ppm；
（3）By step（2）Obtained load caesium, rhenium, the electrolytic silver of phosphorus carry out a vapor heat treatment again, that is, obtain caesium, rhenium,
The catalyst for electrolytic silver of phosphorus modification；Here vapor heat treatment process and step（1）Vapor heat treatment process it is identical.
3. preparation method according to claim 2, it is characterised in that the soluble compound of caesium used is cesium nitrate, sulphur
Sour caesium or perrhenic acid caesium；The soluble compound of rhenium is perrhenic acid, ammonium perrhenate or perrhenic acid caesium；The soluble compound of phosphorus is
Phosphoric acid or phosphate.
4. the catalyst for electrolytic silver of caesium as claimed in claim 1, rhenium, phosphorus modification is in fatty alcohol or the step of aromatic alcohol catalysis oxidation one
Generate the application in corresponding aldehydes or ketones.
5. application according to claim 4, it is characterised in that reaction mass is alcohol, water vapour, air composition gas phase chemical combination
Thing, oxidation reaction are carried out on fixed bed adiabatic reactor, reaction product chilling；Alcohol, the water of gasification are continuous after being mixed with air
Oxidation reaction is carried out into catalytic bed, its reaction condition is as follows：
（1）The mol ratio of oxygen and alcohol is 0.6-2.0 in air；
（2）The weight proportion of alcohol and water is alcohol 70-90% (wt%), water 10-30% (wt%)；
（3）The liquid hourly space velocity (LHSV) of alcohol charging is 6-60 hr-1；
（4）Oxidizing reaction temperature is 450-550 DEG C.
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