CN101778669B - Method of preparing improved catalyst for production of acrylic acid - Google Patents

Method of preparing improved catalyst for production of acrylic acid Download PDF

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CN101778669B
CN101778669B CN200880102720.1A CN200880102720A CN101778669B CN 101778669 B CN101778669 B CN 101778669B CN 200880102720 A CN200880102720 A CN 200880102720A CN 101778669 B CN101778669 B CN 101778669B
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acid
catalyst
acrylic acid
salt
distilled water
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CN101778669A (en
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宋慇擎
车京龙
金镇道
赵贤朱
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LG Chem Ltd
LG Corp
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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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • 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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/28—Molybdenum
    • 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
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/053—Sulfates
    • 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
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/057—Selenium or tellurium; Compounds thereof
    • B01J27/0576—Tellurium; Compounds thereof
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/215—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of saturated hydrocarbyl groups
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

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Abstract

The present invention provides a method of preparing an oxide catalyst for the production of acrylic acid by preparing a catalyst precursor from the solution mixture of molybdenum salt, vanadium salt, tellurium salt and niobium salt and drying and firing thereof. The present invention is characterized by the addition of acid complex mixture comprising carboxylic acid, peroxide and sulfuric acid compounds as an additive to obtain the catalyst precursor. According to the method of the invention, the oxide catalyst for the production of acrylic acid having excellent catalytic activity can be prepared.

Description

For the preparation of the method for producing acrylic acid improved catalysts
Technical field
The present invention relates to a kind of method for the preparation of producing acrylic acid oxide catalyst, or rather, relate to a kind of preparation and have method enhanced activity, that be conducive to produce acrylic acid oxide catalyst with comparing for the production of acrylic acid conventional catalyst, the method is by adding the acid complex mixture Kaolinite Preparation of Catalyst precursor that comprises carboxylic acid, peroxide and sulphate to come for the preparation of producing acrylic acid oxide catalyst.
Background technology
In order to produce acrylic acid by direct oxidation propane, research mainly concentrates on the 4-component composite oxide catalysts as MoVTeNbO catalyst.Do not changing under the condition of catalytic component, for the improvement of catalyst reaction activity, remaining limited, this causes the improvement of catalyst activity unsatisfactory.Therefore, need to develop optionally high activated catalyst of a kind of propane conversion ratio with increase and acrylic acid.
As a kind of effort that increases catalyst activity, attempted adding additive.For example, according to Applied catalysis A:General Vol 257, Issue 1,67 (2004), adds nitric acid can increase catalytic activity in the production of composite oxide catalysts, is about 2.0～2.5 o'clock catalytic activitys the highest in pH value.Yet the catalytic activity of the catalyst of preparing by said method is good not and have a narrow problem of field of activity with regard to commercialization.The open No.2001-006725 of Korean Patent and U.S. Patent No. 6,642,174B2 has recorded the preparation of composite oxide catalysts MoVTeNbO, and this oxide catalyst comprises and a kind of identical composition that forms of the present invention.But at that time, in the preparation process of this catalyst, do not use additive, and the activity of prepared catalyst lags far behind the present invention.
Therefore, in the urgent need to developing a kind of, new method more wide region in the active catalyst of improvement acrylic acid for the preparation of producing.
Summary of the invention
Technical problem
One object of the present invention is for a kind of method for the preparation of producing acrylic acid catalyst is provided, this catalyst in producing acrylic acid process by the gaseous oxidation of propane, there is excellent conversion of propane and acrylic acid selective and there is the catalytic activity of improvement.
Technical problem
By following embodiment of the present invention, can realize above-mentioned purpose of the present invention and other objects.
Be described in more detail below the present invention.
For achieving the above object, the invention provides a kind of method for the preparation of producing acrylic acid oxide catalyst, the method comprises the steps:, by the solution mixture Kaolinite Preparation of Catalyst precursor of molybdenum salt, vanadic salts, tellurium salt and niobium salt, be then dried and calcine.Method of the present invention is characterised in that, comprise to the additional step that adds additive in the solution mixture of those slaines, and now additive is characterised in that, it is the acid complex mixture that comprises carboxylic acid, peroxide and sulphate.
That by said method, prepares is of the present inventionly represented by Chemical formula 1 for the production of acrylic acid oxide catalyst.
Chemical formula 1
Mo 1.0V aTe bNb cO n
In Chemical formula 1,
Mo is molybdenum, and V is vanadium, and Te is that tellurium and Nb are niobium;
A, b, c and n represent respectively the mol ratio of vanadium, tellurium, niobium and oxygen atom, and it is 0.01≤a≤l; 0.01≤b≤l; 0.01≤c≤l; And
N serve as reasons valence and the determined number of weight of other elements.
The invention provides a kind of method for the preparation of producing acrylic acid oxide catalyst, the method comprises the steps:, by the solution mixture Kaolinite Preparation of Catalyst precursor of molybdenum salt, vanadic salts, tellurium salt and niobium salt, be then dried and calcine.Method of the present invention comprises in addition to the step that adds additive in the solution mixture of those slaines, and now this additive is characterised in that, it is the acid complex mixture that comprises carboxylic acid, peroxide and sulphate.
Method of the present invention comprises by making the compound mixture of molybdenum (Mo) salt, vanadium (V) salt, tellurium (Te) salt and niobium (Nb) salt and the step that solvent is prepared solution mixture.At this, described solvent is preferably selected from distilled water, alcohol, ether and carboxylate.In every kind of metal salt compound, the counter ion counterionsl gegenions of metal can be identical or different.Particularly, molybdenum (Mo) salt, vanadium (V) salt and tellurium (Te) salt are dissolved in distilled water and prepare solution mixture, add wherein niobium (Nb) salt being dissolved in distilled water, then fully mix.The example of molybdenum (Mo) salt compound is ammonium paramolybdate, molybdic acid, sodium molybdate and molybdenum trioxide.The example of vanadium (V) salt compound is ammonium metavanadate, as VCl 4halogenation vanadium and as VO (OC 2h 5) 3vanadium alkoxide.The example of tellurium (Te) salt compound is telluric acid and tellurium dioxide, and the example of niobium (Nb) salt compound is ammonium niobium oxalate, niobic acid and niobium oxalate.When adding separately the niobium salt that is dissolved in distilled water, through after a while, produced sediment, even and continue to stir this solution mixture, this sediment still can form only and be dispersed in solution.
Method of the present invention comprises to the step that adds additive in above-mentioned solution mixture.The additive using is in the present invention the acid complex mixture that comprises carboxylic acid, peroxide and sulphate.Sulphate is preferably one or more compounds that are selected from sulfuric acid (concentrated sulfuric acid that particularly concentration is at least 95%), ammonium sulfate and sulfur dioxide.Carboxylic acid is not limited to specifically a kind of, and can accept to have any carboxylic acid of one or more functional groups, but is preferably as the dicarboxylic acids of oxalic acid, butanedioic acid, tartaric acid and glutamic acid at this carboxylic acid.Peroxide is not limited, can use the peroxide of any organic or inorganic, for example, dialkyl peroxide or acyl peroxide.Particularly, consider easy processing and price, more preferably hydrogen peroxide.
For molybdenum (Mo) atom that adds 1mol wherein with molybdenum salt form, the content that is included in each component in acid complex mixture is preferably 0.05～1.5mol.For the molybdenum atom of 1mol, if the content of the content of every kind of compound, especially sulphate is less than 0.05mol, this catalyst in whole range of reaction temperature, can demonstrate low-down conversion of propane and acrylic acid selective.On the contrary, if content is greater than 1.5mol, catalyst can have at low temperatures quite high acrylic acid selectively but have the low-down conversion of propane that mostly is 10% most, and selectively can reduce rapidly when temperature raises.
The additive comprising in catalyst of the present invention plays the effect that improves catalytic activity, but meanwhile it has accelerated the precipitation of the catalyst precarsor in the solution mixture of slaine.By evaporative distillation water, be exactly by adopting rotary vacuum drier evaporative distillation water, this precipitation that can collection catalyst precursor.To not restriction of baking temperature, but must be the temperature that can make water effective evaporation, this temperature be preferably 100 ℃ of left and right or more than.Pulverize dried catalyst precarsor, adopt hydraulic press moulded section, then again pulverize.Obtained catalyst precarsor particle is sieved to prepare uniform powder, then calcine.The preferred size of catalyst precarsor particle is 100～300 μ m.Can after dry and crushing catalyst precursor, calcine immediately, but preferably in moulded section with after pulverizing, calcine.Thereby the density that the reason of first carrying out moulded section is moulded section has increased catalyst has increased the conversion of propane in propane-catalyst reaction process.
Method of the present invention comprises that calcined catalyst precursor is to obtain the step of final catalyst.Calcining generally includes two stages.First stage for to calcine 1～4 hour in air stream at 150～250 ℃, and second stage for to calcine 1～4 hour in nitrogen or inert gas flow at 500～650 ℃.
That by said method, prepares is of the present inventionly represented by Chemical formula 1 for the production of acrylic acid oxide catalyst.
[Chemical formula 1]
Mo 1.0V aTe bNb cO n
In Chemical formula 1,
Mo is molybdenum, and V is vanadium, and Te is that tellurium and Nb are niobium;
A, b, c and n represent respectively the mol ratio of vanadium, tellurium, niobium and oxygen atom, and it is 0.01≤a≤l; 0.01≤b≤l; 0.01≤c≤l; And
N serve as reasons valence and the determined number of weight of other elements.
Catalyst of the present invention is for producing acrylic acid by the gaseous oxidation of propane, provides high conversion of propane and acrylic acid selective simultaneously.
Accompanying drawing explanation
With reference to accompanying drawing, will understand best the application of the preferred embodiment of the present invention, wherein:
Fig. 1 optionally schemes for showing according to embodiment and comparative example's catalyst conversion of propane and acrylic acid in producing acrylic acid process by the gaseous oxidation of propane.
The specific embodiment
As shown in the following examples, reality of the present invention and current preferred embodiment have been described.
Yet, should be appreciated that for this disclosure, those skilled in the art can modify and improve within the spirit and scope of the present invention.
embodiment 1
At room temperature the telluric acid of the ammonium metavanadate of the ammonium paramolybdate of 1.178g, 0.234g and 0.352g is dissolved in the distilled water of 50ml, obtains the solution of clarification.In this solution, add 4ml wherein to dissolve the distilled water of 0.3626g ammonium niobium oxalate, then stir and within 180 minutes, prepare solution mixture.
Oxalic acid aqueous solution (hydrogen ion concentration with 1mol/kg is dissolved in oxalic acid in distilled water), the aqueous sulfuric acid of 0.918g and the aqueous hydrogen peroxide solution of 6.011g (concentration with 1mol/kg is dissolved in hydrogen peroxide in distilled water) to adding 0.403g in this solution mixture, then stir 60 minutes.
Adopt rotary vacuum drier to evaporate distilled water, further dry to be dried thoroughly at 120 ℃, then pulverize and obtain briquetting (compact).Briquetting is again pulverized and obtained the catalyst granules that granularity is 180～250 μ m.The catalyst granules filtering out is calcined first 2 hours under air exists at 200 ℃, then under nitrogen exists, at 600 ℃, calcined for the second time 2 hours.As a result, make final catalyst.Mol ratio based on slaine, the expection composition of catalyst is estimated as Mo 1.0v 0.3te 0.23nb 0.12o n.Yet because the fusing point of Te is relatively low, it is 449.5 ℃, a large amount of Te evaporations in calcination process.Therefore, the actual content of Te is lower than expection.Can generally observe this phenomenon in the following embodiments.
embodiment 2
At room temperature the telluric acid of the ammonium metavanadate of the ammonium paramolybdate of 1.178g, 0.234g and 0.352g is dissolved in the distilled water of 50ml, obtains the solution of clarification.In this solution, add 4ml wherein to dissolve the distilled water of 0.3626g ammonium niobium oxalate, then stir 180 minutes to prepare solution mixture.
Oxalic acid aqueous solution (hydrogen ion concentration with 1mol/kg is dissolved in oxalic acid in distilled water), the aqueous sulfuric acid of 0.75g and the aqueous hydrogen peroxide solution of 7.5g (concentration with 1mol/kg is dissolved in hydrogen peroxide in distilled water) to adding 0.75g in this solution mixture, then stir 60 minutes.
Adopt rotary vacuum drier to evaporate distilled water, further dry to be dried thoroughly at 120 ℃, then pulverize and obtain briquetting.Briquetting is again pulverized and obtained the catalyst granules that granularity is 180～250 μ m.The catalyst granules filtering out is calcined first 2 hours under air exists at 200 ℃, then under nitrogen exists, at 600 ℃, calcined for the second time 2 hours.
embodiment 3
At room temperature the telluric acid of the ammonium metavanadate of the ammonium paramolybdate of 1.178g, 0.234g and 0.352g is dissolved in the distilled water of 50ml, obtains the solution of clarification.In this solution, add 4ml wherein to dissolve the distilled water of 0.3626g ammonium niobium oxalate, then stir 180 minutes to prepare solution mixture.
Oxalic acid aqueous solution (hydrogen ion concentration with 1mol/kg is dissolved in oxalic acid in distilled water), the aqueous sulfuric acid of 1.0g and the aqueous hydrogen peroxide solution of 5.0g (concentration with 1mol/kg is dissolved in hydrogen peroxide in distilled water) to adding 0.5g in this solution mixture, then stir 60 minutes.
Adopt rotary vacuum drier evaporative distillation water, further at 120 ℃, then finish-drying grinds and obtains briquetting.Milling briquetting obtains the catalyst granules that granularity is 180～250 μ m again.The catalyst granules of picking out is calcined first 2 hours under air exists at 200 ℃, then under nitrogen exists, calcines for the second time 2 hours at 600 ℃.
embodiment 4
At room temperature the telluric acid of the ammonium metavanadate of the ammonium paramolybdate of 1.178g, 0.234g and 0.352g is dissolved in the distilled water of 50ml, obtains the solution of clarification.In this solution, add 4ml wherein to dissolve the distilled water of 0.3626g ammonium niobium oxalate, then stir 180 minutes to prepare solution mixture.
Oxalic acid aqueous solution (hydrogen ion concentration with 1mol/kg is dissolved in oxalic acid in distilled water), the aqueous sulfuric acid of 1.0g and the aqueous hydrogen peroxide solution of 0.5g (concentration with 1mol/kg is dissolved in hydrogen peroxide in distilled water) to adding 1.0g in this solution mixture, then stir 60 minutes.
Adopt rotary vacuum drier to evaporate distilled water, further dry to be dried thoroughly at 120 ℃, then pulverize and obtain briquetting.Briquetting is obtained to the catalyst granules that granularity is 180～250 μ m in this pulverizing.The catalyst granules filtering out is calcined first 2 hours under air exists at 200 ℃, then under nitrogen exists, at 600 ℃, calcined for the second time 2 hours.
comparative example 1
At room temperature the telluric acid of the ammonium metavanadate of the ammonium paramolybdate of 1.178g, 0.234g and 0.352g is dissolved in the distilled water of 50ml, obtains the solution of clarification.To the little 4ml of adding of this solution, wherein dissolve the distilled water of 0.3626g ammonium niobium oxalate, then stirred 240 minutes to prepare solution mixture.
Adopt rotary vacuum drier to evaporate distilled water, further dry to carry out finish-drying at 120 ℃, then pulverize and obtain briquetting.Briquetting is again pulverized and obtained the catalyst granules that granularity is 180～250 μ m.The catalyst granules filtering out is calcined first 2 hours under air exists at 200 ℃, then under nitrogen exists, at 600 ℃, calcined for the second time 2 hours.
comparative example 2
At room temperature the telluric acid of the ammonium metavanadate of the ammonium paramolybdate of 1.178g, 0.234g and 0.352g is dissolved in the distilled water of 50ml, obtains the solution of clarification.In this solution, add 4ml wherein to dissolve the distilled water of 0.3626g ammonium niobium oxalate, then stir 180 minutes to prepare solution mixture.
To add in this solution mixture 0.918g aqueous sulfuric acid (with the hydrogen ion concentration of 1mol/kg by sulfuric acid dissolution in distilled water), then stir 60 minutes.
Adopt rotary vacuum drier to evaporate distilled water, further dry to carry out finish-drying at 120 ℃, then pulverize and obtain briquetting.Briquetting is again pulverized and obtained the catalyst granules that granularity is 180～250 μ m.The catalyst granules filtering out is calcined first 2 hours under air exists at 200 ℃, then under nitrogen exists, at 600 ℃, calcined for the second time 2 hours.
comparative example 3
At room temperature the telluric acid of the ammonium metavanadate of the ammonium paramolybdate of 1.178g, 0.234g and 0.352g is dissolved in the distilled water of 50ml, obtains the solution of clarification.In this solution, add 4ml wherein to dissolve the distilled water of 0.3626g ammonium niobium oxalate, then stir 180 minutes to prepare solution mixture.
Oxalic acid aqueous solution (hydrogen ion concentration with 1mol/kg is dissolved in oxalic acid in distilled water) to adding 0.403g in this solution mixture, then stirs 60 minutes.
Adopt rotary vacuum drier to evaporate distilled water, further dry to carry out finish-drying at 120 ℃, then pulverize and obtain briquetting.Briquetting is again pulverized and obtained the catalyst granules that granularity is 180～250 μ m.The catalyst granules filtering out is calcined first 2 hours under air exists at 200 ℃, then under nitrogen exists, at 600 ℃, calcined for the second time 2 hours.
comparative example 4
At room temperature the telluric acid of the ammonium metavanadate of the ammonium paramolybdate of 1.178g, 0.234g and 0.352g is dissolved in the distilled water of 50ml, obtains the solution of clarification.In this solution, add 4ml wherein to dissolve the distilled water of 0.3626g ammonium niobium oxalate, then stir 180 minutes to prepare solution mixture.
Aqueous hydrogen peroxide solution (concentration with 1mol/kg is dissolved in hydrogen peroxide in distilled water) to adding 6.011g in this solution mixture, then stirs 60 minutes.
Adopt rotary vacuum drier evaporative distillation water, further dry to carry out finish-drying at 120 ℃, then pulverize and obtain briquetting.Briquetting is again pulverized and obtained the catalyst granules that granularity is 180～250 μ m.The catalyst granules filtering out is calcined first 2 hours under air exists at 200 ℃, then under nitrogen exists, at 600 ℃, calcined for the second time 2 hours.
comparative example 5
At room temperature the telluric acid of the ammonium metavanadate of the ammonium paramolybdate of 1.178g, 0.234g and 0.352g is dissolved in the distilled water of 50ml, obtains the solution of clarification.In this solution, add 4ml wherein to dissolve the distilled water of 0.3626g ammonium niobium oxalate, then stir 180 minutes to prepare solution mixture.
In this solution mixture, add the oxalic acid aqueous solution (hydrogen ion concentration with 1mol/kg is dissolved in oxalic acid in distilled water) of 0.403g and the aqueous hydrogen peroxide solution (concentration with 1mol/kg is dissolved in hydrogen peroxide in distilled water) of 6.011g, then stir 60 minutes.
Adopt rotary vacuum drier to evaporate distilled water, further dry to carry out finish-drying at 120 ℃, then pulverize and obtain briquetting.Briquetting is again pulverized and obtained the catalyst granules that granularity is 180～250 μ m.The catalyst granules filtering out is calcined first 2 hours under air exists at 200 ℃, then under nitrogen exists, at 600 ℃, calcined for the second time 2 hours.
comparative example 6
At room temperature the telluric acid of the ammonium metavanadate of the ammonium paramolybdate of 1.178g, 0.234g and 0.352g is dissolved in the distilled water of 50ml, obtains the solution of clarification.In this solution, add 4ml wherein to dissolve the distilled water of 0.3626g ammonium niobium oxalate, then stir 180 minutes to prepare solution mixture.
In this solution mixture, add the oxalic acid aqueous solution (hydrogen ion concentration with 1mol/kg is dissolved in oxalic acid in distilled water) of 0.403g and the aqueous sulfuric acid of 0.918g, then stir 60 minutes.
Adopt rotary vacuum drier to evaporate distilled water, further dry to carry out finish-drying at 120 ℃, then pulverize and obtain briquetting.Briquetting is again pulverized and obtained the catalyst granules that granularity is 180～250 μ m.The catalyst granules filtering out is calcined first 2 hours under air exists at 200 ℃, then under nitrogen exists, at 600 ℃, calcined for the second time 2 hours.
comparative example 7
At room temperature the telluric acid of the ammonium metavanadate of the ammonium paramolybdate of 1.178g, 0.234g and 0.352g is dissolved in the distilled water of 50ml, obtains the solution of clarification.In this solution, add 4ml wherein to dissolve the distilled water of 0.3626g ammonium niobium oxalate, then stir 180 minutes to prepare solution mixture.
Oxalic acid aqueous solution (hydrogen ion concentration with 1mol/kg is dissolved in oxalic acid in distilled water), the aqueous sulfuric acid of 0.5g and the aqueous hydrogen peroxide solution of 10g (concentration with 1mol/kg is dissolved in hydrogen peroxide in distilled water) to adding 1.0g in this solution mixture, then stir 60 minutes.
Adopt rotary vacuum drier to evaporate distilled water, further dry to carry out finish-drying at 120 ℃, then pulverize and obtain briquetting.Briquetting is again pulverized and obtained the catalyst granules that granularity is 180～250 μ m.The catalyst granules filtering out is calcined first 2 hours under air exists at 200 ℃, then under nitrogen exists, at 600 ℃, calcined for the second time 2 hours.
Experimental example
The selective oxidation of the catalyst inducement propane that employing is prepared in embodiment 1～4 and comparative example 1～7.
With the catalyst of 0.1g, fill fixed-bed type reactor, with 1,329hr -1air speed per hour at 340～400 ℃ to its input supply gas (propane: oxygen: nitrogen: water=5.85: 11.69: 58.02: 24.44).Result is presented in Fig. 1.To being optionally relatively presented in table 1 of same conversion (25%).
As shown in Figure 1, when by the catalyst of preparation in an embodiment of the present invention during for the production of acrylic acid, increase conversion of propane and acrylic acid is selective, therefore increased acrylic acid productive rate.
Table 1
Precipitating reagent Acrylic acid selective (%)
Embodiment 1 Oxalic acid 0.403, sulfuric acid 0.918g, hydrogen peroxide 6.011 72.68
Embodiment 2 Oxalic acid 0.75, sulfuric acid 0.75, hydrogen peroxide 7.5 71.22
Embodiment 3 Oxalic acid 0.5, sulfuric acid 1.0, hydrogen peroxide 5.0 71.91
Embodiment 4 Oxalic acid 1.0, sulfuric acid 1.0, hydrogen peroxidase 10 .5 71.13
Comparative example 1 - 58.40
Comparative example 2 Sulfuric acid 0.918 69.21
Comparative example 3 Oxalic acid 0.403 64.04
Comparative example 4 Hydrogen peroxide 6.011 66.43
Comparative example 5 Oxalic acid 0.403, hydrogen peroxide 6.011 67.04
Comparative example 6 Oxalic acid 0.403, sulfuric acid 0.918 69.29
Comparative example 7 Oxalic acid 1.0, sulfuric acid 0.5, hydrogen peroxide 10.0 66.24
As shown in table 1, in embodiment 1～4, used the acid complex mixture that comprises 3 kinds of different compounds as precipitating reagent.Compare as precipitating reagent (comparative example 1～6) from the acid complex mixture that adopts single compound or comprise two kinds of different compounds, acrylic acid productive rate is splendid in these cases.Catalyst prepared by the acid complex mixture that employing comprises 3 kinds of different compounds in embodiment 1～4 also has higher acrylic acid yield than comparative example 7 catalyst, comparative example 7 catalyst adopts the acid complex mixture that comprises 3 kinds of different compounds to prepare, but wherein, for the molybdenum of 1mol, the content of additive is over 1.5 times.
Industrial applicibility
As previously mentioned, can be for the preparation of producing acrylic acid oxide catalyst with high catalytic activity by method of the present invention.
Skilled person in the art will appreciate that disclosed concept and the specific embodiment can be easily used as in above-mentioned description revises or designs other for implementing the basis of the embodiment of identical object of the present invention.Those skilled in the art also will appreciate that, such embodiment that is equal to does not depart from as the spirit and scope of the invention as illustrated in appended claims.

Claims (4)

1. for the preparation of a method of producing acrylic acid oxide catalyst, comprise the steps: to carry out Kaolinite Preparation of Catalyst precursor by the solution mixture of molybdenum salt, vanadic salts, tellurium salt and niobium salt; Then be dried and calcine this catalyst precarsor, wherein, the method also comprises to the step that adds additive in the solution mixture of slaine, and additive described here is the acid complex mixture that comprises carboxylic acid, peroxide and sulfuric acid,
Wherein, for the 1mol molybdenum atom adding with molybdenum salt form, the content of carboxylic acid, peroxide and sulfuric acid is respectively 0.05～1.5mol, and wherein, described carboxylic acid is oxalic acid, and described peroxide is hydrogen peroxide.
2. the method for the preparation of producing acrylic acid oxide catalyst according to claim 1, wherein, described catalyst is represented by Chemical formula 1 below
[Chemical formula 1]
Mo 1.0V aTe bNb cO n
Wherein, Mo is molybdenum, and V is vanadium, and Te is that tellurium and Nb are niobium; A, b, c and n represent respectively the mol ratio of vanadium, tellurium, niobium and oxygen atom, and it is 0.01≤a≤l; 0.01≤b≤l; 0.01≤c≤l; And n serve as reasons valence and the determined number of weight of other elements.
3. the method for the preparation of producing acrylic acid oxide catalyst according to claim 1, wherein, by evaporating solvent, the solution mixture by slaine directly obtains described catalyst precarsor, and without using any other separator, and described solvent is water.
4. the method for the preparation of producing acrylic acid oxide catalyst according to claim 1, wherein, first described calcining is carried out 1～4 hour in air stream at 150～250 ℃, then in inert gas flow, carries out 1～4 hour at 500～650 ℃.
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CN113492017A (en) * 2020-04-08 2021-10-12 中国石油天然气股份有限公司 Supported catalyst for preparing acrylic acid by catalytic oxidation of propane, and preparation method and application thereof

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