CN1531998A - Heteropoly acid containing phosphours,molybdinum and tin and its preparing method, and use of said heteropoly acid in preparing oxidizing catalyst - Google Patents
Heteropoly acid containing phosphours,molybdinum and tin and its preparing method, and use of said heteropoly acid in preparing oxidizing catalyst Download PDFInfo
- Publication number
- CN1531998A CN1531998A CNA031182291A CN03118229A CN1531998A CN 1531998 A CN1531998 A CN 1531998A CN A031182291 A CNA031182291 A CN A031182291A CN 03118229 A CN03118229 A CN 03118229A CN 1531998 A CN1531998 A CN 1531998A
- Authority
- CN
- China
- Prior art keywords
- molybdenum
- tin
- phosphorous
- heteropoly acid
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Catalysts (AREA)
Abstract
The present invention discloses a kind of heteropoly acid containing P in phosphide, Mo in molybdic compound and Sn in stannide in the molar ratio of 0.21-1.24 to 0.1-0.36 to 0.05-0.19. The preparation process of the heteropoly acid includes preparing ammonium molybddophosphate with ammonium molybdate and phosphoric acid; and addition of potassium bistannite, sodium bistannite or stannous hydroxide. The heteropoly acid is carried onto diatomite or zeolite to form oxidizing catalyst suitable for use in SO2 concentration of 3-14 % and in 360-640 deg.c and reaching a total conversion rate of 99.5-99.8%. The catalyst has performance indexes near those of cesium-containing oxidizing catalyst and may be used to replace available cesium-containing oxidizing catalyst in sulfuric acid production.
Description
Technical field
The present invention relates to a kind of heteropoly acid and its production and use, particularly a kind of phosphorous, molybdenum, tin heteropoly acid and the method and the application of this heteropoly acid in the preparation oxidation catalyst that prepare this heteropoly acid.
Background technology
Heteropoly acid and heteropolyacid salt with acidity, " accurate liquid phase " behavior of its uniqueness, and have characteristics such as highly acid and strong oxidizing property as the novel catalysis material of a class simultaneously, are subjected to paying attention to widely in the catalyticing research field.
Present heteropoly acid is made the Application of Catalyst example in organic reaction many, disclose a kind of ether-splitting that is used for as Chinese patent publication number 1185992 and separated the rare silicon dioxide carried phosphotungstic acid of system isobutyl and the composite catalyst and the USP 5 of magnesium nitrate, 750,457 disclose a kind of Cs that supports precious metals pd
2.5H
0.5PW
12O
40Catalyst, but do not appear in the newspapers in the application of vanadium catalyst.
According to the using method of the disclosed a kind of heteropoly acid catalyst of Chinese patent publication number 1390643A, a shortcoming when heteropoly acid or heteropolyacid salt are used as solid acid catalyst is that its acidity particularly its acid strength is unstable under common reaction condition.In the highly acid reaction system of needs, can make catalysqt deactivation because of its acid strength reduces gradually; In the more weak reaction system of the acid strength of needs, stronger acid site can cause disadvantageous side reactions such as polymerization, coking again.
The vanadium catalyst that present in addition domestic production sulfuric acid is adopted generally adopts following technology to be prepared from: diatomite is refining, make SiO in the diatomite
2Content reaches more than 83%; With V
2O
5Handle by KOH, make it to become KVO
3Solution is at KVO
3Add H in the solution
2SO
4Form the jelly after neutralizing; Pour terra silicea purificata, jelly, glauber salt and sulphur metering into roller and carry out abundant mixed grind; The formation product is dried, calcined to material after the mixed grind by after the banded extruder moulding, again.This vanadium catalyst exists active low, and mechanical strength is not high, and abrasion are big, the drawback that desired reaction temperature is high.The disclosed a kind of cesium containing mercury sulfate catalyst of Chinese patent publication number 1358569A for this reason, to reducing the temperature of conversion system, improve total conversion and sulphuric acid output and truly have its superiority, but because its expensive price and will use the rare metal caesium has in a large number seriously restricted its scope of application and the market demand.
Summary of the invention
One of purpose of the present invention provides and a kind ofly can reduce the light-off temperature of catalyst and improve its low temperature active, can improve active phosphorous, the molybdenum of temperature in the catalyst, tin heteropoly acid again.
The heteropoly acid of this phosphorous, molybdenum, tin is made up of phosphorus compound, molybdenum compound and tin compound, and wherein phosphorus in the phosphorus compound and the molybdenum in the molybdenum compound, the mol ratio between the tin in the tin compound are 0.21～1.24: 0.1～0.36: 0.05～0.19.
Described phosphorus compound can be selected phosphorous organic compound for use, also can select phosphorous inorganic compound for use, wherein phosphorous inorganic compound can be a kind of in orthophosphoric acid, pyrophosphoric acid, phosphorous acid, polyphosphoric acid and the phosphorus pentoxide or their mixture, but preferably selects 85% orthophosphoric acid for use; Phosphorous organic compound can be selected trimethyl phosphate, diphenyl phosphate, phosphoguanidine for use.
Described molybdenum compound can be selected the organic compound that contains molybdenum for use, also can select the inorganic compound that contains molybdenum for use, and the inorganic compound that wherein contains molybdenum can be a kind of in molybdenum trioxide, molybdenum bisuphide, the molybdenum hydroxide or their mixture; The organic compound that contains molybdenum can be selected ammonium molybdate for use.
Described tin compound can be selected the organic compound of stanniferous for use, also can select the inorganic compound of stanniferous for use, wherein the inorganic compound of stanniferous can be a kind of in butter of tin, stannous chloride, stannic hydroxide, stannous sulfate, potassium hydrogen deutostannic, the inferior stannic acid hydrogen sodium or their mixture, but preferably selects a kind of in stannous sulfate, potassium hydrogen deutostannic, the inferior stannic acid hydrogen sodium for use; The organic compound of stanniferous can be selected bis oxide tributyl tin, di-n-butyltin dilaurate, stannous octoate for use.
Above-mentioned molybdenum compound can substitute with the organic compound of tungsten or the inorganic compound of tungsten.
Above-mentioned phosphorus compound can substitute with the organic compound of boron or the inorganic compound of boron.
Two of purpose of the present invention provides the preparation method of above-mentioned phosphorous, molybdenum, tin heteropoly acid.
The foregoing invention purpose can realize by following technical measures: the preparation method of a kind of phosphorous, molybdenum, tin heteropoly acid, its preparation process is quantitatively to take by weighing ammonium molybdate and quantitatively measure 85% phosphoric acid earlier, both mix the back an amount of water of adding and stir evenly into white slurry, be heated to then and be reaction end when fluidized state makes slurry transfer golden yellow to by white, after being cooled to room temperature, promptly make ammonium phosphomolybdate with quantitative ammonia solvent; After the potassium hydrogen deutostannic that adds amount of calculation again makes both abundant mixings, be heated to fluidized state and keep making after 5～10 minutes the heteropoly acid of phosphorous, molybdenum, tin.
The foregoing invention purpose can also realize by following technical measures: the preparation method of a kind of phosphorous, molybdenum, tin heteropoly acid, its preparation process is quantitatively to take by weighing ammonium molybdate and measure 85% phosphoric acid by doubling dose earlier, both stir evenly into white slurry after mixing, be heated to fluidized state then, after treating that ammonium molybdate dissolves fully, slurry is faint yellow oily solution and promptly makes ammonium phosphomolybdate; After the potassium hydrogen deutostannic that adds amount of calculation again makes both abundant mixings, be heated to fluidized state and keep making after 5～10 minutes the heteropoly acid of phosphorous, molybdenum, tin.
The foregoing invention purpose can also realize by following technical measures: the preparation method of a kind of phosphorous, molybdenum, tin heteropoly acid, its preparation process is quantitatively to take by weighing ammonium molybdate and quantitatively measure 85% phosphoric acid earlier, both mix the back an amount of water of adding and stir evenly into white slurry, be heated to then and be reaction end when fluidized state makes slurry transfer golden yellow to by white, after being cooled to room temperature, promptly make ammonium phosphomolybdate with quantitative ammonia solvent; After the inferior stannic acid hydrogen sodium that adds amount of calculation again makes both abundant mixings, be heated to fluidized state and keep making after 5～10 minutes the heteropoly acid of phosphorous, molybdenum, tin.
The foregoing invention purpose can also realize by following technical measures: the preparation method of a kind of phosphorous, molybdenum, tin heteropoly acid, its preparation process is quantitatively to take by weighing ammonium molybdate and measure 85% phosphoric acid by doubling dose earlier, both stir evenly into white slurry after mixing, be heated to fluidized state then, after treating that ammonium molybdate dissolves fully, slurry is faint yellow oily solution and promptly makes ammonium phosphomolybdate; After the inferior stannic acid hydrogen sodium that adds amount of calculation again makes both abundant mixings, be heated to fluidized state and keep making after 5～10 minutes the heteropoly acid of phosphorous, molybdenum, tin.
The foregoing invention purpose can also realize by following technical measures: the preparation method of a kind of phosphorous, molybdenum, tin heteropoly acid, its preparation process is quantitatively to take by weighing ammonium molybdate and quantitatively measure 85% phosphoric acid earlier, both mix the back an amount of water of adding and stir evenly into white slurry, be heated to then and be reaction end when fluidized state makes slurry transfer golden yellow to by white, after being cooled to room temperature, promptly make ammonium phosphomolybdate with quantitative ammonia solvent; Get quantitative stannous sulfate again and be prepared into stannous hydroxide, and, prepare potassium metavanadate solution according to the prescription in the existing vanadic sulfate Catalyst Production; Stannous hydroxide joined in the potassium metavanadate solution and be heated to stannous hydroxide dissolve fully, make the heteropoly acid of phosphorous, molybdenum, tin after adding the ammonium phosphomolybdate that has prepared then and being heated to fluidized state.
The foregoing invention purpose can also realize by following technical measures: the preparation method of a kind of phosphorous, molybdenum, tin heteropoly acid, its preparation process is quantitatively to take by weighing ammonium molybdate and measure 85% phosphoric acid by doubling dose earlier, both stir evenly into white slurry after mixing, be heated to fluidized state then, after treating that ammonium molybdate dissolves fully, slurry is faint yellow oily solution and promptly makes ammonium phosphomolybdate; Get quantitative stannous sulfate again and be prepared into stannous hydroxide, and, prepare potassium metavanadate solution according to the prescription in the existing vanadic sulfate Catalyst Production; Stannous hydroxide joined in the potassium metavanadate solution and be heated to stannous hydroxide dissolve fully, make the heteropoly acid of phosphorous, molybdenum, tin after adding the ammonium phosphomolybdate that has prepared then and being heated to fluidized state.
Three of purpose of the present invention provides above-mentioned phosphorous, molybdenum, the application of tin heteropoly acid in the preparation oxidation catalyst.
Above-mentioned application can realize by following technical measures: the heteropoly acid of phosphorous, molybdenum, tin is stated from makes catalyst on the diatomaceous carrier and use.Its concrete grammar is that the heteropoly acid with phosphorous, molybdenum, tin joins by the good KVO of formulated in the existing vanadic sulfate Catalyst Production
3In the solution and be heated to fluidized state, add sulfuric acid again and neutralize, the final pH value of control material is between 2～3; Then material was placed in 80 ℃ of baking ovens ageing 2～3 hours, again through and diatomite mixed grind, moulding, drying and calcining formation product.
Above-mentioned application can also realize by following technical measures: the heteropoly acid of phosphorous, molybdenum, tin is stated from makes catalyst on the carrier of zeolite and use.Described zeolite can be a kind of in γ type zeolite, modenite, ZSM series zeolite, the Beta zeolite or their mixture.
Phosphorous, the molybdenum, the tin heteropoly acid that prepare according to prescription provided by the present invention and preparation method are applied in the prescription of the vanadium catalyst of preparing sulfuric acid by oxidizing in the present sulfuric acid industry, it is dense between 3～14% that prepared vanadium catalyst is suitable for sulfur dioxide gas, and manipulate in 360 ℃～640 ℃ temperature range.Can make total conversion reach 99.5%～99.8%.Sulfur dioxide emptying amount after transforming is about 80～300PPM.Made vanadium catalyst product detects through national catalyst inspection center, and the low temperature active of this product is: the activity the when activity the when activity the when activity in the time of 360 ℃ is 18%, 390 ℃ is 40.8%, 410 ℃ is 63.5%, 485 ℃ is 89.9%.After the vanadium catalyst batch suitability for industrialized production, its product is through 100,000 tons of/year on probation showing of device of producing sulfuric acid; The industrial initiation temperature of this type product is 300～350 ℃; its Heat stability is good can significantly improve total conversion, and can reduce the emptying of form waste gas of sulfur dioxide in a large number; have remarkable environmental benefit and economic benefit, go for the production instructions for use of industrial scale fully.Simultaneously every performance indications of this product near and reached the current every performance indications that contain the vanadium catalyst product of caesium, the alternative vanadium catalyst that contains caesium uses in gas washing in SA production fully.
The specific embodiment
Phosphorous, the molybdenum of present embodiment, the heteropoly acid of tin are made up of phosphorus compound, molybdenum compound and tin compound, and wherein phosphorus in the phosphorus compound and the molybdenum in the molybdenum compound, the mol ratio between the tin in the tin compound are 0.21～1.24: 0.1～0.36: 0.05～0.19.
Phosphorus compound can be selected phosphorous organic compound for use, also can select phosphorous inorganic compound for use, wherein phosphorous inorganic compound can be a kind of in orthophosphoric acid, pyrophosphoric acid, phosphorous acid, polyphosphoric acid and the phosphorus pentoxide or their mixture, but preferably selects 85% orthophosphoric acid for use; Phosphorous organic compound can be selected trimethyl phosphate, diphenyl phosphate, phosphoguanidine for use.
Molybdenum compound can be selected the organic compound that contains molybdenum for use, also can select the inorganic compound that contains molybdenum for use, and the inorganic compound that wherein contains molybdenum can be a kind of in molybdenum trioxide, molybdenum bisuphide, the molybdenum hydroxide or their mixture; The organic compound that contains molybdenum can be selected ammonium molybdate for use.
Tin compound can be selected the organic compound of stanniferous for use, also can select the inorganic compound of stanniferous for use, wherein the inorganic compound of stanniferous can be a kind of in butter of tin, stannous chloride, stannic hydroxide, stannous sulfate, potassium hydrogen deutostannic, the inferior stannic acid hydrogen sodium or their mixture, but preferably selects a kind of in stannous sulfate, potassium hydrogen deutostannic, the inferior stannic acid hydrogen sodium for use; The organic compound of stanniferous can be selected bis oxide tributyl tin, di-n-butyltin dilaurate, stannous octoate for use.
Molybdenum compound can substitute with the organic compound of tungsten or the inorganic compound of tungsten.
Phosphorus compound can substitute with the organic compound of boron or the inorganic compound of boron.
Be embodiments of the invention below, but the present invention is not limited to following examples.
Embodiment 1:
A, get 40 gram ammonium molybdates and add the 100ml water and stir into white pulpous state, add 85% phosphoric acid 30ml, stir evenly and be heated to when fluidized state makes slurry transfer golden yellow to by white and be reaction end, be cooled to room temperature after, promptly make ammonium phosphomolybdate with the 80ml ammonia solvent;
B or get phosphoric acid 70ml adds ammonium molybdate 40 grams and stirs into white pulpous state and be heated to fluidized state, treat that ammonium molybdate dissolves fully after, the faint yellow oily solution of slurry melt into is promptly made ammonium phosphomolybdate;
C, get 14.23 the gram stannous hydroxides be dissolved in 40 the gram potassium hydroxide solution in prepare potassium hydrogen deutostannic;
Be heated to fluidized state behind d, the potassium hydrogen deutostannic mixing that the ammonium phosphomolybdate and the c item of a item or b item preparation prepared and keep making after 5～10 minutes the heteropoly acid of phosphorous, molybdenum, tin, potassium;
E, by the prescription of present industrial production vanadic sulfate catalyst, prepare KVO
3Solution, the heteropoly acid of phosphorous, the molybdenum that then the d item is prepared, tin, potassium also is heated to fluidized state, adds 1+1 sulfuric acid again and neutralizes, and the final pH value of control material is between 2～3; Then material was placed in 80 ℃ of baking ovens ageing 2～3 hours;
F, the sulphur of terra silicea purificata (silicone content 〉=83%) and amount of calculation joined carry out abundant mixed grind in the edge runner, e item prepared materials is joined to continue in the edge runner to grind to take out to the requirement that is fit to extrusion then and carry out extrusion modling, oven dry, calcining and form product.
Embodiment 2:
A, prepare ammonium phosphomolybdate by a item among the embodiment 1 or the identical method of b item;
B, get 17.77 gram potassium hydrogen deutostannics and join in the ammonium phosphomolybdate of a item preparation, prepare the heteropoly acid of phosphorous, molybdenum, tin, potassium by the d item identical operations method among the embodiment 1;
C, all the other operating procedures are undertaken by the operating procedure of e item among the embodiment 1 and f item.
Embodiment 3:
A, prepare ammonium phosphomolybdate by a item among the embodiment 1 or the identical method of b item;
B, get the inferior stannic acid hydrogen sodium of 16.33 grams and join in the ammonium phosphomolybdate of a item preparation, prepare the heteropoly acid of phosphorous, molybdenum, tin, sodium by the d item identical operations method among the embodiment 1;
C, all the other operating procedures are undertaken by the operating procedure of e item among the embodiment 1 and f item.
Embodiment 4,
A, prepare ammonium phosphomolybdate by a item among the embodiment 1 or the identical method of b item;
B, get stannous sulfate 20 and restrain that to be equipped with stannous hydroxide standby;
C, press the prescription of vanadic sulfate catalyst prod, preparation KVO
3Solution adds the stannous hydroxide of b item preparation also then it is dissolved fully, adds the ammonium phosphomolybdate that a item prepares then, is heated to the heteropoly acid that makes phosphorous, molybdenum, vanadium, tin, potassium behind the fluidized state;
D, all the other operating procedures are undertaken by the operating procedure of e item among the embodiment 1 and f item.
Employed terra silicea purificata can replace with zeolite among the above embodiment 1,2,3,4, and zeolite can be a kind of in γ type zeolite, modenite, ZSM series zeolite, the Beta zeolite or their mixture.
The vanadic sulfate catalyst that above embodiment 1,2,3,4 is prepared, its method of measuring the conversion ratio of Sulphur Dioxide sulfur trioxide is carried out according to the chemical industry ministry standard of HG2086-91.
The product testing result of above embodiment and pilot product (in batches each 5 tons of products) detect its testing result such as following table through national catalyst inspection center:
Embodiment sample detection result
| Sample number into spectrum | Heat-resisting back Sulphur Dioxide rate (%) | Sample strength N/cm | Remarks | |||
| ????360° | ????390℃ | ????410℃ | ????485℃ | |||
| Embodiment 1 | ????18 | ????40.1 | ????63.8 | ????90.4 | ????56 | Shape of product is an annular |
| Embodiment 2 | ????17 | ????41.0 | ????53.4 | ????83.4 | ????75 | Shape of product is a cylindricality |
| Embodiment 3 | ????16.5 | ????39.9 | ????49.8 | ????83.1 | ????91 | The same |
| Embodiment 4 | ????19 | ????43 | ????65 | ????89.9 | ????85 | Shape of product is an annular |
| 5 tons of pilot products | ????19 | ????35 | ????53.1 | ????82.5 | The cylindrical products that national inspection centers are detected | |
| 5 tons of pilot products | ????18 | ????40.8 | ????63.5 | ????69.9 | The same product is an annular | |
Claims (18)
1, the heteropoly acid of a kind of phosphorous, molybdenum, tin, it is characterized in that being made up of phosphorus compound, molybdenum compound and tin compound, wherein phosphorus in the phosphorus compound and the molybdenum in the molybdenum compound, the mol ratio between the tin in the tin compound are 0.21～1.24: 0.1～0.36: 0.05～0.19.
2, the heteropoly acid of a kind of phosphorous, molybdenum according to claim 1, tin is characterized in that described phosphorus compound can select phosphorous organic compound for use, and described phosphorous organic compound can be selected trimethyl phosphate, diphenyl phosphate, phosphoguanidine for use.
3, the heteropoly acid of a kind of phosphorous, molybdenum according to claim 1, tin, it is characterized in that described phosphorus compound can select phosphorous inorganic compound for use, described phosphorous inorganic compound can be a kind of in orthophosphoric acid, pyrophosphoric acid, phosphorous acid, polyphosphoric acid and the phosphorus pentoxide or their mixture.
4, the heteropoly acid of a kind of phosphorous, molybdenum according to claim 3, tin is characterized in that described phosphorous inorganic compound preferably selects 85% orthophosphoric acid for use.
5, the heteropoly acid of a kind of phosphorous, molybdenum according to claim 1, tin is characterized in that described phosphorus compound can substitute with the organic compound of boron or the inorganic compound of boron.
6, the heteropoly acid of a kind of phosphorous, molybdenum according to claim 1, tin is characterized in that described molybdenum compound can select the organic compound that contains molybdenum for use, and the described organic compound that contains molybdenum is preferably selected ammonium molybdate for use.
7, the heteropoly acid of a kind of phosphorous, molybdenum according to claim 1, tin, it is characterized in that described molybdenum compound can select the inorganic compound that contains molybdenum for use, the described inorganic compound that contains molybdenum can be a kind of in molybdenum trioxide, molybdenum bisuphide, the molybdenum hydroxide or their mixture.
8, the heteropoly acid of a kind of phosphorous, molybdenum according to claim 1, tin is characterized in that described molybdenum compound can substitute with the organic compound of tungsten or the organic compound of tungsten.
9, the heteropoly acid of a kind of phosphorous, molybdenum according to claim 1, tin is characterized in that described tin compound can select the organic compound of stanniferous for use.The organic compound of stanniferous can be selected bis oxide tributyl tin, di-n-butyltin dilaurate, stannous octoate for use.
10, the heteropoly acid of a kind of phosphorous, molybdenum according to claim 1, tin, it is characterized in that described tin compound can select the inorganic compound of stanniferous for use, wherein the inorganic compound of stanniferous can be a kind of in butter of tin, stannous chloride, stannic hydroxide, stannous sulfate, potassium hydrogen deutostannic, the inferior stannic acid hydrogen sodium or their mixture, but preferably selects a kind of in stannous sulfate, potassium hydrogen deutostannic, the inferior stannic acid hydrogen sodium for use.
11, the preparation method of a kind of phosphorous, molybdenum as claimed in claim 1, tin heteropoly acid, it is characterized in that: its preparation process is quantitatively to take by weighing ammonium molybdate and quantitatively measure 85% phosphoric acid earlier, both mix the back an amount of water of adding and stir evenly into white slurry, be heated to then and be reaction end when fluidized state makes slurry transfer golden yellow to by white, after being cooled to room temperature, promptly make ammonium phosphomolybdate with quantitative ammonia solvent; Add again after the potassium hydrogen deutostannic of amount of calculation or inferior stannic acid hydrogen sodium makes both abundant mixings, be heated to fluidized state and keep making after 5～10 minutes the heteropoly acid of phosphorous, molybdenum, tin.
12, the preparation method of a kind of phosphorous, molybdenum as claimed in claim 1, tin heteropoly acid, it is characterized in that: its preparation process is quantitatively to take by weighing ammonium molybdate and measure 85% phosphoric acid by doubling dose earlier, both stir evenly into white slurry after mixing, be heated to fluidized state then, after treating that ammonium molybdate dissolves fully, slurry is faint yellow oily solution and promptly makes ammonium phosphomolybdate; After the inferior stannic acid hydrogen of the potassium hydrogen deutostannic sodium that adds amount of calculation again makes both abundant mixings, be heated to fluidized state and keep making after 5～10 minutes the heteropoly acid of phosphorous, molybdenum, tin.
13, the preparation method of a kind of phosphorous, molybdenum as claimed in claim 1, tin heteropoly acid, it is characterized in that: its preparation process is quantitatively to take by weighing ammonium molybdate and quantitatively measure 85% phosphoric acid earlier, both mix the back an amount of water of adding and stir evenly into white slurry, be heated to then and be reaction end when fluidized state makes slurry transfer golden yellow to by white, after being cooled to room temperature, promptly make ammonium phosphomolybdate with quantitative ammonia solvent; Get quantitative stannous sulfate again and be prepared into stannous hydroxide, and, prepare potassium metavanadate solution according to the prescription in the existing vanadic sulfate Catalyst Production; Stannous hydroxide joined in the potassium metavanadate solution and be heated to stannous hydroxide dissolve fully, make the heteropoly acid of phosphorous, molybdenum, tin after adding the ammonium phosphomolybdate that has prepared then and being heated to fluidized state.
14, the preparation method of a kind of phosphorous, molybdenum as claimed in claim 1, tin heteropoly acid, it is characterized in that: its preparation process is quantitatively to take by weighing ammonium molybdate and measure 85% phosphoric acid by doubling dose earlier, both stir evenly into white slurry after mixing, be heated to fluidized state then, after treating that ammonium molybdate dissolves fully, slurry is faint yellow oily solution and promptly makes ammonium phosphomolybdate; Get quantitative stannous sulfate again and be prepared into stannous hydroxide, and, prepare potassium metavanadate solution according to the prescription in the existing vanadic sulfate Catalyst Production; Stannous hydroxide joined in the potassium metavanadate solution and be heated to stannous hydroxide dissolve fully, make the heteropoly acid of phosphorous, molybdenum, tin after adding the ammonium phosphomolybdate that has prepared then and being heated to fluidized state.
15, a kind of phosphorous, molybdenum as claimed in claim 1, the application of tin heteropoly acid in the preparation oxidation catalyst is characterized in that heteropoly acid with phosphorous, molybdenum, tin is stated to make catalyst on the diatomaceous carrier and use.
16, phosphorous, molybdenum according to claim 15, the application of tin heteropoly acid in the preparation oxidation catalyst is characterized in that: it is concrete uses is that heteropoly acid with phosphorous, molybdenum, tin joins by the good KVO of formulated in the existing vanadic sulfate Catalyst Production
3In the solution and be heated to fluidized state, add sulfuric acid again and neutralize, the final pH value of control material is between 2～3; Then material was placed in 80 ℃ of baking ovens ageing 2～3 hours, again through and diatomite mixed grind, moulding, drying and calcining formation product.
17, a kind of phosphorous, molybdenum as claimed in claim 1, the application of tin heteropoly acid in the preparation oxidation catalyst is characterized in that heteropoly acid with phosphorous, molybdenum, tin is stated to make catalyst on the carrier of zeolite and use.
18, phosphorous, molybdenum according to claim 17, the application of tin heteropoly acid in the preparation oxidation catalyst is characterized in that: described zeolite can be a kind of in γ type zeolite, modenite, ZSM series zeolite, the Beta zeolite or their mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA031182291A CN1531998A (en) | 2003-03-26 | 2003-03-26 | Heteropoly acid containing phosphours,molybdinum and tin and its preparing method, and use of said heteropoly acid in preparing oxidizing catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA031182291A CN1531998A (en) | 2003-03-26 | 2003-03-26 | Heteropoly acid containing phosphours,molybdinum and tin and its preparing method, and use of said heteropoly acid in preparing oxidizing catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1531998A true CN1531998A (en) | 2004-09-29 |
Family
ID=34284891
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA031182291A Pending CN1531998A (en) | 2003-03-26 | 2003-03-26 | Heteropoly acid containing phosphours,molybdinum and tin and its preparing method, and use of said heteropoly acid in preparing oxidizing catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1531998A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102225207A (en) * | 2011-04-20 | 2011-10-26 | 南开大学 | Dehydrocholic acid-molybdenum heteropoly salt-dehydrocholic acid compound and synthesis method thereof |
| CN103073925A (en) * | 2013-01-30 | 2013-05-01 | 河南大学 | Surface-modified ammonium phosphotungstate/ammonium phosphomolybdate ultrafine particle and preparation method thereof |
| CN107008498A (en) * | 2017-04-10 | 2017-08-04 | 中南大学 | A kind of method for preparing phosphato-molybdic heteropolyacid solution |
-
2003
- 2003-03-26 CN CNA031182291A patent/CN1531998A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102225207A (en) * | 2011-04-20 | 2011-10-26 | 南开大学 | Dehydrocholic acid-molybdenum heteropoly salt-dehydrocholic acid compound and synthesis method thereof |
| CN102225207B (en) * | 2011-04-20 | 2012-10-03 | 南开大学 | Dehydrocholic acid-molybdenum heteropoly salt-dehydrocholic acid compound and synthesis method thereof |
| CN103073925A (en) * | 2013-01-30 | 2013-05-01 | 河南大学 | Surface-modified ammonium phosphotungstate/ammonium phosphomolybdate ultrafine particle and preparation method thereof |
| CN103073925B (en) * | 2013-01-30 | 2014-07-23 | 河南大学 | Surface-modified ammonium phosphotungstate/ammonium phosphomolybdate ultrafine particle and preparation method thereof |
| CN107008498A (en) * | 2017-04-10 | 2017-08-04 | 中南大学 | A kind of method for preparing phosphato-molybdic heteropolyacid solution |
| CN107008498B (en) * | 2017-04-10 | 2019-09-13 | 中南大学 | A method of preparing phosphato-molybdic heteropolyacid solution |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1255215C (en) | Improved catalyst for the manufacture of acrylonitrile | |
| CN1158625A (en) | Method of producing polytetra hydrofurane | |
| CN1792443A (en) | Catalysts for oxidation of methanol to formaldehyde | |
| CN110639492A (en) | Catalyst for preparing methyl acrylate from methyl acetate and formaldehyde and application thereof | |
| CN1647854A (en) | Catalyst for selectively oxidizing methyl acrylic aldehyde to synthesize methyl propenoic acid and its use | |
| CN1022608C (en) | Catalyst for the prodn. of methacrylic acid | |
| CN1451478A (en) | Method for reactivating catalyst for production of methacrylic acid | |
| CN1531998A (en) | Heteropoly acid containing phosphours,molybdinum and tin and its preparing method, and use of said heteropoly acid in preparing oxidizing catalyst | |
| CN106732750A (en) | A kind of monomolecular dispersion heteropolyacid catalyst preparation method of methacrolein oxidation preparing isobutene acid | |
| CN1218915C (en) | Solid acid catalyst for preparing ethylene glycol by ethylene oxide hydration | |
| CN1223579C (en) | Method for preparing p-chloro cyanobenzene | |
| CN1137101C (en) | Ammoxidation process of preparing 2-cyano pyrazine | |
| CN107597173A (en) | A kind of catalyst of phenol hydroxylation synthesizing benzene diphenol and preparation method thereof | |
| CN1048197C (en) | Maleic anhydride catalyst with heavy rare earth oxide and its application | |
| CN1310046A (en) | Fluidized bed catalyst for ammoxidating propylene to produce acrylonitrile | |
| CN1225460C (en) | Preparation of 3-cyanopyridine | |
| CN1074309C (en) | Fluid bed catalyst for the preparation of aromatic nitrile halide | |
| CN1218917C (en) | Process for preparing ethylene glycol by ethylene oxide catalytic hydration | |
| CN1226095C (en) | Solid phosphoric acid catalyst and its prepn process | |
| CN1204113C (en) | Preparation of tephthalyl intrile | |
| CN105728021A (en) | Composite carrier catalyst used for iso-butane dehydrogenation producing isobutylene and preparation method thereof | |
| CN1181913C (en) | Solid acid catalyst for preparing ethandiol by epoxyethane hydration | |
| CN104707627A (en) | Catalyst and preparation method thereof | |
| CN1164578C (en) | Fluidized bed catalyst for preparing 2-cyano pyrazine | |
| NL2030024B1 (en) | Method for preparing nitrobenzene by polyoxometalate catalysis |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |