CN103240075A - Rubidium-cesium-vanadium catalyst for producing sulfuric acid at low temperature, and preparation method thereof - Google Patents
Rubidium-cesium-vanadium catalyst for producing sulfuric acid at low temperature, and preparation method thereof Download PDFInfo
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- CN103240075A CN103240075A CN2013101622568A CN201310162256A CN103240075A CN 103240075 A CN103240075 A CN 103240075A CN 2013101622568 A CN2013101622568 A CN 2013101622568A CN 201310162256 A CN201310162256 A CN 201310162256A CN 103240075 A CN103240075 A CN 103240075A
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Abstract
The invention discloses a rubidium-cesium-vanadium catalyst for producing sulfuric acid at a low temperature, and a preparation method thereof. The rubidium-cesium-vanadium catalyst comprises the following components in a mass ratio: 4-5% of rubidium hydroxide, 2-3% of cesium hydroxide, 4-6% of vanadium pentoxide, 6-10% of potassium hydroxide and the balance of kieselguhr. The invention provides a catalyst for producing sulfuric acid with high activity at a low temperature, wherein cesium hydroxide and rubidium hydroxide are byproducts obtained after lithium and lithium salts are extracted from lithium mica; therefore, the production cost of the rubidium-cesium-vanadium catalyst is greatly reduced, and simultaneously, a low-temperature plasma dryer is used for drying; and the produced catalyst has evenly dispersed metal particles, is small in particle size and high in catalytic efficiency.
Description
Technical field:The present invention relates to rubidium caesium vanadium catalyst that a kind of Catalysts and its preparation method that sulfuric acid is used of producing, particularly temperature production sulfuric acid use and preparation method thereof.
Background technology: sulfuric acid is a kind of important Inorganic Chemicals, mainly adopts contact method production.The sulfur dioxide catalytic oxidation is that the conversion procedure of sulfur trioxide is the key link of gas washing in SA production, and the height of Sulphur Dioxide rate not only has influence on output and the cost of sulfuric acid, and significant to reducing environmental pollution.
Effective, the most direct way of conversion ratio that improves sulfur dioxide is the highly active low temperature catalyst of preparation.But up to the present to do the vanadium catalyst of co-catalyst be only catalyst to alkali metal salt.And caesium, the alkali-metal catalytic effect that helps of rubidium are best, but because the rubidium caesium belongs to rare metal, and output seldom, and is expensive, general manufacturing enterprise is difficult to bear, thereby is difficult to promote the use of.
Vanadium catalyst is to load on the diatomite with the active constituent that major catalyst vanadic anhydride and co-catalyst alkali metal salt are formed to make.Along with the development of catalyst research, its low temperature active improves constantly.The vanadium catalyst that uses the earliest is co-catalyst with sylvite. after nineteen fifties, change potassium sodium salt-mixture gradually into and make co-catalyst, its industrial serviceability temperature has reduced more than 30 ℃.Later 1980s, that progressively develops salt-mixture with potassium, sodium and caesium and be co-catalyst contains the caesium low temperature catalyst, and serviceability temperature has reduced by 20 ℃-30 ℃ again. but expensive because of cesium compound, the Catalyst Production cost is very high.Up to now, also do not produce this eka cesium, rubidium, vanadium catalyst product at home.
Rubidium, caesium, vanadium catalyst are mainly used in low-temperature catalyzed flue gas SO
2Transform SO
3, absorb back preparation sulfuric acid.Caesium, rubidium, vanadium catalyst article are a kind of vanadium catalysts through rubidium, caesium oxide modifying.
Show according to relevant industry statistic data, in China's gas washing in SA production metallurgical off-gas acid-making account for the gas washing in SA production total amount 31%, acid production with sulphur account for the gas washing in SA production total amount 47%, pyrite-based sulfuric acid production account for the gas washing in SA production total amount 20% other be raw material relieving haperacidity such as gypsum, hydrogen sulfide, sulphur coal.To reach 9,500 ten thousand tons to predict national sulfuric acid total output in 2015 in " sulfuric acid industry " 12 " development plan ".
In recent years, because environmental protection is severe day by day, to sulfur dioxide (SO2) emissions, change to overall control from concentration limit gradually.National environmental protection portion is in " sulfuric acid industry pollutant emission standard " (GB 26132-2010) of issue, and the sulfur dioxide pollution thing discharge standard limit value of gas washing in SA production is 400mg/m
3, in order to reduce the device sulfur dioxide emissioning concentration, using caesium rubidium vanadium catalyst is trend of the times.
By to alkali metal Cs, Rb and Li and lanthanide series La, Ce, Pr, the promoting catalysis of discovering these elements of rare metal promoting catalysis such as Nb improves along with the increase of element atomic number.The promoting catalysis maximum of rubidium in the alkali metal, and the promoting catalysis of rubidium caesium is best, resultant effect is best.
In order to solve serious environmental problem day by day, S0 in the control sulfuric acid plant tail gas
2Concentration of emission, development very is badly in need of at the caesium rubidium vanadium catalyst that greater activity is arranged of low temperature.Developing highly active caesium rubidium low-temperature vanadium catalyst is of great immediate significance.
Summary of the invention:The invention provides rubidium caesium vanadium catalyst that a kind of temperature production sulfuric acid uses and preparation method thereof, be primary raw material with diatomite, comprise cesium hydroxide, rubidium hydroxide, vanadic anhydride and potassium hydroxide etc., it is a kind of production sulfuric acid catalyst of low temperature high activity, its cesium hydroxide and rubidium hydroxide are to be accessory substance after raw material extracts lithium and lithium salts with the lepidolite, greatly reduce the production cost of caesium rubidium vanadium catalyst, use the low-temperature plasma drier to carry out drying simultaneously, the catalyst dispersed metal particle of producing is even, and particle diameter is little, the catalytic efficiency height.
The rubidium caesium vanadium catalyst that a kind of temperature production sulfuric acid of the present invention is used comprises that following quality is than component: rubidium hydroxide 4-5%, and cesium hydroxide 2-3%, vanadic anhydride 4-6%, potassium hydroxide 6-10%, surplus is diatomite.
The rubidium caesium vanadium catalyst that temperature production sulfuric acid of the present invention is used, described catalyst is made up of than component following quality: rubidium hydroxide 4-5%, cesium hydroxide 2-3%, vanadic anhydride 5-6%, potassium hydroxide 6-8%, surplus is diatomite.
Rubidium hydroxide of the present invention and cesium hydroxide are to be that raw material is carried the accessory substance that obtains in the process of lithium and lithium salts with the lepidolite.
The preparation method of the rubidium caesium vanadium catalyst that a kind of temperature production sulfuric acid is used, its method is as follows:
(1) diatomaceous processing: it is in the 40-50 Wt% sulfuric acid solution that diatomite is added concentration, be heated to 80-95 ℃, remove the metal impurities ion in the diatomite, filter, Separation of Solid and Liquid gets solids, filtrate is reclaimed, solids carries out drying with drier, and the control baking temperature is 100-120 ℃, gets diatomite 1;
(2) rubidium, caesium, the preparation of vanadium liquid: with the cesium hydroxide of above-mentioned mass ratio, rubidium hydroxide and potassium hydroxide, adding hot water dissolves, the control water temperature is at 80-90 ℃, make to add calcium hydroxide behind the solution and react, and the ph of control reaction solution is between 10-12, filter then, Separation of Solid and Liquid, solid is removed, and gets mother liquor; Add barium hydroxide in mother liquor, precipitation is removed the solid blanc fixe, getting filtrate is mixed solution mother liquor 1, adds potassium hydroxide and vanadic anhydride and heating for dissolving in mother liquor 1, filters, the ph that the smart filtrate that obtains adds the smart filtrate of acid adjusting is 2-3, makes rubidium, caesium, vanadium mixed liquor 2;
(3) preparation of rubidium, caesium, vanadium catalyst: the diatomite 1 of (1) step preparation and rubidium, caesium, the vanadium mixed liquor 2 of (2) step preparation are mixed, and adding accounts for 2-3 % sodium sulphate and the 1-2 % sulphur that mixes the back gross mass, it is even to carry out mixed grind, and extruded moulding, be dried to its water content≤1 Wt% with drier then, carry out roasting at last, the control sintering temperature is 500-580 ℃, roasting time 20-35 minute, cool naturally, get rubidium, caesium, vanadium catalyst product.
The preparation method of the rubidium caesium vanadium catalyst that temperature production sulfuric acid of the present invention is used, step (1) is filtered, Separation of Solid and Liquid, get solids, water content≤10 Wt% of control solids, solids carries out drying with drier, and the control baking temperature is 110 ℃, and control dried solids water content≤1 Wt%, get diatomite 1.
The preparation method of the rubidium caesium vanadium catalyst that temperature production sulfuric acid of the present invention is used, its step (2) add the ph value that sulfuric acid is regulated mixed solution.
Preparation method of the present invention, its described drying and roasting preferably adopt low temperature plasma to carry out drying and roasting.
Rubidium caesium vanadium catalyst that temperature production sulfuric acid of the present invention is used and preparation method thereof, the caesium of producing, rubidium, vanadium catalyst are because the cesium hydroxide of its use, raw materials such as rubidium hydroxide, it is the accessory substance of gained when being raw material extraction lithium and lithium salts with the lepidolite, therefore, significantly reduced production cost of products of the present invention.Simultaneously, drying in process of production adopts the plasma drier to carry out drying and roasting, shortened drying and roasting time, avoided the reduction of long-time conventional roasting and elevated temperature heat, the sintering that causes is excessive, make its aperture diminish, vanadium wherein, rubidium, caesium, it is big that the metallic of potassium becomes, active decline.Therefore make the caesium rubidium vanadium catalyst of producing improve its pore structure with this method, advantage such as namely its specific area is big, does not reunite, and dispersed particle is even, and particle diameter is little.
When being to use the inventive method to produce caesium, rubidium, vanadium catalyst and existing vanadium catalyst below to carry out desulfurization effect relatively, as table 1:
Table 1
Illustrate: on to show the gained data be to be raw material when producing sulfuric acid with the iron ore, last three row are ratio datas of desulfurization under different temperatures, intensity data refers to the hardness of catalyst prod, rate of wear then is the consumption rate after the catalyst use.
The technological process of production of the present invention is:
Diatomite → add sulfuric acid is except metal impurities → press filtration → plasma drying → add sulphur and sodium sulphate → mixed grind → extruded moulding → plasma drying → plasma roasting → product.
The specific embodiment:Below the present invention is done further complete explanation;
It is that the low-temperature plasma drier carries out that low temperature plasma is all adopted in drying in the production process of the present invention and calcining.
Embodiment 1
This routine caesium, rubidium, each constituent mass ratio of vanadium catalyst are: rubidium hydroxide 5%, and cesium hydroxide 3%, vanadic anhydride 6%, potassium hydroxide 8%, surplus is diatomite.
Example 2
This routine caesium, rubidium, each constituent mass ratio of vanadium catalyst are: rubidium hydroxide 4%, and cesium hydroxide 3%, vanadic anhydride 6%, potassium hydroxide 6%, surplus is diatomite.
The preparation method: above-described embodiment all adopts following method to be prepared: diatomaceous processing: (1), diatomite is added concentration is in the 40-50 Wt% sulfuric acid solution, be heated to 80-95 ℃, remove the metal impurities ion in the diatomite, described foreign ion is mainly elements such as iron, magnesium, manganese aluminium; Filter with filter press, make Separation of Solid and Liquid, and the water content≤10 Wt % of control solids, getting solids, filtrate is reclaimed, when being used for extracting lithium and lithium salts such as lithium carbonate or lithium sulfate when lepidolite is produced, the solution that complex acid is used, solids carries out drying with the low-temperature plasma gas dryer then, and the control baking temperature is 100-120 ℃, get diatomite 1, and the water content≤1 Wt % of control diatomite 1;
(2) rubidium, caesium, the preparation of vanadium liquid: with the cesium hydroxide of above-mentioned mass ratio, rubidium hydroxide and potassium hydroxide add hot water and dissolve, and the control water temperature is at 80-90 ℃, be generally 90 ℃ clear water, adding calcium hydroxide reacts after making solution, and the ph of control reaction solution is generally 12 between 10-12, filter then, Separation of Solid and Liquid, solid is removed, and gets mother liquor; Add barium hydroxide in mother liquor, precipitation is removed solid sediment barium sulfate, getting filtrate is mixed solution mother liquor 1, adds potassium hydroxide and vanadic anhydride and heating for dissolving in mother liquor 1, filters, the ph that the smart filtrate that obtains adds the smart filtrate of acid adjusting is 2-3, makes rubidium, caesium, vanadium mixed liquor 2;
(3) rubidium, caesium, the preparation of vanadium catalyst: with the diatomite 1 of (1) step preparation and the rubidium of (2) step preparation, caesium, vanadium mixed liquor 2 mixes, the ratio of the two adding, with diatomite 1 and rubidium, caesium, can be prepared into solid shape after vanadium mixed liquor 2 mixes gets final product, add simultaneously and account for the 2-3 % sodium sulphate that mixes the back gross mass and 1-2 % sulphur to carry out mixed grind even, and extruded moulding, shape can be made into general chrysanthemum or nail type etc., be dried to its water content≤1 Wt% with the low-temperature plasma drier then, carry out roasting with the low-temperature plasma drier at last, the control sintering temperature is 530-600 ℃, roasting time 20-35 minute, naturally cool, get rubidium, caesium, the vanadium catalyst product.
Claims (7)
1. rubidium caesium vanadium catalyst that temperature production sulfuric acid is used comprises that following quality is than component: rubidium hydroxide 4-5%, and cesium hydroxide 2-3%, vanadic anhydride 4-6%, potassium hydroxide 6-10%, surplus is diatomite.
2. the rubidium caesium vanadium catalyst of using according to the described temperature production sulfuric acid of claim 1 is characterized in that described catalyst is made up of than component following quality: rubidium hydroxide 4-5%, and cesium hydroxide 2-3%, vanadic anhydride 5-6%, potassium hydroxide 6-8%, surplus is diatomite.
3. the rubidium caesium vanadium catalyst of using according to claim 1 or 2 described temperature production sulfuric acid is characterized in that described rubidium hydroxide and cesium hydroxide are to prepare after raw material is carried lithium and lithium salts with the lepidolite.
4. the preparation method of a rubidium caesium vanadium catalyst of using according to the described temperature production sulfuric acid of claim 1, its method is as follows:
(1) diatomaceous processing: it is in the 40-50 Wt% sulfuric acid solution that diatomite is added concentration, be heated to 80-95 ℃, remove the metal impurities ion in the diatomite, filter, Separation of Solid and Liquid gets solids, filtrate is reclaimed, solids carries out drying with drier, and the control baking temperature is 100-120 ℃, gets diatomite 1;
(2) rubidium, caesium, the preparation of vanadium liquid: with the cesium hydroxide of above-mentioned mass ratio, rubidium hydroxide and potassium hydroxide, adding hot water dissolves, the control water temperature is at 80-90 ℃, make to add calcium hydroxide behind the solution and react, and the ph of control reaction solution is between 10-12, filter then, Separation of Solid and Liquid, solid is removed, and gets mother liquor; Add barium hydroxide in mother liquor, precipitation is removed the solid blanc fixe, getting filtrate is mixed solution mother liquor 1, adds potassium hydroxide and vanadic anhydride and heating for dissolving in mother liquor 1, filters, the ph that the smart filtrate that obtains adds the smart filtrate of acid adjusting is 2-3, makes rubidium caesium vanadium mixed liquor 2;
(3) preparation of rubidium, caesium, vanadium catalyst: the diatomite 1 of (1) step preparation and the rubidium caesium vanadium mixed liquor 2 of (2) step preparation are mixed, and adding accounts for 2-3 % sodium sulphate and the 1-2 % sulphur that mixes the back gross mass, it is even to carry out mixed grind, and extruded moulding, be dried to its water content≤1 Wt% with drier then, carry out roasting at last, the control sintering temperature is 500-580 ℃, roasting time 20-35 minute, cool naturally, get rubidium, caesium, vanadium catalyst product.
5. the preparation method of the rubidium caesium vanadium catalyst of using according to the described temperature production sulfuric acid of claim 4, it is characterized in that step (1) filtration, Separation of Solid and Liquid, get solids, water content≤10 Wt% of control solids, solids carries out drying with drier, and the control baking temperature is 110 ℃, and control dried solids water content≤1 Wt%, get diatomite 1.
6. the preparation method of the rubidium caesium vanadium catalyst of using according to the described temperature production sulfuric acid of claim 4 is characterized in that step (2) is to add the ph value that sulfuric acid is regulated mixed solution.
7. the caesium rubidium vanadium catalyst of using according to claim 4 or 5 described temperature production sulfuric acid is characterized in that step (1), (3) described drying and roasting employing low temperature plasma carry out drying and roasting.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104888754A (en) * | 2015-06-02 | 2015-09-09 | 江西合纵锂业科技有限公司 | Rubidium-cesium-vanadium catalyst for producing sulfuric acid through lithium-deposition mother liquor and preparation method |
| CN105413716A (en) * | 2015-12-07 | 2016-03-23 | 威顿（铜仁）化工有限责任公司 | Post-neutralization preparation method of vanadium catalyst |
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Patent Citations (5)
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| EP1303640B1 (en) * | 2000-07-25 | 2004-10-06 | Phelps Dodge Corporation | Processing elemental sulfur-bearing materials using high temperature pressure leaching for sulfuric acid production and metal recovery |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104888754A (en) * | 2015-06-02 | 2015-09-09 | 江西合纵锂业科技有限公司 | Rubidium-cesium-vanadium catalyst for producing sulfuric acid through lithium-deposition mother liquor and preparation method |
| CN105413716A (en) * | 2015-12-07 | 2016-03-23 | 威顿（铜仁）化工有限责任公司 | Post-neutralization preparation method of vanadium catalyst |
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Application publication date: 20130814 |