CN102921404B - Preparation method of titanium-tungsten composite powder for denitrification catalyst - Google Patents

Preparation method of titanium-tungsten composite powder for denitrification catalyst Download PDF

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CN102921404B
CN102921404B CN201210331984.2A CN201210331984A CN102921404B CN 102921404 B CN102921404 B CN 102921404B CN 201210331984 A CN201210331984 A CN 201210331984A CN 102921404 B CN102921404 B CN 102921404B
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titanium
preparation
titanium liquid
concentrated
composite powder
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CN102921404A (en
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陈建立
孙亮
豆君
赵海娟
邱巧锐
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Longbai Group Co.,Ltd.
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HENAN BAILILIAN CHEMICAL CO Ltd
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Abstract

The invention discloses a preparation method of titanium-tungsten composite powder for a denitrification catalyst. The preparation method comprises the following steps of: adding a hydrolysis crystal seed and an ammonium metatungstate solution in titanium concentrate liquid of titanium pigment, which is produced by adopting a sulfuric acid process; and after a hydrolysis reaction, washing, bleaching, calcining and crushing to obtain the titanium-tungsten composite powder. According to the preparation method disclosed by the invention, the titanium concentrate liquid produced by adopting the sulfuric acid process is used as a raw material and a tungsten solution is added in the hydrolysis process of the titanium solution, so that tungsten and titanium are combined uniformly and tightly in the hydrolysis process; and in addition, the content of the tungsten subjected to hydrolysis cannot be reduced along with washing and bleaching. For a factory with the whole sulfuric acid production process, the preparation method has the advantages that the subsequent step of adding the tungsten is reduced and the production process is shortened.

Description

The preparation method of titanium tungsten composite powder for a kind of denitrating catalyst
Technical field
The present invention relates to the preparation method of a kind of denitrating catalyst titanium tungsten composite powder.
Background technology
The flue gas that coal combustion generates is the nitrogen oxide as leading taking nitric oxide and nitrogen dioxide, and it is the major reason that forms photochemical fog and acid rain, is also a kind of important greenhouse gases simultaneously.Along with the enforcement of " thermal power plant's air pollution emission standard " that country puts into effect, it is the instant task of environmental protection that the denitration of flue gas is administered.SCR(SCR) gas denitrifying technology is the effective technology of the solution Pollution Index in Air Nitric Oxides that generally adopts in the world at present.Under the effect of catalyst, by the reducing agent such as ammonia, urea, nitrous oxides selectivity harmful in flue gas is catalysed and reduced into clean harmless nitrogen G&W, its denitration efficiency can reach more than 90%.The key of this technology and core are exactly denitrating catalyst.
Denitrating catalyst is taking nano titanium oxide as carrier, active component vanadic anhydride and co-catalyst tungstic acid in load, existing many preparation methods that use titanium tungsten composite powder about denitrating catalyst at present, as Chinese patent, application number is 201110201646 and 200810212079, but the raw material that these patents are used is all metatitanic acid, this method is relatively suitable for not having the factory of the preparation of titanium liquid and hydrolysis process, and they can use commercially available metatitanic acid to make raw material; And for the factory with whole Production By Sulfuric Acid Process technique, these methods seem again and comparatively bother.
Summary of the invention
For the problems of the prior art, the object of the invention is to provide the preparation method of a kind of denitrating catalyst titanium tungsten composite powder
Technical scheme of the present invention is: the preparation method of titanium tungsten composite powder for a kind of denitrating catalyst, in the concentrated titanium liquid of Titanium White Production By Sulfuric Acid Process, add hydrolysis crystal seed and ammonium metatungstate solution, after hydrolysis, pulverize and obtain this titanium tungsten composite powder through detergent bleach calcining.
Further, described concentrated titanium concentration is with TiO 2count 180 ~ 220 g/L.
Further, the concentration of described ammonium metatungstate solution is 800-1200 g/L.
Further, the preparation method of described hydrolysis crystal seed is: by concentration with TiO 2the concentrated titanium liquid of counting 180 ~ 220 g/L is added in the soda bath of 6 ~ 10wt%, and the volume ratio of concentrated titanium liquid and soda bath is 3.0 ~ 3.2:1, controls reaction temperature and is not less than 85 DEG C, when being stirred to its stability and reaching 70-110mL.
The method comprises the following steps:
1) the concentrated titanium liquid of Titanium White Production By Sulfuric Acid Process is heated to 96 DEG C and insulation, concentrated titanium concentration is with TiO 2meter 180 ~ 220 g/L;
2) hydrolysis crystal seed is added to concentrated titanium liquid, addition is the concentrated long-pending 2.5-3.0% of titanium liquid;
3) ammonium metatungstate solution is heated to 90 ~ 100 DEG C, is then added in concentrated titanium liquid, addition is with mass ratio WO 3/ TiO 2meter 5-10:95-90;
4) will concentrate after titanium liquid is incubated 15 ~ 20min and be warming up to 112 DEG C, after it becomes steel grey, be warming up to 114 DEG C, after reaction 1h, start moisturizing, make TiO 2concentration is 150-170 g/L.
5) hydrolyzation material steps d being obtained washs, bleaches, two washings, and the filter cake after press filtration is at 450-550 DEG C of temperature lower calcination 2-5 h; Then pulverize.
Further, the ammonium metatungstate solution and step 2 of step 3)) crystal seed together be added in titanium liquid.
Further, when the ammonium metatungstate solution of step 3) is warming up to 112 DEG C in step 4), be added in titanium liquid.
Further, when the ammonium metatungstate solution of step 3) becomes steel grey in step 4), be added in titanium liquid.
The present invention is taking the concentrated titanium liquid of Production By Sulfuric Acid Process as raw material, in the process of the hydrolysis of titanium liquid, adds tungsten solution, in the process of hydrolysis, make like this tungsten and titanium evenly, combine closely, and after hydrolysis, the content of tungsten can and not bleached and reduce along with washing.For the factory that has whole Production By Sulfuric Acid Process technique, the method has reduced the follow-up step that adds tungsten, has shortened production technology.
Detailed description of the invention
Below in conjunction with embodiment, the present invention will be further described.
Embodiment 1
Step 1: get concentrated titanium liquid 500 L that measure, titanium concentration is (with TiO 2meter) 180 g/L, be heated to 96 DEG C of heat preservation for standby use;
Step 2: the preparation of hydrolysis crystal seed: by the titanium liquid phase that is heated to the titanium liquid 4.5L(of 85 DEG C and step 1 with) join in the soda bath that 85 DEG C of 1.5L mass fractions are 6%, be incubated in 85 DEG C of whipping process and survey its stability, until stability stops while reaching 70-110mL;
Step 3: compound concentration is 800g/L ammonium metatungstate solution;
Step 4: the crystal seed that 5.04L step 2 is prepared joins in the ready titanium liquid of step 1;
Step 5: the ammonium metatungstate solution that 6.78L step 3 is prepared and step 4 join in the ready titanium liquid of step 1 simultaneously;
Step 6: be warming up to 112 DEG C after step 5 being added to the titanium liquid insulation 15min of crystal seed and tungsten solution, wait after becoming steel grey and be warming up to 114 DEG C, start moisturizing 92.7L after 1h, 2h has mended, and hydrolysis finishes;
Step 7: the hydrolyzation material that step 6 is obtained carries out washing, bleaches, two washes according to the technique of Production By Sulfuric Acid Process, then by the filter cake after press filtration at 450 DEG C of temperature lower calcination 5h;
Step 8: the calcining material that step 7 is obtained is pulverized, and obtains TiO 2/ WO 3the denitrating catalyst of=95:5 titanium tungsten composite powder.
Embodiment 2:
Step 1: get concentrated titanium liquid 500 L that measure, titanium concentration is (with TiO 2meter) 195 g/L, be heated to 96 DEG C of heat preservation for standby use;
Step 2: the preparation of hydrolysis crystal seed: by the titanium liquid phase that is heated to the titanium liquid 4.65L(of 85 DEG C and step 1 with) join in the soda bath that 85 DEG C of 1.5L mass fractions are 8%, be incubated in 85 DEG C of whipping process and survey its stability, until stability stops while reaching 70-110mL;
Step 3: compound concentration is 1100g/L ammonium metatungstate solution;
Step 4: the crystal seed that 5.56L step 2 is prepared joins in the ready titanium liquid of step 1;
Step 5: the ammonium metatungstate solution that 5.36L step 3 is prepared and step 4 join in the ready titanium liquid of step 1 simultaneously;
Step 6: be warming up to 112 DEG C after step 5 being added to the titanium liquid insulation 15min of crystal seed and tungsten solution, wait after becoming steel grey and be warming up to 114 DEG C, start moisturizing 103.6L after 1h, 2h has mended, and hydrolysis finishes;
Step 7: the hydrolyzation material that step 6 is obtained carries out washing, bleaches, two washes according to the technique of Production By Sulfuric Acid Process, then by the filter cake after press filtration at 450 DEG C of temperature lower calcination 3h;
Step 8: the calcining material that step 7 is obtained is pulverized, and obtains TiO 2/ WO 3the denitrating catalyst of=94:6 titanium tungsten composite powder.
Embodiment 3:
Step 1: get concentrated titanium liquid 500 L that measure, titanium concentration is (with TiO 2meter) 200 g/L, be heated to 96 DEG C of heat preservation for standby use;
Step 2: the preparation of hydrolysis crystal seed: by the titanium liquid phase that is heated to the titanium liquid 4.73L(of 85 DEG C and step 1 with) join in the soda bath that 85 DEG C of 1.5L mass fractions are 8%, be incubated in 85 DEG C of whipping process and survey its stability, until stability stops while reaching 70-110mL;
Step 3: compound concentration is 1200g/L ammonium metatungstate solution;
Step 4: the crystal seed that 5.6L step 2 is prepared joins in the ready titanium liquid of step 1;
Step 5: be warming up to 112 DEG C after step 4 being added to the titanium liquid insulation 15min of crystal seed, wait after becoming steel grey and be warming up to 114 DEG C, start moisturizing 82.6L after 1h, 2h has mended, and hydrolysis finishes;
Step 6: the ammonium metatungstate solution that 5.04L step 3 is prepared joins in the titanium liquid that step 5 has just been warming up to 112 DEG C;
Step 7: the hydrolyzation material that step 5 is obtained carries out washing, bleaches, two washes according to the technique of Production By Sulfuric Acid Process, then by the filter cake after press filtration at 500 DEG C of temperature lower calcination 3h;
Step 8: the calcining material that step 7 is obtained is pulverized, and obtains TiO 2/ WO 3the denitrating catalyst of=93:7 titanium tungsten composite powder.
Embodiment 4:
Step 1: get concentrated titanium liquid 500 L that measure, titanium concentration is (with TiO 2meter) 200 g/L, be heated to 96 DEG C of heat preservation for standby use;
Step 2: the preparation of hydrolysis crystal seed: by the titanium liquid phase that is heated to the titanium liquid 4.73L(of 85 DEG C and step 1 with) join in the soda bath that 85 DEG C of 1.5L mass fractions are 8%, be incubated in 85 DEG C of whipping process and survey its stability, until stability stops while reaching 70-110mL;
Step 3: compound concentration is 1000g/L ammonium metatungstate solution;
Step 4: the crystal seed that 5.7L step 2 is prepared joins in the ready titanium liquid of step 1;
Step 5: the ammonium metatungstate solution that 6.05L step 3 is prepared joins in the ready titanium liquid of step 1;
Step 6: be warming up to 112 DEG C after step 5 being added to the titanium liquid insulation 20min of crystal seed and tungsten solution, wait after becoming steel grey and be warming up to 114 DEG C, start moisturizing 161L after 1h, 2h has mended, and hydrolysis finishes;
Step 7: the hydrolyzation material that step 6 is obtained carries out washing, bleaches, two washes according to the technique of Production By Sulfuric Acid Process, then by the filter cake after press filtration at 450 DEG C of temperature lower calcination 4h;
Step 8: the calcining material that step 7 is obtained is pulverized, and obtains TiO 2/ WO 3the denitrating catalyst of=95:5 titanium tungsten composite powder.
Embodiment 5:
Step 1: get concentrated titanium liquid 500 L that measure, titanium concentration is (with TiO 2meter) 205 g/L, be heated to 96 DEG C of heat preservation for standby use;
Step 2: the preparation of hydrolysis crystal seed: by the titanium liquid phase that is heated to the titanium liquid 4.65L(of 85 DEG C and step 1 with) join in the soda bath that 85 DEG C of 1.5L mass fractions are 8%, be incubated in 85 DEG C of whipping process and survey its stability, until stability stops while reaching 70-110mL;
Step 3: compound concentration is 1100g/L ammonium metatungstate solution;
Step 4: the crystal seed that 5.74L step 2 is prepared joins in the ready titanium liquid of step 1;
Step 5: be warming up to 112 DEG C after step 5 being added to the titanium liquid insulation 20min of crystal seed and tungsten solution, wait after becoming steel grey and be warming up to 114 DEG C, start moisturizing 144L after 1h, 2h has mended, and hydrolysis finishes;
Step 6: the ammonium metatungstate solution that 5.63L step 3 is prepared adds when titanium liquid has just become steel grey in step 5;
Step 7: the hydrolyzation material that step 5 is obtained carries out washing, bleaches, two washes according to the technique of Production By Sulfuric Acid Process, then by the filter cake after press filtration at 550 DEG C of temperature lower calcination 2h;
Step 8: the calcining material that step 7 is obtained is pulverized, and obtains TiO 2/ WO 3the denitrating catalyst of=94:6 titanium tungsten composite powder.
Embodiment 6:
Step 1: get concentrated titanium liquid 500 L that measure, titanium concentration is (with TiO 2meter) 220g/L, be heated to 96 DEG C of heat preservation for standby use;
Step 2: the preparation of hydrolysis crystal seed: by the titanium liquid phase that is heated to the titanium liquid 4.8L(of 85 DEG C and step 1 with) join in the soda bath that 85 DEG C of 1.5L mass fractions are 10%, be incubated in 85 DEG C of whipping process and survey its stability, until stability stops while reaching 70-110mL;
Step 3: compound concentration is 1200g/L ammonium metatungstate solution;
Step 4: the crystal seed that 6.27 L steps 2 are prepared joins in the ready titanium liquid of step 1;
Step 5: the ammonium metatungstate solution that 5.53L step 3 is prepared joins in the ready titanium liquid of step 1;
Step 6: be warming up to 112 DEG C after step 5 being added to the titanium liquid insulation 30min of crystal seed and tungsten solution, wait after becoming steel grey and be warming up to 114 DEG C, start moisturizing 141.44L after 1h, 2h has mended, and hydrolysis finishes;
Step 7: the hydrolyzation material that step 6 is obtained carries out washing, bleaches, two washes according to the technique of Production By Sulfuric Acid Process, then by the filter cake after press filtration at 550 DEG C of temperature lower calcination 2h;
Step 8: the calcining material that step 7 is obtained is pulverized, and obtains TiO 2/ WO 3the denitrating catalyst of=90:10 titanium tungsten composite powder.
Above embodiment is only that the technical scheme that the present invention is recorded illustrates, and all simple distortion of making in the situation that not departing from core of the present invention or amendment all fall into protection scope of the present invention.

Claims (4)

1. a preparation method for titanium tungsten composite powder for denitrating catalyst, is characterized in that, the method comprises the following steps:
1) the concentrated titanium liquid of Titanium White Production By Sulfuric Acid Process is heated to 96 DEG C and insulation, concentrated titanium concentration is with TiO 2meter 180 ~ 220 g/L;
2) hydrolysis crystal seed is added to concentrated titanium liquid, addition is the concentrated long-pending 2.5-3.0% of titanium liquid, and the preparation method of described hydrolysis crystal seed is: by concentration with TiO 2the concentrated titanium liquid of counting 180 ~ 220 g/L is added in the soda bath of 6 ~ 10wt%, and the volume ratio of concentrated titanium liquid and soda bath is 3.0 ~ 3.2:1, controls reaction temperature and is not less than 85 DEG C, when being stirred to its stability and reaching 70-110mL;
3) ammonium metatungstate solution is heated to 90 ~ 100 DEG C, is then added in concentrated titanium liquid, addition is with mass ratio WO 3/ TiO 2meter 5-10:95-90;
4) will concentrate after titanium liquid is incubated 15 ~ 30min and be warming up to 112 DEG C, after it becomes steel grey, be warming up to 114 DEG C, after reaction 1h, start moisturizing, make TiO 2concentration is 150-170 g/L;
5) hydrolyzation material step 4) being obtained washs, bleaches, two washings, and the filter cake after press filtration, at 450-550 DEG C of temperature lower calcination 2-5 h, is then pulverized.
2. the preparation method of titanium tungsten composite powder for a kind of denitrating catalyst according to claim 1, is characterized in that ammonium metatungstate solution and the step 2 of step 3)) crystal seed together be added in titanium liquid.
3. the preparation method of titanium tungsten composite powder for a kind of denitrating catalyst according to claim 1, is characterized in that, the ammonium metatungstate solution of step 3) is added in titanium liquid be warming up to 112 DEG C in step 4) time.
4. the preparation method of titanium tungsten composite powder for a kind of denitrating catalyst according to claim 1, is characterized in that, the ammonium metatungstate solution of step 3) is added in titanium liquid become steel grey in step 4) time.
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CN103586017A (en) * 2013-11-22 2014-02-19 西南化工研究设计院有限公司 Preparation method of titanium and tungsten powder for flue gas denitration catalyst and product prepared through preparation method

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CN102000585A (en) * 2010-08-16 2011-04-06 华电电力科学研究院 Denitration catalyst and preparation method thereof

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CA2523889A1 (en) * 2003-04-28 2004-11-11 Nissan Chemical Industries, Ltd. Heterogeneous catalyst and process for producing oxirane compound with the catalyst

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CN102000585A (en) * 2010-08-16 2011-04-06 华电电力科学研究院 Denitration catalyst and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103586017A (en) * 2013-11-22 2014-02-19 西南化工研究设计院有限公司 Preparation method of titanium and tungsten powder for flue gas denitration catalyst and product prepared through preparation method
CN103586017B (en) * 2013-11-22 2015-03-25 西南化工研究设计院有限公司 Preparation method of titanium and tungsten powder for flue gas denitration catalyst and product prepared through preparation method

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