CN105195118A - Macroporous structure titanium oxide desulfurization catalyst and preparation method thereof - Google Patents
Macroporous structure titanium oxide desulfurization catalyst and preparation method thereof Download PDFInfo
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- CN105195118A CN105195118A CN201510656121.6A CN201510656121A CN105195118A CN 105195118 A CN105195118 A CN 105195118A CN 201510656121 A CN201510656121 A CN 201510656121A CN 105195118 A CN105195118 A CN 105195118A
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Abstract
The invention relates to the technical field of preparation of macroporous titanium oxide, and in particular relates to a macroporous structure titanium oxide desulfurization catalyst and a preparation method thereof. According to the method provided by the invention, a titanous sulfate and aluminum nitrate solution and a urea solution are merged and precipitated; the finally obtained titanium oxide is relatively large in pore diameter, pore volume and specific surface area; and the high-temperature stability is good. The macroporous titanium oxide prepared by the method is especially suitable for being used as the catalyst in the field of sulfur recovery, and has the characteristics of high desulphurization efficiency and high organic sulfur hydrolysis ability.
Description
Technical field
The present invention relates to the preparing technical field of macropore titanium oxide, especially a kind of macroporous structure titanium oxide desulphurization catalyst and manufacture method thereof.Be specially adapted to use as catalyst for recovering sulfur.
Background technology
Titanium oxide has certain pore structure and specific area, reveals excellent catalytic performance to numerous reaction table, is thus widely used as catalyst or carrier at Coal Chemical Industry, petroleum chemical industry.
JP58223440 discloses a kind of catalyst for clause recovering sulfur, and this catalyst is by the titanium oxide of 70 ~ 80wt% as active ingredient, and the alumino-silicate material composition as a supplement of 20 ~ 30wt%, through making two kinds of components kneadings, granulations.This catalyst duct is little, pore volume and specific area low, its sulphur recovery activity is not ideal enough.
CN1126595C discloses a kind of titanium oxide catalyst, and this catalyst is by the titanium oxide of 10 ~ 90wt% as active ingredient, the activated alumina material formation as a supplement of 45 ~ 85wt%.Preparation method is mixed by titanium oxide powder and aluminium hydroxide dry powder, joins in the solution such as calcium nitrate, and adds auxiliary material etc. and obtain through kneading, extruded moulding, oven dry and roasting.This catalyst organic sulfur compound hydrolysing activity and claus reaction activity all not ideal enough, may little with duct, pore volume is low relevant with specific area.
Considerable document shows, be less than 5nm by the titanium oxide catalyst for recovering sulfur average pore size of conventional kneading method manufacture, pore volume is lower than 0.3ml/g, and specific area is lower than 150m
2/ g, very difficult manufacture has macroporous (being greater than 50nm) and high specific surface area (is greater than 200m
2/ g) titanium oxide or its precursor.Because pore structure, specific area are one of important indicators of catalyst, therefore this area is devoted to how to improve the macroporous structure of this kind of catalyst always and is obtained higher specific area, but more difficult breakthrough always.
In order to overcome deficiency of the prior art, the invention provides the preparation method of a kind of specific area and the larger titanium oxide desulphurization catalyst of pore volume.This preparation method has that process is simple, raw material is easy to get, the feature of easy control of reaction.Titanium oxide desulphurization catalyst involved in the present invention is with aluminum nitrate, titanium sulfate and urea for raw material, adopts coprecipitation preparation.The titanium oxide catalyst specific area obtained is 200 ~ 250m
2/ g, pore volume is 0.5 ~ 0.6ml/g, and most probable pore size, between 50-l00nm, is especially suitable for use as catalyst for recovering sulfur, has the advantages that desulfuration efficiency is high, tempreture organic sulphur hydrolysis ability is strong.
Summary of the invention
In order to overcome the deficiency of existing technology, the invention provides a kind of macroporous structure titanium oxide desulphurization catalyst and manufacture method thereof.
The technical solution adopted for the present invention to solve the technical problems is: this macroporous structure titanium oxide desulphurization catalyst is by following solution formula, is formed by suitable preparation technology's manufacture:
Aluminum nitrate solution 100g ~ 200gA1
20
3/ L
Titanium sulfate solution 40g ~ 50gTiO
2/ L
Urea liquid 20wt% ~ 30wt%
The preparation method of titanium oxide desulphurization catalyst of the present invention, comprises the steps:
A, respectively preparation aluminum nitrate solution and titanium sulfate solution; Wherein the concentration of aluminum nitrate solution is 100 ~ 200gA1
20
3/ L, the concentration of titanium sulfate solution is 40 ~ 50gTiO
2/ L;
B, aluminum nitrate solution and part of sulfuric acid titanium solution are joined in settling tank, pass into CO simultaneously
2gas, keep temperature in settling tank to be 20 ~ 50 DEG C, the time is 0.5 ~ 1.5 hour;
C, under the control temperature of step b, be that the urea liquid of 20 ~ 30wt% is passed in settling tank by concentration, the reaction time is 1 ~ 3 hour;
D, under the control temperature and pH value of step c, said mixture stablizes 0.5 ~ 3.0 hour;
E, the solidliquid mixture of steps d gained to be filtered, obtain liquid containing ammonium sulfate and ammonium nitrate reaction mother liquor and containing aluminum oxidation titanium filter cake, to filter cake cyclic washing, until in cleaning solution sulfate ion concentration lower than 0.1g/L;
Filter cake drying after the washing that f, step e obtain, obtains titania precursor body;
G, to be moved in hydrothermal device by this presoma and to carry out hydrothermal aging 3 ~ 5h in 180 ~ 200 DEG C, then dry, roasting obtains titanium oxide desulphurization catalyst;
Drying described in step f and g can adopt conventional drying equipment to carry out drying, such as baking oven or micro-wave drying device, and baking temperature is 110 ~ 130 DEG C, and drying time is 30 ~ 120 minutes;
Roasting described in step g refers in special roasting apparatus in 400 ~ 600 DEG C of roastings 3 ~ 5 hours.The character of the product obtained is as follows: specific area is 200 ~ 250m2/g, and pore volume is 0.5 ~ 0.6ml/g, can a few aperture be 50-l00nm.
According to another embodiment of the invention, comprise further, the washing described in step e is for be washed till sulfate ion concentration lower than 0.1g/L by 40 ~ 90 DEG C of deionized waters.
According to another embodiment of the invention, comprise further, the drying described in step f adopts infrared dryer dry, and baking temperature is 110 ~ 130 DEG C, and drying time is 10 ~ 30 minutes.
Beneficial effect of the present invention:
1. technique before the present invention comparatively, can obtain the 50-l00nm macropore titanium oxide that aperture is larger, the titanium oxide in this aperture contributes to the application in sulphur recovery field.
2. preparation condition of the present invention and technique simple and easy to control, be conducive to large-scale production.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described.In the present invention, wt% represents mass fraction, and V% represents volume fraction.
In the present invention, specific area and pore volume adopt low temperature liquid nitrogen determination of adsorption method, and bore dia adopts mercurous method to measure.
eXAMPLE l
Be 200gA1 by concentration
20
3concentration is 50gTiO by/L aluminum nitrate solution 100ml
2/ L titanium sulfate solution 1.6L joins in the steel bomb of 5L, then opens intake valve, passes into the CO that concentration is 99v%
2gas, is set as 30 DEG C by the temperature in reactor, keeps this state 60 minutes, then closes CO
2gas; Slowly add the urea liquid that 200ml concentration is 20wt%, the reaction time is 3 hours, and then product leaves standstill and stablizes 120 minutes, and slurries filter and use 60 DEG C of deionized waters to be washed till neutrality.120 DEG C of dryings 30 minutes in microwave drying oven.Take out dry thing, be positioned in 180 hydrothermal treatment consists 3 hours in Hydrothermal Synthesis still, by 120 DEG C of microwave dryings 30 minutes, Muffle furnace 400 DEG C of roastings 3 hours, obtain titanium oxide Ti-1, the character of gained is in Table l.
embodiment 2
Be 200gA1 by concentration
20
3concentration is 50gTiO by/L aluminum nitrate solution 50ml
2/ L titanium sulfate solution 1.8L joins in the steel bomb of 5L, then opens intake valve, passes into the CO that concentration is 99v%
2gas, is set as 20 DEG C by the temperature in reactor, keeps this state 30 minutes; Then slowly add the urea liquid that 200ml concentration is 30wt%, the reaction time is 2 hours, and then leave standstill and stablize 30 minutes, slurries filter and use 40 DEG C of deionized waters to be washed till neutrality.120 DEG C of dryings 120 minutes in common drying box.Take out dry thing, be positioned in 200 DEG C of hydrothermal treatment consists 3 hours in Hydrothermal Synthesis still, through microwave 120 DEG C of dryings 40 minutes, 500 DEG C roastings 4 hours, obtain titanium oxide Ti-2, the character of gained was in Table l.
embodiment 3
Be 100gA1 by concentration
20
3concentration is 50gTiO by/L aluminum nitrate solution 300ml
2/ L titanium sulfate solution 1.4L joins in the steel bomb of 5L, then opens intake valve, passes into the CO that concentration is 99v%
2gas, is set as 40 DEG C by the temperature in reactor, keeps this state 90 minutes; Then slowly add the urea liquid that 400ml concentration is 20wt%, the reaction time is 2 hours, and then leave standstill and stablize 60 minutes, slurries filter and use 40 DEG C of deionized waters to be washed till neutrality.120 DEG C of dryings 90 minutes in common drying box.Take out dry thing, be positioned in 180 DEG C of hydrothermal treatment consists 4 hours in Hydrothermal Synthesis still, through microwave 120 DEG C of dryings 60 minutes, 600 DEG C roastings 5 hours, obtain titanium oxide Ti-3, the character of gained was in Table l.
embodiment 4
Be 200gA1 by concentration
20
3concentration is 40gTiO by/L aluminum nitrate solution 100ml
2/ L titanium sulfate solution 2.0L joins in the steel bomb of 5L, then opens intake valve, passes into the CO that concentration is 99v%
2gas, is set as 50 DEG C by the temperature in reactor, keeps this state 30 minutes; Then slowly add the urea liquid that 500ml concentration is 20wt%, the reaction time is 1 hour, and then leave standstill and stablize 90 minutes, slurries filter and use 50 DEG C of deionized waters to be washed till neutrality.120 DEG C of dryings 60 minutes in common drying box, 500 DEG C of roastings 3 hours in Muffle furnace, obtain titanium oxide Ti-4, the character of gained is in Table l.
table 1macroporous structure titanium oxide desulphurization catalyst physico-chemical property
| Catalyst is numbered | Ti-1 | Ti-2 | Ti-3 | Ti-4 |
| Titanium oxide content, wt% | 90 | 80 | 70 | 80 |
| Specific area, m 2/g | 204 | 230 | 245 | 212 |
| Pore volume, ml/g | 0.51 | 0.57 | 0.59 | 0.52 |
| Most probable bore dia, nm | 55 | 65 | 97 | 52 |
Claims (5)
1. a macroporous structure titanium oxide desulphurization catalyst, is characterized in that: this catalyst is by following solution formula, is formed by suitable preparation technology's manufacture:
Aluminum nitrate solution 100g ~ 200gA1203/L
Titanium sulfate solution 40g ~ 50gTiO2/L
Urea liquid 20wt% ~ 30wt%.
2. a preparation technology for macroporous structure titanium oxide desulphurization catalyst according to claim 1, is characterized in that, comprise the steps:
A, respectively preparation aluminum nitrate solution and titanium sulfate solution; Wherein the concentration of aluminum nitrate solution is 100 ~ 200gA1
20
3/ L, the concentration of titanium sulfate solution is 40 ~ 50gTiO
2/ L;
B, aluminum nitrate solution and part of sulfuric acid titanium solution are joined in settling tank, pass into CO simultaneously
2gas, keep temperature in settling tank to be 20 ~ 50 DEG C, the time is 0.5 ~ 1.5 hour;
C, under the control temperature of step b, be that the urea liquid of 20 ~ 30wt% is passed in settling tank by concentration, the reaction time is 1 ~ 3 hour;
D, under the control temperature and pH value of step c, said mixture stablizes 0.5 ~ 3.0 hour;
E, the solidliquid mixture of steps d gained to be filtered, obtain liquid containing ammonium sulfate and ammonium nitrate reaction mother liquor and containing aluminum oxidation titanium filter cake, to filter cake cyclic washing, until in cleaning solution sulfate ion concentration lower than 0.5g/L;
Filter cake drying after the washing that f, step e obtain, obtains titania precursor body;
G, to be moved in hydrothermal device by this presoma and to carry out hydrothermal aging 3 ~ 5h in 180 ~ 200 DEG C, then dry, roasting obtains titanium oxide desulphurization catalyst;
Drying described in step f and g can adopt conventional drying equipment to carry out drying, such as baking oven or micro-wave drying device, and baking temperature is 110 ~ 130 DEG C, and drying time is 30 ~ 120 minutes;
Roasting described in step g refers in special roasting apparatus in 400 ~ 600 DEG C of roastings 3 ~ 5 hours.The character of the product obtained is as follows: specific area is 200 ~ 250m2/g, and pore volume is 0.5 ~ 0.6ml/g, can a few aperture be 50-l00nm.
3. preparation technology according to claim 2, is characterized in that, the washing described in step e is for be washed till sulfate ion concentration lower than 0.1g/L by 40 ~ 90 DEG C of deionized waters.
4. preparation technology according to claim 2, is characterized in that, the drying described in step f adopts infrared dryer dry, and baking temperature is 110 ~ 130 DEG C, and drying time is 10 ~ 30 minutes.
5. according to preparation technology according to claim 2, its feature exists, and in described titanium oxide desulphurization catalyst, titanium oxide content is 70wt% ~ 90wt%, is preferably 80wt% ~ 90wt%; Alumina content is 10 ~ 30wt%, is preferably 10wt% ~ 20wt%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108816241A (en) * | 2018-06-04 | 2018-11-16 | 常州新日催化剂有限公司 | The preparation method of iron molybdenum Division A League Matches of French Football alcohol oxidation making formaldehyde catalyst |
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| CB03 | Change of inventor or designer information |
Inventor after: Shen Jun Inventor after: Zhu Xuejun Inventor after: Liu Xianguo Inventor after: Zhu Shangang Inventor after: Hu Jia Inventor before: Shen Jun Inventor before: Liu Xianguo Inventor before: Zhu Shangang Inventor before: Hu Jia |
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Effective date of registration: 20160121 Address after: 213000, No. 78, Avenue, Binjiang chemical industry park, Xinbei Town, Xinbei District, Jiangsu, Changzhou Applicant after: Changzhou new Sichuan Chemical Technology Development Co., Ltd. Applicant after: CHANGZHOU NEW SOLAR CATALYSTS CO., LTD. Address before: 213000 Binjiang, Changzhou, new North Industrial Park, Jiangsu Port Road, No. 78 Applicant before: CHANGZHOU NEW SOLAR CATALYSTS CO., LTD. |
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Application publication date: 20151230 |