CN1194076C - Catalyst for hydrorefining paraffin wax and its preparing process and usage - Google Patents
Catalyst for hydrorefining paraffin wax and its preparing process and usage Download PDFInfo
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- CN1194076C CN1194076C CNB011295031A CN01129503A CN1194076C CN 1194076 C CN1194076 C CN 1194076C CN B011295031 A CNB011295031 A CN B011295031A CN 01129503 A CN01129503 A CN 01129503A CN 1194076 C CN1194076 C CN 1194076C
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Abstract
The present invention discloses a catalyst for hydrorefining paraffin wax, a preparation method thereof and the application. The carrier is characterized in that the surface of aluminum oxide contains titanium dioxide through a chemical treatment to improve the characteristics of the carrier. All active ingredients of the catalyst are immersed in a W-Mo-Ni solution and the metal ingredients are jointly absorbed by competition to prepare the special catalyst with high activity for hydrorefining paraffin wax.
Description
Technical field
The present invention relates to petrochemical complex Hydrobon Catalyst And Its Preparation Method and purposes, particularly relate to a kind of hydrorefining paraffin wax Ti-base catalyst and its production and use.
Background technology
Paraffin is to be major ingredient with the normal paraffin, and normal temperature is solid down, and molecular-weight average is bigger, and generally between 300～500, carbon number is C
20～C
30Hydrorefining paraffin wax mainly is that paraffin is mixed into reactor with a certain proportion of hydrogen at a certain temperature, and under the effect of catalyzer, heteroatoms generation chemical reactions such as the S in hydrogen and the paraffin, N, O correspondingly generate H
2S, NH
3, H
2By products such as O are to remove impurity.Unsaturated hydrocarbons in the paraffin and hydrogen generation addition reaction reach capacity, and its purpose is intended to keep the normal paraffin basic comprising, and removing with 3,4 benzopyrenes is the carcinogenic substance and the non-hydrocarbons (S, N, O) such as condensed-nuclei aromatics of representative.In order to make paraffin molecule fully carry out chemical reaction in catalyst active center, catalyzer must possess enough big specific surface area and big pore volume and unimpeded duct, for reactant and product molecule provide ideal reacting environment.Secondly, theoretically, in order to keep normal paraffin, this process does not allow to take place cracking reaction, otherwise will cause oil content in paraffin wax and penetration degree to increase, and fusing point descends.For this reason, catalyzer should have few solid acid of trying one's best on the one hand, and based on weak acid; On the other hand, require catalyzer low-temperature reactivity height.It is worthy of note that undesirable components in the paraffin (being heteroatomss such as S, N, O) content is very low, General N is below the 15ppm, and S is below the 10ppm.This just needs catalyst metal components to have excellent hydrogenation activity, be that hydrodenitrification (HDN), hydrogenating desulfurization (HDS) and condensed-nuclei aromatics saturability (FDA) are strong, the active ingredient kind of mating in carrier and promoter metal and quantitatively also be considerable simultaneously.
CN 94117757, and CN 92111470, and CN 92111133 documents such as grade have announced that they developed is used for the hydrorefined catalyzer of petroleum wax series products, and its carrier is an aluminum oxide.These patents have generally been emphasized the alumina pore structure properties.The patent US5 of the applicant---Beijing Haishunde Titanium Catalyst Co., Ltd., 962,367 and CN 94195180.4 announced the production method of titanium dioxide with certain pore structure, and the catalyzer that the titania support of being produced by this method makes has been used in the industrial installation respond well.This method has emphasized that titanium dioxide cryogenic reducting performance and low-temp reaction performance are good.
On catalyst activity component, CN 92111133 and CN 94117757 have emphasized the effect of Mo-Ni series in hydrogenation process; CN 92111470 has then emphasized the effect of W-Ni in hydrogenation process.96109049 of patent CN have announced a kind of Mo-Ni (Co)-P/Al for preparing the superelevation metal content
2O
3Hydrotreating catalyst and preparation method, this method have emphasized the method for preparation superelevation metal component Mo-Ni-P two component solutions and the importance of a step pickling process.About the method for ultrahigh concentration W-Mo-Ni three component metals solution impregnation on carrier being yet there are no report, only find to have the report that adopts two step method or multistep processes with single stage method.The shortcoming of this method is a preparation process complexity not only, but also may bring detrimentally affect to some physical and chemical performance of catalyzer.
Summary of the invention
One of purpose of the present invention is in order to overcome the above-mentioned shortcoming that the prior art low-temperature reactivity is poor, hydrogenation activity is low, a kind of new titanium foundation stone wax Hydrobon catalyst of superior performance to be provided.
Two of purpose of the present invention provides a kind of preparation method of new titanium foundation stone wax Hydrobon catalyst.
Three of purpose of the present invention provides a kind of purposes of new titanium foundation stone wax Hydrobon catalyst.
One of the present invention's catalyst for hydrogen refining of paraffin wax is achieved in that
Catalyst for hydrogen refining of paraffin wax of the present invention is made up of carrier and the active ingredient that is carried on the carrier, it is characterized in that:
Carrier is made up of aluminum oxide and titanium dioxide, presses the weight percent meter of carrier, and alumina content is 20～99%, and content of titanium dioxide is 1～80%;
Active ingredient comprises W, Mo, Ni, P element, and content by weight percentage is respectively: WO
315～25 (w) %, MoO
38～15 (w) %, NiO 2～5 (w) %, P 1.5～4.5 (w) %, all the other are carrier.
In the time of concrete enforcement, alumina content is preferably 80～99% in the above-mentioned carrier, and content of titanium dioxide is preferably 1～20%.Above-mentioned carrier specific surface area can be 200～400m
2/ g, pore volume can be 0.5～0.8ml/g, intensity is greater than 140N/em.The specific surface area of above-mentioned catalyzer can be 140～210m2/g, and pore volume can be at 0.30～0.50ml/g.
The preparation method of the present invention's two catalyst for hydrogen refining of paraffin wax is achieved in that
The preparation of carrier is according to foregoing component, adds titanium dioxide in aluminum oxide, through kneading, extruded moulding and drying, carries out that roasting makes again.The drying temperature of the preparation of described carrier can be 100～110 ℃, and maturing temperature can be at 450～600 ℃.Described active ingredient W-Mo-Ni-P adopts the single stage method dip loading on carrier, and active ingredient at room temperature once is mixed with the aqueous solution of desired concn, wherein WO with ammonium tungstate, ammonium molybdate, nickelous nitrate, phosphoric acid
3Concentration is 15～40g/100ml; MoO
3Concentration is 10～25g/100ml, and NiO concentration is 2～6g/100ml, and P concentration is 3～6g/100ml.
The present invention's three is above-mentioned catalyst for hydrogen refining of paraffin wax application in hydrorefining paraffin wax technology, its processing condition are: temperature of reaction is 200～300 ℃, reaction pressure is 2.5～15.0Mpa, and LHSV is 0.2～2.0h-1, and hydrogen wax is 100～300 than (v/v).
Be described in further detail technical scheme of the present invention below.
The present invention includes two aspects of preparation of the Hydrobon catalyst of the preparation of carrier of titanium dioxide (technical grade)+aluminum oxide (technical grade) and this carrier.Carrier is with a certain proportion of titanium dioxide and aluminum oxide mixing, extrusion, drying, roasting and make, and this helps adjusting pore structure and surface properties.Preparation of catalysts is that drying, activation make after adopting W-Mo-Ni three component solution single-steepings.Concrete steps are as follows:
(1), will adopt the titanium dioxide of method preparation of the applicant's CN 94195180 patents to mix mutually with the aluminum oxide of excellent performance, wherein the titanium oxide ratio is in 1～80% scope, through chemical treatment, with the ordinary method extruded moulding is the trifolium shape, dry under 100～110 ℃ then, roasting in 450～600 ℃ scope.
(2), at room temperature, be made into required highly concentrated solution, i.e. WO with wolframic acid ammonia, molybdenum acid ammonia, nickelous nitrate
3Concentration between 15～40g/100ml, MoO
3Between 10～25g/100ml, NiO is between 2～6g/100ml.Adopt the single stage method direct impregnation on carrier above-mentioned highly concentrated solution then.
Prepared titanium base carrier has following character according to the present invention:
(1), specific surface area is 200～400m
2/ g, pore volume is 0.5～0.8ml/g, and the aperture is adjustable, and physical strength is greater than 140N/cm (little of φ 1.6mm trifolium).
(2), because the introducing of titanium dioxide has changed original alumina surface structure and character, particularly changed dispersing property, reducing property and the activity of metal.
Prepared W-Mo-Ni-P/ carrier catalyst for hydrogen refining of paraffin wax has following character according to the present invention:
(1), active component content is: WO
315～25%, MoO
38～15%, NiO 2～5%, P1.5～4.5%.
(2), specific surface area 140～210m
2/ g, pore volume 0.3～0.4ml/g, mean pore size 7.5～11.0nm, physical strength 〉=200N/cm (little of φ 1.6mm trifolium).
(3), detect, active metal W, Mo, Ni have preferable dispersion state on catalyst surface through XPD
Advantage of the present invention is:
(1), titanium base carrier of the present invention and catalyzer, compare with disclosed wax hydrofining special-purpose catalyst, its preparation technology's flow process is short, simple to operate, easy row, production cost are low.And adopt new catalytic material-titanium dioxide and single stage method dipping W-Mo-Ni three component solution, the performance of catalyzer is greatly improved.
(2), catalyzer of the present invention is specially adapted to the hydrorefining paraffin wax process.Its reason is to have adopted the titanium dioxide novel material, and the low-temperature performance of catalyzer is good.Catalyzer is more using under the demulcent condition, has prevented C-C bond rupture in the paraffin distillate; Adopt W-Mo-Ni-P three component solution single-steeping methods, improved the hydrogenation ability of catalyzer, particularly help the enhancing of condensed-nuclei aromatics saturability in the paraffinic hydrocarbon.Processing condition are: temperature of reaction is 200～300 ℃, and reaction pressure is 2.5～15.0Mpa, and LHSV is 0.2～2.0h-1, and hydrogen wax is 100～300 than (v/v).
(3), catalyzer of the present invention, also can be used for hydrofining (hydrogenating desulfurization, the hydrodenitrification) process of heavy and low-density oil cut.
Description of drawings
Fig. 1 is the active comparison diagram of little anti-hydrodesulfurization reaction.
Embodiment
In order to further specify all main points of the present invention, enumerate following examples and comparative example.Protection scope of the present invention is as the criterion with claims, is not subjected to the restriction of following embodiment.
Embodiment 1
(1), the preparation of carrier
Take by weighing titanium valve and the aluminium powder (being respectively the commercially available titanium dioxide and the hydrate of aluminium hydroxide) that gross weight is 1000 grams in 6: 4 ratios, add 40ml acetate, 100ml concentration is 21% nitric acid and an amount of water purification, after mixing, extruded moulding is trifolium shape (φ 1.6mm), after air drying spends the night, dried 2 hours down at 110 ℃.Dry sample is raised to 550 ℃, constant temperature 3 hours with the heat-up rate of 100 ℃/h in High Temperature Furnaces Heating Apparatus.
(2), Preparation of catalysts
Take by weighing the carrier 100g of step (1) preparation, stable, limpid, transparent aqueous solution that adding 200ml contains W-Mo-Ni-P (contain 32gWO in every 100ml solution
3, 17gMoO
3, 6gNiO 3gP), at room temperature flooded 2 hours, and the unnecessary mother liquor of elimination, the sample of gained 110 ± 5 ℃ of down oven dry 2 hours, rise to 500 ℃, constant temperature activation 3 hours with dry sample with the heat-up rate of 100 ℃/h after air drying spends the night.
Embodiment 2
(1), the preparing carriers step is identical with embodiment 1, but the ratio of titanium valve and aluminium powder is 1: 9.
(2), catalyst soakage and drying step and embodiment 1 corresponding section are identical.
Comparative example 1
(1), the preparation of carrier is in the titanium valve and the aluminium powder of 0: 10 ratio, its step is identical with embodiment 1, preparation comparative example 1 carrier.
(2), Preparation of Catalyst is identical with embodiment 1.
Comparative example 2
(1), the preparation of carrier is identical with comparative example 1.
(2), Preparation of Catalyst
Add the aqueous solution that 200ml contains Mo-Ni-P in the carrier of 100g, step afterwards is identical with embodiment 1.
Comparative example 3
(1), the preparation of carrier is identical with comparative example 1.
(2), Preparation of catalysts
Add the aqueous solution that 200ml contains W-Ni in the 100g carrier, step afterwards is identical with comparative example 1.
More than the physico-chemical property of each routine prepared carrier and catalyzer list in the table one.The activity of each routine sample of micro anti-evaluation is seen Fig. 1 and table two.The quality index that catalyst activity is estimated used paraffin character and reaction process condition and generation wax sees Table three.
As can be seen, under same reaction conditions, the above-mentioned little anti-thiophene hds conversion of each routine sample (%) is also variant from table two and Fig. 1, and in an embodiment, the activity of example 1 is the highest; The desulphurizing activated height of embodiment sample than comparative sample.In comparative example, example 1 sample ratio 2 and example 3 sample height.The catalyzer that this catalyzer that shows that titanium base carrier among the present invention and active metal component are formed makes than usual way, the hydrodesulfurization reaction performance is good.
By the small-sized hydrorefining paraffin wax evaluation result of 100ml (seeing Table three) as can be seen, the prepared catalyst hydrogenation activity of the present invention is much higher.Particularly paraffin wax product condensed-nuclei aromatics saturability (FDA value) is judged behind the hydrogenation, and the FDA of embodiment 1 is than low many of comparative example 1.This shows that catalyzer aromatic hydrocarbons saturability of the present invention is strong.
Table four, table five and table six are respectively the hydrogenation activity data of catalyzer of the present invention under the differential responses condition.In general, industrial paraffin Hydrobon catalyst temperature of reaction is not less than 270 degree, and pressure is in middle pressure scope (7.0Mpa), and air speed is about 1.0; And catalyzer of the present invention can under low pressure use; Can be lower than under 270 degree in temperature and use; Air speed is greater than using more than 1.0.
This shows that the present invention adopts titanium base carrier and one step of high density active ingredient pickling process, and the final catalyst activity is all had tangible contribution.This contribution causes catalyzer (as than under the low reaction temperatures or under the lower pressure) under demulcent condition more to use in the hydrorefining paraffin wax process.
The physico-chemical property of table one, catalyst sample
| Sample number into spectrum | Embodiment 1 | Embodiment 2 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |||||
| Carrier | Catalyzer | Carrier | Catalyzer | Carrier | Catalyzer | Carrier | Catalyzer | Carrier | Catalyzer | |
| WO 3(w)％ | 16.91 | 16.31 | 17.02 | 32.0 | ||||||
| MoO 3(w)％ | 10.21 | 9.98 | 10.53 | 25.5 | ||||||
| NiO(w)％ | 3.77 | 4.18 | 3.97 | 5.02 | 4.85 | |||||
| P(w)％ | 2.66 | 2.94 | 2.85 | 2.65 | ||||||
| Specific surface area m 2/g | 320 | 180 | 340 | 204 | 360 | 178.6 | 360 | 175 | 360 | 168 |
| Pore volume ml/g | 0.75 | 0.35 | 0.70 | 0.46 | 0.77 | 0.385 | 0.77 | 0.35 | 0.77 | 0.33 |
| Heap compares g/ml | 0.65 | 0.93 | 0.55 | 0.84 | 0.50 | 0.92 | 0.50 | 0.89 | 0.50 | 0.91 |
| Intensity N/cm | 180 | 243 | 175 | 210 | 179 | 220 | 179 | 200 | 179 | 210 |
Table two, little anti-thiophene hds conversion (%)
| Temperature ℃ | Embodiment 1 | Embodiment 2 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| 235 | 50.86 | 51.41 | 47.24 | 36.53 | 40.05 |
| 250 | 82.45 | 72.5 | 68.08 | 53.82 | 63.91 |
| 265 | 97.33 | 96.08 | 94.93 | 85.95 | 90.51 |
Table three, wax hydrofining evaluation result
| Project | Paraffin character | Embodiment 1 | Embodiment 2 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Processing condition | ||||||
| Temperature of reaction, ℃ | 240 | 240 | 240 | 240 | 240 | |
| Reaction pressure, MPa | 6.0 | 6.0 | 6.0 | 6.0 | 6.0 | |
| Air speed, h -1 | 0.8 | 0.8 | 0.8 | 0.8 | 0.8 | |
| Hydrogen/wax ratio | 300 | 300 | 300 | 300 | 300 | |
| Quality product | ||||||
| Oleaginousness, % | 0.4 | 0.38 | 0.41 | 0.39 | 0.4 | 0.41 |
| Color, number | +17 | ＞+30 | ＞+30 | ＞+30 | ＞+30 | ＞+30 |
| Colorimetric, number | 3 | ＜1 | ＜1 | ＜1 | ＜1 | ＜1 |
| Readily carbonizable substance | Do not pass through | By | By | By | By | By |
| Light stability, number | 5~6 | 3 | 3~4 | 3 | 4 | 4 |
| Fusing point, ℃ | 57.8 | 57.6 | 57.1 | 57.5 | 57.2 | 57.4 |
| The FDA value, nm | ||||||
| 280~289 | Exceed standard | 0.014 | 0.028 | 0.075 | 0.096 | 0.083 |
| 290~299 | Exceed standard | 0.009 | 0.015 | 0.030 | 0.056 | 0.046 |
| 300~359 | Exceed standard | 0.004 | 0.006 | 0.010 | 0.015 | 0.017 |
| 360~400 | Exceed standard | 0.002 | 0.003 | 0.005 | 0.008 | 0.007 |
Evaluation result under table four, the embodiment 1 catalyzer low pressure condition
| Project | Second line of distillation | Subtract three-way | |
| Processing condition | |||
| Temperature of reaction, ℃ | 270 | 270 | 270 |
| Reaction pressure, Mpa | 3.0 | 3.0 | 3.0 |
| Air speed, h -1 | 0.6 | 0.8 | 0.8 |
| Hydrogen/wax ratio | 300 | 300 | 300 |
| Quality product | |||
| Oleaginousness, % | |||
| Color, number | ＞+30 | ＞+30 | ＞+30 |
| Colorimetric, number | ＜1 | ＜1 | ＜1 |
| Readily carbonizable substance | By | By | By |
| Light stability, number | 2 | 2-3 | 2-3 |
| Heat-resistant quality, number | 28 | 28 | 28 |
| The FDA value, nm | |||
| 280～289 | 0.014 | 0.015 | 0.015 |
| 290～299 | 0.009 | 0.010 | 0.010 |
| 300～359 | 0.004 | 0.005 | 0.005 |
| 360～400 | 0.002 | 0.002 | 0.002 |
Evaluation result under table five, the different air speeds of embodiment 1 catalyzer
| Project | |||||
| Processing condition | |||||
| Temperature of reaction, ℃ | 270 | 270 | 270 | 270 | 270 |
| Reaction pressure, MPa | 6.0 | 6.0 | 6.0 | 6.0 | 6.0 |
| Air speed, h -1 | 0.8 | 1.0 | 1.2 | 1.5 | 2.0 |
| Hydrogen/wax ratio | 300 | 300 | 300 | 300 | 300 |
| Quality product | |||||
| Color, number | ＞+30 | ＞+30 | ＞+30 | ＞+30 | ＞+30 |
| Colorimetric, number | ＜1 | ＜1 | ＜1 | ＜1 | ＜1 |
| Readily carbonizable substance | By | By | By | By | By |
| Light stability, number | 2-3 | 3 | 3 | 4 | 4 |
| The FDA value, nm | |||||
| 280~289 | 0.014 | 0.019 | |||
| 290~299 | 0.012 | 0.015 | |||
| 300~359 | 0.006 | 0.008 | |||
| 360~400 | 0.001 | 0.002 |
Evaluation result under table six, the embodiment 1 catalyzer differing temps
| Project | |||||
| Processing condition | |||||
| Temperature of reaction, ℃ | 210 | 230 | 250 | 270 | 290 |
| Reaction pressure, MPa | 6.0 | 6.0 | 6.0 | 6.0 | 6.0 |
| Air speed, h -1 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 |
| Hydrogen/wax ratio | 300 | 300 | 300 | 300 | 300 |
| Quality product | |||||
| Color, number | ＞+30 | ＞+30 | ＞+30 | ＞+30 | ＞+30 |
| Colorimetric, number | ＜1 | ＜1 | ＜1 | ＜1 | ＜1 |
| Readily carbonizable substance | By | By | By | By | By |
| Light stability, number | 4 | 3 | 3 | 3 | 2-3 |
| Fusing point, ℃ | 59.6 | 59.7 | 56.7 | ||
| The FDA value, nm | |||||
| 280~289 | 0.017 | 0.014 | 0.011 | ||
| 290~299 | 0.013 | 0.012 | 0.009 | ||
| 300~359 | 0.009 | 0.006 | 0.005 | ||
| 360~400 | 0.002 | 0.001 | 0.000 |
Claims (7)
1. a catalyst for hydrogen refining of paraffin wax is made up of carrier and the active ingredient that is carried on the carrier, it is characterized in that:
Carrier is made up of aluminum oxide and titanium dioxide, presses the weight percent meter of carrier, and alumina content is 20～99%, and content of titanium dioxide is 1～80%;
Active ingredient is elementary composition by W, Mo, Ni, P, is respectively by the content of the weight percent meter of catalyzer: WO
315～25%, MoO
38～15%, NiO 2～5%, and P 1.5～4.5%, and all the other are carrier.
2. catalyzer as claimed in claim 1 is characterized in that: press the weight percent meter of carrier in the described carrier, alumina content is 80～99%, and content of titanium dioxide is 1～20%.
3. catalyzer as claimed in claim 1 is characterized in that: described carrier specific surface area is 200～400m
2/ g, pore volume 0.5～0.8ml/g, intensity is greater than 140N/cm.
4. catalyzer as claimed in claim 1 is characterized in that: the specific surface area of described catalyzer is 140～210m
2/ g, pore volume 0.30～0.50ml/g.
5. as the described Preparation of catalysts method of one of claim 1～4, it is characterized in that:
The preparation of described carrier be in aluminum oxide, add titanium dioxide, through kneading, extruded moulding and drying, carry out again that roasting makes;
Described active ingredient W-Mo-Ni-P adopts the single stage method dip loading on carrier, and active ingredient at room temperature once is mixed with the aqueous solution of required concentration, wherein WO with ammonium tungstate, ammonium molybdate, nickelous nitrate, phosphoric acid
3Concentration is 15～40g/100ml; MoO
3Concentration is 10～25g/100ml, and NiO concentration is 2～6g/100ml, and P concentration is 3～6g/100ml.
6. Preparation of catalysts method as claimed in claim 5 is characterized in that: the drying temperature of the preparation of described carrier is 100～110 ℃, 450～600 ℃ of maturing temperatures.
7. as the application of the described catalyzer of one of claim 1～4 in hydrorefining paraffin wax technology.
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|---|---|---|---|
| CNB011295031A CN1194076C (en) | 2001-06-22 | 2001-06-22 | Catalyst for hydrorefining paraffin wax and its preparing process and usage |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011295031A CN1194076C (en) | 2001-06-22 | 2001-06-22 | Catalyst for hydrorefining paraffin wax and its preparing process and usage |
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| CN1194076C true CN1194076C (en) | 2005-03-23 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100429294C (en) * | 2005-10-26 | 2008-10-29 | 北京三聚环保新材料股份有限公司 | Refined hydrogenation catalyst and its preparation method |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1331995C (en) * | 2004-10-29 | 2007-08-15 | 中国石油化工股份有限公司 | Paraffin hydrogenation refining catalyst and its preparation method |
| US8697598B2 (en) | 2005-04-21 | 2014-04-15 | China Petroleum & Chemical Corporation | Hydrogenation catalyst and use thereof |
| CN1318546C (en) * | 2005-10-26 | 2007-05-30 | 长春惠工催化剂有限责任公司 | Co-impregnated solution for preparing hydrogenation refining catalyst and its preparation process |
| CN100446856C (en) * | 2006-07-26 | 2008-12-31 | 中国石油大庆石化公司研究院 | Petroleum wax hydrofining catalyst and its prepn process |
| CN101172226B (en) * | 2006-11-01 | 2011-08-24 | 中国石油化工股份有限公司 | Ultra-fine titanium aluminum composite oxide and preparation method thereof |
| CN111672504B (en) * | 2020-06-03 | 2024-03-19 | 北京海顺德钛催化剂有限公司 | Catalyst for moving bed and/or fluidized bed denitration device and preparation method and application thereof |
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2001
- 2001-06-22 CN CNB011295031A patent/CN1194076C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100429294C (en) * | 2005-10-26 | 2008-10-29 | 北京三聚环保新材料股份有限公司 | Refined hydrogenation catalyst and its preparation method |
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