CN110314675A - TiO2Modified alumina base magnesium aluminate spinel and preparation method thereof and sulfur-resistant transformation catalyst - Google Patents
TiO2Modified alumina base magnesium aluminate spinel and preparation method thereof and sulfur-resistant transformation catalyst Download PDFInfo
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Abstract
The present invention relates to sulfur-resistant transformation catalyst fields, disclose TiO2Modified alumina base magnesium aluminate spinel and preparation method thereof and sulfur-resistant transformation catalyst.The TiO prepared using the method for the invention2Modified alumina base magnesium aluminate spinel, avoids the use of organic solvent, reduces preparation cost.Use the TiO2Modified alumina base magnesium aluminate spinel as carrier, the catalyst being prepared overcome the Yishui River and the shortcomings that, widened the application range of catalyst, made it that all there is preferable activity and stability in 200-500 DEG C of temperature range.
Description
Technical field
The present invention relates to sulfur-resistant transformation catalyst fields, and in particular to TiO2Modified alumina base magnesium aluminate spinel and its
Preparation method and sulfur-resistant transformation catalyst.
Background technique
CO conversion reaction is widely used in ammonia from coal, synthesis ammonia, in the industry such as hydrogen manufacturing, for CO in modulation synthesis gas with
H2Ratio, comply with the needs of different chemical processes.With traditional Fe-Cr base high temperature transformation catalyst and Cu-Zn
Base low temperature conversion catalyst is compared, and Co-Mo sulfur-tolerant shift catalyst shift activity is high, using wide temperature region, not by the shadow of sulfur poisoning
It rings, thus is widely used.Existing Co-Mo base sulfur-resistant transformation catalyst is broadly divided into two major classes, one is being free of
The como shift catalyst of alkali metal promoter.It is carrier that such catalyst, which mostly uses greatly magnesium aluminate spinel, as being widely used
The K8-11 catalyst of BASF Corp. of Germany.Such catalyst intensity with higher is suitable in high temperature, high pressure (3-8Mpa), height
It is reacted under the conditions of water-gas ratio, but low temperature active is poor, and requires have higher sulfur content in conversion gas, otherwise activity decay is tight
Weight.Another kind of is the Co-Mo base transformation catalyst containing alkali metal promoter (predominantly potassium), such as US3850840A and
Catalyst disclosed in CN87107892A etc..Such catalyst has preferable activity under the conditions of low temperature and low-sulfur, but in height
The presence of the lower potassium of temperature can promote alumina catalyst support that hydration reaction occurs, and influence the stable structure of catalyst, thus catalyst activity
Decline is serious.
By by TiO2It is introduced into carrier that be modified to catalyst be to solve current cobalt-molybdenum series catalyst low temperature active
And the effective ways of water resistant and performance difference.CN1429763A is by using by TiO2、MgO、Al2O3, four kinds of groups of cement are grouped as
Complex carrier prepares como shift catalyst, although alkali metal containing does not have preferable low temperature (250-300 to the catalyst
DEG C) and low-sulfur (> 0.01v/v) activity.CN103447049B has invented a kind of being free of using aluminium titanium-based magnesium aluminate spinel as carrier
The como shift catalyst of potassium, compared to the catalyst of not titaniferous, titanium-containing catalyst has better activity stability, is suitable for
The transformation of high CO content (>=60%) synthesis gas.CN1096494A discloses a kind of wide temperature range and sulfurrange type without alkali metal promoter
Sulfur-resistant CO conversion catalyst, carrier are made of magnesia, aluminium oxide and titanium dioxide, pass through suspension intermediate processing system
It is standby.CN1087192C, CN102151574B then be used directly TiO2Sulfur-resistant transformation catalyst is prepared as carrier, such catalysis
Agent has good anti-hydration energy, low temperature active and structural stability.
But in method provided by foregoing invention, titaniferous materials are added in carrier in a manner of solid mostly, are passed through
Kneading method preparation, titanium material cannot have good combination with other elements, and utilization efficiency is low, limits the performance of its effectiveness.
Although CN103447049B introduces titanium elements using infusion process, since it uses organic titanium or TiCl4For titanium source, need to make
Use volatile organism as solvent, preparation cost is high, is unfavorable for industrialized production.
Summary of the invention
Goal of the invention of the invention be in order to overcome it is of the existing technology Ti is introduced into carrier in a manner of solid when knot
Close problem bad, that utilization rate is low and with organic titanium or TiCl4To need organic solvent, problem at high cost when titanium source, provide
TiO2Modified alumina base magnesium aluminate spinel and preparation method thereof and sulfur-resistant transformation catalyst.
To achieve the goals above, first aspect present invention provides a kind of TiO2Modified alumina base magnesium aluminate spinel
Preparation method, method includes the following steps:
(1) use infusion process by magnesium compound load in γ-Al2O3On matrix, then it is dried and roasts；
(2) use infusion process by TiOSO4It is supported on the matrix of step (1) preparation, is then dried；And
(3) matrix prepared by step (2) is placed in ammonia spirit and is heat-treated, be then dried and roast.
Second aspect of the present invention provides the TiO of first aspect the method preparation2Modified alumina base magnalium point is brilliant
Stone.
Third aspect present invention provides a kind of sulfur-resistant transformation catalyst, which contains carrier and load on the carrier
Active component, wherein the carrier be second aspect of the present invention described in TiO2Modified alumina base magnesium aluminate spinel, institute
Stating active component is cobalt, molybdenum and potassium.
The present invention uses water-soluble TiOSO4TiO is prepared for raw material2Modified alumina base magnesium aluminate spinel, avoids
The use of organic solvent reduces preparation cost, and the good dispersion of titanium, can farthest be covered on alumina base magnesium
On aluminate.
Catalyst of the present invention has used above-mentioned TiO2Modified oxidized aluminium base magnesium aluminate spinel overcomes and contains as carrier
Potassium catalyst under severe conditions the Yishui River and the shortcomings that, widened the application range of catalyst, kept it wider at 200-500 DEG C
All there is preferable Activity and stabill in temperature range.
Detailed description of the invention
Fig. 1 is XRD diagram after catalyst hydro-thermal process of the present invention.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of TiO2The preparation method of modified alumina base magnesium aluminate spinel, this method include following
Step:
(1) use infusion process by magnesium compound load in γ-Al2O3On matrix, then it is dried and roasts；
(2) use infusion process by TiOSO4It is supported on the matrix of step (1) preparation, is then dried；And
(3) matrix prepared by step (2) is placed in ammonia spirit and is heat-treated, be then dried and roast.
In the present invention, the γ-Al2O3Matrix, magnesium compound, TiOSO4Respectively with Al2O3、MgO、TiO2The quality of meter
Than for 100:1-20:1-15, preferably 100:1-15:1-8.
In the present invention, the γ-Al2O3Matrix can be various shape commonly used in the art, such as ball-type, tooth ball-type
Or bar shaped, preferably ball-type.
In the present invention, in step (1), the dipping method is preferably equi-volume impregnating.
In the present invention, the maceration extract used in dipping process contain magnesium compound and be optionally selected from lanthanum compound,
One of calcium compound, zirconium compounds and cerium compound are a variety of；
Preferably, the magnesium compound can be water soluble salt, such as can be selected from but be not limited only to magnesium nitrate, chlorination
One of magnesium, magnesium acetate and magnesium bicarbonate are a variety of.The lanthanum compound, calcium compound, zirconium compounds and cerium compound can
Think that the water soluble salt of corresponding element, the lanthanum compound for example can be in lanthanum chloride, lanthanum nitrate, lanthanum acetate and lanthanum sulfates
It is one or more；The calcium compound can for example be selected from one of calcium chloride and calcium nitrate or a variety of, the zirconium chemical combination
Object can for example be selected from one of zirconium chloride and zirconium nitrate or a variety of；The cerium compound for example can selected from cerous chloride and
One of cerous nitrate is a variety of.
In the present invention, it is 100-150 DEG C that the drying condition in step (1), which includes: temperature, time 6-18h；The roasting
The condition of burning includes: that temperature is 400-1000 DEG C, time 1-5h.In the present invention, in step (1) through drying and roasting step it
After obtain alumina base magnesium aluminate spinel particle.
In the present invention, in step (2), TiOSO is used4The alumina base magnalium point that solution impregnation steps (1) obtain is brilliant
Stone particle, the dipping method are preferably equi-volume impregnating.
In the present invention, in step (2), the condition of the drying includes: that temperature is 80-150 DEG C, time 3-12h.
In the present invention, by TiOSO4After being impregnated on alumina base magnesium aluminate spinel, it need to be heat-treated in weak aqua ammonia.
Preferably, in step (3), the condition of the heat treatment includes: that temperature is 50-100 DEG C, time 1-5h, the mistake of heat treatment
The pH value of ammonia spirit is kept greater than 11 in journey.
During the treatment, it may occur that following reaction:
TiOSO4+2NH3·H2O=TiO (OH)2↓+(NH4)2SO4
TiO(OH)2=TiO2+H2O
3(NH4)2SO4=4NH3↑+3SO2↑+N2↑+6H2O
In the present invention, ammonia spirit used in step (3) can be the ammonia spirit of any appropriate concentration range, only
It wants the pH value that can guarantee ammonia spirit in heat treatment process to be kept greater than 11, such as can be 0.1-0.5mol/L.
The present invention in such a way that infusion process introduces titanium, with it is conventional the use of solids containing titanium such as metatitanic acid is starting material
Kneading method is compared, and the dispersibility of titanium is more preferable, can farthest be covered on alumina base magnesium aluminate spinel, enhances catalyst
The anti-hydration energy of carrier；With use TiCl4Or organic titanium such as butyl titanate is compared for the infusion process of starting material, the present invention
Use water-soluble TiOSO4For raw material, the use of organic solvent is avoided, preparation cost is reduced.Moreover, carrier of the present invention
The sulfate ion of middle introducing can pass through formation (NH4)2SO4It is removed in a manner of roasting later, does not need massive laundering, simply
It is easy.
In the present invention, it is 100-150 DEG C that the condition of drying described in step (3), which includes: temperature, time 6-18h；
The condition of the roasting includes: that temperature is 500-600 DEG C, time 1-5h.
The present invention also provides the TiO prepared by the above method2Modified alumina base magnesium aluminate spinel.
With above-mentioned TiO2Modified alumina base magnesium aluminate spinel be carrier, can by infusion process by active component Co,
Mo, K load prepare sulfur-resistant transformation catalyst thereon, wherein the maceration extract contains cobalt compound, molybdenum compound and potassium chemical combination
Object.The cobalt compound can be soluble cobalt, such as can be cobalt nitrate, cobalt acetate, cobalt chloride, cobaltous sulfate and alkali formula carbon
One of sour cobalt is a variety of；Molybdenum compound can be soluble molybdenum salt, such as can for ammonium molybdate, sodium molybdate, potassium molybdate and
One of phosphomolybdic acid is a variety of, preferably ammonium molybdate；Potassium compound can be soluble potassium salt, such as can for potassium carbonate,
One of potassium chloride, potassium hydroxide, potassium nitrate are a variety of, preferably potassium carbonate.
The introducing of each component preferably passes through equi-volume impregnating, each component utilization efficiency in catalyst of the present invention
Height is uniformly dispersed, and easy to operate.
In the present invention, active component is loaded into TiO using infusion process2Modified alumina base magnesia alumina spinel carrier
On, sulfur-resistant transformation catalyst of the present invention can be obtained in dry and roasting.The condition of the drying can be normal for this field
Drying condition, it preferably includes: temperature is 100-150 DEG C, more preferably 120 DEG C；Time is 8-18h, more preferably
12h.The condition of the roasting can be roasting condition commonly used in the art, it preferably includes: temperature is 450-600 DEG C, more excellent
550-600 DEG C of selection of land；Time is 2-5h.
The present invention provides a kind of sulfur-resistant transformation catalyst, which contains above-mentioned TiO2Modified alumina base magnalium
The active component of spinel carrier and load on this carrier, wherein the active component is cobalt, molybdenum and potassium.
Preferably, on the basis of the total weight of the catalyst, the content of the carrier is 60-95 weight %, cobalt component
Content in terms of oxide is 1-10 weight %, and content of the molybdenum component in terms of molybdenum trioxide is 2-20 weight %, and potassium component is with oxygen
The content for changing potassium meter is 1-15 weight %.
Preferably, in the carrier, on the basis of the total weight of the carrier, the content of magnesium in terms of MgO is 1-15 weight
% is measured, such as can be any value in two point value institute compositing range of 2,5,7,10,12,15 weight % and any of the above, it is excellent
Selection of land, the content of magnesium in terms of MgO are 1-10 weight %；With TiO2The Ti content of meter is 1-10 weight %, for example, can for 2,3,
4, any value in two point value institute compositing range of 5,6,7,8,9,10 weight % and any of the above, it is preferable that with TiO2Meter
Ti content is 1-8 weight %；With Al2O3The aluminium content of meter be 80-95 weight %, such as can for 85,87,89,92 weight % with
And any value in two point value institute compositing range of any of the above.
Catalyst of the present invention not only has preferable intensity and water resistant and performance, high temperature (250-500 DEG C), under make
Used time not water and not phase transformation, and there is excellent low temperature active (200-250 DEG C), it is wider at 200-500 DEG C using wide temperature region
Within the temperature range of all have preferable Activity and stabill.
The present invention will be described in detail by way of examples below.
Raw material used in following embodiment is as follows:
Spherical gamma-Al2O3: purchased from the product of Zibo Rui Feng chemical company, specific surface area 200m2/ g, average pore size
7nm, intensity are 110N/, water absorption rate 63%.
Technical grade magnesium nitrate hexahydrate: the product purchased from Shanxi Jiao cheng City star Chemical Co., Ltd..
Titanyl sulfate: the product purchased from Shanghai Yi Hui Chemical Co., Ltd..
The test of water absorption rate described in embodiment is carried out by method commonly used in the art.
Embodiment 1
Weigh 740g spherical gamma-Al2O3Carrier, water absorption rate 63%.364g technical grade magnesium nitrate hexahydrate is taken, use is water-soluble
466ml is settled to after solution.By magnesium nitrate solution incipient impregnation to 740g γ-Al2O3On carrier, 120 DEG C of dry 12h, 800 DEG C
3h is roasted, 813g alumina base magnesia alumina spinel carrier is obtained, measuring its water absorption rate is 56%.61g titanyl sulfate is taken to be dissolved in water
In be settled to 455ml, it is dry at 120 DEG C on incipient impregnation to mentioned-above alumina base magnesia alumina spinel carrier
12h.70 DEG C are placed on to room temperature by the carrier after drying is cool, are heat-treated 3h in the ammonia spirit of 0.5mol/L.Later by it
The dry 12h at 120 DEG C, in 550 DEG C of roasting 3h to get to TiO2Modified alumina base magnesia alumina spinel carrier 828g, with
On the basis of the total weight of carrier, the content of magnesium in terms of MgO is 6.9 weight %, with TiO2The Ti content of meter is 3.7 weight %, remaining
Amount is γ-Al2O3, water absorption rate: 50%.
Basic cobaltous carbonate 64.34g, ammonium heptamolybdate 106.55g are taken, potassium carbonate 97.47g is configured to total immersion according to a conventional method
Stain liquid, incipient impregnation to aforementioned TiO2In modified alumina base magnesia alumina spinel carrier, 120 DEG C of dry 12h, 600 DEG C of roastings
3h is burnt, finished catalyst A1 is obtained.On the basis of the total weight of catalyst, content of the cobalt component in terms of oxide is 4 weight %,
Content of the molybdenum component in terms of molybdenum trioxide is 8.5 weight %, and content of the potassium component in terms of potassium oxide is 6.5 weight %.
Embodiment 2
Sulfur-resistant transformation catalyst A2 is prepared according to method similar to Example 1, unlike, it is prepared according to following processes
TiO2Modified alumina base magnesia alumina spinel carrier:
Weigh 679g spherical gamma-Al2O3Carrier, water absorption rate 63%.527g technical grade magnesium nitrate hexahydrate is taken, use is water-soluble
428ml is settled to after solution.By magnesium nitrate solution incipient impregnation to 679g γ-Al2O3On carrier, 110 DEG C of dry 15h, 900 DEG C
3h is roasted, 762g alumina base magnesia alumina spinel carrier is obtained, measuring its water absorption rate is 52%.132g titanyl sulfate is taken to be dissolved in water
In be settled to 396ml, it is dry at 120 DEG C on incipient impregnation to mentioned-above alumina base magnesia alumina spinel carrier
12h.60 DEG C are placed on to room temperature by the carrier after drying is cool, are heat-treated 4h in the ammonia spirit of 0.3mol/L.Later by it
The dry 12h at 120 DEG C, in 500 DEG C of roasting 5h to get to TiO2Modified alumina base magnesia alumina spinel carrier, with carrier
Total weight on the basis of, content of magnesium in terms of MgO is 10 weight %, with TiO2The Ti content of meter is 8 weight %, and surplus is γ-
Al2O3, water absorption rate: 48%.
Embodiment 3
Sulfur-resistant transformation catalyst A3 is prepared according to method similar to Example 1, unlike, it is prepared according to following processes
TiO2Modified alumina base magnesia alumina spinel carrier:
Weigh 687g spherical gamma-Al2O3Carrier, water absorption rate 63%.500g Magnesium dichloride hexahydrate is taken, it is fixed after being dissolved with water
Hold to 433ml.By magnesium chloride solution incipient impregnation to 687g γ-Al2O3On carrier, 100 DEG C of dry 12h, 500 DEG C of roasting 3h,
787g alumina base magnesia alumina spinel carrier is obtained, measuring its water absorption rate is 50%.Take 82g titanyl sulfate is soluble in water to be settled to
394ml, on incipient impregnation to mentioned-above alumina base magnesia alumina spinel carrier, the dry 12h at 120 DEG C.It will dry
Carrier afterwards is cool to be placed on 80 DEG C to room temperature, is heat-treated 3h in the ammonia spirit of 0.3mol/L.It is done at 120 DEG C later
Dry 12h, in 500 DEG C of roasting 5h to get arrive TiO2Modified alumina base magnesia alumina spinel carrier, using the total weight of carrier as base
Standard, vehicle group become: the content of magnesium in terms of MgO is 12 weight %, with TiO2The Ti content of meter is 5 weight %, and surplus is γ-
Al2O3, water absorption rate: 50%.
Embodiment 4
Sulfur-resistant transformation catalyst A4 is prepared according to method similar to Example 1, unlike, according to following Process Duties
Active component:
Cabaltous nitrate hexahydrate 287g, sodium molybdate 206g are taken, potassium hydroxide 110g is configured to co-impregnation liquid according to a conventional method,
Incipient impregnation is to aforementioned TiO2In modified alumina base magnesia alumina spinel carrier, 120 DEG C of dry 12h, 550 DEG C of roasting 3h,
Obtain finished catalyst A4.On the basis of the total weight of catalyst, content of the cobalt component in terms of oxide is 8 weight %, molybdenum group
The content divided in terms of molybdenum trioxide is 12 weight %, and content of the potassium component in terms of potassium oxide is 9 weight %.
Comparative example 1
Sulfur-resistant transformation catalyst is prepared according to method similar to Example 1, unlike, it is not loaded in comparative example 1
The step of Ti.Finally obtain finished catalyst D1.
Comparative example 2
Sulfur-resistant transformation catalyst is prepared according to method similar to Example 1, unlike, comparative example 2 uses TiO2、
Al2O3TiO is obtained by the method for kneading with MgO2Modified magnesia alumina spinel carrier.Finally obtain finished catalyst D2.
Test case
1, the normal pressure activity of catalyst
The normal pressure activity rating condition of catalyst are as follows: loaded catalyst 0.5g, granularity 20-40 mesh, reaction pressure
0.1Mpa, gas space velocity 6000h-1, 200-500 DEG C of reaction temperature, unstripped gas composition: CO 81.45%, H29.92%, N2
8.55%, H2S 0.08%, water-gas ratio 1.0, with the activity of CO conversion ratio characterization catalyst.
First In-situ sulphiding, conditions of vulcanization is needed before carrying out catalyst activity evaluation are as follows: H2/H2S (99.2%/0.8% (v/
V)), 50ml/min, pressure 0.1Mpa, 450 DEG C of temperature, vulcanization time 5h.
CO conversion ratio calculation formula is XCO=[(C1-C2)/C1] * 100%, C1For CO concentration at reactor inlet, (v/v is done
Base (removing vapor)), C2For reactor exit CO concentration (v/v, butt (removing vapor)).
Catalyst A1-A4, D1-D2 are tested respectively according to the method described above in different temperatures (200 DEG C, 300 DEG C, 400 DEG C, 500
DEG C) under normal pressure activity, be as a result shown in Table 1.
Table 1
2, catalyst hydration-resisting performance evaluation
Catalyst A1, D1 and D2 are put into water heating kettle, a certain amount of deionized water is added, 200 DEG C are heated to after sealing
Hydro-thermal process 15 hours, with XRD its object phase change is detected after dry, catalyst hydration-resisting is indicated with object phase change amplitude size
The power of performance.
As shown in table 1, compared with comparative example catalyst D1, D2, catalyst A1-A4 has higher work at 200-500 DEG C
Property, and at a high temperature of 500 DEG C, D1 catalyst inactivation is serious, and catalyst activity of the present invention is then substantially unchanged, Er Qie
500 DEG C of activity is always held at 65% or more.
As shown in Figure 1, after the hydrothermal treatment, the hydration that apparent alumina catalyst support has occurred in catalyst A1, D1 is anti-
It answers, but the hydration peak of A1 alumina catalyst is smaller, indicates it with better anti-hydration energy.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (11)
1. a kind of TiO2The preparation method of modified alumina base magnesium aluminate spinel, method includes the following steps:
(1) use infusion process by magnesium compound load in γ-Al2O3On matrix, then it is dried and roasts；
(2) use infusion process by TiOSO4It is supported on the matrix of step (1) preparation, is then dried；And
(3) matrix prepared by step (2) is placed in ammonia spirit and is heat-treated, be then dried and roast.
2. according to the method described in claim 1, wherein, the γ-Al2O3Matrix, magnesium compound, TiOSO4Respectively with Al2O3、
MgO、TiO2The mass ratio of meter is 100:1-20:1-15.
3. in step (1), the infusion process is equi-volume impregnating according to the method described in claim 1, wherein,
Preferably, the maceration extract used in dipping process contain magnesium compound and be optionally selected from lanthanum compound, calcium compound,
One of zirconium compounds and cerium compound are a variety of；
Preferably, the magnesium compound is selected from one of magnesium nitrate, magnesium chloride, magnesium acetate and magnesium bicarbonate or a variety of.
4. method according to claim 1 or 3, wherein in step (1), the condition of the drying includes: that temperature is
100-150 DEG C, time 6-18h；The condition of the roasting includes: that temperature is 400-1000 DEG C, time 1-5h.
5. according to the method described in claim 1, wherein, in step (2), the infusion process is equi-volume impregnating.
6. method according to claim 1 or 5, wherein in step (2), the condition of the drying includes: that temperature is
80-150 DEG C, time 3-12h.
7. according to the method described in claim 1, wherein, in step (3), the condition of the heat treatment includes: that temperature is 50-
100 DEG C, time 1-5h, the pH value of ammonia spirit is kept greater than 11 during heat treatment.
8. according to the method described in claim 1, wherein, in step (3), the condition of the drying includes: that temperature is 100-
150 DEG C, time 6-18h；The condition of the roasting includes: that temperature is 500-600 DEG C, time 1-5h.
9. the TiO of the preparation of the method as described in any one of claim 1-82Modified alumina base magnesium aluminate spinel.
10. a kind of sulfur-resistant transformation catalyst, which contains carrier and loads the active component on the carrier, and feature exists
In the carrier is TiO as claimed in claim 92Modified alumina base magnesium aluminate spinel, the active component are cobalt, molybdenum
And potassium.
11. catalyst according to claim 10, wherein on the basis of the total weight of the catalyst, the carrier
Content is 60-95 weight %, and content of the cobalt component in terms of oxide is 1-10 weight %, content of the molybdenum component in terms of molybdenum trioxide
For 2-20 weight %, content of the potassium component in terms of potassium oxide is 1-15 weight %；
Preferably, in the carrier, on the basis of the total weight of the carrier, the content of magnesium in terms of MgO is 1-15 weight %,
With TiO2The Ti content of meter is 1-10 weight %, with Al2O3The aluminium content of meter is 80-95 weight %.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111410543A (en) * | 2020-04-24 | 2020-07-14 | 朔州西廊煤炭科技有限公司 | Method for preparing functional ceramic engineering material combustion-supporting catalyst by utilizing coal solid waste or bauxite solid waste |
| CN112090435A (en) * | 2019-06-18 | 2020-12-18 | 国家能源投资集团有限责任公司 | Cobalt-molybdenum-based sulfur-tolerant shift catalyst and preparation method and application thereof |
| CN112517008A (en) * | 2020-12-29 | 2021-03-19 | 福州大学 | Preparation method of Fe-doped magnesium aluminate spinel catalyst and application of Fe-doped magnesium aluminate spinel catalyst in desulfurization field |
| CN113880124A (en) * | 2020-07-01 | 2022-01-04 | 中国石油天然气股份有限公司 | Method for preparing magnesium aluminate spinel by impregnation |
| CN114471589A (en) * | 2020-10-27 | 2022-05-13 | 中国石油化工股份有限公司 | Catalyst, method for sulfur-tolerant shift catalytic reaction and method for preparing methane |
| CN116440961A (en) * | 2023-04-09 | 2023-07-18 | 珠海谦信新材料有限公司 | Co/TiO2 catalyst modified by La and Al, preparation method and application in synthesis gas to low-carbon alcohol |
| CN117164369A (en) * | 2023-09-05 | 2023-12-05 | 冷水江市博晟新材料有限公司 | Ramming material of medium-frequency induction furnace and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102049257A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Catalyst for simultaneously reducing SO2 and NO with CO as well as preparation and application of catalyst |
| CN107398262A (en) * | 2016-05-19 | 2017-11-28 | 神华集团有限责任公司 | Catalyst for methanation in presence of sulfur and preparation method thereof and magnesium aluminate spinel complex carrier and preparation method thereof |
-
2018
- 2018-03-28 CN CN201810264420.9A patent/CN110314675B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102049257A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Catalyst for simultaneously reducing SO2 and NO with CO as well as preparation and application of catalyst |
| CN107398262A (en) * | 2016-05-19 | 2017-11-28 | 神华集团有限责任公司 | Catalyst for methanation in presence of sulfur and preparation method thereof and magnesium aluminate spinel complex carrier and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| R. E. CARTER: "Mechanism of Solid-state Reaction Between Magnesium -Oxide and Aluminum Oxide and Between Magnesium Oxide and Ferric Oxide", 《JOURNAL OF THE AMERICAN CERAMIC SOCIETY》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112090435A (en) * | 2019-06-18 | 2020-12-18 | 国家能源投资集团有限责任公司 | Cobalt-molybdenum-based sulfur-tolerant shift catalyst and preparation method and application thereof |
| CN111410543A (en) * | 2020-04-24 | 2020-07-14 | 朔州西廊煤炭科技有限公司 | Method for preparing functional ceramic engineering material combustion-supporting catalyst by utilizing coal solid waste or bauxite solid waste |
| CN113880124A (en) * | 2020-07-01 | 2022-01-04 | 中国石油天然气股份有限公司 | Method for preparing magnesium aluminate spinel by impregnation |
| CN114471589A (en) * | 2020-10-27 | 2022-05-13 | 中国石油化工股份有限公司 | Catalyst, method for sulfur-tolerant shift catalytic reaction and method for preparing methane |
| CN112517008A (en) * | 2020-12-29 | 2021-03-19 | 福州大学 | Preparation method of Fe-doped magnesium aluminate spinel catalyst and application of Fe-doped magnesium aluminate spinel catalyst in desulfurization field |
| CN112517008B (en) * | 2020-12-29 | 2023-10-27 | 福州大学 | Preparation method of Fe-doped magnesia-alumina spinel catalyst and application of Fe-doped magnesia-alumina spinel catalyst in desulfurization field |
| CN116440961A (en) * | 2023-04-09 | 2023-07-18 | 珠海谦信新材料有限公司 | Co/TiO2 catalyst modified by La and Al, preparation method and application in synthesis gas to low-carbon alcohol |
| CN117164369A (en) * | 2023-09-05 | 2023-12-05 | 冷水江市博晟新材料有限公司 | Ramming material of medium-frequency induction furnace and preparation method thereof |
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