CN108654630A - A kind of sulfur-resistant transformation catalyst and preparation method thereof - Google Patents
A kind of sulfur-resistant transformation catalyst and preparation method thereof Download PDFInfo
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- CN108654630A CN108654630A CN201710202348.2A CN201710202348A CN108654630A CN 108654630 A CN108654630 A CN 108654630A CN 201710202348 A CN201710202348 A CN 201710202348A CN 108654630 A CN108654630 A CN 108654630A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/882—Molybdenum and cobalt
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
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Abstract
The present invention relates to water gas shift reation field, a kind of sulfur-resistant transformation catalyst and preparation method thereof is disclosed, which includes：Cobalt molybdate, support material and water are subjected to kneading；The product that the kneading is obtained carries out extrusion molding, is then dried, roasts and obtain sulfur-resistant transformation catalyst.Preparation method rate of metal provided by the invention is high, has preferable stability and higher activity, and can eliminate nitrate anion and decompose the problem of environmental pollution brought.
Description
Technical field
The present invention relates to water gas shift reation fields, and in particular, to a kind of preparation method of sulfur-resistant transformation catalyst, with
And the sulfur-resistant transformation catalyst prepared by this method.
Background technology
CO reacts under the effect of the catalyst with water vapour, generates CO2With H2Process, referred to as water-gas shift
(Water Gas shift, WGS) reacts.Water-gas shift has very important effect in chemical industry, is widely used in hydrogen
Production, ammonia synthesizing industry and using production processes such as the adjustings of hydrogen-carbon ratio in the Chemical Manufacture that synthesis gas is carried out as raw material.
Water-gas shift process by production the characteristics of can be divided into (1) high temperature shift (High TemperatureShift,
HTS), custom catalysts are Fe-Cr catalyst, and operation temperature is between 300-500 DEG C；(2) low-temperature conversion (Low
Temperature Shift, LTS), generally using Cu-Zn materials as catalyst, operation temperature is between 200-270 DEG C；(3) resistance to
Sulphur converts (S-tolerant Shift), using hydrogen sulfide containing producing synthesis gas from coal as raw material, generally uses Co -- Mo catalyst.
With the development of China's residual oil, heavy-oil hydrogenation and coal hydrogen technology, especially in recent years China's coal chemical technology it is rapid into
Step, to the demand of sulfur-resistant transformation catalyst every year at 2500 tons or more.
The preparation process of sulfur-resistant transformation catalyst can mainly use kneading method and infusion process.Kneading method is by Co, Mo precursor
It is mixed with support precursor and crosslinking agent solid-state, extrusion forming；The catalyst carrier of forming is prepared in infusion process first, so
Co, Mo are configured to the maceration extract of required concentration respectively afterwards, Co, Mo are supported on carrier in a manner of co-impregnation or step impregnation
Surface.In the above method, active component is often added with Co, Mo soluble-salt, such as nitrate, acetate, ammonium salt form, such as Co
Using cobalt nitrate, cobalt acetate etc., Mo is using ammonium tetramolybdate, ammonium heptamolybdate etc..However these soluble-salts, after catalyst preparation
Generation such as NO will be decomposed in continuous roasting processX、COX, the acid waste gas such as ammonia, seriously pollute environment.Prior art usually exists
Setting carries out absorption processing to above-mentioned discharge gas in preparation process, but increases manufacturing cost.
The preparation process of existing sulfur-resistant transformation catalyst cannot be guaranteed that cobalt comes into full contact with molybdenum, and cobalt molybdenum is respectively independently present in
Carrier surface forms rich cobalt or the probability in the areas Fu Muchou is very big, cannot play the modification of cobalt well, and then influence resistance to
The activity and stability of sulfur change catalyst.
CN1219500A discloses a kind of CO sulfur-resistant transformation catalysts and preparation method, which uses kneading method, living
Property group is divided into Co, Ni, Mo, W soluble-salt, such as nitrate, acetate, ammonium salt.First each component of catalyst carrier is mixed
Uniformly, the solution of active component soluble-salt is then added, mediate uniformly and shapes, dry, roasting.0-200 DEG C of water is used to steam afterwards
Vapour handles catalyst.This method is raw material using soluble-salt, and release NO can be decomposed in roasting processX, direct emission influence ring
Border, if increasing NOXAbsorption plant then increases catalyst preparation cost, in addition, this method inevitably forms the rich cobalt in part
Or the areas Fu Muchou, the modification of cobalt cannot be played well.
Invention content
The purpose of the invention is to overcome to generate acid or alkaline exhaust gas in existing sulfur-resistant transformation catalyst preparation process
Environment and activity of sulfur tolerant CO shift and the relatively low problem of stability are polluted, a kind of preparation of sulfur-resistant transformation catalyst is provided
Method and sulfur-resistant transformation catalyst obtained by this method.
To achieve the goals above, the present invention provides a kind of preparation method of sulfur-resistant transformation catalyst, including：By molybdic acid
Cobalt, support material and water carry out kneading；The product that the kneading is obtained carries out extrusion molding, is then dried, roasts
To sulfur-resistant transformation catalyst.
The present invention also provides sulfur-resistant transformation catalysts prepared by the above method.
The present invention directly uses cobalt molybdate as the cobalt of sulfur-resistant transformation catalyst and the common active source of molybdenum, overcomes existing
There is active metal Co and Mo in technology to form the partly defect in rich cobalt or the areas Fu Muchou, improves rate of metal, formed more
Co-Mo-S activity phases, and then there is preferable stability and higher activity；In addition, directly preparing sulphur-resistant conversion with cobalt molybdate
Catalyst can eliminate nitrate anion and decompose the problem of environmental pollution brought.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Attached drawing is to be used to provide further understanding of the present invention, an and part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the XRD diffracting spectrums of molybdic acid hydrate cobalt prepared by the embodiment of the present invention 1 and cobalt molybdate.
Specific implementation mode
The specific implementation mode of the present invention is described in detail below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
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 preparation method of sulfur-resistant transformation catalyst, including：Cobalt molybdate, support material and water are carried out
Kneading；The product that the kneading is obtained carries out extrusion molding, is then dried, roasts and obtain sulfur-resistant transformation catalyst.
Cobalt molybdate is alternatively referred to as cobalt oxide molybdenum (CoMoO4), it is the mixed oxide that cobalt and molybdenum are formed, it is anti-in water-gas shift
Field is answered, sulfur-resistant transformation catalyst mostly uses cobalt and the presoma of molybdenum is prepared with carrier by kneading method and infusion process, the present invention
In, sulphur-resistant conversion is prepared instead of existing directly as the cobalt of sulfur-resistant transformation catalyst and the common active source of molybdenum using cobalt molybdate
The kneading method and infusion process of catalyst overcome active metal Co in the prior art and Mo and form the rich cobalt in part or the areas Fu Muchou
Defect improves rate of metal.
It should be noted that cobalt molybdate of the present invention and cobalt molybdenum heteropolyacid are entirely different, cobalt molybdate in the present invention
Co：Mo atomic ratios are 1:1, and Co in cobalt molybdenum heteropolyacid：Mo atomic ratios are mostly between 0.1-0.2, and the present inventor sends out
It is existing, it is more advantageous to as the common active source of cobalt and molybdenum using cobalt molybdate and improves activity of sulfur tolerant CO shift and stability.
The cobalt molybdate can be anhydrous molybdic acid cobalt in the present invention, or molybdic acid hydrate cobalt, the present invention do not have this
There is special restriction.
, according to the invention it is preferred to before kneading, cobalt molybdate, support material and water are subjected to ball milling.The present invention is to described
There is no particular limitation for the condition of ball milling, as long as so that cobalt molybdate and support material come into full contact with, the ball milling can be
It is completed in ball mill.
There is no particular limitation to the kneading by the present invention, and the kneading can be completed in kneading machine, in the present invention,
It is preferred that limiting the condition for carrying out the kneading as acidity.
A preferred embodiment of the invention, the introducing crosslinked agent during kneading, for example, by molybdic acid
Cobalt, carrier, crosslinking agent and water carry out the kneading.
There is no particular limitation to the crosslinking agent by the present invention, can be various crosslinking agents commonly used in the art,
It is preferred that the acidity in kneading process is provided by the crosslinking agent, for example, the crosslinking agent is selected from organic and or inorganic acids.Institute
At least one of formic acid, acetic acid and propionic acid can be selected from by stating organic acid；The inorganic acid can be selected from nitric acid, hydrochloric acid and sulfuric acid
At least one of.In order to avoid nitrate anion decomposes the problem of environmental pollution brought, the preferably described crosslinking agent does not contain nitrate anion,
Most preferably, the crosslinking agent is acetic acid.
In the present invention, to the support material, there is no particular limitation, as long as load commonly used in the art can be provided
Body forms, and may include finished product carrier in the support material, can also include support precursor, and support precursor is being urged
Roasting process in agent preparation process can be converted into finished product carrier.
, according to the invention it is preferred to the support material includes magnesium aluminate spinel and/or magnesia alumina spinel carrier presoma, institute
It includes magnesium-containing compound and aluminum contained compound to state magnesia alumina spinel carrier presoma.
There is no particular limitation to the magnesium-containing compound and aluminum contained compound by the present invention, as long as under the roasting condition can
Generate magnesium aluminate spinel.It is preferred that the magnesium-containing compound is selected from least one of magnesia, magnesium nitrate and magnesium hydroxide,
The aluminum contained compound is boehmite and/or magnesium aluminium oxide aluminate, it is preferable that the magnesium-containing compound is selected from
At least one of magnesia, magnesium nitrate and magnesium hydroxide, the aluminum contained compound be boehmite and/or aluminium oxide, most
Preferably, the magnesium-containing compound is magnesia, and the aluminum contained compound is boehmite.
, according to the invention it is preferred to which the support material is magnesia alumina spinel carrier presoma, using this kind of preferred implementation side
Formula is more advantageous to the activity and stability for improving catalyst.
The present invention is wider to magnesium-containing compound in support material and the range of choice of aluminum contained compound weight ratio, preferably described
The weight ratio of magnesium-containing compound and aluminum contained compound is 0.1-1：1, further preferably 0.2-0.4：1.
In order to further improve the stability and activity of sulfur-resistant transformation catalyst, the preferably described support material, which also contains, to be carried
Body auxiliary agent, the carrier auxiliary agent are selected from least one of zirconium oxide, cerium oxide, lanthana and manganese oxide.
As long as addition carrier auxiliary agent improves the stability and activity of sulfur-resistant transformation catalyst, to the use of carrier auxiliary agent
The range of choice of amount is wider, and the weight ratio of the preferably described carrier auxiliary agent and the aluminum contained compound is 0.01-0.5：1, further
Preferably 0.07-0.35：1.
When also containing carrier auxiliary agent in the support material, the occasion of introduction of the carrier auxiliary agent is not limited particularly
It is fixed, it can be by cobalt molybdate, magnesium-containing compound, aluminum contained compound, carrier auxiliary agent and the common kneading of water, can also be by cobalt molybdate
Roasting, grinding after being mixed with carrier auxiliary agent, then with the common kneading of magnesium-containing compound, aluminum contained compound and water, the present invention do not have this
There is special restriction, preferably by cobalt molybdate, magnesium-containing compound, aluminum contained compound, carrier auxiliary agent and the common kneading of water.
The present invention is wider to the range of choice of the dosage of the cobalt molybdate and support material, can be according to metal active group
The content requirement divided is determined, and the weight ratio of the preferably described cobalt molybdate and support material is 0.05-0.5：1；Further preferably
For 0.1-0.3：1, it is still more preferably 0.1-0.2：1.
According to the present invention, in order to be more advantageous to follow-up extrusion molding operation, preferably this method further includes in kneading process
Introduce extrusion aid.The present invention is not particularly limited the extrusion aid, preferably sesbania powder.
The present invention is wider to the range of choice of the additive amount of the extrusion aid, and the additive amount of the preferably described extrusion aid is molybdic acid
The 1-3% of cobalt and support material total weight.
According to the present invention, extrusion molding is used to the product that the kneading obtains further being shaped to catalyst.It can lead to
The product that the kneading obtains is shaped to bar shaped agent by the method for crossing extrusion molding on extruder, and the diameter of cross section can be with
For 1-5mm.The bar shaped agent of forming is further dried and roasts.
There is no particular limitation for condition of the present invention to the drying, and preferably dry temperature is -100 DEG C of room temperature, time
For 3-24h.
According to the present invention, during the roasting, support precursor (for example, magnesia alumina spinel carrier presoma) conversion
For corresponding carrier (for example, magnesia alumina spinel carrier), and so that metal active constituent Co and Mo are combined with carrier.It is preferred that feelings
Under condition, the calcination temperature is 400-700 DEG C, time 3-8h；It is further preferred that temperature is 500-600 DEG C, time 4-
6h。
In the present invention, the cobalt molybdate can be the cobalt molybdate of existing various specifications, can be commercially available, also may be used
To be obtained by existing various methods.Under preferable case, the method further includes using following steps (1) or step (1)
(2) process prepares cobalt molybdate：
(1) water soluble cobaltous salt, water-soluble molybdenum salt are contacted with precipitating reagent, is then filtered, obtain molybdic acid hydrate cobalt；With
And
(2) the molybdic acid hydrate cobalt for obtaining step (1) roasts.
In the preparation process of cobalt molybdate, it after filtration, can be roasted, can not also be roasted, when not roasting, be obtained
To be molybdic acid hydrate cobalt；Upon firing, the temperature of the roasting can be 400-700 DEG C, and the time can be 3-8h；It is preferred that
Ground, temperature are 500-600 DEG C, time 4-6h.
, according to the invention it is preferred to which filtering obtained solid product is washed and is dried.The washing and drying can be by
It is carried out according to this field conventional technical means.For example, the drying carries out 3-24h at room temperature.
A preferred embodiment of the invention, also added with complexing agent in the contact process.Adding complexing agent can
To more effectively control the crystallite dimension of cobalt molybdate, and then it is more conducive to the activity and stabilization for improving sulfur-resistant transformation catalyst
Property.
Addition opportunity of the present invention to complexing agent, there is no particular limitation, can be first by water soluble cobaltous salt and water-soluble molybdenum
After salt mixing, complexing agent is then added, is eventually adding precipitating reagent；Or first by complexing agent and water soluble cobaltous salt or water solubility
After a kind of mixing in molybdenum salt, remaining another kind is then added, is eventually adding precipitating reagent；It can also be part complexing agent and water
Dissolubility cobalt salt mixes, and part complexing agent is mixed with water-soluble molybdenum salt, then by water soluble cobaltous salt and water solubility containing complexing agent
Molybdenum salting liquid mixes, and is eventually adding precipitating reagent.
In accordance with the present invention it is preferred that the complexing agent is in citric acid, ethylenediamine tetra-acetic acid, ammonium hydroxide and amion acetic acid
At least one, most preferably citric acid.
In accordance with the present invention it is preferred that the addition of the addition of the complexing agent and the water-soluble molybdenum salt in terms of molybdenum element
Molar ratio be 0.1-1：1, further preferably 0.2-0.8：1, most preferably 0.2-0.35：1.
, according to the invention it is preferred to which the condition of the contact includes：It carries out under agitation, temperature is 50-80 DEG C, the time
For 0.1-2h, pH 5-7；It is further preferred that temperature is 55-70 DEG C, time 0.25-1h, pH 6-7；It is further excellent
It is 0.5-1h, pH 6.2-6.5 to select the time.
There is no particular limitation for type and additive amount of the present invention to the precipitating reagent, as long as so that water soluble cobaltous salt and water
Molybdenum salts can fully carry out coprecipitation reaction, and the preferably described precipitating reagent is alkaline precipitating agent, still more preferably institute
It states precipitating reagent and is selected from least one of ammonium hydroxide, sodium carbonate and sodium hydroxide.
In the present invention, the additive amount of preferably precipitating reagent makes the contact be carried out under the conditions of pH is 5-7, further preferably
PH is 6-7, and still more preferably pH is 6.2-6.5.
The present invention is wider to the range of choice of the relative usage of the water soluble cobaltous salt and water-soluble molybdenum salt, it is preferable that with
The molar ratio of elemental metal, water soluble cobaltous salt and water-soluble molybdenum salt is 1-3:1, further preferably 1-1.5:1, most preferably
1:1.Being smoothed out for cobalt molybdate reaction can not only be ensured using this kind of preferred embodiment, and be more advantageous to having for raw material
Effect utilizes.
In the method provided by the invention, the water soluble cobaltous salt can select the cobalt compound of this field routine,
Preferably, the water soluble cobaltous salt is selected from least one of cobalt nitrate, cobalt acetate, cobaltous sulfate, cobalt chloride and cobalt carbonate；It is optimal
Selection of land, the water soluble cobaltous salt is cobalt nitrate and/or cobalt acetate, such as cabaltous nitrate hexahydrate and/or four acetate hydrate cobalts.
In the method provided by the invention, the water-soluble molybdenum salt can select the molybdenum compound of this field routine,
Preferably, the water-soluble molybdenum salt is selected from ammonium molybdate and/or sodium molybdate；It is further preferred that the water-soluble molybdenum salt is molybdic acid
Ammonium, most preferably, the water-soluble molybdenum salt are ammonium heptamolybdate, such as four hydration ammonium heptamolybdates.
The present invention also provides the sulfur-resistant transformation catalysts prepared by the above method.The sulfur-resistant transformation catalyst is not only stablized
Property it is good, service life is long, and activity preferably.And sulfur-resistant transformation catalyst is directly prepared with cobalt molybdate can eliminate nitrate anion point
The problem of environmental pollution that solution is brought.
Present invention is further described in detail with comparative example by the following examples.
Embodiment 1
(1) preparation of cobalt molybdate
Weigh 35.6g Co (NO3)2·6H2O is dissolved in 20mL deionized waters, and 6g monohydrate potassiums are then added, obtain
To the cobalt salt solution containing citric acid；Weigh 21.8g (NH4)6Mo7O24·4H2O, which is dissolved in 30mL deionized waters, obtains molybdenum salt
Solution；In 55 DEG C of water-baths, under agitation, the cobalt salt solution containing citric acid is added drop-wise in molybdenum salting liquid, is dripped simultaneously
Add ammonium hydroxide (a concentration of 25 weight %) so that system pH is maintained at 6.2-6.5, solid product is obtained by filtration, then in reaction 0.5h
After being washed with deionized, molybdic acid hydrate cobalt is obtained, then 3h is roasted at 500 DEG C, obtains cobalt molybdate, to cobalt molybdate and 500
DEG C roasting before molybdic acid hydrate cobalt carry out XRD analysis, XRD diffracting spectrums as shown in Figure 1, cobalt molybdate produced by the present invention with
ICSD-23808 standard crystal structures are consistent, have monocline crystalline phase；
(2) preparation of sulfur-resistant transformation catalyst
Cobalt molybdate 27g, boehmite 140g, magnesia 50g, zirconium oxide 30g and sesbania powder 3g obtained by step (1) is taken to exist
It is mixed in kneading machine, deionized water 50g is added and acetic acid 5g is mediated, forms homogeneous mixture；By mixture on banded extruder at
Then shape (bar shaped of a diameter of 3mm), drying at room temperature 3h roast 5h in 500 DEG C, obtain sulfur-resistant transformation catalyst C-1.
Embodiment 2
(1) preparation of cobalt molybdate
Weigh 35.6g Co (NO3)2·6H2O is dissolved in 20mL deionized waters, and mono- citrate hydrates of 10.5g are then added
Acid obtains the cobalt salt solution containing citric acid；Weigh 21.8g (NH4)6Mo7O24·4H2O is dissolved in 30mL deionized waters, so
10.5g monohydrate potassiums are added afterwards, obtain the molybdenum salting liquid containing citric acid；It, under agitation, will in 60 DEG C of water-baths
Cobalt salt solution containing citric acid is added drop-wise in the molybdenum salting liquid containing citric acid, while it is (a concentration of that sodium hydroxide solution is added dropwise
25 weight %) so that system pH is maintained at 6.2-6.5,1h is reacted, solid product is obtained by filtration, is then washed with deionized
Afterwards, 3h is roasted at 500 DEG C, obtains cobalt molybdate；
(2) preparation of sulfur-resistant transformation catalyst
Take cobalt molybdate 27g, boehmite 140g, magnesia 28g and zirconium oxide 10g obtained by step (1) in kneading machine
Mixing, is added deionized water 50g, acetic acid 5g and sesbania powder 3g is mediated, and forms homogeneous mixture；By mixture on banded extruder at
Then shape (bar shaped of a diameter of 3mm), drying at room temperature 5h roast 4h in 600 DEG C, obtain sulfur-resistant transformation catalyst C-2.
Embodiment 3
(1) preparation of cobalt molybdate
Weigh 32.8g Co (CH3COO)2·4H2O is dissolved in 20mL deionized waters, obtains cobalt salt solution；Weigh 21.8g
(NH4)6Mo7O24·4H2O is dissolved in 30mL deionized waters, and 10.5g monohydrate potassiums are then added, obtain containing citric acid
Molybdenum salting liquid；In 70 DEG C of water-baths, under agitation, cobalt salt solution is added drop-wise in the molybdenum salting liquid containing citric acid,
The sodium carbonate liquor that 1mol/L is added dropwise simultaneously makes system pH be maintained at 6.2-6.5, reacts 0.5h, solid product is obtained by filtration,
Then it is washed with deionized；
(2) preparation of sulfur-resistant transformation catalyst
In drying at room temperature 3h after taking cobalt molybdate hydrate 27g obtained by step (1) to be mixed with zirconium oxide 50g, then in 500 DEG C
3h is roasted, 200 mesh or less and boehmite 140g, magnesia 56g, deionized water 40g, acetic acid 5g and sesbania powder 3g are ground to
It mediates, forms homogeneous mixture；Mixture is shaped into (bar shaped of a diameter of 3mm) on banded extruder, drying at room temperature 5h, then in
550 DEG C of roasting 6h, obtain sulfur-resistant transformation catalyst C-3.
Embodiment 4
According to the method for embodiment 1 monohydrate potassium is added without the difference is that in the preparation process of cobalt molybdate.It obtains
Sulfur-resistant transformation catalyst C-4.
Embodiment 5
According to the method for embodiment 2, the difference is that in the preparation process of cobalt molybdate, sodium hydroxide solution is added dropwise and makes system
PH is maintained at 6.6-7.Obtain sulfur-resistant transformation catalyst C-5.
Embodiment 6
According to the method for embodiment 2, the difference is that in the preparation process of cobalt molybdate, sodium hydroxide solution is added dropwise and makes system
PH is maintained at 5.8-6.Obtain sulfur-resistant transformation catalyst C-6.
Embodiment 7
According to the method for embodiment 1, the difference is that in the preparation process of sulfur-resistant transformation catalyst, zirconium oxide is not used, is used
The boehmite of phase homogenous quantities replaces zirconium oxide.Obtain sulfur-resistant transformation catalyst C-7.
Embodiment 8
According to the method for embodiment 1, unlike, do not include the preparation of step (1) cobalt molybdate, cobalt molybdate in step (2)
For the commercially available product commercially available from An Naiji chemical companies.Obtain sulfur-resistant transformation catalyst C-8.
Comparative example 1
Weigh 35.6g Co (NO3)2·6H2O is dissolved in 20mL deionized waters, obtains cobalt salt solution；Weigh 21.8g
(NH4)6Mo7O24·4H2O is dissolved in 30mL deionized waters, obtains molybdenum salting liquid；By cobalt salt solution, molybdenum salting liquid, intend thin water
Aluminium stone 140g, it magnesia 50g, is mixed in kneading machine, deionized water 50g is added and acetic acid 5g is mediated, forms homogeneous mixture；
Mixture is shaped into (bar shaped of a diameter of 3mm) on banded extruder, then drying at room temperature 3h roasts 5h in 500 DEG C, obtains resistant to sulfur
Transformation catalyst D-1.
Comparative example 2
Weigh 35.6g Co (NO3)2·6H2O is dissolved in 20mL deionized waters, obtains cobalt salt solution；Weigh 21.8g
(NH4)6Mo7O24·4H2O is dissolved in 30mL deionized waters, obtains molybdenum salting liquid；By cobalt salt solution, molybdenum salting liquid, intend thin water
Aluminium stone 140g, magnesia 50g, zirconium oxide 30g and sesbania powder 3g are mixed in kneading machine, and deionized water 50g and acetic acid 5g is added
It mediates, forms homogeneous mixture；Mixture is shaped into (bar shaped of a diameter of 3mm) on banded extruder, drying at room temperature 3h, then in
500 DEG C of roasting 5h, obtain sulfur-resistant transformation catalyst D-2.
Comparative example 3
Weigh 35.6g Co (NO3)2·6H2O is dissolved in 20mL deionized waters, and 6g monohydrate potassiums are added, are contained
There is the cobalt salt solution of citric acid；Weigh 21.8g (NH4)6Mo7O24·4H2O is dissolved in 30mL deionized waters, and it is molten to obtain molybdenum salt
Liquid；By the cobalt salt solution containing citric acid, molybdenum salting liquid, boehmite 140g, magnesia 50g, zirconium oxide 30g and sesbania powder
3g is mixed in kneading machine, and deionized water 50g is added and acetic acid 5g is mediated, forms homogeneous mixture；By mixture in banded extruder
Then upper forming (bar shaped of a diameter of 3mm), drying at room temperature 3h roast 5h in 500 DEG C, obtain sulfur-resistant transformation catalyst D-3.
Comparative example 4
Weigh 28.92g (NH4)6Mo7O24·4H2O is dissolved in 260mL deionized waters, is heated to 150 DEG C, will
Co (the NO of 5.8g3)2·6H2O is dissolved in 30mL deionized waters and 3mL hydrogen peroxide (volume fraction 30%)；Both the above is molten
Liquid mixes, and reacts 1h in 150 DEG C of solution, using filtering, is concentrated by evaporation, is filtered for multiple times, crystallizes, obtain Primary product.
Then Primary product is dissolved in deionized water, after heating for dissolving, continues to be concentrated by evaporation, heat filtering, stood, crystallized, filtering is set
2h is kept at 80 DEG C in drying box, is finally separating green crystal and green-blue crystals out of ink, wherein blackish green crystal is CoMo10
Heteropoly acid；
Take CoMo obtained by step (1)10Heteropoly acid 13.5g, boehmite 70g, magnesia 25g, zirconium oxide 15g and sesbania
Powder 1.5g is mixed in kneading machine, and deionized water 25g is added and acetic acid 2.5g is mediated, forms homogeneous mixture；Mixture is existed
(bar shaped of a diameter of 3mm) is shaped on banded extruder, then drying at room temperature 3h roasts 5h in 500 DEG C, obtains sulfur-resistant transformation catalyst
D-4。
Test case 1
Assess the activity and stability of sulfur-resistant transformation catalyst：
It is carried out on minisize reaction evaluating apparatus.Catalyst filling amount is 0.5g, 20~40 mesh.
Catalyst uses 3% (v/v) H using preceding2S/H2(H2S and H2Gaseous mixture, H2The volume content of S is 3%) in sulphur
Change and is vulcanized at 250 DEG C of temperature, time 5h.
Evaluating catalyst condition：400 DEG C, 0.1MPa, it is H that unstripped gas, which forms (v/v),2O/CO/N2/H2/H2S=
49.89%/40.76%/4.33%/4.86%/0.15%.
Accelerate inactivation condition be：500 DEG C, 3.0MPa, unstripped gas composition is ibid constant, keeps 5h.
Evaluation test, experimental result such as table 1 are carried out under above-mentioned evaluation condition using the catalyst vulcanizated as fresh dose
It is shown.Then acceleration inactivation is carried out under the conditions of above-mentioned acceleration inactivates, obtains deactivator, and commented under above-mentioned evaluation condition
Valence is tested.Experimental result is as shown in table 2.
Table 1
Table 2
Sulfur-resistant transformation catalyst provided by the invention is can be seen that from the data of above-described embodiment, comparative example and table 1, table 2
It directly uses cobalt molybdate as the cobalt of sulfur-resistant transformation catalyst and the common active source of molybdenum, overcomes activity gold in the prior art
Belong to the defect that Co and Mo form the rich cobalt in part or the areas Fu Muchou, improve rate of metal, catalyst have preferably activity and
Stability.
Particularly, it can be seen that in cobalt molybdate preparation process from the comparing result of embodiment 1 and embodiment 4, add network
Mixture is more advantageous to the activity and stability for improving catalyst；It can be seen that from the comparing result of embodiment 1 and embodiment 6
In cobalt molybdate preparation process, it is more advantageous to raising using currently preferred water soluble cobaltous salt, water-soluble molybdenum salt contact conditions and urges
The activity and stability of agent.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In the skill of the present invention
In art conception range, technical scheme of the present invention can be carried out a variety of simple variants, including each technical characteristic with it is any its
His suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, belongs to
Protection scope of the present invention.
Claims (10)
1. a kind of preparation method of sulfur-resistant transformation catalyst, including：Cobalt molybdate, support material and water are subjected to kneading；It will be described
Product that kneading obtains carries out extrusion molding, is then dried, roasts and obtain sulfur-resistant transformation catalyst.
2. preparation method according to claim 1, wherein the introducing crosslinked agent during kneading, it is preferably described
Crosslinking agent is selected from organic and or inorganic acids.
3. preparation method according to claim 1, wherein the support material includes magnesium aluminate spinel and/or magnalium point
Spar support precursor, the magnesia alumina spinel carrier presoma include magnesium-containing compound and aluminum contained compound, described to contain magnesium
It closes object and is selected from least one of magnesia, magnesium nitrate and magnesium hydroxide, the aluminum contained compound is boehmite and/or oxygen
Change aluminium；
Preferably, the weight ratio of magnesium-containing compound and aluminum contained compound is 0.1-1：1；
It is preferred that the support material also contains carrier auxiliary agent, the carrier auxiliary agent is selected from zirconium oxide, cerium oxide, lanthana and oxidation
The weight ratio of at least one of manganese, the preferably described carrier auxiliary agent and the aluminum contained compound is 0.01-0.5：1.
4. preparation method according to claim 1, wherein the weight ratio of the cobalt molybdate and support material is 0.05-
0.5：1, preferably 0.1-0.3：1；
Preferably, the calcination temperature is 400-700 DEG C, time 3-8h.
5. according to the preparation method described in any one of claim 1-4, wherein the method further includes using following steps
(1) or step (1) and the process of (2) prepare cobalt molybdate：
(1) water soluble cobaltous salt, water-soluble molybdenum salt are contacted with precipitating reagent, is then filtered, obtain molybdic acid hydrate cobalt；And
(2) the molybdic acid hydrate cobalt for obtaining step (1) roasts.
6. preparation method according to claim 5, wherein also added with complexing agent in the contact process；
Preferably, the complexing agent is selected from least one of citric acid, ethylenediamine tetra-acetic acid, ammonium hydroxide and amion acetic acid；
Preferably, the addition of the complexing agent and the molar ratio of the addition of the water-soluble molybdenum salt in terms of molybdenum element are 0.1-1：
1。
7. preparation method according to claim 5 or 6, wherein
The precipitating reagent is selected from least one of ammonium hydroxide, sodium carbonate and sodium hydroxide.
8. preparation method according to claim 5 or 6, wherein
The condition of the contact includes：It carries out under agitation, temperature is 50-80 DEG C, time 0.1-2h, pH 5-7；
Preferably, temperature is 55-70 DEG C, time 0.25-1h, pH 6-7.
9. preparation method according to claim 5 or 6, wherein with elemental metal, water soluble cobaltous salt and water-soluble molybdenum salt
Molar ratio be 1-3:1, preferably 1-1.5:1；
Preferably, the water soluble cobaltous salt is selected from least one of cobalt nitrate, cobalt acetate, cobaltous sulfate, cobalt chloride and cobalt carbonate；
The water-soluble molybdenum salt is selected from ammonium molybdate and/or sodium molybdate.
10. the sulfur-resistant transformation catalyst prepared by the method described in any one of claim 1-9.
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