CN110237852A - The modified sulfur-resistant transformation catalyst and preparation method thereof of the titanium compound of sulphate-containing ion - Google Patents
The modified sulfur-resistant transformation catalyst and preparation method thereof of the titanium compound of sulphate-containing ion Download PDFInfo
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
- C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
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Abstract
The present invention relates to the catalyst fields that water gas shift reaction uses, disclose sulfur-resistant transformation catalyst and preparation method thereof, the sulfur-resistant transformation catalyst contains the metal active constituent on carrier and the load carrier, and the carrier modification has the titanium compound and coagent of sulphate-containing ion.This method comprises: carrier is impregnated in the solution containing coagent presoma and the titanium compound of sulphate-containing ion, then successively it is dried and roasts；(2) product that step (1) obtains is impregnated in the solution containing metal active constituent presoma, is then successively dried and roasts, obtain the sulfur-resistant transformation catalyst.Method for preparing catalyst provided by the invention is easy, and obtained catalyst activity is high, and anti-hydration is good.
Description
Technical field
The present invention relates to the catalyst fields that water gas shift reaction uses, and in particular, to the titanium of sulphate-containing ion
Compound modified sulfur-resistant transformation catalyst and preparation method thereof.
Background technique
Sulfur-tolerant water gas shift is the reaction process that synthesizes the fields such as ammonia, synthesizing methanol, hydrogen manufacturing and must undergo, and sulphur-resistant conversion is urged
Agent is wherein essential key player.With the development of China's residual oil, heavy-oil hydrogenation and coal hydrogen technology, especially
The rapid progress of China's coal chemical technology in recent years, to the demand of sulfur-resistant transformation catalyst every year at 2500 tons or more.
The main component of sulfur-resistant transformation catalyst is the metals such as Co, Mo, K, Mg, Al, rare earth.By using temperature to be divided into high temperature
Sulfur-resistant transformation catalyst and low temperature sulfur tolerant shift catalyst.High temperature sulfur-resistant transformation catalyst uses magnesium aluminate spinel for carrier, Co,
Mo is active component.Low temperature sulfur tolerant shift catalyst uses the activated alumina of part magnesium aluminate spinel for carrier, active component
For Co, Mo, auxiliary agent K.
Conversion reaction is reaction under the conditions of high-temperature water vapor, and temperature can be up to 470 DEG C, and water vapour and dry gas compare highest
It can achieve 2:1.And the high water vapour of high temperature and dry gas can make carrier that aquation, recurring structure phase occur than working condition
Become, leads to catalyst inactivation.Therefore, other than catalytic activity, stability is also that should consider in transformation catalyst R&D process
An important factor for.
CN103447049A discloses a kind of cobalt molybdenum system CO sulfur-resistant transformation catalyst and preparation method, including carrier, activity
Component, the carrier are the surface layer magnesium aluminate spinel of aluminium titanium-based, and active component is cobalt, molybdenum.The appearance of catalyst is spherical shape.Catalysis
The preparation method of agent: titanium is introduced on alumina and prepares aluminium titanium complex carrier；Magnesium is uniformly introduced on aluminium titanium complex carrier, is roasted
Phase inversion is aluminium titanium-based surface layer magnesium aluminate spinel；Active component is introduced in the magnesia alumina spinel carrier of aluminium titanium-based surface layer, is prepared into and urges
Agent.The catalyst low-temperature activity and low-sulfur activity are good, and stability is strong, long service life.
Existing method improves the catalytic activity and stability of sulfur-resistant transformation catalyst to a certain extent, but still up for
It further increases.
Summary of the invention
The purpose of the invention is to overcome the drawbacks described above of the prior art, provide a kind of sulfur-resistant transformation catalyst and its
Preparation method, the sulfur-resistant transformation catalyst can effectively improve its stability while not reducing activity.
To achieve the goals above, the first aspect of the present invention provides a kind of sulfur-resistant transformation catalyst, which urges
Agent contains the metal active constituent on carrier and the load carrier, and the carrier modification has the titanizing of sulphate-containing ion
Close object and coagent.
Preferably, the metal active constituent contains cobalt/cobalt oxide and molybdenum oxide；It is further preferred that with the resistant to sulfur
On the basis of the total weight of transformation catalyst, the content of the carrier is 64-90 weight %；The content of the cobalt/cobalt oxide is 2-6
Weight %；The content of the molybdenum oxide is 5-10 weight %；The content of the coagent is 2-15 weight %；Containing sulfate radicals
The content of the titanium compound of ion is 2-6 weight %.
The second aspect of the present invention provides a kind of preparation method of sulfur-resistant transformation catalyst, method includes the following steps:
(1) carrier is carried out in the solution containing coagent presoma and the titanium compound component of sulphate-containing ion
Dipping, is then successively dried and roasts；
(2) product that step (1) obtains is impregnated in the solution containing metal active constituent presoma, then according to
It is secondary to be dried and roast, obtain the sulfur-resistant transformation catalyst.
The third aspect of the present invention provides a kind of preparation method of sulfur-resistant transformation catalyst, method includes the following steps:
(1) carrier is impregnated in the solution of the titanium compound component containing sulphate-containing ion, then successively into
Row is dry and roasts；
(2) product that step (1) obtains is impregnated in the solution containing coagent precursor, then successively into
Row is dry and roasts；
(3) product that step (2) obtains is impregnated in the solution containing metal active constituent presoma, then according to
It is secondary to be dried and roast, obtain the sulfur-resistant transformation catalyst.
The fourth aspect of the present invention provides a kind of preparation method of sulfur-resistant transformation catalyst, method includes the following steps:
(1) carrier is impregnated in the solution containing coagent precursor, is then successively dried and roasts；
(2) product that step (1) obtains is soaked in the solution of the titanium compound component containing sulphate-containing ion
Then stain is successively dried and roasts；
(3) product that step (2) obtains is impregnated in the solution containing metal active constituent presoma, then according to
It is secondary to be dried and roast, obtain the sulfur-resistant transformation catalyst.
The fifth aspect of the present invention provides a kind of sulfur-resistant transformation catalyst of method preparation as described above.
The carrier of catalyst provided by the invention is modified using the titanium compound and coagent of sulphate-containing ion,
The hydration-resisting stability of catalyst is effectively increased, and its activity is not also influenced.Under preferable case, using containing sulfate radicals
The titanium compound and active component of ion gradually carry out modification carrier to carrier, and the hydration-resisting for further improving catalyst is steady
It is qualitative.In addition, the titanium compound of sulphate-containing ion is water-soluble, and preparation process is simple compared to organic titanium and titanium tetrachloride,
And it is at low cost.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
Fig. 1 is the XRD diagram after the sulfur-resistant transformation catalyst hydrothermal treatment that embodiment 1, comparative example 1 and comparative example 2 obtain.
Specific embodiment
Detailed description of the preferred embodiments 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 inventor has found in the course of the study, the activity of sulfur tolerant CO shift and stability of the prior art
One of lower reason is that water-insoluble titanium compound (for example, organic titanium or titanium tetrachloride etc.) has been used to repair carrier
Decorations, and when the titanizing that water-insoluble titanium compound (for example, organic titanium or titanium tetrachloride etc.) is replaced with to sulphate-containing ion is closed
Coagent is cooperated to modify carrier again after object, on the one hand, to effectively increase catalyst under the premise of not reducing active
Hydration-resisting stability；On the other hand, preparation process is simplified, is reduced costs.
Based on discovery as above, the first aspect of the present invention provides a kind of sulfur-resistant transformation catalyst, sulphur-resistant conversion catalysis
Agent contains the metal active constituent on carrier and the load carrier, and the carrier modification has the titanizing of sulphate-containing ion to close
Object and coagent.
Preferably, the titanium compound of the sulphate-containing ion is titanyl sulfate and/or titanium sulfate.
Preferably, the metal active constituent is cobalt/cobalt oxide and molybdenum oxide.
In the sulfur-resistant transformation catalyst provided by the invention, it is preferable that with the gross weight of the sulfur-resistant transformation catalyst
On the basis of amount, the content of the carrier is 60-96 weight %, preferably 64-90 weight %；The content of the cobalt/cobalt oxide is
0.5-10 weight %, preferably 2-6 weight %；The content of the molybdenum oxide is 3-15 weight %, preferably 5-10 weight %；
The content of the coagent is 0.5-20 weight %, preferably 2-15 weight %；The titanium compound of sulphate-containing ion contains
Amount is 0.5-8 weight %, preferably 2-6 weight %.
The present invention is wider to the range of choice of the carrier, and various carriers commonly used in the art are used equally for this hair
It is bright, in order to further improve the intensity and activity of catalyst, it is preferable that the carrier is Al2O3Carrier.
According to the present invention, the coagent can be this field routine for modifying the coagent of carrier, but be
Further increase the activity and stability of the sulfur-resistant transformation catalyst, the coagent be alkaline earth oxide and/
Or lanthanide metal oxide；The preferred magnesium oxide of alkaline earth oxide and/or calcium oxide, the preferred lanthanum of lanthanide metal oxide
Oxide and/or cerium oxide
There is no particular limitation for preparation method of the present invention to the sulfur-resistant transformation catalyst, as long as above-mentioned urge can be obtained
The preparation method of agent is used equally for the present invention.
The second aspect of the present invention, provides a kind of preparation method of sulfur-resistant transformation catalyst, and this method includes following step
It is rapid:
(1) carrier is carried out in the solution containing coagent presoma and the titanium compound component of sulphate-containing ion
Dipping, is then successively dried and roasts；
(2) product that step (1) obtains is impregnated in the solution containing metal active constituent presoma, then according to
It is secondary to be dried and roast, obtain the sulfur-resistant transformation catalyst.
The third aspect of the present invention, provides a kind of preparation method of preferred sulfur-resistant transformation catalyst, and this method includes
Following steps:
(1) carrier is impregnated in the solution containing coagent precursor, is then successively dried and roasts；
(2) product that step (1) obtains is soaked in the solution of the titanium compound component containing sulphate-containing ion
Then stain is successively dried and roasts；
(3) product that step (2) obtains is impregnated in the solution containing metal active constituent presoma, then according to
It is secondary to be dried and roast, obtain the sulfur-resistant transformation catalyst.
Under the conditions of this is preferred, the stability of obtained sulfur-resistant transformation catalyst, which accesses, to be further increased.
The fourth aspect of the present invention provides a kind of preparation method of more preferably sulfur-resistant transformation catalyst, this method
The following steps are included:
(1) carrier is impregnated in the solution of the titanium compound component of sulphate-containing ion, is then successively done
Dry and roasting；
(2) product that step (1) obtains is impregnated in the solution containing coagent precursor, then successively into
Row is dry and roasts；
(3) product that step (2) obtains is impregnated in the solution containing metal active constituent presoma, then according to
It is secondary to be dried and roast, obtain the sulfur-resistant transformation catalyst.
Under conditions of this is more highly preferred to, the stability of obtained sulfur-resistant transformation catalyst, which accesses, further to be mentioned
It is high.
In each method as above of the invention, solution used is preferably aqueous solution in each step, for example, containing before coagent
Drive the aqueous solution of the titanium compound of body and sulphate-containing ion, the aqueous solution of the titanium compound of sulphate-containing ion, containing active
The aqueous solution of auxiliary agent precursor, the aqueous solution containing metal active constituent presoma.Wherein, in each solution the dosage of water according to load
Depending on the water absorption rate of body, the water absorption rate of carrier is typically larger than 0.4, preferably greater than 0.5.
In each method as above of the invention, the titanium compound component of used sulphate-containing ion is preferably titanyl sulfate
Or titanium sulfate, sulfuric acid can also be contained, wherein sulfuric acid content can be 0.1-30 weight %.
In each method as above of the invention, there is no particular limitation for the pattern of the carrier, can be known in the art
The pattern of the various alumina supports with modified oxide, such as spherical shape, bar shaped, bunge bedstraw herb type and tooth are spherical, and the present invention is excellent
It is selected as spherical shape.
In each method as above of the invention, the metal active constituent is preferably cobalt/cobalt oxide and molybdenum oxide, forerunner
There is no particular limitation for the selection of body, as long as presoma maceration extract can be prepared into, for example, the cobalt/cobalt oxide presoma
It can be selected from least one of cobalt nitrate, cobalt acetate, basic cobaltous carbonate and cobalt hydroxide；The molybdenum oxide presoma is selected from
At least one of ammonium tetramolybdate, ammonium heptamolybdate and potassium molybdate.
In each method as above of the invention, it is preferred that the titanium compound, described of the carrier, the sulphate-containing ion
The dosage of coagent presoma, the cobalt/cobalt oxide presoma and the molybdenum oxide presoma makes, and resistant to sulfur obtained becomes
In catalyst changeout, on the basis of the total weight of sulfur-resistant transformation catalyst, the content of the carrier is 60-96 weight %, preferably
64-90 weight %；The content of the cobalt/cobalt oxide is 0.5-10 weight %, preferably 2-6 weight %；The molybdenum oxide contains
Amount is 3-15 weight %, preferably 5-10 weight %；The content of the coagent is 0.5-20 weight %, preferably 2-15 weight
Measure %；The content of the titanium compound of sulphate-containing ion is 0.5-8 weight %, preferably 2-6 weight %.
In each method as above of the invention, the coagent can be this field routine for modifying the activity of carrier
Auxiliary agent, but in order to further increase the activity of the sulfur-resistant transformation catalyst and stability, the coagent is preferably alkaline earth
Metal oxide and/or lanthanide metal oxide, wherein the preferred magnesium oxide of alkaline earth oxide and/or calcium oxide, lanthanum
The preferred lanthanum-oxides of series metal oxide and/or cerium oxide；As a result, magnesium oxide presoma be selected from magnesium nitrate, magnesium acetate and
At least one of magnesium chloride；Calcium oxide presoma is selected from least one of calcium nitrate, calcium acetate and calcium chloride；Lanthanum oxidation
Object presoma is selected from least one of lanthanum nitrate, lanthanum acetate and lanthanum chloride；Cerium oxide is selected from cerous nitrate, cerous acetate and chlorination
At least one of cerium.
In each method as above of the invention, for the ease of the titanium compound, coagent and activity of sulphate-containing ion
Component is evenly dispersed on the carrier, and the condition of dipping described in each step of each method as above can be identical, can also not
Together, it is independent include: dipping temperature be 25-50 DEG C, dip time 2-12h.
In each method as above of the invention, dry condition can use the drying condition of this field routine in each step,
Dry condition may be the same or different in each step, it is preferred that dry condition described in each step is each independently
Include: temperature be 100-200 DEG C, the time be 4-30 hours.
In each method as above of the invention, the condition roasted in each step can use the roasting condition of this field routine,
The condition roasted in each step may be the same or different, it is preferred that the condition of roasting described in each step is each independently
Include: temperature be 400-800 DEG C, the time be 2-8 hours.
Present invention sulfur-resistant transformation catalyst as described above and method produced above sulfur-resistant transformation catalyst obtained
It can be used in water gas shift reaction, specifically, the method in water gas shift reaction includes: in H2S/H2Mixing
Under atmosphere, sulfur-resistant transformation catalyst is subjected to vulcanizing treatment, then by the sulfur-resistant transformation catalyst after water-gas and vulcanizing treatment
It is contacted, water gas shift reaction is carried out under the conditions of water gas shift reaction, wherein the sulfur-resistant transformation catalyst is served as reasons
The sulfur-resistant transformation catalyst of method preparation provided by the invention.
According to the present invention, it is 200-500 DEG C that the condition of the vulcanizing treatment, which may include: curing temperature, H2S/H2Mixing
Sulfur content is 0.3-5 volume %, H in atmosphere2S/H2Gaseous mixture volume space velocity be 100-3000h-1, vulcanization time 5-
10h。
In a preferred embodiment, it is 450 DEG C that the condition of the vulcanizing treatment, which includes: curing temperature, H2S/H2's
Sulfur content is 3 volume %, H in mixed atmosphere2S/H2Gaseous mixture volume space velocity be 3000h-1, vulcanization time 5h.
There is no particular limitation to the water gas shift reaction condition by the present invention, can be the conventional selection of this field,
For example, the water gas shift reaction condition may include: to carry out in fixed bed reactors, reaction temperature is 150-500 DEG C,
Reaction pressure is 0.1-6.8MPa, and the molar ratio of water vapour and raw material dry gas is 1:0.4-1.5, raw material dry gas composition: 30-90 body
The N of CO, 2-6 volume % of product %2, 5-20 volume % CO2, 0.05-2 volume % H2S, remaining is H2, the body of raw material dry gas
Product air speed is 1000-20000h-1。
The present invention will be described in detail by way of examples below.
In following embodiment and comparative example,
The composition of sulfur-resistant transformation catalyst by the ZSX Primus II type Xray fluorescence spectrometer of Rigaku company into
Row measurement；
Water gas shift/WGS rate (%)=(C1-C2)/[C1 (1+C2)] × 100%
In formula: C1 is CO content in unstripped gas, % (butt)；
C2 is CO content in product gas, % (butt).
The hydration-resisting ability measuring method of catalyst: the sulfur-resistant transformation catalyst of preparation is put into water heating kettle, addition is gone
Ionized water did not had catalyst, and under severe conditions, i.e., hydro-thermal process for 24 hours, tests alumina catalyst by XRD at 200 DEG C
It is hydrated situation, characterizes its hydration-resisting stability.Wherein, hydration reaction occurs for part aluminium oxide after catalyst hydro-thermal process, generates
AlOOH, characteristic peak, which is that the peak of 14.3 ° of AlOOH is smaller, shows that hydration-resisting ability is stronger,
Titanyl sulfate is technical grade sulfuric acid oxygen titanium, and sulfuric acid content is≤7 weight %.
Alumina balls diameter of carrier is 3-5mm.
Embodiment 1
The present embodiment is for illustrating sulfur-resistant transformation catalyst provided by the invention and preparation method thereof
It weighs technical grade sulfuric acid oxygen titanium 1.2g, magnesium nitrate 6.5g, lanthanum nitrate 0.6g and is dissolved in deionized water, aoxidized in 15.5g
Iso volumetric impregnation is carried out in aluminium ball, 120 DEG C of dry 12h after room temperature is dried, 500 DEG C of roasting 3h obtain modified carrier.
After weighing 2.0g ammonium heptamolybdate ammonia solvent, 1.9g citric acid and 2.5g cobalt acetate is added, stirring and dissolving is prepared
After co-impregnation liquid, iso volumetric impregnation is carried out, 12 DEG C of dry 12h, 500 DEG C of roasting 3h after room temperature is dried obtain sulphur-resistant conversion catalysis
Agent.
The composition of the catalyst are as follows: 77.5 weight % carriers, 3.2 weight %Co2O3, 8.0 weight %MoO3, weight 5.1%
MgO, 0.7 weight %La2O3With 5.5 weight % titanyl sulfates.
XRD after obtained sulfur-resistant transformation catalyst hydrothermal treatment is as shown in Figure 1, peak height is as shown in table 1.
Comparative example 1
This comparative example is for illustrating sulfur-resistant transformation catalyst of reference and preparation method thereof
According to the method for embodiment 1, unlike, technical grade sulfuric acid oxygen titanium is not added, its weight is added into carrier,
Obtain sulfur-resistant transformation catalyst.
The composition of the catalyst are as follows: 83 weight % carriers, 3.2 weight %Co2O3, 8.0 weight %MoO3, 5.1 weight %
MgO and 0.7 weight %La2O3。
XRD after obtained sulfur-resistant transformation catalyst hydrothermal treatment is as shown in Figure 1, peak height is as shown in table 1.
Comparative example 2
This comparative example is for illustrating sulfur-resistant transformation catalyst of reference and preparation method thereof
Butyl titanate 2.1g is weighed, ethyl alcohol is dissolved in, iso volumetric impregnation is carried out on 15.5g alumina balls, after room temperature is dried
120 DEG C of dry 12h, 500 DEG C of roasting 3h.
Magnesium nitrate 6.5g, lanthanum nitrate 0.6g are weighed, deionized water is dissolved in, second of iso volumetric impregnation is carried out, after room temperature is dried
120 DEG C of dry 12h, 500 DEG C of roasting 3h.
After weighing 2.0g ammonium heptamolybdate ammonia solvent, 1.9g citric acid and 2.5g cobalt acetate is added, stirring and dissolving is prepared
After co-impregnation liquid, iso volumetric impregnation is carried out, 120 DEG C of dry 12h, 500 DEG C of roasting 3h after room temperature is dried obtain sulphur-resistant conversion catalysis
Agent.
The composition of the catalyst are as follows: 80.5 weight % carriers, 3.2 weight %Co2O3, 8.0 weight %MoO3, 5.1 weight %
MgO, 0.7 weight %La2O3With 2.5 weight %TiO2。
XRD after obtained sulfur-resistant transformation catalyst hydrothermal treatment is as shown in Figure 1, peak height is as shown in table 1.
Comparative example 3
This comparative example is for illustrating sulfur-resistant transformation catalyst of reference and preparation method thereof
According to the method for comparative example 2, unlike, weigh with the equimolar titanium tetrachloride of titanyl sulfate, be dissolved in acetone,
Iso volumetric impregnation, 120 DEG C of dry 12h, 500 DEG C of roasting 3h after room temperature is dried are carried out on 15.5g alumina balls.
The composition of the catalyst are as follows: 80.5 weight % carriers, 3.2 weight %Co2O3, 8.0 weight %MoO3, 5.1 weight %
MgO, 0.7 weight %La2O3With 2.5 weight %TiO2。
AlOOH height is shown in Table 1 after catalyst carries out 200 DEG C of hydro-thermal process for 24 hours.
Embodiment 2
The present embodiment is for illustrating sulfur-resistant transformation catalyst provided by the invention and preparation method thereof
It weighs technical grade sulfuric acid oxygen titanium 0.45g, magnesium nitrate 7.6g, lanthanum nitrate 1.3g and is dissolved in deionized water, in 16.7g oxygen
Change and carry out iso volumetric impregnation in aluminium ball, 100 DEG C of dry 8h after room temperature is dried, 400 DEG C of roasting 5h obtain modified carrier.
After weighing 1.25g ammonium heptamolybdate ammonia solvent, 1.8g citric acid and 0.63g basic cobaltous carbonate is added, stirs molten
After solution is configured to the water stain liquid of total immersion, iso volumetric impregnation is carried out, 150 DEG C of dry 10h after room temperature is dried, 600 DEG C of roasting 3h obtain resistant to sulfur
Transformation catalyst.
The composition of the catalyst are as follows: 83.5 weight % carriers, 2 weight %Co2O3, 5 weight %MoO3, 6 weight %MgO,
1.5 weight %La2O3With 2 weight % titanyl sulfates.
AlOOH height is shown in Table 1 after catalyst carries out 200 DEG C of hydro-thermal process for 24 hours.
Embodiment 3
The present embodiment is for illustrating sulfur-resistant transformation catalyst provided by the invention and preparation method thereof
It weighs technical grade sulfuric acid oxygen titanium 1.36g, magnesium nitrate 7.0g, cerous nitrate 0.5g and is dissolved in deionized water, in 14.3g oxygen
Change and carry out iso volumetric impregnation in aluminium ball, 180 DEG C of dry 6h after room temperature is dried, 800 DEG C of roasting 2h obtain modified carrier.
After weighing 2.5g ammonium heptamolybdate ammonia solvent, 3.6g citric acid and 4.7g cobalt acetate is added, stirring and dissolving is prepared
After co-impregnation liquid, iso volumetric impregnation is carried out, 200 DEG C of dry 12h, 500 DEG C of roasting 3h after room temperature is dried obtain sulphur-resistant conversion catalysis
Agent.
The composition of the catalyst are as follows: 71.5 weight % carriers, 6 weight %Co2O3, 10 weight %MoO3, 5.5 weight %
MgO, 1 weight %CeO2With 6 weight % titanyl sulfates.
AlOOH height is shown in Table 1 after catalyst carries out 200 DEG C of hydro-thermal process for 24 hours.
Embodiment 4
The present embodiment is for illustrating sulfur-resistant transformation catalyst provided by the invention and preparation method thereof
According to the method for embodiment 1, unlike, the dosage of technical grade sulfuric acid oxygen titanium is 1.75g, obtains sulphur-resistant conversion and urges
Agent.
The composition of the catalyst are as follows: 75.0 weight % carriers, 3.2 weight %Co2O3, 8.0 weight %MoO3, 5.1 weight %
MgO, 0.7 weight %La2O3With 8 weight % titanyl sulfates.
AlOOH height is shown in Table 1 after catalyst carries out 200 DEG C of hydro-thermal process for 24 hours.
Embodiment 5
The present embodiment is for illustrating sulfur-resistant transformation catalyst provided by the invention and preparation method thereof
It weighs technical grade sulfuric acid oxygen titanium 1.2g and is dissolved in deionized water, iso volumetric impregnation, room temperature are carried out on 15.5g alumina balls
120 DEG C of dry 12h, 500 DEG C of roasting 3h after drying.
It weighs magnesium nitrate 6.5g and lanthanum nitrate 0.6g and is dissolved in deionized water, second of iso volumetric impregnation is carried out, after room temperature is dried
120 DEG C of dry 4h, 500 DEG C of roasting 3h.
After weighing 2.0g ammonium heptamolybdate ammonia solvent, 1.9g citric acid and 2.5g cobalt acetate is added, stirring and dissolving is prepared
After the water stain liquid of total immersion, third time iso volumetric impregnation is carried out, room temperature dries rear 120 DEG C of dryings for 24 hours, 500 DEG C of roasting 3h.
The composition of the catalyst are as follows: 77.5 weight % carriers, 3.2 weight %Co2O3, 8.0 weight %MoO3, 5.1 weight %
MgO, 0.7 weight %La2O3With 5.5 weight % titanyl sulfates.
AlOOH height is shown in Table 1 after catalyst carries out 200 DEG C of hydro-thermal process for 24 hours.
Embodiment 6
The present embodiment is for illustrating sulfur-resistant transformation catalyst provided by the invention and preparation method thereof
It weighs magnesium nitrate 6.5g and lanthanum nitrate 0.6g is dissolved in deionized water, iso volumetric impregnation is carried out on 15.5g alumina balls,
120 DEG C of dry 12h, 500 DEG C of roasting 3h after room temperature is dried.
It weighs technical grade sulfuric acid oxygen titanium 1.2g and is dissolved in deionized water, carry out second of iso volumetric impregnation, room temperature is dried 120 DEG C latter
Dry 4h, 500 DEG C of roasting 3h.
After weighing 2.0g ammonium heptamolybdate ammonia solvent, 1.9g citric acid and 2.5g cobalt acetate is added, stirring and dissolving is prepared
After the water stain liquid of total immersion, third time iso volumetric impregnation is carried out, room temperature dries rear 120 DEG C of dryings for 24 hours, 500 DEG C of roasting 3h.
The composition of the catalyst are as follows: 77.5 weight % carriers, 3.2 weight %Co2O3, 8.0 weight %MoO3, 5.1 weight %
MgO, 0.7 weight %La2O3With 5.5 weight % titanyl sulfates.
AlOOH height is shown in Table 1 after catalyst carries out 200 DEG C of hydro-thermal process for 24 hours.
Embodiment 7
The present embodiment is for illustrating sulfur-resistant transformation catalyst provided by the invention and preparation method thereof
According to the method for embodiment 1, unlike, 0.04g 98%H is added in aqueous solution2SO4Solution, and by titanyl sulfate
The titanium sulfate for the quality such as replacing with, obtains sulfur-resistant transformation catalyst.
The composition of the catalyst are as follows: 77.5 weight % carriers, 3.2 weight %Co2O3, 8.0 weight %MoO3, 5.1 weight %
MgO, 0.7 weight %La2O3With 5.5 weight % titanium sulfates.
AlOOH height is shown in Table 1 after catalyst carries out 200 DEG C of hydro-thermal process for 24 hours.
Test example 1
The sulfur-resistant transformation catalyst of embodiment 1-7 and comparative example 1-3 provided by the invention are evaluated
It is carried out on minisize reaction evaluating apparatus.20-40 mesh catalyst filling amount is 1g.
1, catalyst vulcanization
By catalyst and vulcanization gas (H2S and H2Gaseous mixture, wherein H2The volume content of S is 3%) in curing temperature 450
The 5h that is in contact at DEG C is vulcanized.Obtain sulphurized catalyst.
2, evaluating catalyst
Sulphurized catalyst is in contact as fresh dose with unstripped gas and carries out evaluating catalyst.
Condition are as follows: 450 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%.
It the results are shown in Table 1.
Table 1
| Catalyst | Active (CO conversion ratio, %) | AlOOH peak heights |
| Embodiment 1 | 41 | 535 |
| Comparative example 1 | 39 | 1517 |
| Comparative example 2 | 40 | 815 |
| Comparative example 3 | 39 | 850 |
| Embodiment 2 | 31 | 585 |
| Embodiment 3 | 52 | 531 |
| Embodiment 4 | 40 | 519 |
| Embodiment 5 | 41 | 432 |
| Embodiment 6 | 41 | 480 |
| Embodiment 7 | 40 | 541 |
From embodiment and table 1 result can be seen that catalyst provided by the invention do not reduce its it is active under the premise of,
Anti-hydration significantly improves.In addition, the method provided by the invention for preparing sulfur-resistant transformation catalyst, the sulphate-containing ion used
Titanium compound be water solubility, it is not only highly-safe, can also and the common impregnated carrier of coagent, preparation process is simple, non-
It is very suitable for industrial production.
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 (10)
1. a kind of sulfur-resistant transformation catalyst, which contains the metal active on carrier and the load carrier
Component, which is characterized in that the carrier modification has the titanium compound and coagent of sulphate-containing ion.
2. sulfur-resistant transformation catalyst according to claim 1, wherein the metal active constituent contains cobalt/cobalt oxide and molybdenum
Oxide；
Preferably, on the basis of the total weight of the sulfur-resistant transformation catalyst, the content of the carrier is 60-96 weight %, excellent
It is selected as 64-90 weight %；The content of the cobalt/cobalt oxide is 0.5-10 weight %, preferably 2-6 weight %；The molybdenum oxide
Content be 3-15 weight %, preferably 5-10 weight %；The content of the coagent is 0.5-20 weight %, preferably 2-
15 weight %；The content of the titanium compound of sulphate-containing ion is 0.5-8 weight %, preferably 2-6 weight %；
Preferably, the carrier is Al2O3Carrier；
Preferably, the coagent is alkaline earth oxide and/or lanthanide metal oxide；Alkaline earth oxide is preferred
Magnesium oxide and/or calcium oxide, the preferred lanthanum-oxides of lanthanide metal oxide and/or cerium oxide.
3. sulfur-resistant transformation catalyst according to claim 1 or 2, wherein the titanium compound of the sulphate-containing ion is
Titanyl sulfate and/or titanium sulfate.
4. a kind of method for preparing sulfur-resistant transformation catalyst, method includes the following steps:
(1) carrier is soaked in the solution containing coagent presoma and the titanium compound component of sulphate-containing ion
Then stain is successively dried and roasts；
(2) product that step (1) obtains is impregnated in the solution containing metal active constituent presoma, then successively into
Row is dry and roasts, and obtains the sulfur-resistant transformation catalyst.
5. a kind of method for preparing sulfur-resistant transformation catalyst, method includes the following steps:
(1) carrier is impregnated in the solution of the titanium compound component containing sulphate-containing ion, is then successively done
Dry and roasting；
(2) product that step (1) obtains is impregnated in the solution containing coagent precursor, is then successively done
Dry and roasting；
(3) product that step (2) obtains is impregnated in the solution containing metal active constituent presoma, then successively into
Row is dry and roasts, and obtains the sulfur-resistant transformation catalyst.
6. a kind of method for preparing sulfur-resistant transformation catalyst, method includes the following steps:
(1) carrier is impregnated in the solution containing coagent precursor, is then successively dried and roasts；
(2) product that step (1) obtains is impregnated in the solution of the titanium compound component containing sulphate-containing ion, so
It is successively dried and roasts afterwards；
(3) product that step (2) obtains is impregnated in the solution containing metal active constituent presoma, then successively into
Row is dry and roasts, and obtains the sulfur-resistant transformation catalyst.
7. method according to any one of claims 4 to 6, wherein the metal active constituent contain cobalt/cobalt oxide and
Molybdenum oxide；
Preferably, before the carrier, the titanium compound of the sulphate-containing ion, the coagent presoma, cobalt/cobalt oxide
The dosage for driving body and molybdenum oxide presoma makes, in sulfur-resistant transformation catalyst obtained, with the gross weight of sulfur-resistant transformation catalyst
On the basis of amount, the content of the carrier is 60-96 weight %, preferably 64-90 weight %；The content of the cobalt/cobalt oxide is
0.5-10 weight %, preferably 2-6 weight %；The content of the molybdenum oxide is 3-15 weight %, preferably 5-10 weight %；
The content of the coagent is 0.5-20 weight %, preferably 2-15 weight %；The titanium compound of sulphate-containing ion contains
Amount is 0.5-8 weight %, preferably 2-6 weight %；
Preferably, the carrier is Al2O3Carrier；
Preferably, the cobalt/cobalt oxide presoma in cobalt nitrate, cobalt acetate, basic cobaltous carbonate and cobalt hydroxide at least one
Kind；The molybdenum oxide presoma is selected from least one of ammonium tetramolybdate, ammonium heptamolybdate and potassium molybdate；
Preferably, the coagent precursor is alkaline earth oxide precursor and/or lanthanide metal oxide precursor；
The preferred magnesium oxide precursor of alkaline earth oxide precursor and/or calcium oxide precursor, body before lanthanide metal oxide
The preferred lanthanum-oxides precursor of body and/or cerium oxide precursor；Magnesium oxide presoma is selected from magnesium nitrate, magnesium acetate and chlorination
At least one of magnesium；Calcium oxide presoma is selected from least one of calcium nitrate, calcium acetate and calcium chloride；Before lanthanum-oxides
It drives body and is selected from least one of lanthanum nitrate, lanthanum acetate and lanthanum chloride；Cerium oxide is in cerous nitrate, cerous acetate and cerium chloride
At least one.
8. method according to any one of claims 4 to 6, wherein the condition of the drying includes: that temperature is 100-
200 DEG C, the time is 4-30 hours；The condition of roasting includes: that temperature is 400-800 DEG C, and the time is 2-8 hours.
9. method according to any one of claims 4 to 6, wherein the titanium compound component of the sulphate-containing ion
Also contain sulfuric acid, on the basis of the weight of the titanium compound of sulphate-containing ion, the content of sulfuric acid is 0.1-30 weight %.
10. the sulfur-resistant transformation catalyst of the preparation of method described in any one of claim 4-9.
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| CN114100670A (en) * | 2020-08-31 | 2022-03-01 | 中国石油化工股份有限公司 | Sulfur-tolerant shift catalyst and preparation method thereof |
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| 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 |
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