CN105536689B - A kind of supported dearsenic agent and preparation method thereof - Google Patents
A kind of supported dearsenic agent and preparation method thereof Download PDFInfo
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- CN105536689B CN105536689B CN201510920454.5A CN201510920454A CN105536689B CN 105536689 B CN105536689 B CN 105536689B CN 201510920454 A CN201510920454 A CN 201510920454A CN 105536689 B CN105536689 B CN 105536689B
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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Abstract
Supported dearsenic agent of the present invention includes the active component of carrier and load on the carrier；The carrier is porous unformed magnesium aluminate spinel, and the active component is CuO and/or NiO.Since the carrier is porous unformed magnesium aluminate spinel, better crystallinity degree, material internal is combined by strong Mg and Al O ionic bonds, fundamentally effectively increases the intensity of material and resistance to hydration performance.The preparation method of supported dearsenic agent of the present invention, simple production process, production cost are low.
Description
Technical field
The present invention relates to coal chemical technologies, and in particular to a kind of supported dearsenic agent and preparation method thereof.
Background technology
Coal is the valuable source in China, and producing synthesis gas from coal technology is one of main Land use systems of coal resource.Feed coal
In contain arsenide, mainly with AsH in raw gas obtained3Form exists, and many catalyst that coal industrially uses are such as
High temperature conversion catalyst etc. is very sensitive to arsenide, and the arsenide of hundreds of ppb (parts per billion) can cause to urge
Agent is poisoned and is inactivated, and the normal operation of device is influenced.Therefore, in chemical industry synthesis, producing synthesis gas from coal purification will solve
Key technology, the research and exploitation for carrying out Hydrodearsenic Catalyst have important practical significance and application value.
Currently, there are two types of main arsenic removing methods：First, physisorphtion：It is adsorbed using copper sulphate alumina silicate bead micro
Arsenide (polarity absorption), but this method holds that arsenic amount is small (0.1~0.3%), and adsorbent consumption is big, short life and generates big
Waste material is measured, environmental pollution is easily caused.Second is that peroxide oxidation method dearsenification：Using the strong oxidizing property of dicumyl peroxide (CHP),
The arsenide of reduction-state is oxidized to arsenic (V), but CHP storage and transportations operation is relatively hazardous, and this method is also easy to produce arsenious waste solution, pollution
Equipment and environment.
Chinese patent literature CN1323872 A disclose a kind of dearsenic catalyst, using activated carbon as catalyst carrier, urge
Agent active component is metal oxide.In the preparation method of the dearsenic catalyst, need active component with metallic salt form
It is carried on carrier.However, since soluble metallic salt decomposes the temperature needs for generating its correspondence metal oxide 220
DEG C or more, and in aerobic environment, when temperature is higher than 120 DEG C, spontaneous combustion will takes place in activated carbon surface, more than 170 DEG C
When activated carbon completely burned can occur.Therefore, this must can be just prepared in the protection of inert atmosphere using the above method
Hydrodearsenic Catalyst.Meanwhile although the carrier is by processing, but still there are specific surface areas small, Kong Rong little, the dispersion of duct aperture are uneven
The problems such as even.Test result shows that the Hydrodearsenic Catalyst was operated by 240 hours, and arsenic-removing rate is reduced to 95%, it is difficult to further carry
The adsorption capacity and arsenic-removing rate of Hydrodearsenic Catalyst are risen, stability is poor.
Invention content
For this purpose, it is to be solved by this invention be Hydrodearsenic Catalyst in the prior art adsorption capacity is small, arsenic-removing rate is low and performance
The poor problem of stability, to provide a kind of adsorption capacity is big, arsenic-removing rate is high, stability is high supported dearsenic agent and
Preparation method.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：
A kind of supported dearsenic agent of the present invention includes the active component of carrier and load on the carrier；
The carrier is porous unformed magnesium aluminate spinel, and the active component is CuO and/or NiO.
The specific surface area 100m of the magnesium aluminate spinel2/ g~300m2/g。
Preferably, calculated with metal oxide weight, the active component account for the carrier percentage composition be 5wt%~
30wt%；
It is highly preferred that being calculated with metal oxide weight, the percentage composition that the active component accounts for the carrier is
10wt%~20wt%.
Preferably, the active component be CuO and NiO, the CuO account for the carrier percentage composition be 10wt%~
The percentage composition that 15wt%, the NiO account for the carrier is 5wt%~10wt%.
The preparation method of supported dearsenic agent of the present invention, includes the following steps：
S1, magnesium source and silicon source and acidic aqueous solution carry out to kneading, the molar ratio in source of aluminium and the magnesium source presses MgO/
Al2O3It is calculated as 1：2, the acidic aqueous solution is aqueous solution of nitric acid, concentration 2mol/L；
S2, into the mixture after kneading add amount of the mixture 0.5wt% inorganic additive, be uniformly mixed it is laggard
Row molding, the inorganic additive are at least one of orthophosphoric acid, boric acid, silicic acid；
S3, processing is dried in mixture after molding；
S4, it is roasted, porous unformed magnesia alumina spinel carrier is obtained after cooling；
S5, the aqueous solution of copper predecessor and/or nickel predecessor and the magnesia alumina spinel carrier incipient impregnation are stood 5
Then the load is made in 110 DEG C~120 DEG C dry 6h~8h, 400 DEG C~500 DEG C roasting 4h~5h in sample by~7h
Type dearsenic catalyst.
Preferably, in the step S1, source of aluminium is boehmite, Al2O3Powder, Al2O3·H2O、Al2O3·3H2O、
At least one of aluminum nitrate, the magnesium source are lightweight basic magnesium carbonate, Mg (OH)2, at least one of light MgO.
Preferably, in the step S2, the inorganic additive includes orthophosphoric acid, boric acid, silicic acid；The orthophosphoric acid, boron
The molar ratio of acid and silicic acid is with P：B：Si is calculated as 1:1~1.2:0.8~2.
Preferably, in the step S3, drying temperature is 80 DEG C~120 DEG C, drying time 0.5h-8h.
Preferably, in the step S4, the calcination temperature is 400 DEG C -600 DEG C, roasting time 0.5h-15h.
The above technical solution of the present invention has the following advantages over the prior art：
1, supported dearsenic agent of the present invention includes the active component of carrier and load on the carrier；Institute
It is porous unformed magnesium aluminate spinel to state carrier, and the active component is CuO and/or NiO.Since the carrier is fixed for porous nothing
Type magnesium aluminate spinel, better crystallinity degree, material internal are combined by strong Mg- and Al-O ionic bonds, fundamentally substantially increase material
The intensity of material and resistance to hydration performance to improve the adsorption capacity and arsenic-removing rate of Hydrodearsenic Catalyst, and then increase the load
Type Hydrodearsenic Catalyst stability.
2, supported dearsenic agent of the present invention adds inorganic additive, inorganic additive packet used in preparation process
Include at least one of silicon compound, phosphorus compound and boron compound；Such inorganic additive has the oxytropism of height, can be light
The case for easily occupying metal ion in Spinel, on the one hand increases Lewis acid position and the intensity of material surface, on the other hand
Crystals and surface are facilitated to form impurity substitutional defect.It not only can effectively disperse active phase, but also appropriate can drop
Interaction force between low layer-like active same vehicle, to effectively improve the activity and stability of catalyst.
3, supported dearsenic agent of the present invention, using copper oxide and/or nickel oxide as active component, using dipping
Method synthesizes, and simple production process, specific surface area is larger, active metal component good dispersion, by controlling above-mentioned active component
Ratio can be obtained with the Hydrodearsenic Catalyst held more than 15wt% arsenic, and the depth dearsenification of coal synthesis gas may be implemented, and efficiency is up to
99% or more.
4, supported dearsenic agent of the present invention, hydration-resisting ability is strong, and stability is high, can with high liquid to steam ratio,
It is used under high pressure, hot conditions；After 2400h is operated, arsenic-removing rate remains to up to 98.8% or more.
5, the preparation method of supported dearsenic agent of the present invention, includes the following steps：S1, by magnesium source and silicon source and acid
Property aqueous solution carry out kneading, the molar ratio in source of aluminium and the magnesium source presses MgO/Al2O3It is calculated as 1：2, the acidic aqueous solution is
Aqueous solution of nitric acid, concentration 2mol/L；S2, into the mixture after kneading add amount of the mixture 0.5wt% inorganic addition
Agent is molded after mixing, and the inorganic additive is at least one of orthophosphoric acid, boric acid, silicic acid；S3, it will be molded
Processing is dried in mixture afterwards；S4, it is roasted, porous unformed magnesia alumina spinel carrier is obtained after cooling；S5, by copper
The aqueous solution of predecessor and/or nickel predecessor stands 5~7h with the magnesia alumina spinel carrier incipient impregnation, then by sample
The support type dearsenic catalyst is made in 110 DEG C~120 DEG C dry 6~8h, 400 DEG C~500 DEG C 4~5h of roasting.Production
It is simple for process, production cost is low.
Description of the drawings
In order to make the content of the present invention more clearly understood, it below according to specific embodiments of the present invention and combines
Attached drawing, the present invention is described in further detail, wherein
Fig. 1 is the dearsenification design sketch of the support type dearsenic catalyst described in embodiment 6.
Specific implementation mode
To make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with attached drawing to the reality of the present invention
The mode of applying is described in further detail.
The present invention can be embodied in many different forms, and should not be construed as limited to embodiment set forth herein.
On the contrary, providing these embodiments so that the disclosure will be thorough and complete, and the design of the present invention will be fully conveyed to
Those skilled in the art, the present invention will only be defined by the appended claims.
Embodiment 1
The present embodiment provides a kind of supported dearsenic agent, including carrier and the active component that is supported on carrier；Carrier
For porous unformed magnesium aluminate spinel, active component CuO；The specific surface area of magnesium aluminate spinel is 172.5m2/g。
Preferably, it is calculated with CuO weight, the percentage composition that active component accounts for carrier is 15wt%.
The preparation method of supported dearsenic agent, includes the following steps：
S1, magnesium source and silicon source and acidic aqueous solution carry out to kneading, the molar ratio in silicon source and magnesium source presses MgO/Al2O3It is calculated as
1：2, acidic aqueous solution is aqueous solution of nitric acid, concentration 2mol/L；
In the present embodiment, silicon source Al2O3·H2O, magnesium source are light MgO.
S2, into the mixture after kneading add amount of the mixture 0.5wt% inorganic additive, be uniformly mixed it is laggard
Row molding, inorganic additive are at least one of orthophosphoric acid, boric acid, silicic acid；
In the present embodiment, inorganic additive includes orthophosphoric acid, boric acid, silicic acid；The molar ratio of orthophosphoric acid, boric acid and silicic acid with
P：B：Si is calculated as 1:1.2:2.
S3, processing is dried in mixture after molding；In the present embodiment, drying temperature is 120 DEG C, and drying time is
8h。
S4, it is roasted, porous unformed magnesia alumina spinel carrier is obtained after cooling；Calcination temperature is 500 DEG C, when roasting
Between be 12h.
S5, the aqueous solution and magnesia alumina spinel carrier incipient impregnation of copper predecessor and/or nickel predecessor are stood into 5h, so
Afterwards by sample in 110 DEG C of dry 6h, 400 DEG C of roasting 4h, support type dearsenic catalyst obtained.
Embodiment 2
The present embodiment provides a kind of supported dearsenic agent, including carrier and the active component that is supported on carrier；Carrier
For porous unformed magnesium aluminate spinel, active component CuO；The specific surface area of magnesium aluminate spinel is 158.7m2/g。
Preferably, it is calculated with CuO weight, the percentage composition that active component accounts for carrier is 15wt%.
The preparation method of supported dearsenic agent, includes the following steps：
S1, magnesium source and silicon source and acidic aqueous solution carry out to kneading, the molar ratio in silicon source and magnesium source presses MgO/Al2O3It is calculated as
1：2, acidic aqueous solution is aqueous solution of nitric acid, concentration 2mol/L；
In the present embodiment, silicon source Al2O3·H2O, magnesium source are light MgO.
S2, into the mixture after kneading add amount of the mixture 0.5wt% inorganic additive, be uniformly mixed it is laggard
Row molding, inorganic additive are at least one of orthophosphoric acid, boric acid, silicic acid；
In the present embodiment, inorganic additive includes orthophosphoric acid, boric acid, silicic acid；The molar ratio of orthophosphoric acid, boric acid and silicic acid with
P：B：Si is calculated as 1:1.2:2.
S3, processing is dried in mixture after molding；In the present embodiment, drying temperature is 120 DEG C, and drying time is
8h。
S4, it is roasted, porous unformed magnesia alumina spinel carrier is obtained after cooling；Calcination temperature is 500 DEG C, when roasting
Between be 12h.
S5, the aqueous solution and magnesia alumina spinel carrier incipient impregnation of copper predecessor and/or nickel predecessor are stood into 7h, so
Afterwards by sample in 120 DEG C of dry 8h, 500 DEG C of roasting 5h, support type dearsenic catalyst obtained.
Embodiment 3
The present embodiment provides a kind of supported dearsenic agent, including carrier and the active component that is supported on carrier；Carrier
For porous unformed magnesium aluminate spinel, active component CuO；The specific surface area of magnesium aluminate spinel is 170.4m2/g。
Preferably, it is calculated with CuO weight, the percentage composition that active component accounts for carrier is 15wt%.
The preparation method of supported dearsenic agent, includes the following steps：
S1, magnesium source and silicon source and acidic aqueous solution carry out to kneading, the molar ratio in silicon source and magnesium source presses MgO/Al2O3It is calculated as
1：2, acidic aqueous solution is aqueous solution of nitric acid, concentration 2mol/L；
In the present embodiment, silicon source Al2O3·H2O, magnesium source are light MgO.
S2, into the mixture after kneading add amount of the mixture 0.5wt% inorganic additive, be uniformly mixed it is laggard
Row molding, inorganic additive are at least one of orthophosphoric acid, boric acid, silicic acid；
In the present embodiment, inorganic additive includes orthophosphoric acid, boric acid, silicic acid；The molar ratio of orthophosphoric acid, boric acid and silicic acid with
P：B：Si is calculated as 1:1.2:2.
S3, processing is dried in mixture after molding；In the present embodiment, drying temperature is 120 DEG C, and drying time is
8h。
S4, it is roasted, porous unformed magnesia alumina spinel carrier is obtained after cooling；Calcination temperature is 500 DEG C, when roasting
Between be 12h.
S5, the aqueous solution and magnesia alumina spinel carrier incipient impregnation of copper predecessor and/or nickel predecessor are stood into 5h, so
Afterwards by sample in 110 DEG C of dry 6h, 400 DEG C of roasting 4h, support type dearsenic catalyst obtained.
Embodiment 4
The present embodiment provides a kind of supported dearsenic agent, including carrier and the active component that is supported on carrier；Carrier
For porous unformed magnesium aluminate spinel, active component NiO；The specific surface area of magnesium aluminate spinel is 169.8m2/g。
Preferably, it is calculated with NiO weight, the percentage composition that active component accounts for carrier is 15wt%.
The preparation method of supported dearsenic agent, includes the following steps：
S1, magnesium source and silicon source and acidic aqueous solution carry out to kneading, the molar ratio in silicon source and magnesium source presses MgO/Al2O3It is calculated as
1：2, acidic aqueous solution is aqueous solution of nitric acid, concentration 2mol/L；
In the present embodiment, silicon source Al2O3·H2O, magnesium source are light MgO.
S2, into the mixture after kneading add amount of the mixture 0.5wt% inorganic additive, be uniformly mixed it is laggard
Row molding, inorganic additive are at least one of orthophosphoric acid, boric acid, silicic acid；
In the present embodiment, inorganic additive includes orthophosphoric acid, boric acid, silicic acid；The molar ratio of orthophosphoric acid, boric acid and silicic acid with
P：B：Si is calculated as 1:1.2:2.
S3, processing is dried in mixture after molding；In the present embodiment, drying temperature is 120 DEG C, and drying time is
8h。
S4, it is roasted, porous unformed magnesia alumina spinel carrier is obtained after cooling；Calcination temperature is 500 DEG C, when roasting
Between be 12h.
S5, the aqueous solution and magnesia alumina spinel carrier incipient impregnation of copper predecessor and/or nickel predecessor are stood into 5h, so
Afterwards by sample in 110 DEG C of dry 6h, 400 DEG C of roasting 4h, support type dearsenic catalyst obtained.
Embodiment 5
The present embodiment provides a kind of supported dearsenic agent, including carrier and the active component that is supported on carrier；Carrier
For porous unformed magnesium aluminate spinel, active component NiO；The specific surface area of magnesium aluminate spinel is 159.1m2/g。
Preferably, it is calculated with NiO weight, the percentage composition that active component accounts for carrier is 15wt%.
The preparation method of supported dearsenic agent, includes the following steps：
S1, magnesium source and silicon source and acidic aqueous solution carry out to kneading, the molar ratio in silicon source and magnesium source presses MgO/Al2O3It is calculated as
1：2, acidic aqueous solution is aqueous solution of nitric acid, concentration 2mol/L；
In the present embodiment, silicon source Al2O3·H2O, magnesium source are light MgO.
S2, into the mixture after kneading add amount of the mixture 0.5wt% inorganic additive, be uniformly mixed it is laggard
Row molding, inorganic additive are at least one of orthophosphoric acid, boric acid, silicic acid；
In the present embodiment, inorganic additive includes orthophosphoric acid, boric acid, silicic acid；The molar ratio of orthophosphoric acid, boric acid and silicic acid with
P：B：Si is calculated as 1:1.2:2.
S3, processing is dried in mixture after molding；In the present embodiment, drying temperature is 120 DEG C, and drying time is
8h。
S4, it is roasted, porous unformed magnesia alumina spinel carrier is obtained after cooling；Calcination temperature is 500 DEG C, when roasting
Between be 12h.
S5, the aqueous solution and magnesia alumina spinel carrier incipient impregnation of copper predecessor and/or nickel predecessor are stood into 5h, so
Afterwards by sample in 110 DEG C of dry 6h, 400 DEG C of roasting 4h, support type dearsenic catalyst obtained.
Embodiment 6
The present embodiment provides a kind of supported dearsenic agent, including carrier and the active component that is supported on carrier；Carrier
For porous unformed magnesium aluminate spinel, active component is CuO and NiO；The specific surface area of magnesium aluminate spinel is 157.8m2/g。
Preferably, it is calculated with metal oxide weight, active component accounts for the 15wt% of the percentage composition of carrier, wherein CuO
For 10wt%, NiO 5wt%.
The preparation method of supported dearsenic agent, includes the following steps：
S1, magnesium source and silicon source and acidic aqueous solution carry out to kneading, the molar ratio in silicon source and magnesium source presses MgO/Al2O3It is calculated as
1：2, acidic aqueous solution is aqueous solution of nitric acid, concentration 2mol/L；
In the present embodiment, silicon source Al2O3Powder, magnesium source are light MgO.
S2, into the mixture after kneading add amount of the mixture 0.5wt% inorganic additive, be uniformly mixed it is laggard
Row molding, inorganic additive are at least one of orthophosphoric acid, boric acid, silicic acid；
In the present embodiment, inorganic additive includes orthophosphoric acid, boric acid, silicic acid；The molar ratio of orthophosphoric acid, boric acid and silicic acid with
P：B：Si is calculated as 1:1.2:2.
S3, processing is dried in mixture after molding；In the present embodiment, drying temperature is 120 DEG C, and drying time is
8h。
S4, it is roasted, porous unformed magnesia alumina spinel carrier is obtained after cooling；Calcination temperature is 500 DEG C, when roasting
Between be 12h.
S5, the aqueous solution and magnesia alumina spinel carrier incipient impregnation of copper predecessor and/or nickel predecessor are stood into 5h, so
Afterwards by sample in 110 DEG C of dry 6h, 400 DEG C of roasting 4h, support type dearsenic catalyst obtained.
Embodiment 7
The present embodiment provides a kind of supported dearsenic agent, including carrier and the active component that is supported on carrier；Carrier
For porous unformed magnesium aluminate spinel, active component is CuO and NiO；The specific surface area of magnesium aluminate spinel is 152.5m2/g。
Preferably, it is calculated with metal oxide weight, active component accounts for the 20wt% of the percentage composition of carrier, wherein CuO
For 15wt%, NiO 5wt%.
The preparation method of supported dearsenic agent, includes the following steps：
S1, magnesium source and silicon source and acidic aqueous solution carry out to kneading, the molar ratio in silicon source and magnesium source presses MgO/Al2O3It is calculated as
1：2, acidic aqueous solution is aqueous solution of nitric acid, concentration 2mol/L；
In the present embodiment, silicon source is boehmite, and magnesium source is lightweight basic magnesium carbonate.
S2, into the mixture after kneading add amount of the mixture 0.5wt% inorganic additive, be uniformly mixed it is laggard
Row molding, inorganic additive are at least one of orthophosphoric acid, boric acid, silicic acid；
In the present embodiment, inorganic additive includes orthophosphoric acid.
S3, processing is dried in mixture after molding；In the present embodiment, drying temperature is 80 DEG C, and drying time is
8h。
S4, it is roasted, porous unformed magnesia alumina spinel carrier is obtained after cooling；Calcination temperature is 400 DEG C, when roasting
Between be 15h.
S5, the aqueous solution and magnesia alumina spinel carrier incipient impregnation of copper predecessor and/or nickel predecessor are stood into 5h, so
Afterwards by sample in 120 DEG C of dry 6h, 500 DEG C of roasting 4h, support type dearsenic catalyst obtained.
Embodiment 8
The present embodiment provides a kind of supported dearsenic agent, including carrier and the active component that is supported on carrier；Carrier
For porous unformed magnesium aluminate spinel, active component is CuO and NiO；The specific surface area of magnesium aluminate spinel is 198.7m2/g。
Preferably, it is calculated with metal oxide weight, active component accounts for the 22wt% of the percentage composition of carrier, wherein CuO
For 12wt%, NiO 10wt%.
The preparation method of supported dearsenic agent, includes the following steps：
S1, magnesium source and silicon source and acidic aqueous solution carry out to kneading, the molar ratio in silicon source and magnesium source presses MgO/Al2O3It is calculated as
1：2, acidic aqueous solution is aqueous solution of nitric acid, concentration 2mol/L；
In the present embodiment, silicon source Al2O3·3H2O, magnesium source are lightweight Mg (OH)2。
S2, into the mixture after kneading add amount of the mixture 0.5wt% inorganic additive, be uniformly mixed it is laggard
Row molding, inorganic additive are at least one of orthophosphoric acid, boric acid, silicic acid；
In the present embodiment, inorganic additive includes orthophosphoric acid, boric acid, silicic acid；The molar ratio of orthophosphoric acid, boric acid and silicic acid with
P：B：Si is calculated as 1:1.1:1.
S3, processing is dried in mixture after molding；In the present embodiment, drying temperature is 100 DEG C, and drying time is
4h。
S4, it is roasted, porous unformed magnesia alumina spinel carrier is obtained after cooling；Calcination temperature is 600 DEG C, when roasting
Between be 0.5h.
S5, the aqueous solution and magnesia alumina spinel carrier incipient impregnation of copper predecessor and/or nickel predecessor are stood into 6h, so
Afterwards by sample in 110 DEG C of dry 8h, 450 DEG C of roasting 4.5h, support type dearsenic catalyst obtained.
Embodiment 9
The present embodiment provides a kind of supported dearsenic agent, including carrier and the active component that is supported on carrier；Carrier
For porous unformed magnesium aluminate spinel, active component NiO；The specific surface area of magnesium aluminate spinel is 174.4m2/g。
Preferably, it is calculated with NiO weight, the percentage composition that active component accounts for carrier is 5wt%.
The preparation method of supported dearsenic agent, includes the following steps：
S1, magnesium source and silicon source and acidic aqueous solution carry out to kneading, the molar ratio in silicon source and magnesium source presses MgO/Al2O3It is calculated as
1：2, acidic aqueous solution is aqueous solution of nitric acid, concentration 2mol/L；
In the present embodiment, silicon source Al2O3Powder, magnesium source are light MgO.
S2, into the mixture after kneading add amount of the mixture 0.5wt% inorganic additive, be uniformly mixed it is laggard
Row molding, inorganic additive are at least one of orthophosphoric acid, boric acid, silicic acid；
In the present embodiment, inorganic additive includes orthophosphoric acid, boric acid, silicic acid；The molar ratio of orthophosphoric acid, boric acid and silicic acid with
P：B：Si is calculated as 1:1:0.8.
S3, processing is dried in mixture after molding；In the present embodiment, drying temperature is 120 DEG C, and drying time is
0.5h。
S4, it is roasted, porous unformed magnesia alumina spinel carrier is obtained after cooling；Calcination temperature is 500 DEG C, when roasting
Between be 12h.
S5, the aqueous solution and magnesia alumina spinel carrier incipient impregnation of copper predecessor and/or nickel predecessor are stood into 7h, so
Afterwards by sample in 115 DEG C of dry 7h, 500 DEG C of roasting 4h, support type dearsenic catalyst obtained.
Embodiment 10
The present embodiment provides a kind of supported dearsenic agent, including carrier and the active component that is supported on carrier；Carrier
For porous unformed magnesium aluminate spinel, active component is CuO and NiO；The specific surface area of magnesium aluminate spinel is 100.0m2/g。
Preferably, it is calculated with metal oxide weight, active component accounts for the 20wt% of the percentage composition of carrier, wherein CuO
For 12wt%, NiO 8wt%.The preparation method of supported dearsenic agent, includes the following steps：
S1, magnesium source and silicon source and acidic aqueous solution carry out to kneading, the molar ratio in silicon source and magnesium source presses MgO/Al2O3It is calculated as
1：2, acidic aqueous solution is aqueous solution of nitric acid, concentration 2mol/L；
In the present embodiment, silicon source is aluminum nitrate, and magnesium source is light MgO.
S2, into the mixture after kneading add amount of the mixture 0.5wt% inorganic additive, be uniformly mixed it is laggard
Row molding, inorganic additive are at least one of orthophosphoric acid, boric acid, silicic acid；
In the present embodiment, inorganic additive includes boric acid, silicic acid.
S3, processing is dried in mixture after molding；In the present embodiment, drying temperature is 100 DEG C, and drying time is
6h。
S4, it is roasted, porous unformed magnesia alumina spinel carrier is obtained after cooling；Calcination temperature is 600 DEG C, when roasting
Between be 1h.
S5, the aqueous solution and magnesia alumina spinel carrier incipient impregnation of copper predecessor and/or nickel predecessor are stood into 5h, so
Afterwards by sample in 115 DEG C of dry 7h, 400 DEG C of roasting 5h, support type dearsenic catalyst obtained.
Embodiment 11
The present embodiment provides a kind of supported dearsenic agent, including carrier and the active component that is supported on carrier；Carrier
For porous unformed magnesium aluminate spinel, active component CuO；The specific surface area of magnesium aluminate spinel is 179.8m2/g。
Preferably, it is calculated with CuO weight, the percentage composition that active component accounts for carrier is 30wt%.
The preparation method of supported dearsenic agent, includes the following steps：
S1, magnesium source and silicon source and acidic aqueous solution carry out to kneading, the molar ratio in silicon source and magnesium source presses MgO/Al2O3It is calculated as
1：2, acidic aqueous solution is aqueous solution of nitric acid, concentration 2mol/L；
In the present embodiment, silicon source is boehmite, and magnesium source is Mg (OH)2。
S2, into the mixture after kneading add amount of the mixture 0.5wt% inorganic additive, be uniformly mixed it is laggard
Row molding, inorganic additive are at least one of orthophosphoric acid, boric acid, silicic acid；
In the present embodiment, inorganic additive includes orthophosphoric acid, boric acid, silicic acid；The molar ratio of orthophosphoric acid, boric acid and silicic acid with
P：B：Si is calculated as 1:1.1:1.
S3, processing is dried in mixture after molding；In the present embodiment, drying temperature is 120 DEG C, and drying time is
8h。
S4, it is roasted, porous unformed magnesia alumina spinel carrier is obtained after cooling；Calcination temperature is 400 DEG C, when roasting
Between be 14h.
S5, the aqueous solution and magnesia alumina spinel carrier incipient impregnation of copper predecessor and/or nickel predecessor are stood into 6h, so
Afterwards by sample in 120 DEG C of dry 6h, 450 DEG C of roasting 4.5h, support type dearsenic catalyst obtained.
Embodiment 12
The present embodiment provides a kind of supported dearsenic agent, including carrier and the active component that is supported on carrier；Carrier
For porous unformed magnesium aluminate spinel, active component CuO；The specific surface area of magnesium aluminate spinel is 300.0m2/g。
Preferably, it is calculated with CuO weight, the percentage composition that active component accounts for carrier is 10wt%.
The preparation method of supported dearsenic agent, includes the following steps：
S1, magnesium source and silicon source and acidic aqueous solution carry out to kneading, the molar ratio in silicon source and magnesium source presses MgO/Al2O3It is calculated as
1：2, acidic aqueous solution is aqueous solution of nitric acid, concentration 2mol/L；
In the present embodiment, silicon source Al2O3Powder, magnesium source are light MgO.
S2, into the mixture after kneading add amount of the mixture 0.5wt% inorganic additive, be uniformly mixed it is laggard
Row molding, inorganic additive are at least one of orthophosphoric acid, boric acid, silicic acid；
In the present embodiment, inorganic additive is silicic acid.
S3, processing is dried in mixture after molding；In the present embodiment, drying temperature is 120 DEG C, and drying time is
8h。
S4, it is roasted, porous unformed magnesia alumina spinel carrier is obtained after cooling；Calcination temperature is 500 DEG C, when roasting
Between be 12h.
S5, the aqueous solution and magnesia alumina spinel carrier incipient impregnation of copper predecessor and/or nickel predecessor are stood into 6h, so
Afterwards by sample in 110 DEG C of dry 6h, 500 DEG C of roasting 4h, support type dearsenic catalyst obtained.
Experimental example 1
The intensity of support type dearsenic catalyst obtained in embodiment 1-6, pore volume, aperture and specific surface area are carried out
Test, test result is as follows shown in table：
Experimental example 2
The activity of support type dearsenic catalyst described in embodiment 1-6 is tested, test condition：Temperature：250
DEG C, pressure：5.0MPa, air speed：3000h-1, steam-to-gas ratio：1.5, unstripped gas forms (wt%)：H213%, CO 17%,
CO29.0%, H2O 60%, HCl 30ppm, H2S 1000ppm, As 0.22ppm, acquired results are as follows：
| Catalyst | Import arsenic content (ppm) | Export arsenic content (ppb) | Arsenic-removing rate (%) | Arsenic holds (wt%) |
| Embodiment 1 | 0.22 | 7.71 | 96.5 | 14 |
| Embodiment 2 | 0.22 | 9.89 | 95.5 | 13 |
| Embodiment 3 | 0.22 | 10.6 | 95.2 | 13 |
| Embodiment 4 | 0.22 | 6.38 | 97.1 | 14 |
| Embodiment 5 | 0.22 | 9.68 | 95.6 | 13 |
| Embodiment 6 | 0.22 | ＜ 2 | ＞ 99 | ＞ 15 |
From upper table data it is found that the support type dearsenic catalyst that the embodiment of the present invention is prepared is imitated with significant dearsenification
Fruit, the arsenic of support type dearsenic catalyst, which holds, in embodiment 6 is up to 15wt% or more；Arsenic-removing rate is up to 99%.Illustrate to use this hair
Support type dearsenic catalyst in bright embodiment has higher dearsenification activity.For the operating condition of actual production, temperature is carried out
Degree and air speed experiment, in 250-350 DEG C of temperature range, air speed 3000-5000h-1, pressure：5.0~6.0MPa, steam-to-gas ratio 1.0
~1.8, dearsenification and transformation side reaction can meet the manufacturing technique requirent of factory.
Experimental example 3
As shown in Figure 1, support type dearsenic catalyst described in embodiment 6 is up to 2400 hours operating (temperature：
250 DEG C, pressure：5.0MPa, air speed：3000h-1, steam-to-gas ratio：1.5, unstripped gas forms (wt%)：H213%, CO 17%,
CO29.0%, H2O 60%, HCl 30ppm, H2S 1000ppm, As 0.22ppm) during, arsenic-removing rate remains to reach 98.8%
More than, not only Hydrodearsenic Catalyst stability is preferable, and can keep higher dearsenification activity.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
Variation is still in the protection scope of this invention.
Claims (9)
1. a kind of supported dearsenic agent, the supported dearsenic agent is grouped by the activearm of carrier and load on the carrier
At；It is characterized in that, the carrier is porous unformed magnesium aluminate spinel, the active component is CuO and/or NiO；With metal
Oxide weight calculates, and the percentage composition that the active component accounts for the carrier is 5wt%~30wt%；
The preparation of the carrier includes the following steps：
S1, magnesium source and silicon source and acidic aqueous solution carry out to kneading, the molar ratio in source of aluminium and the magnesium source presses MgO/Al2O3
It is calculated as 1：2, the acidic aqueous solution is aqueous solution of nitric acid, concentration 2mol/L；
S2, into the mixture after kneading add amount of the mixture 0.5wt% inorganic additive, carry out into after mixing
Type, the inorganic additive are at least one of orthophosphoric acid, boric acid, silicic acid；
S3, processing is dried in mixture after molding；
S4, it is roasted, porous unformed magnesia alumina spinel carrier is obtained after cooling.
2. supported dearsenic agent according to claim 1, which is characterized in that the specific surface area of the magnesium aluminate spinel
100m2/ g~300m2/g。
3. supported dearsenic agent according to claim 1 or 2, which is characterized in that it is calculated with metal oxide weight, it is described
The percentage composition that active component accounts for the carrier is 10wt%~20wt%.
4. supported dearsenic agent according to claim 1 or 2, which is characterized in that the active component is CuO and NiO, institute
It is 10wt%~15wt% to state CuO and account for the percentage composition of the carrier, and the percentage composition that the NiO accounts for the carrier is 5wt%
~10wt%.
5. a kind of preparation method of claim 1-4 any one of them supported dearsenic agents, which is characterized in that including walking as follows
Suddenly：
S5, the aqueous solution of copper predecessor and/or nickel predecessor and the magnesia alumina spinel carrier incipient impregnation stand to 5~
7h, then by sample in 110 DEG C~120 DEG C dry 6~8h, 400 DEG C~500 DEG C roast 4~5h, and the support type for being made described is de-
Arsenic catalyst.
6. the preparation method of supported dearsenic agent according to claim 5, which is characterized in that described in the step S1
Silicon source is boehmite, Al2O3Powder, Al2O3·H2O、Al2O3·3H2O, at least one of aluminum nitrate, the magnesium source is light
Matter basic magnesium carbonate, Mg (OH)2, at least one of light MgO.
7. the preparation method of supported dearsenic agent according to claim 5 or 6, which is characterized in that in the step S2, institute
It includes orthophosphoric acid, boric acid, silicic acid to state inorganic additive；The molar ratio of the orthophosphoric acid, boric acid and silicic acid is with P：B：Si is calculated as 1:1
~1.2:0.8~2.
8. the preparation method of supported dearsenic agent according to claim 5 or 6, which is characterized in that in the step S3, do
Dry temperature is 80 DEG C~120 DEG C, drying time 0.5h-8h.
9. the preparation method of supported dearsenic agent according to claim 5 or 6, which is characterized in that in the step S4, institute
It is 400 DEG C -600 DEG C to state calcination temperature, roasting time 0.5h-15h.
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| CN112875734B (en) * | 2021-02-02 | 2023-01-20 | 新地能源工程技术有限公司 | Single crystal phase magnesia-alumina spinel, preparation method thereof and methane steam reforming catalyst |
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| CN1229836A (en) * | 1998-03-20 | 1999-09-29 | 中国石油化工总公司 | Hydrocarbon dearsoniumizer, its prepn. method and use in dearsoniumizing hydrocarbon |
| CN103143398A (en) * | 2011-12-06 | 2013-06-12 | 福州大学 | Magnesium aluminate spinel carrier, and preparation method and application thereof |
| CN104475171A (en) * | 2014-12-16 | 2015-04-01 | 沈阳三聚凯特催化剂有限公司 | Hydrogenating desulfuration and dearsenification catalyst and preparation method of carrier thereof |
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| CN103143398A (en) * | 2011-12-06 | 2013-06-12 | 福州大学 | Magnesium aluminate spinel carrier, and preparation method and application thereof |
| CN104475171A (en) * | 2014-12-16 | 2015-04-01 | 沈阳三聚凯特催化剂有限公司 | Hydrogenating desulfuration and dearsenification catalyst and preparation method of carrier thereof |
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