CN105536689A - Loaded type dearsenicating agent and preparation method thereof - Google Patents

Loaded type dearsenicating agent and preparation method thereof Download PDF

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CN105536689A
CN105536689A CN201510920454.5A CN201510920454A CN105536689A CN 105536689 A CN105536689 A CN 105536689A CN 201510920454 A CN201510920454 A CN 201510920454A CN 105536689 A CN105536689 A CN 105536689A
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carrier
active component
aqueous solution
acid
dearsenic agent
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CN105536689B (en
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江莉龙
曹彦宁
沈丽娟
赵素云
冯续
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SHEYANG SANJU KAITE CATALYST Co Ltd
CHEMICAL FERTILIZER CATALYST STATE ENGINEERING RESEARCH CENTER FUZHOU UNIV
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SHEYANG SANJU KAITE CATALYST Co Ltd
CHEMICAL FERTILIZER CATALYST STATE ENGINEERING RESEARCH CENTER FUZHOU UNIV
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/281Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/103Arsenic compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/20Heavy metals or heavy metal compounds

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  • Inorganic Chemistry (AREA)
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Abstract

The invention relates to a loaded type dearsenicating agent comprising a carrier and an active component loaded on the carrier. The carrier is a porous amorphous magnesia alumina spinel, and the active component comprises CuO and/or NiO. Because the carrier is the porous amorphous magnesia alumina spinel, the crystallinity is good and strong Mg- and Al-O ionic bonds are combined in the interior of the material, the material strength and hydration resistance are fundamentally effectively improved. The preparation method of the loaded type dearsenicating agent is simple in production process and low in production cost.

Description

A kind of supported dearsenic agent and preparation method thereof
Technical field
The present invention relates to coal chemical technology, be specifically related to a kind of supported dearsenic agent and preparation method thereof.
Background technology
Coal is the valuable source of China, and producing synthesis gas from coal technology is one of main Land use systems of coal resource.All containing arsenide in feed coal, main with AsH in obtained raw gas 3form exists, and many catalyst of the industrial use of coal are as very responsive to arsenide in high temperature conversion catalyst etc., and the arsenide of hundreds of ppb (partsperbillion) just can cause catalyst poisoning and inactivation, affects the normal operation of device.Therefore, in chemical industry synthesis, producing synthesis gas from coal purification is the key technology that will solve, and research and the exploitation of carrying out Hydrodearsenic Catalyst have important practical significance and using value.
At present, main arsenic removing method has two kinds: one to be physisorphtion: utilize copper sulphate alumina silicate bead to adsorb trace arsenide (polarity absorption), but the method holds arsenic amount little (0.1 ~ 0.3%), adsorbent consumption is large, life-span is short and produce a large amount of waste material, easily causes environmental pollution.Two is the dearsenifications of peroxide oxidation method: the strong oxidizing property utilizing dicumyl peroxide (CHP), the arsenide of reduction-state is oxidized to arsenic (V), but CHP accumulating operation is more dangerous, and the method easily produces containing arsenic waste solution, contaminated equipment and environment.
Chinese patent literature CN1323872A discloses a kind of dearsenic catalyst, and using active carbon as catalyst carrier, catalyst activity component is metal oxide.In the preparation method of this dearsenic catalyst, need active component to be carried on carrier with metallic salt form.But, need more than 220 DEG C because the temperature generating its corresponding metal oxide occurs to decompose soluble metallic salt, and in aerobic environment, when temperature is higher than 120 DEG C, activated carbon surface will start spontaneous combustion occurs, and during more than 170 DEG C, active carbon can occur to burn completely.Therefore, said method is utilized just must can to prepare this Hydrodearsenic Catalyst in the protection of inert atmosphere.Meanwhile, although described carrier is through process, but still there is the problems such as specific area is little, pore volume is little, the dispersion of aperture, duct is uneven.Test result shows, described Hydrodearsenic Catalyst was through running in 240 hours, and namely arsenic-removing rate reduces to 95%, and be difficult to the adsorption capacity and the arsenic-removing rate that promote Hydrodearsenic Catalyst further, stability is poor.
Summary of the invention
For this reason, to be solved by this invention is the problem that in prior art, the adsorption capacity of Hydrodearsenic Catalyst is little, arsenic-removing rate is low and stability is poor, thus provides supported dearsenic agent that a kind of adsorption capacity is large, arsenic-removing rate is high, stability is high and preparation method thereof.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows:
A kind of supported dearsenic agent of the present invention, comprises carrier and load active component on the carrier; Described carrier is the unformed magnesium aluminate spinel of porous, and described active component is CuO and/or NiO.
The specific area 100m of described magnesium aluminate spinel 2/ g ~ 300m 2/ g.
Preferably, calculate with metal oxide weight, the percentage composition that described active component accounts for described carrier is 5wt% ~ 30wt%;
More preferably, calculate with metal oxide weight, the percentage composition that described active component accounts for described carrier is 10wt% ~ 20wt%.
Preferably, described active component is CuO and NiO, and the percentage composition that described CuO accounts for described carrier is 10wt% ~ 15wt%, and the percentage composition that described NiO accounts for described carrier is 5wt% ~ 10wt%.
The preparation method of supported dearsenic agent of the present invention, comprises the steps:
S1, kneading is carried out in magnesium source and aluminium source and acidic aqueous solution, the mol ratio in described aluminium source and described magnesium source presses MgO/Al 2o 3count 1:2, described acidic aqueous solution is aqueous solution of nitric acid, concentration 2mol/L;
S2, in the mixture after kneading, add the inorganic additive of the 0.5wt% of amount of the mixture, carry out shaping after mixing, described inorganic additive is at least one in orthophosphoric acid, boric acid, silicic acid;
S3, the mixture after shaping is carried out drying process;
S4, carry out roasting, after cooling, obtain the unformed magnesia alumina spinel carrier of porous;
S5, the aqueous solution of copper predecessor and/or nickel predecessor and described magnesia alumina spinel carrier incipient impregnation are left standstill 5 ~ 7h, then by sample in 110 DEG C ~ 120 DEG C dry 6h ~ 8h, 400 DEG C ~ 500 DEG C roasting 4h ~ 5h, obtained described support type dearsenic catalyst.
Preferably, in described step S1, described aluminium source is boehmite, Al 2o 3powder, Al 2o 3h 2o, Al 2o 33H 2at least one in O, aluminum nitrate, described magnesium source is lightweight basic magnesium carbonate, Mg (OH) 2, at least one in light MgO.
Preferably, in described step S2, described inorganic additive comprises orthophosphoric acid, boric acid, silicic acid; The mol ratio of described orthophosphoric acid, boric acid and silicic acid counts 1:1 ~ 1.2:0.8 ~ 2 with P:B:Si.
Preferably, in described step S3, baking temperature is 80 DEG C ~ 120 DEG C, and drying time is 0.5h-8h.
Preferably, in described step S4, described sintering temperature is 400 DEG C-600 DEG C, and roasting time is 0.5h-15h.
Technique scheme of the present invention has the following advantages compared to existing technology:
1, supported dearsenic agent of the present invention, comprises carrier and load active component on the carrier; Described carrier is the unformed magnesium aluminate spinel of porous, and described active component is CuO and/or NiO.Because described carrier is the unformed magnesium aluminate spinel of porous, better crystallinity degree, material internal is combined by strong Mg-and Al-O ionic bond, fundamentally substantially increase the intensity of material and resistance to hydration performance, thus improve adsorption capacity and the arsenic-removing rate of Hydrodearsenic Catalyst, and then add described supported dearsenic agent stability.
2, supported dearsenic agent of the present invention, adds inorganic additive in preparation process, and inorganic additive used comprises at least one in silicon compound, phosphorus compound and boron compound; This type of inorganic additive has the oxytropism of height, can occupy the case of metal ion in Spinel easily, adds Lewis acid position and the intensity of material surface on the one hand, facilitates crystals and surface to form impurity substitutional defect on the other hand.Not only can dispersed activity phase effectively, and the interaction force between reduction layer-like active same vehicle that can be suitable, thus effectively improve activity and the stability of catalyst.
3, supported dearsenic agent of the present invention, adopt cupric oxide and/or nickel oxide as active component, employing infusion process is synthesized, production technology is simple, specific area is comparatively large, active metal component good dispersion, can obtain having the Hydrodearsenic Catalyst being greater than 15wt% arsenic and holding by the ratio controlling above-mentioned active component, and the degree of depth dearsenification of coal synthesis gas can be realized, efficiency is up to more than 99%.
4, supported dearsenic agent of the present invention, hydration-resisting ability is strong, and stability is high, can use having under high liquid to steam ratio, high pressure, hot conditions; After 2400h running, arsenic-removing rate still can up to more than 98.8%.
5, the preparation method of supported dearsenic agent of the present invention, comprise the steps: S1, kneading is carried out in magnesium source and aluminium source and acidic aqueous solution, the mol ratio in described aluminium source and described magnesium source presses MgO/Al 2o 3count 1:2, described acidic aqueous solution is aqueous solution of nitric acid, concentration 2mol/L; S2, in the mixture after kneading, add the inorganic additive of the 0.5wt% of amount of the mixture, carry out shaping after mixing, described inorganic additive is at least one in orthophosphoric acid, boric acid, silicic acid; S3, the mixture after shaping is carried out drying process; S4, carry out roasting, after cooling, obtain the unformed magnesia alumina spinel carrier of porous; S5, the aqueous solution of copper predecessor and/or nickel predecessor and described magnesia alumina spinel carrier incipient impregnation are left standstill 5 ~ 7h, then by sample in 110 DEG C ~ 120 DEG C drying 6 ~ 8h, 400 DEG C ~ 500 DEG C roasting 4 ~ 5h, obtained described support type dearsenic catalyst.Production technology is simple, production cost is low.
Accompanying drawing explanation
In order to make content of the present invention be more likely to be clearly understood, below according to a particular embodiment of the invention and by reference to the accompanying drawings, the present invention is further detailed explanation, wherein
Fig. 1 is the dearsenification design sketch of the support type dearsenic catalyst described in embodiment 6.
Detailed description of the invention
In order to make the object, technical solutions and advantages of the present invention clearly, below in conjunction with accompanying drawing, embodiments of the present invention are described in further detail.
The present invention can implement in many different forms, and should not be understood to be limited to embodiment set forth herein.On the contrary, provide these embodiments, make the disclosure to be thorough and complete, and design of the present invention fully will be conveyed to those skilled in the art, the present invention will only be limited by claim.
Embodiment 1
The present embodiment provides a kind of supported dearsenic agent, comprises carrier and the active component of load on carrier; Carrier is the unformed magnesium aluminate spinel of porous, and active component is CuO; The specific area of magnesium aluminate spinel is 172.5m 2/ g.
Preferably, with CuO Weight computation, the percentage composition that active component accounts for carrier is 15wt%.
The preparation method of supported dearsenic agent, comprises the steps:
S1, kneading is carried out in magnesium source and aluminium source and acidic aqueous solution, the mol ratio in aluminium source and magnesium source presses MgO/Al 2o 3count 1:2, acidic aqueous solution is aqueous solution of nitric acid, concentration 2mol/L;
In the present embodiment, aluminium source is Al 2o 3h 2o, magnesium source is light MgO.
S2, in the mixture after kneading, add the inorganic additive of the 0.5wt% of amount of the mixture, carry out shaping after mixing, inorganic additive is at least one in orthophosphoric acid, boric acid, silicic acid;
In the present embodiment, inorganic additive comprises orthophosphoric acid, boric acid, silicic acid; The mol ratio of orthophosphoric acid, boric acid and silicic acid counts 1:1.2:2 with P:B:Si.
S3, the mixture after shaping is carried out drying process; In the present embodiment, baking temperature is 120 DEG C, and drying time is 8h.
S4, carry out roasting, after cooling, obtain the unformed magnesia alumina spinel carrier of porous; Sintering temperature is 500 DEG C, and roasting time is 12h.
S5, the aqueous solution of copper predecessor and/or nickel predecessor and magnesia alumina spinel carrier incipient impregnation are left standstill 5h, then by sample in 110 DEG C of dry 6h, 400 DEG C of roasting 4h, obtained support type dearsenic catalyst.
Embodiment 2
The present embodiment provides a kind of supported dearsenic agent, comprises carrier and the active component of load on carrier; Carrier is the unformed magnesium aluminate spinel of porous, and active component is CuO; The specific area of magnesium aluminate spinel is 158.7m 2/ g.
Preferably, with CuO Weight computation, the percentage composition that active component accounts for carrier is 15wt%.
The preparation method of supported dearsenic agent, comprises the steps:
S1, kneading is carried out in magnesium source and aluminium source and acidic aqueous solution, the mol ratio in aluminium source and magnesium source presses MgO/Al 2o 3count 1:2, acidic aqueous solution is aqueous solution of nitric acid, concentration 2mol/L;
In the present embodiment, aluminium source is Al 2o 3h 2o, magnesium source is light MgO.
S2, in the mixture after kneading, add the inorganic additive of the 0.5wt% of amount of the mixture, carry out shaping after mixing, inorganic additive is at least one in orthophosphoric acid, boric acid, silicic acid;
In the present embodiment, inorganic additive comprises orthophosphoric acid, boric acid, silicic acid; The mol ratio of orthophosphoric acid, boric acid and silicic acid counts 1:1.2:2 with P:B:Si.
S3, the mixture after shaping is carried out drying process; In the present embodiment, baking temperature is 120 DEG C, and drying time is 8h.
S4, carry out roasting, after cooling, obtain the unformed magnesia alumina spinel carrier of porous; Sintering temperature is 500 DEG C, and roasting time is 12h.
S5, the aqueous solution of copper predecessor and/or nickel predecessor and magnesia alumina spinel carrier incipient impregnation are left standstill 7h, then by sample in 120 DEG C of dry 8h, 500 DEG C of roasting 5h, obtained support type dearsenic catalyst.
Embodiment 3
The present embodiment provides a kind of supported dearsenic agent, comprises carrier and the active component of load on carrier; Carrier is the unformed magnesium aluminate spinel of porous, and active component is CuO; The specific area of magnesium aluminate spinel is 170.4m 2/ g.
Preferably, with CuO Weight computation, the percentage composition that active component accounts for carrier is 15wt%.
The preparation method of supported dearsenic agent, comprises the steps:
S1, kneading is carried out in magnesium source and aluminium source and acidic aqueous solution, the mol ratio in aluminium source and magnesium source presses MgO/Al 2o 3count 1:2, acidic aqueous solution is aqueous solution of nitric acid, concentration 2mol/L;
In the present embodiment, aluminium source is Al 2o 3h 2o, magnesium source is light MgO.
S2, in the mixture after kneading, add the inorganic additive of the 0.5wt% of amount of the mixture, carry out shaping after mixing, inorganic additive is at least one in orthophosphoric acid, boric acid, silicic acid;
In the present embodiment, inorganic additive comprises orthophosphoric acid, boric acid, silicic acid; The mol ratio of orthophosphoric acid, boric acid and silicic acid counts 1:1.2:2 with P:B:Si.
S3, the mixture after shaping is carried out drying process; In the present embodiment, baking temperature is 120 DEG C, and drying time is 8h.
S4, carry out roasting, after cooling, obtain the unformed magnesia alumina spinel carrier of porous; Sintering temperature is 500 DEG C, and roasting time is 12h.
S5, the aqueous solution of copper predecessor and/or nickel predecessor and magnesia alumina spinel carrier incipient impregnation are left standstill 5h, then by sample in 110 DEG C of dry 6h, 400 DEG C of roasting 4h, obtained support type dearsenic catalyst.
Embodiment 4
The present embodiment provides a kind of supported dearsenic agent, comprises carrier and the active component of load on carrier; Carrier is the unformed magnesium aluminate spinel of porous, and active component is NiO; The specific area of magnesium aluminate spinel is 169.8m 2/ g.
Preferably, with NiO Weight computation, the percentage composition that active component accounts for carrier is 15wt%.
The preparation method of supported dearsenic agent, comprises the steps:
S1, kneading is carried out in magnesium source and aluminium source and acidic aqueous solution, the mol ratio in aluminium source and magnesium source presses MgO/Al 2o 3count 1:2, acidic aqueous solution is aqueous solution of nitric acid, concentration 2mol/L;
In the present embodiment, aluminium source is Al 2o 3h 2o, magnesium source is light MgO.
S2, in the mixture after kneading, add the inorganic additive of the 0.5wt% of amount of the mixture, carry out shaping after mixing, inorganic additive is at least one in orthophosphoric acid, boric acid, silicic acid;
In the present embodiment, inorganic additive comprises orthophosphoric acid, boric acid, silicic acid; The mol ratio of orthophosphoric acid, boric acid and silicic acid counts 1:1.2:2 with P:B:Si.
S3, the mixture after shaping is carried out drying process; In the present embodiment, baking temperature is 120 DEG C, and drying time is 8h.
S4, carry out roasting, after cooling, obtain the unformed magnesia alumina spinel carrier of porous; Sintering temperature is 500 DEG C, and roasting time is 12h.
S5, the aqueous solution of copper predecessor and/or nickel predecessor and magnesia alumina spinel carrier incipient impregnation are left standstill 5h, then by sample in 110 DEG C of dry 6h, 400 DEG C of roasting 4h, obtained support type dearsenic catalyst.
Embodiment 5
The present embodiment provides a kind of supported dearsenic agent, comprises carrier and the active component of load on carrier; Carrier is the unformed magnesium aluminate spinel of porous, and active component is NiO; The specific area of magnesium aluminate spinel is 159.1m 2/ g.
Preferably, with NiO Weight computation, the percentage composition that active component accounts for carrier is 15wt%.
The preparation method of supported dearsenic agent, comprises the steps:
S1, kneading is carried out in magnesium source and aluminium source and acidic aqueous solution, the mol ratio in aluminium source and magnesium source presses MgO/Al 2o 3count 1:2, acidic aqueous solution is aqueous solution of nitric acid, concentration 2mol/L;
In the present embodiment, aluminium source is Al 2o 3h 2o, magnesium source is light MgO.
S2, in the mixture after kneading, add the inorganic additive of the 0.5wt% of amount of the mixture, carry out shaping after mixing, inorganic additive is at least one in orthophosphoric acid, boric acid, silicic acid;
In the present embodiment, inorganic additive comprises orthophosphoric acid, boric acid, silicic acid; The mol ratio of orthophosphoric acid, boric acid and silicic acid counts 1:1.2:2 with P:B:Si.
S3, the mixture after shaping is carried out drying process; In the present embodiment, baking temperature is 120 DEG C, and drying time is 8h.
S4, carry out roasting, after cooling, obtain the unformed magnesia alumina spinel carrier of porous; Sintering temperature is 500 DEG C, and roasting time is 12h.
S5, the aqueous solution of copper predecessor and/or nickel predecessor and magnesia alumina spinel carrier incipient impregnation are left standstill 5h, then by sample in 110 DEG C of dry 6h, 400 DEG C of roasting 4h, obtained support type dearsenic catalyst.
Embodiment 6
The present embodiment provides a kind of supported dearsenic agent, comprises carrier and the active component of load on carrier; Carrier is the unformed magnesium aluminate spinel of porous, and active component is CuO and NiO; The specific area of magnesium aluminate spinel is 157.8m 2/ g.
Preferably, calculate with metal oxide weight, active component accounts for the 15wt% of the percentage composition of carrier, and wherein, CuO is 10wt%, NiO is 5wt%.
The preparation method of supported dearsenic agent, comprises the steps:
S1, kneading is carried out in magnesium source and aluminium source and acidic aqueous solution, the mol ratio in aluminium source and magnesium source presses MgO/Al 2o 3count 1:2, acidic aqueous solution is aqueous solution of nitric acid, concentration 2mol/L;
In the present embodiment, aluminium source is Al 2o 3powder, magnesium source is light MgO.
S2, in the mixture after kneading, add the inorganic additive of the 0.5wt% of amount of the mixture, carry out shaping after mixing, inorganic additive is at least one in orthophosphoric acid, boric acid, silicic acid;
In the present embodiment, inorganic additive comprises orthophosphoric acid, boric acid, silicic acid; The mol ratio of orthophosphoric acid, boric acid and silicic acid counts 1:1.2:2 with P:B:Si.
S3, the mixture after shaping is carried out drying process; In the present embodiment, baking temperature is 120 DEG C, and drying time is 8h.
S4, carry out roasting, after cooling, obtain the unformed magnesia alumina spinel carrier of porous; Sintering temperature is 500 DEG C, and roasting time is 12h.
S5, the aqueous solution of copper predecessor and/or nickel predecessor and magnesia alumina spinel carrier incipient impregnation are left standstill 5h, then by sample in 110 DEG C of dry 6h, 400 DEG C of roasting 4h, obtained support type dearsenic catalyst.
Embodiment 7
The present embodiment provides a kind of supported dearsenic agent, comprises carrier and the active component of load on carrier; Carrier is the unformed magnesium aluminate spinel of porous, and active component is CuO and NiO; The specific area of magnesium aluminate spinel is 152.5m 2/ g.
Preferably, calculate with metal oxide weight, active component accounts for the 20wt% of the percentage composition of carrier, and wherein, CuO is 15wt%, NiO is 5wt%.
The preparation method of supported dearsenic agent, comprises the steps:
S1, kneading is carried out in magnesium source and aluminium source and acidic aqueous solution, the mol ratio in aluminium source and magnesium source presses MgO/Al 2o 3count 1:2, acidic aqueous solution is aqueous solution of nitric acid, concentration 2mol/L;
In the present embodiment, aluminium source is boehmite, and magnesium source is lightweight basic magnesium carbonate.
S2, in the mixture after kneading, add the inorganic additive of the 0.5wt% of amount of the mixture, carry out shaping after mixing, inorganic additive is at least one in orthophosphoric acid, boric acid, silicic acid;
In the present embodiment, inorganic additive comprises orthophosphoric acid.
S3, the mixture after shaping is carried out drying process; In the present embodiment, baking temperature is 80 DEG C, and drying time is 8h.
S4, carry out roasting, after cooling, obtain the unformed magnesia alumina spinel carrier of porous; Sintering temperature is 400 DEG C, and roasting time is 15h.
S5, the aqueous solution of copper predecessor and/or nickel predecessor and magnesia alumina spinel carrier incipient impregnation are left standstill 5h, then by sample in 120 DEG C of dry 6h, 500 DEG C of roasting 4h, obtained support type dearsenic catalyst.
Embodiment 8
The present embodiment provides a kind of supported dearsenic agent, comprises carrier and the active component of load on carrier; Carrier is the unformed magnesium aluminate spinel of porous, and active component is CuO and NiO; The specific area of magnesium aluminate spinel is 198.7m 2/ g.
Preferably, calculate with metal oxide weight, active component accounts for the 22wt% of the percentage composition of carrier, and wherein, CuO is 12wt%, NiO is 10wt%.
The preparation method of supported dearsenic agent, comprises the steps:
S1, kneading is carried out in magnesium source and aluminium source and acidic aqueous solution, the mol ratio in aluminium source and magnesium source presses MgO/Al 2o 3count 1:2, acidic aqueous solution is aqueous solution of nitric acid, concentration 2mol/L;
In the present embodiment, aluminium source is Al 2o 33H 2o, magnesium source is lightweight Mg (OH) 2.
S2, in the mixture after kneading, add the inorganic additive of the 0.5wt% of amount of the mixture, carry out shaping after mixing, inorganic additive is at least one in orthophosphoric acid, boric acid, silicic acid;
In the present embodiment, inorganic additive comprises orthophosphoric acid, boric acid, silicic acid; The mol ratio of orthophosphoric acid, boric acid and silicic acid counts 1:1.1:1 with P:B:Si.
S3, the mixture after shaping is carried out drying process; In the present embodiment, baking temperature is 100 DEG C, and drying time is 4h.
S4, carry out roasting, after cooling, obtain the unformed magnesia alumina spinel carrier of porous; Sintering temperature is 600 DEG C, and roasting time is 0.5h.
S5, the aqueous solution of copper predecessor and/or nickel predecessor and magnesia alumina spinel carrier incipient impregnation are left standstill 6h, then by sample in 110 DEG C of dry 8h, 450 DEG C of roasting 4.5h, obtained support type dearsenic catalyst.
Embodiment 9
The present embodiment provides a kind of supported dearsenic agent, comprises carrier and the active component of load on carrier; Carrier is the unformed magnesium aluminate spinel of porous, and active component is NiO; The specific area of magnesium aluminate spinel is 174.4m 2/ g.
Preferably, with NiO Weight computation, the percentage composition that active component accounts for carrier is 5wt%.
The preparation method of supported dearsenic agent, comprises the steps:
S1, kneading is carried out in magnesium source and aluminium source and acidic aqueous solution, the mol ratio in aluminium source and magnesium source presses MgO/Al 2o 3count 1:2, acidic aqueous solution is aqueous solution of nitric acid, concentration 2mol/L;
In the present embodiment, aluminium source is Al 2o 3powder, magnesium source is light MgO.
S2, in the mixture after kneading, add the inorganic additive of the 0.5wt% of amount of the mixture, carry out shaping after mixing, inorganic additive is at least one in orthophosphoric acid, boric acid, silicic acid;
In the present embodiment, inorganic additive comprises orthophosphoric acid, boric acid, silicic acid; The mol ratio of orthophosphoric acid, boric acid and silicic acid counts 1:1:0.8 with P:B:Si.
S3, the mixture after shaping is carried out drying process; In the present embodiment, baking temperature is 120 DEG C, and drying time is 0.5h.
S4, carry out roasting, after cooling, obtain the unformed magnesia alumina spinel carrier of porous; Sintering temperature is 500 DEG C, and roasting time is 12h.
S5, the aqueous solution of copper predecessor and/or nickel predecessor and magnesia alumina spinel carrier incipient impregnation are left standstill 7h, then by sample in 115 DEG C of dry 7h, 500 DEG C of roasting 4h, obtained support type dearsenic catalyst.
Embodiment 10
The present embodiment provides a kind of supported dearsenic agent, comprises carrier and the active component of load on carrier; Carrier is the unformed magnesium aluminate spinel of porous, and active component is CuO and NiO; The specific area of magnesium aluminate spinel is 100.0m 2/ g.
Preferably, calculate with metal oxide weight, active component accounts for the 20wt% of the percentage composition of carrier, and wherein, CuO is 12wt%, NiO is 8wt%.The preparation method of supported dearsenic agent, comprises the steps:
S1, kneading is carried out in magnesium source and aluminium source and acidic aqueous solution, the mol ratio in aluminium source and magnesium source presses MgO/Al 2o 3count 1:2, acidic aqueous solution is aqueous solution of nitric acid, concentration 2mol/L;
In the present embodiment, aluminium source is aluminum nitrate, and magnesium source is light MgO.
S2, in the mixture after kneading, add the inorganic additive of the 0.5wt% of amount of the mixture, carry out shaping after mixing, inorganic additive is at least one in orthophosphoric acid, boric acid, silicic acid;
In the present embodiment, inorganic additive comprises boric acid, silicic acid.
S3, the mixture after shaping is carried out drying process; In the present embodiment, baking temperature is 100 DEG C, and drying time is 6h.
S4, carry out roasting, after cooling, obtain the unformed magnesia alumina spinel carrier of porous; Sintering temperature is 600 DEG C, and roasting time is 1h.
S5, the aqueous solution of copper predecessor and/or nickel predecessor and magnesia alumina spinel carrier incipient impregnation are left standstill 5h, then by sample in 115 DEG C of dry 7h, 400 DEG C of roasting 5h, obtained support type dearsenic catalyst.
Embodiment 11
The present embodiment provides a kind of supported dearsenic agent, comprises carrier and the active component of load on carrier; Carrier is the unformed magnesium aluminate spinel of porous, and active component is CuO; The specific area of magnesium aluminate spinel is 179.8m 2/ g.
Preferably, with CuO Weight computation, the percentage composition that active component accounts for carrier is 30wt%.
The preparation method of supported dearsenic agent, comprises the steps:
S1, kneading is carried out in magnesium source and aluminium source and acidic aqueous solution, the mol ratio in aluminium source and magnesium source presses MgO/Al 2o 3count 1:2, acidic aqueous solution is aqueous solution of nitric acid, concentration 2mol/L;
In the present embodiment, aluminium source is boehmite, and magnesium source is Mg (OH) 2.
S2, in the mixture after kneading, add the inorganic additive of the 0.5wt% of amount of the mixture, carry out shaping after mixing, inorganic additive is at least one in orthophosphoric acid, boric acid, silicic acid;
In the present embodiment, inorganic additive comprises orthophosphoric acid, boric acid, silicic acid; The mol ratio of orthophosphoric acid, boric acid and silicic acid counts 1:1.1:1 with P:B:Si.
S3, the mixture after shaping is carried out drying process; In the present embodiment, baking temperature is 120 DEG C, and drying time is 8h.
S4, carry out roasting, after cooling, obtain the unformed magnesia alumina spinel carrier of porous; Sintering temperature is 400 DEG C, and roasting time is 14h.
S5, the aqueous solution of copper predecessor and/or nickel predecessor and magnesia alumina spinel carrier incipient impregnation are left standstill 6h, then by sample in 120 DEG C of dry 6h, 450 DEG C of roasting 4.5h, obtained support type dearsenic catalyst.
Embodiment 12
The present embodiment provides a kind of supported dearsenic agent, comprises carrier and the active component of load on carrier; Carrier is the unformed magnesium aluminate spinel of porous, and active component is CuO; The specific area of magnesium aluminate spinel is 300.0m 2/ g.
Preferably, with CuO Weight computation, the percentage composition that active component accounts for carrier is 10wt%.
The preparation method of supported dearsenic agent, comprises the steps:
S1, kneading is carried out in magnesium source and aluminium source and acidic aqueous solution, the mol ratio in aluminium source and magnesium source presses MgO/Al 2o 3count 1:2, acidic aqueous solution is aqueous solution of nitric acid, concentration 2mol/L;
In the present embodiment, aluminium source is Al 2o 3powder, magnesium source is light MgO.
S2, in the mixture after kneading, add the inorganic additive of the 0.5wt% of amount of the mixture, carry out shaping after mixing, inorganic additive is at least one in orthophosphoric acid, boric acid, silicic acid;
In the present embodiment, inorganic additive is silicic acid.
S3, the mixture after shaping is carried out drying process; In the present embodiment, baking temperature is 120 DEG C, and drying time is 8h.
S4, carry out roasting, after cooling, obtain the unformed magnesia alumina spinel carrier of porous; Sintering temperature is 500 DEG C, and roasting time is 12h.
S5, the aqueous solution of copper predecessor and/or nickel predecessor and magnesia alumina spinel carrier incipient impregnation are left standstill 6h, then by sample in 110 DEG C of dry 6h, 500 DEG C of roasting 4h, obtained support type dearsenic catalyst.
Experimental example 1
Test the intensity of support type dearsenic catalyst obtained in embodiment 1-6, pore volume, aperture and specific area, test result is as shown in the table:
Experimental example 2
The activity of the 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 composition (wt%): H 213%, CO17%, CO 29.0%, H 2o60%, HCl30ppm, H 2s1000ppm, As0.22ppm, acquired results is as follows:
Catalyst Import arsenic content (ppm) Outlet 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, the support type dearsenic catalyst that the embodiment of the present invention prepares has significant dearsenification effect, and in embodiment 6, the arsenic of support type dearsenic catalyst holds up to more than 15wt%; Arsenic-removing rate is up to 99%.Illustrate and use the support type dearsenic catalyst in the embodiment of the present invention to have higher dearsenification activity.For the operating condition of actual production, carry out temperature and air speed test, 250-350 DEG C of temperature range, air speed 3000-5000h -1, pressure: 5.0 ~ 6.0MPa, steam-to-gas ratio is 1.0 ~ 1.8, and dearsenification and conversion side reaction all can meet the manufacturing technique requirent of factory.
Experimental example 3
As shown in Figure 1, the support type dearsenic catalyst described in embodiment 6 is in the running (temperature: 250 DEG C, pressure: 5.0MPa, the air speed: 3000h that reach 2400 hours -1, steam-to-gas ratio: 1.5, unstripped gas composition (wt%): H 213%, CO17%, CO 29.0%, H 2o60%, HCl30ppm, H 2s1000ppm, As0.22ppm) in process, arsenic-removing rate still can reach more than 98.8%, and not only Hydrodearsenic Catalyst stability is better, and can keep higher dearsenification activity.
Obviously, above-described embodiment is only for clearly example being described, and the restriction not to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.And thus the apparent change of extending out or variation be still among protection scope of the present invention.

Claims (10)

1. a supported dearsenic agent, comprises carrier and load active component on the carrier; It is characterized in that, described carrier is the unformed magnesium aluminate spinel of porous, and described active component is CuO and/or NiO.
2. supported dearsenic agent according to claim 1, is characterized in that, the specific area 100m of described magnesium aluminate spinel 2/ g ~ 300m 2/ g.
3. supported dearsenic agent according to claim 1 and 2, is characterized in that, calculate with metal oxide weight, the percentage composition that described active component accounts for described carrier is 5wt% ~ 30wt%.
4. the supported dearsenic agent according to any one of claim 1-3, is characterized in that, calculate with metal oxide weight, the percentage composition that described active component accounts for described carrier is 10wt% ~ 20wt%.
5. the supported dearsenic agent according to any one of claim 1-4, it is characterized in that, described active component is CuO and NiO, and the percentage composition that described CuO accounts for described carrier is 10wt% ~ 15wt%, and the percentage composition that described NiO accounts for described carrier is 5wt% ~ 10wt%.
6. a preparation method for the supported dearsenic agent described in any one of claim 1-5, is characterized in that, comprises the steps:
S1, kneading is carried out in magnesium source and aluminium source and acidic aqueous solution, the mol ratio in described aluminium source and described magnesium source presses MgO/Al 2o 3count 1:2, described acidic aqueous solution is aqueous solution of nitric acid, concentration 2mol/L;
S2, in the mixture after kneading, add the inorganic additive of the 0.5wt% of amount of the mixture, carry out shaping after mixing, described inorganic additive is at least one in orthophosphoric acid, boric acid, silicic acid;
S3, the mixture after shaping is carried out drying process;
S4, carry out roasting, after cooling, obtain the unformed magnesia alumina spinel carrier of porous;
S5, the aqueous solution of copper predecessor and/or nickel predecessor and described magnesia alumina spinel carrier incipient impregnation are left standstill 5 ~ 7h, then by sample in 110 DEG C ~ 120 DEG C drying 6 ~ 8h, 400 DEG C ~ 500 DEG C roasting 4 ~ 5h, obtained described support type dearsenic catalyst.
7. the preparation method of supported dearsenic agent according to claim 6, is characterized in that, in described step S1, described aluminium source is boehmite, Al 2o 3powder, Al 2o 3h 2o, Al 2o 33H 2at least one in O, aluminum nitrate, described magnesium source is lightweight basic magnesium carbonate, Mg (OH) 2, at least one in light MgO.
8. the preparation method of the supported dearsenic agent according to claim 6 or 7, is characterized in that, in described step S2, described inorganic additive comprises orthophosphoric acid, boric acid, silicic acid; The mol ratio of described orthophosphoric acid, boric acid and silicic acid counts 1:1 ~ 1.2:0.8 ~ 2 with P:B:Si.
9. the preparation method of the supported dearsenic agent according to any one of claim 6-8, is characterized in that, in described step S3, baking temperature is 80 DEG C ~ 120 DEG C, and drying time is 0.5h-8h.
10. the preparation method of the supported dearsenic agent according to any one of claim 6-9, is characterized in that, in described step S4, described sintering temperature is 400 DEG C-600 DEG C, and roasting time is 0.5h-15h.
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