CN106000280A - Dearsenication agent, and preparation method and application thereof - Google Patents
Dearsenication agent, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a dearsenication agent, and a preparation method and an application thereof. The dearsenication agent includes a carrier and an active component loaded on the carrier; the carrier is magnesium aluminum spinel; and the active component includes NiMn2O4 spinel. The preparation method of the dearsenication agent includes the following steps: carrying out isopyknic impregnation standing on an aqueous solution of a nickel precursor and a manganese precursor and the magnesium aluminate spinel for 4-8h to obtain a sample; drying the sample at 120-140DEG C for 4-8h; and roasting the dried sample at 350-550DEG C environment for 2-6h to prepare the dearsenication agent. The dearsenication agent has good stability and high arsenic capacity, and can be used in dearsenication treatment of coal-to-syngas under high-pressure, high-temperature, high-steam/gas ratio and high-CO concentration conditions with low-degree water-gas shift side reaction and other side reactions, such as methanation and Fischer-Tropsch synthesis.
Description
Technical field
The present invention relates to coal chemical technology, be specifically related to a kind of Hydrodearsenic Catalyst and preparation method and application.
Background technology
Coal is the valuable source of China, producing synthesis gas from coal technology be coal resource main Land use systems it
One.Generally, coal first adds through various gasification technologies, such as water coal slurry pressurized gasification technology, fine coal
After the pressure gasification such as gasification technology and fixed bed pressured gasification technology, then purify through catalyst and be catalyzed,
After regulation H/C, obtain producing synthesis gas from coal.These synthesis gas can synthesize follow-up various products, as
Ammonia, methanol, hydrogen, oil and ethylene glycol etc..
The gas composition that above-mentioned gasification technology obtains is extremely complex, except having high pressure, high concentration H2S
And outside the feature of high steam-to-gas ratio and high concentration CO, meanwhile, also produce trace O2、AsH3、HCN、
Other impurity such as heavy metal, these impurity are required for removing or convert.And the removing of arsenide therein
Most important, because follow-up various catalyst, such as water gas converting catalyst etc. to arsenide very
Sensitivity, the arsenide of tens ppb (parts per billion) just can cause catalyst poisoning quickly to be lost
Live, affect the properly functioning of device.So, producing synthesis gas from coal is before the use, it is necessary to carry out it
Dearsenization processes.
At present, conventional dearsenization is for carry out dearsenization process at supported on carriers active component.As, carry
Body can select activated carbon, porous unformed magnalium crystallization stone etc., and active component can select metal oxygen
Compound etc..Chinese patent literature CN105536689A discloses a kind of supported dearsenic agent and preparation thereof
Method.This supported dearsenic agent with porous unformed magnalium crystallization stone as carrier, CuO and/or NiO be
Active component.This supported dearsenic agent has the advantage that adsorption capacity is big, arsenic-removing rate is big, stability is high.
But, there is following distinguishing feature in technical scheme disclosed in above-mentioned patent documentation: 1) activity
Component, particularly CuO, itself can be used as the catalyst of water gas shift reaction, in dearsenization process
In be easily caused producing synthesis gas from coal generation Water gas shift/WGS side reaction and other side reactions such as methanation, expense
Torr synthesis etc.；2) porous unformed magnalium crystallization stone character is unstable, and unformed form is easily by extraneous (special
It is not high pressure, high temperature, high steam-to-gas ratio, high concentration CO) impact, cause its performance change, Jin Erhui
The generation of the Water gas shift/WGS side reaction of producing synthesis gas from coal during aggravation dearsenization.
Summary of the invention
It is that Hydrodearsenic Catalyst is easily caused producing synthesis gas from coal during dearsenization and sends out to this end, to be solved by this invention
Unboiled water gas conversion side reaction and other side reactions such as problem such as methanation, F-T synthesis, thus carry
For during a kind of dearsenization, Water gas shift/WGS side reaction is low, adsorption capacity big, dearsenization precision is good, dearsenization
Hydrodearsenic Catalyst that rate is high, stability is high and preparation method thereof.
For solving above-mentioned technical problem, the technical solution used in the present invention is as follows:
Hydrodearsenic Catalyst provided by the present invention, including carrier and load active component on the carrier；
Described carrier is magnesium aluminate spinel；Described active component includes NiMn2O4Spinelle.
The specific surface area of described magnesium aluminate spinel is 150m2/ g～280m2/g；The knot of described magnesium aluminate spinel
Crystalline substance degree is 85～95%.
Described active component is (4.5～30) with the mass ratio of described carrier: 100.
Further, described active component is (5～22) with the mass ratio of described carrier: 100.
Described active component also includes NiO and/or MnO2；Described NiO and the mass ratio of described carrier
For (5～15): 100；Described MnO2It is (5～15) with the mass ratio of described carrier: 100.
Present invention also offers the preparation method of above-mentioned Hydrodearsenic Catalyst, comprise the steps:
The aqueous solution of nickel predecessor and manganese predecessor is stood with described magnesium aluminate spinel incipient impregnation
4～8h, obtain sample；
Described sample is dried at 120 DEG C～140 DEG C 4～8h again；
Dried described sample is placed in roasting 2～6h under 350 DEG C～550 DEG C of environment, prepares described de-
Arsenical.
The preparation method of described magnesium aluminate spinel, comprises the steps:
S1, magnesium source and aluminum source and acidic aqueous solution are carried out kneading, wherein, source of aluminium and described magnesium
The mol ratio in source presses MgO/Al2O3Being calculated as (0.8～1.2): (1.5～2), described acidic aqueous solution is
Aqueous solution of nitric acid and/or aqueous acetic acid, the molar concentration of described acidic aqueous solution is 1mol/L-3
mol/L；
S2, by the mixture after kneading and additive in mass ratio for (0.64～1.2): 125 mix equal
Being shaped after even, wherein, described additive is at least one in oxalic acid, citric acid, silicic acid；
S3, the mixture after molding is dried, roasting, obtain described magnesium aluminate spinel after cooling.
In described step S1, source of aluminium is Al2O3·H2O, boehmite, Al2O3·3H2O、
Aluminum nitrate, Al2O3At least one in powder；
Described magnesium source is MgO, Mg (OH)2, at least one in basic magnesium carbonate；
In described step S2, described additive is oxalic acid, citric acid and silicic acid, wherein, described oxalic acid,
Described citric acid, the mol ratio of described silicic acid are 1:(0.8～1.2): (0.8～2).
The temperature of described drying steps is 70 DEG C～130 DEG C, and the time is 2h-10h；
The temperature of described calcination steps is 550 DEG C-650 DEG C, and roasting time is 2h-8h.
It addition, present invention also offers the application in producing synthesis gas from coal dearsenicating technology of the above-mentioned Hydrodearsenic Catalyst,
The reaction condition of described producing synthesis gas from coal dearsenicating technology is as follows: temperature is 250-300 DEG C, pressure: 4.0
～6.0MPa, steam-to-gas ratio be 1.0～1.8, CO content is 40-50wt% in producing synthesis gas from coal.
Compared with prior art, there is advantages that
1) Hydrodearsenic Catalyst that the embodiment of the present invention is provided, is carrier by selecting magnesium aluminate spinel, and will
It is carried on NiMn thereon2O4Spinelle is as active component.The magnesium aluminate spinel of high-crystallinity is not only
Abundant duct can be provided, and have under the conditions of high pressure, high temperature, high steam-to-gas ratio and high concentration CO
There is higher stability, producing synthesis gas from coal carries out dearsenization process, will not undergo phase transition, be hydrated instead
Answer and other reactions, thus ensure that the stability that dearsenization is reacted.And active component NiMn2O4Point
Spar is inert to the catalysis characteristics of Water gas shift/WGS side reaction, and Stability Analysis of Structures, arsenic hold height.Select
Magnesium aluminate spinel and NiMn2O4Spinelle respectively as carrier and active component, both crystal structure phases
With, not only conjugation is high so that active component can effectively participate in dearsenization reaction；And stability is strong,
Effectively reduce the generation of side reaction and other side reactions making Water gas shift/WGS, it is ensured that dearsenization is imitated
Really.
2) Hydrodearsenic Catalyst that the embodiment of the present invention is provided, by selecting magnesium aluminate spinel and NiMn2O4
Spinelle, in the face of the H of producing synthesis gas from coal middle and high concentration2During S, NiMn2O4Will not be by H2S vulcanizes
And lose activity, sulfur tolerance is good.
3) Hydrodearsenic Catalyst that the embodiment of the present invention is provided, uses NiMn2O4As active component, pass through
Infusion process synthesizes, and production technology is simple, and specific surface area is relatively big, and active metal component good dispersion is logical
Cross and control the ratio of above-mentioned active component and can obtain that there is the Hydrodearsenic Catalyst held more than 15wt% arsenic, and can
To realize the degree of depth dearsenization of coal synthesis gas, efficiency is up to more than 99%.
4) Hydrodearsenic Catalyst that the embodiment of the present invention is provided, simulation producing synthesis gas from coal be CO 45wt%,
CO2Wt 5.0%, H2S 1000ppm, As 0.23ppm, remaining be H2Under conditions of, in temperature
Be 300 DEG C, pressure be 4.0MPa, air speed be 3000h-1, under conditions of steam-to-gas ratio is 1.5, will be de-
Arsenical processes for the dearsenization simulating producing synthesis gas from coal, through test, Water gas shift/WGS side reaction activity
(% in terms of CO conversion ratio) is less than 6%, and arsenic-removing rate remains to up to more than 98.8%.
5) preparation method of the Hydrodearsenic Catalyst that the embodiment of the present invention is provided, by by before nickel predecessor and manganese
The aqueous solution driving thing stands 4～8h with described magnesium aluminate spinel incipient impregnation, then by the sample after dipping
In 120 DEG C～140 DEG C dry 4～8h, 350 DEG C～550 DEG C of roastings 2～6h, prepare described Hydrodearsenic Catalyst.Logical
Crossing dipping makes nickel predecessor and manganese predecessor be well dispersed in magnesia alumina spinel carrier, then through roasting
Make NiO and MnO2It is converted into NiMn2O4Spinelle, production technology is simple, production cost is low.
Detailed description of the invention
In order to the object, technical solutions and advantages of the present invention are better described, below in conjunction with concrete real
Execute example the present invention is described further.The present invention can be embodied in many different forms, and should not
This is considered limited to embodiment set forth herein.On the contrary, it is provided that these embodiments so that the disclosure
To 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
Present embodiments provide a kind of Hydrodearsenic Catalyst and preparation method thereof.This Hydrodearsenic Catalyst is by carrier and load
Active component on carrier；Carrier be specific surface area be 173.2m2/ g, degree of crystallinity are the magnalium of 88%
Spinelle, active component is NiMn2O4Spinelle, active component is 12:100 with the mass ratio of carrier.
The preparation method of the Hydrodearsenic Catalyst described in the present embodiment, comprises the steps:
S1, by magnesium source-light MgO, aluminum source-Al2O3·3H2O and acidic aqueous solution carry out kneading, aluminum
The mol ratio in source and magnesium source presses MgO/Al2O3Being calculated as 1:2, acidic aqueous solution is aqueous solution of nitric acid, dense
Degree 2mol/L；
S2, mixture after kneading add inorganic additive, it is ensured that the mixture after kneading and nothing
The mass ratio of machine additive is 1:125, is shaped after mix homogeneously, and wherein, inorganic additive is
Mol ratio is the mixed liquor of the oxalic acid of 1:1.2:2, citric acid and silicic acid；
S3, by the mixture after molding at 120 DEG C be dried 6h；
S4, by dried mixture roasting 6h at 600 DEG C, obtaining specific surface area is 173.2m2/g、
Degree of crystallinity is the magnesium aluminate spinel of 88%；
S5, by quiet with magnesia alumina spinel carrier incipient impregnation for the aqueous solution of nickel predecessor and manganese predecessor
Put 6h, then the sample after dipping is dried 6h, 400 DEG C of roasting 4h at 120 DEG C, prepare Hydrodearsenic Catalyst.
Embodiment 2
Present embodiments provide a kind of Hydrodearsenic Catalyst and preparation method thereof.This Hydrodearsenic Catalyst is by carrier and load
Active component on carrier；Carrier be specific surface area be 158.9m2/ g, degree of crystallinity are the magnalium of 86%
Spinelle, active component is NiMn2O4Spinelle, active component is 12:100 with the mass ratio of carrier.
The preparation method of the Hydrodearsenic Catalyst described in the present embodiment, comprises the steps:
S1, magnesium source-lightweight basic magnesium carbonate, aluminum source-boehmite and acidic aqueous solution are carried out kneading,
The mol ratio in aluminum source and magnesium source presses MgO/Al2O3Being calculated as 0.8:2, acidic aqueous solution is aqueous solution of nitric acid,
Concentration 2mol/L；
S2, mixture after kneading add inorganic additive, it is ensured that the mixture after kneading and nothing
The mass ratio of machine additive is 0.64:125, is shaped after mix homogeneously, wherein, and inorganic additive
For the mixed liquor that mol ratio is the oxalic acid of 1:1.0:2, citric acid and silicic acid；
S3, by the mixture after molding at 110 DEG C be dried 6h；
S4, by dried mixture roasting 8h at 550 DEG C, obtaining specific surface area is 158.9m2/g、
Degree of crystallinity is the magnesium aluminate spinel of 86%；
S5, by quiet with magnesia alumina spinel carrier incipient impregnation for the aqueous solution of nickel predecessor and manganese predecessor
Put 7h, then the sample after dipping is dried 4h, 500 DEG C of roasting 5h at 120 DEG C, prepare Hydrodearsenic Catalyst.
Embodiment 3
Present embodiments provide a kind of Hydrodearsenic Catalyst and preparation method thereof.This Hydrodearsenic Catalyst is by carrier and load
Active component on carrier；Carrier be specific surface area be 171.1m2/ g, degree of crystallinity are the magnalium of 90%
Spinelle, active component is NiMn2O4Spinelle, active component is 12:100 with the mass ratio of carrier.
The preparation method of the Hydrodearsenic Catalyst described in the present embodiment, comprises the steps:
S1, by magnesium source-light MgO, aluminum source-Al2O3·H2O and acidic aqueous solution carry out kneading, aluminum
The mol ratio in source and magnesium source presses MgO/Al2O3Being calculated as 1.2:1.5, acidic aqueous solution is aqueous solution of nitric acid,
Concentration 2mol/L；
S2, mixture after kneading add inorganic additive, it is ensured that the mixture after kneading and nothing
The mass ratio of machine additive is 1.2:125, is shaped after mix homogeneously, wherein, and inorganic additive
For the mixed liquor that mol ratio is the oxalic acid of 1:1.0:1.5, citric acid and silicic acid；
S3, by the mixture after molding at 80 DEG C be dried 8h；
S4, by dried mixture roasting 6h at 650 DEG C, obtaining specific surface area is 171.1m2/g、
Degree of crystallinity is the magnesium aluminate spinel of 90%；
S5, by quiet with magnesia alumina spinel carrier incipient impregnation for the aqueous solution of nickel predecessor and manganese predecessor
Put 4h, then the sample after dipping is dried 6h, 400 DEG C of roasting 4h at 120 DEG C, prepare Hydrodearsenic Catalyst.
Embodiment 4
Present embodiments provide a kind of Hydrodearsenic Catalyst and preparation method thereof.This Hydrodearsenic Catalyst is by carrier and load
Active component on carrier；Carrier be specific surface area be 169.7m2/ g, degree of crystallinity are the magnalium of 85%
Spinelle, active component is NiMn2O4Spinelle, active component is 15:100 with the mass ratio of carrier.
The preparation method of the Hydrodearsenic Catalyst described in the present embodiment, comprises the steps:
S1, by magnesium source-Mg (OH)2, aluminum source-boehmite and acidic aqueous solution carry out kneading, aluminum source
MgO/Al is pressed with the mol ratio in magnesium source2O3Being calculated as 1:2, acidic aqueous solution is aqueous solution of nitric acid, concentration
2mol/L；
S2, mixture after kneading add inorganic additive, it is ensured that the mixture after kneading and nothing
The mass ratio of machine additive is 1:125, is shaped after mix homogeneously, and wherein, inorganic additive is
Mol ratio is the mixed liquor of the oxalic acid of 1:1.2:2, citric acid and silicic acid；
S3, by the mixture after molding at 100 DEG C be dried 4h；
S4, by dried mixture roasting 5h at 600 DEG C, obtaining specific surface area is 169.7m2/g、
Degree of crystallinity is the magnesium aluminate spinel of 85%；
S5, by quiet with magnesia alumina spinel carrier incipient impregnation for the aqueous solution of nickel predecessor and manganese predecessor
Put 5h, then the sample after dipping is dried 6h, 550 DEG C of roasting 4h at 140 DEG C, prepare Hydrodearsenic Catalyst.
Embodiment 5
Present embodiments provide a kind of Hydrodearsenic Catalyst and preparation method thereof.This Hydrodearsenic Catalyst is by carrier and load
Active component on carrier；Carrier be specific surface area be 158.8m2/ g, degree of crystallinity are the magnalium of 88%
Spinelle, active component is NiMn2O4Spinelle, active component is 20:100 with the mass ratio of carrier.
The preparation method of the Hydrodearsenic Catalyst described in the present embodiment, comprises the steps:
S1, by magnesium source-light MgO, aluminum source-Al2O3·3H2O and acidic aqueous solution carry out kneading,
The mol ratio in aluminum source and magnesium source presses MgO/Al2O3Being calculated as 1:2, acidic aqueous solution is aqueous solution of nitric acid,
Concentration 2mol/L；
S2, mixture after kneading add inorganic additive, it is ensured that the mixture after kneading and nothing
The mass ratio of machine additive is 1:125, is shaped after mix homogeneously, and wherein, inorganic additive is
Mol ratio is the mixed liquor of the oxalic acid of 1:1.0:2, citric acid and silicic acid；
S3, by the mixture after molding at 100 DEG C be dried 6h；
S4, by dried mixture roasting 8h at 550 DEG C, obtaining specific surface area is 158.8m2/g、
Degree of crystallinity is the magnesium aluminate spinel of 88%；
S5, by quiet with magnesia alumina spinel carrier incipient impregnation for the aqueous solution of nickel predecessor and manganese predecessor
Put 6h, then the sample after dipping is dried 6h, 450 DEG C of roasting 4h at 120 DEG C, prepare Hydrodearsenic Catalyst.
Embodiment 6
Present embodiments provide a kind of Hydrodearsenic Catalyst and preparation method thereof.This Hydrodearsenic Catalyst is by carrier and load
Active component on carrier；Carrier be specific surface area be 157.9m2/ g, degree of crystallinity are the magnalium of 92%
Spinelle, active component is NiMn2O4Spinelle, active component is 15:100 with the mass ratio of carrier.
The preparation method of the Hydrodearsenic Catalyst described in the present embodiment, comprises the steps:
S1, magnesium source-light MgO, aluminum source-boehmite and acidic aqueous solution are carried out kneading, aluminum
The mol ratio in source and magnesium source presses MgO/Al2O3Being calculated as 1:2, acidic aqueous solution is aqueous solution of nitric acid, dense
Degree 2mol/L；
S2, mixture after kneading add inorganic additive, it is ensured that the mixture after kneading and nothing
The mass ratio of machine additive is 1:125, is shaped after mix homogeneously, and wherein, inorganic additive is
Mol ratio is the mixed liquor of the oxalic acid of 1:1.2:2, citric acid and silicic acid；
S3, by the mixture after molding at 120 DEG C be dried 6h；
S4, by dried mixture roasting 8h at 600 DEG C, obtaining specific surface area is 157.9m2/g、
Degree of crystallinity is the magnesium aluminate spinel of 92%；
S5, by quiet with magnesia alumina spinel carrier incipient impregnation for the aqueous solution of nickel predecessor and manganese predecessor
Put 5h, then the sample after dipping is dried 6h, 500 DEG C of roasting 4h at 120 DEG C, prepare Hydrodearsenic Catalyst.
Embodiment 7
Present embodiments provide a kind of Hydrodearsenic Catalyst and preparation method thereof.This Hydrodearsenic Catalyst is by carrier and load
Active component on carrier；Carrier be specific surface area be 200m2/ g, degree of crystallinity are the magnalium point of 89%
Spar, active component is NiMn2O4Spinelle, active component is 20:100 with the mass ratio of carrier.
The preparation method of the Hydrodearsenic Catalyst described in the present embodiment, comprises the steps:
S1, by magnesium source-Mg (OH)2, aluminum source-Al2O3Powder and acidic aqueous solution carry out kneading, aluminum source and
The mol ratio in magnesium source presses MgO/Al2O3Being calculated as 1:2, acidic aqueous solution is aqueous solution of nitric acid, concentration 2
mol/L；
S2, mixture after kneading add inorganic additive, it is ensured that the mixture after kneading and nothing
The mass ratio of machine additive is 1:125, is shaped after mix homogeneously, and wherein, inorganic additive is
Mol ratio is the mixed liquor of the oxalic acid of 1:0.8:0.8, citric acid and silicic acid；
S3, by the mixture after molding at 130 DEG C be dried 2h；
S4, by dried mixture roasting 2h at 650 DEG C, obtaining specific surface area is 200m2/g、
Degree of crystallinity is the magnesium aluminate spinel of 89%；
S5, by quiet with magnesia alumina spinel carrier incipient impregnation for the aqueous solution of nickel predecessor and manganese predecessor
Put 8h, then the sample after dipping is dried 8h, 350 DEG C of roasting 6h at 130 DEG C, prepare Hydrodearsenic Catalyst.
Embodiment 8
Present embodiments provide a kind of Hydrodearsenic Catalyst and preparation method thereof.This Hydrodearsenic Catalyst is by carrier and load
Active component on carrier；Carrier be specific surface area be 280m2/ g, degree of crystallinity are the magnalium point of 91%
Spar, active component is NiMn2O4Spinelle, active component is 30:100 with the mass ratio of carrier.
The preparation method of the Hydrodearsenic Catalyst described in the present embodiment, comprises the steps:
S1, by magnesium source-Mg (OH)2, aluminum source-Al2O3Powder and acidic aqueous solution carry out kneading, aluminum source and
The mol ratio in magnesium source presses MgO/Al2O3Being calculated as 1:2, acidic aqueous solution is aqueous solution of nitric acid, concentration 3
mol/L；
S2, mixture after kneading add inorganic additive, it is ensured that the mixture after kneading and nothing
The mass ratio of machine additive is 1:125, is shaped after mix homogeneously, and wherein, inorganic additive is
Mol ratio is the mixed liquor of the oxalic acid of 1:0.8:1, citric acid and silicic acid；
S3, by the mixture after molding at 70 DEG C be dried 10h；
S4, by dried mixture roasting 5h at 580 DEG C, obtaining specific surface area is 280m2/g、
Degree of crystallinity is the magnesium aluminate spinel of 91%；
S5, by quiet with magnesia alumina spinel carrier incipient impregnation for the aqueous solution of nickel predecessor and manganese predecessor
Put 6h, then the sample after dipping is dried 6h, 500 DEG C of roasting 4h at 125 DEG C, prepare Hydrodearsenic Catalyst.
Embodiment 9
Present embodiments provide a kind of Hydrodearsenic Catalyst and preparation method thereof.This Hydrodearsenic Catalyst is by carrier and load
Active component on carrier；Carrier be specific surface area be 230m2/ g, degree of crystallinity are the magnalium point of 93%
Spar, active component is NiMn2O4Spinelle, active component is 5:100 with the mass ratio of carrier.
The preparation method of the Hydrodearsenic Catalyst described in the present embodiment, comprises the steps:
S1, by magnesium source-Mg (OH)2, aluminum source-Al2O3Powder and acidic aqueous solution carry out kneading, aluminum source and
The mol ratio in magnesium source presses MgO/Al2O3Being calculated as 1:2, acidic aqueous solution is aqueous solution of nitric acid, concentration 1
mol/L；
S2, mixture after kneading add inorganic additive, it is ensured that the mixture after kneading and nothing
The mass ratio of machine additive is 1:125, is shaped after mix homogeneously, and wherein, inorganic additive is
Mol ratio is the mixed liquor of the oxalic acid of 1:0.8:1.2, citric acid and silicic acid；
S3, by the mixture after molding at 100 DEG C be dried 7h；
S4, by dried mixture roasting 5h at 580 DEG C, obtaining specific surface area is 230m2/g、
Degree of crystallinity is the magnesium aluminate spinel of 93%；
S5, by quiet with magnesia alumina spinel carrier incipient impregnation for the aqueous solution of nickel predecessor and manganese predecessor
Put 6h, then the sample after dipping is dried 5h, 550 DEG C of roasting 4h at 140 DEG C, prepare Hydrodearsenic Catalyst.
Embodiment 10
Present embodiments provide a kind of Hydrodearsenic Catalyst and preparation method thereof.This Hydrodearsenic Catalyst is by carrier and load
Active component on carrier；Carrier be specific surface area be 157.9m2/ g, degree of crystallinity are the magnalium of 87%
Spinelle, active component is NiMn2O4Spinelle, MnO2, wherein, NiMn2O4Spinelle,
MnO2It is 10:5:100 with the mass ratio of carrier.
The preparation method of the Hydrodearsenic Catalyst described in the present embodiment, comprises the steps:
S1, magnesium source-light MgO, aluminum source-boehmite and acidic aqueous solution are carried out kneading, aluminum
The mol ratio in source and magnesium source presses MgO/Al2O3Being calculated as 1:2, acidic aqueous solution is aqueous solution of nitric acid, dense
Degree 2mol/L；
S2, mixture after kneading add inorganic additive, it is ensured that the mixture after kneading and nothing
The mass ratio of machine additive is 1:125, is shaped after mix homogeneously, and wherein, inorganic additive is
Mol ratio is the mixed liquor of the oxalic acid of 1:1.2:2, citric acid and silicic acid；
S3, by the mixture after molding at 120 DEG C be dried 6h；
S4, by dried mixture roasting 8h at 600 DEG C, obtaining specific surface area is 157.9m2/g、
Degree of crystallinity is the magnesium aluminate spinel of 87%；
S5, by quiet with magnesia alumina spinel carrier incipient impregnation for the aqueous solution of nickel predecessor and manganese predecessor
Put 6h, then the sample after dipping is dried 6h, 400 DEG C of roasting 4h at 120 DEG C, prepare Hydrodearsenic Catalyst.
Comparative example 1
This comparative example provides a kind of Hydrodearsenic Catalyst and preparation method thereof.This Hydrodearsenic Catalyst is by carrier and load
Active component on carrier；Carrier be specific surface area be 160.1m2The magnesium aluminate spinel of/g, activity group
It is divided into NiO and MnO2, NiO, MnO2It is 10:5:100 with the mass ratio of carrier.
The preparation method of the Hydrodearsenic Catalyst described in this comparative example, comprises the steps:
S1, magnesium source-light MgO, aluminum source-boehmite and acidic aqueous solution are carried out kneading, aluminum
The mol ratio in source and magnesium source presses MgO/Al2O3Being calculated as 1:2, acidic aqueous solution is aqueous solution of nitric acid, dense
Degree 2mol/L；
S2, mixture after kneading add inorganic additive, it is ensured that the mixture after kneading and nothing
The mass ratio of machine additive is 1:125, is shaped after mix homogeneously, and wherein, inorganic additive is
Mol ratio is the mixed liquor of the oxalic acid of 1:1.2:2, citric acid and silicic acid；
S3, by the mixture after molding at 120 DEG C be dried 6h；
S4, by dried mixture roasting 8h at 600 DEG C, obtaining specific surface area is 157.9m2/g、
Degree of crystallinity is the magnesium aluminate spinel of 92%；
S5, by quiet with magnesia alumina spinel carrier incipient impregnation for the aqueous solution of nickel predecessor and manganese predecessor
Put 5h, then the sample after dipping is dried 6h at 120 DEG C, prepare Hydrodearsenic Catalyst.
Experimental example 1
To the intensity of Hydrodearsenic Catalyst obtained in embodiment 1-10 and comparative example 1, pore volume, aperture and
Specific surface area is tested, and test result is as shown in table 1 below:
Table 1
Experimental example 2
The activity of the Hydrodearsenic Catalyst described in embodiment 1-10 and comparative example 1 is tested, test condition:
Temperature is 300 DEG C, and pressure is 4.0MPa, and air speed is 3000h-1, steam-to-gas ratio is 1.5；Unstripped gas group
Becoming (wt%): CO is 45%, CO2It is 5.0%, H2S be 1000ppm, As be 0.23ppm,
Remaining is H2.Acquired results is as shown in table 2 below:
Table 2
Knowable to upper table 2 data, the Hydrodearsenic Catalyst that the embodiment of the present invention prepares coal during dearsenization
The activity of preparing synthetic gas generation Water gas shift/WGS side reaction is less than 5.5%, and arsenic holds height, has significantly
Dearsenization effect.In embodiment 6, the arsenic of Hydrodearsenic Catalyst holds up to more than 16wt%；Arsenic-removing rate is up to 99%；
Water gas shift/WGS side reaction is less than 3%.Show to use the Hydrodearsenic Catalyst in the embodiment of the present invention not only to have relatively
High dearsenization activity, and under the conditions of high temperature, high pressure, high concentration CO, Water gas shift/WGS side reaction
Conversion ratio is low.For the operating condition of actual production, carry out temperature and air speed test, at 250-300 DEG C
Temperature range, air speed 3000-5000h-1, pressure: 4.0～6.0MPa, steam-to-gas ratio is 1.0～1.8, de-
Arsenic and conversion side reaction all can meet the manufacturing technique requirent of factory.
Obviously, above-described embodiment is only for clearly demonstrating example, and not to embodiment party
The restriction of formula.For those of ordinary skill in the field, the most also may be used
To make other changes in different forms.Here without also all of embodiment being given
With exhaustive.And the obvious change thus extended out or variation are still in the guarantor of the invention
Protect among scope.
Claims (10)
1. a Hydrodearsenic Catalyst, including carrier and load active component on the carrier；Its feature
Being, described carrier is magnesium aluminate spinel；Described active component includes NiMn2O4Spinelle.
Hydrodearsenic Catalyst the most according to claim 1, it is characterised in that the ratio of described magnesium aluminate spinel
Surface area is 150m2/ g～280m2/g；
The degree of crystallinity of described magnesium aluminate spinel is 85～95%.
Hydrodearsenic Catalyst the most according to claim 1 and 2, it is characterised in that described active component with
The mass ratio of described carrier is (4.5～30): 100.
Hydrodearsenic Catalyst the most according to claim 3, it is characterised in that described active component is with described
The mass ratio of carrier is (5～22): 100.
5. according to the Hydrodearsenic Catalyst according to any one of claim 1-4, it is characterised in that described activity
Component also includes NiO and/or MnO2；
Described NiO is (5～15) with the mass ratio of described carrier: 100；
Described MnO2It is (5～15) with the mass ratio of described carrier: 100.
6. the preparation method of the Hydrodearsenic Catalyst described in an any one of claim 1-5, it is characterised in that
Comprise the steps:
The aqueous solution of nickel predecessor and manganese predecessor is stood with described magnesium aluminate spinel incipient impregnation
4～8h, obtain sample；
Described sample is dried at 120 DEG C～140 DEG C 4～8h again；
Dried described sample is placed in roasting 2～6h under 350 DEG C～550 DEG C of environment, prepares described de-
Arsenical.
Preparation method the most according to claim 6, it is characterised in that described magnesium aluminate spinel
Preparation method, comprises the steps:
S1, magnesium source and aluminum source and acidic aqueous solution are carried out kneading, wherein, source of aluminium and described magnesium
The mol ratio in source presses MgO/Al2O3Being calculated as (0.8～1.2): (1.5～2), described acidic aqueous solution is
Aqueous solution of nitric acid and/or aqueous acetic acid, the molar concentration of described acidic aqueous solution is 1mol/L-3
mol/L；
S2, by the mixture after kneading and additive in mass ratio for (0.64～1.2): 125 mix equal
Being shaped after even, wherein, described additive is at least one in oxalic acid, citric acid, silicic acid；
S3, the mixture after molding is dried, roasting, obtain described magnesium aluminate spinel after cooling.
Preparation method the most according to claim 7, it is characterised in that in described step S1,
Source of aluminium is Al2O3·H2O, boehmite, Al2O3·3H2O, aluminum nitrate, Al2O3In powder
At least one；
Described magnesium source is MgO, Mg (OH)2, at least one in basic magnesium carbonate；
In described step S2, described additive is oxalic acid, citric acid and silicic acid, wherein, described oxalic acid,
Described citric acid, the mol ratio of described silicic acid are 1:(0.8～1.2): (0.8～2).
9. according to the preparation method according to any one of claim 6-8, it is characterised in that described dry
The temperature of dry step is 70 DEG C～130 DEG C, and the time is 2h-10h；
The temperature of described calcination steps is 550 DEG C-650 DEG C, and roasting time is 2h-8h.
10. the answering in producing synthesis gas from coal dearsenicating technology of the Hydrodearsenic Catalyst according to any one of claim 1-5
With, it is characterised in that the reaction condition of described producing synthesis gas from coal dearsenicating technology is as follows: temperature is
250-300 DEG C, pressure: 4.0～6.0MPa, steam-to-gas ratio is 1.0～1.8, CO contains in producing synthesis gas from coal
Amount is 40-50wt%.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4869735A (en) * | 1987-04-30 | 1989-09-26 | Mitsubishi Jukogyo K.K. | Adsorbent for arsenic compound and method for removing arsenic compound from combustion gas |
| 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 |
| CN101485971A (en) * | 2008-05-29 | 2009-07-22 | 北京三聚环保新材料股份有限公司 | Normal temperature de-arsenic agent |
-
2016
- 2016-05-30 CN CN201610371223.8A patent/CN106000280B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4869735A (en) * | 1987-04-30 | 1989-09-26 | Mitsubishi Jukogyo K.K. | Adsorbent for arsenic compound and method for removing arsenic compound from combustion gas |
| US4869735B1 (en) * | 1987-04-30 | 1993-01-26 | Mitsubishi Heavy Ind Ltd | Adsorbent for arsenic compound and method for removing arsenic compound from combustion gas |
| 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 |
| CN101485971A (en) * | 2008-05-29 | 2009-07-22 | 北京三聚环保新材料股份有限公司 | Normal temperature de-arsenic agent |
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