CN107233890A - A kind of nickel-base catalyst of attapulgite load of zinc modification and its preparation method and application - Google Patents
A kind of nickel-base catalyst of attapulgite load of zinc modification and its preparation method and application Download PDFInfo
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- CN107233890A CN107233890A CN201710625783.6A CN201710625783A CN107233890A CN 107233890 A CN107233890 A CN 107233890A CN 201710625783 A CN201710625783 A CN 201710625783A CN 107233890 A CN107233890 A CN 107233890A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
- C01B2203/1058—Nickel catalysts
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1076—Copper or zinc-based catalysts
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1082—Composition of support materials
Abstract
The invention discloses a kind of nickel-base catalyst of the attapulgite load of zinc modification, composition includes Concave-convex clay rod, Ni and Zn, and Concave-convex clay rod is carrier, and Ni and Zn are active component, and Ni and Zn are supported on Concave-convex clay rod.When the nickel-base catalyst of the attapulgite load of zinc modification of the present invention is applied in catalytic reforming bio oil and its model thing hydrogen manufacturing, conversion ratio >=90% of raw material can be realized, hydrogen yield >=88%, hydrogen selective >=92%, active high, selectivity height, long lifespan, stability good (>=100h), cheap advantage, disclosure satisfy that the industrial requirement of catalyzing and reforming biologic oil hydrogen manufacturing.
Description
Technical field
The present invention relates to catalyst field, a kind of nickel-base catalyst of the attapulgite load of zinc modification is related in particular to
And its preparation method and application.
Background technology
Hydrogen Energy, due to high combustion efficiency, product is pollution-free is considered as optimal energy carrier, and hydrogen still most base
The chemical raw material of plinth, can be applied in the techniques such as synthesis ammonia, fuel cell power generation, petroleum refining.Currently, the acquisition of hydrogen is main
The reforming technique of gasification and natural gas and hydrocarbon by coal and oil, these processes can consume non-renewable unavoidably
Resource, increase environmental pollution.
In recent years, biomass because reserves are big, renewable and use during will not increase the content of carbon dioxide in air,
It is widely used in gasification and thermal cracking processes and prepares liquid fuel (biodiesel) and gaseous fuel (hydrogen and synthesis gas).
And a kind of water-soluble liquid portion can be produced in gasification of biomass or thermal cracking processes, it is referred to as bio oil, main bag
Containing some oxygen-containing organic compounds, it is difficult to be directly used as fuel.In order to improve the utilization rate of biomass, increase many of hydrogen feedstock
Sample, bio oil is used in catalytically reforming hydrogen producing to turn into study hotspot.
Because bio oil has certain viscosity and acidity, and catalytically reforming hydrogen producing occurs mainly in 400 DEG C~700 DEG C bars
Under part, so the efficiency in order to improve catalyzing and reforming biologic oil hydrogen manufacturing, the selection of catalyst has reformed into key issue.Have at present
A kind of nickel-base catalyst of attapulgite load, it is current during high temperature steam reforming easily occur active metal nickel sintering with
And monometallic nickel as active component when, easily form carbon deposit in the avtive spot of catalyst.Both of these case can cause catalysis
The obvious inactivation of agent.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of active high, selectivity height, long lifespan, stability is good, make
The nickel-base catalyst of the attapulgite load of simple, the cheap zinc modification of Preparation Method.
In order to solve the above-mentioned technical problem, the present invention is adopted the following technical scheme that：A kind of attapulgite load of zinc modification
Nickel-base catalyst, composition includes Concave-convex clay rod, Ni and Zn, and Concave-convex clay rod is carrier, and Ni and Zn are active component,
Ni and Zn are supported on Concave-convex clay rod.
Further, Ni content is 10wt.%~20wt.%, and Zn content is 5wt.%~20wt.%.Implementing
In the process of the present invention, inventor is had found, active component content is less than this scope, and the avtive spot of catalyst can be caused not enough,
It is low to catalytic reaction efficiency；And active component is crossed higher than this scope, it can be caused to reunite in carrier surface, reduce avtive spot；
Ni and Zn content is more or less than this scope, is all unfavorable for the formation of Ni-Zn alloys in the catalyst, it is impossible to play anti-sintering
Effect.
Further, Ni and Zn are supported on Concave-convex clay rod by chemical precipitation method.This method is easy to operate, and
The metal dispersity of catalyst can be improved.
The present invention also provide the nickel-base catalyst of the attapulgite load of above-mentioned zinc modification in catalytic reforming bio oil and its
Application in model thing hydrogen manufacturing.
Further, catalytic reforming bio oil and its reaction condition of model thing hydrogen manufacturing are：Catalyst amount 1g~5g, it is former
Feeding coal 1g/h~15g/h of material, raw water carbon mol ratio 1~20, reaction temperature is 400 DEG C~700 DEG C.Implementing the present invention
During, inventor has found, under this reaction condition, it is possible to achieve conversion ratio >=90% of raw material, hydrogen yield >=88%, hydrogen
Gas selectivity >=92%.
The present invention also provides the preparation method of the nickel-base catalyst of the attapulgite load of above-mentioned zinc modification, including following step
Suddenly：
(1) Concave-convex clay rod is weighed, progress acidification is mixed with inorganic acid, then the attapulgite after acidifying is glued
Soil is washed, filtered, being dried, being ground, being sieved, calcination processing, obtains modified attapulgite clay；
(2) nickel salt and zinc salt are weighed, is dissolved in deionized water, modified attapulgite clay is then added, raw material is made
Suspension；
(3) under agitation, precipitating reagent is added into raw material suspension, regulation pH value is to 9.8~10.2, then 60
DEG C~80 DEG C under the conditions of stir 4h~6h, then stand aging 18h~24h at the same temperature, obtain mix products；
(4) mix products filtered, dried, being ground, being sieved, calcination processing, obtain catalyst precursor；
(5) catalyst precursor is placed in reductase 12 h~4h in reducing atmosphere under the conditions of 600 DEG C~800 DEG C, produces institute
The nickel-base catalyst of the attapulgite load for the zinc modification stated.
Further, the chemical precipitation agent is sodium hydroxide, one kind in ammoniacal liquor and urea, concentration be 3mol/L~
5mol/L。
Further, the drop rate of the precipitating reagent is controlled in 1mL/min~5mL/min.Implementing the mistake of the present invention
Cheng Zhong, inventor has found that drop rate is controlled in the range of this, is conducive to active component Ni's and Zn homogeneously crystallized, improves
Metal dispersity.
Further, the nickel salt is one kind of Nickelous nitrate hexahydrate, six hydration nickel sulfate and Nickel dichloride hexahydrate.
Further, the zinc salt is zinc nitrate hexahydrate or Zinc vitriol.
Further, the inorganic acid used in the acidification of Concave-convex clay rod is one kind of hydrochloric acid, sulfuric acid and nitric acid, dense
Spend for 3mol/L~10mol/L.
Further, the solid-liquid ratio of Concave-convex clay rod and inorganic acid is 1g/4mL.
Further, the acidification of Concave-convex clay rod is carried out under the conditions of stirring, 60 DEG C~80 DEG C, and time 3h~
6h。
Further, the process that is made of raw material suspension is that 2h~4h is stirred under the conditions of 60 DEG C~80 DEG C.
Further, in step (1) and (4), calcination process be in tube furnace with 2 DEG C/min heating rate,
2h~4h is calcined under the conditions of 500 DEG C~700 DEG C.In implementing the present invention, it may, inventor has found, heating rate exceedes this model
Enclose, the hole of carrier can be caused to cave in, and can fill the crystallization water in attapulgite clay in this temperature and calcination time
Divide evaporation, and energy increasing specific surface area, the sediment of Ni and Zn in catalyst precursor is fully decomposed.
Further, in step (1) and (4), screening process is to obtain particle diameter with the sieve screening of the mesh of 60 mesh~80 to be
0.18mm~0.25mm particle.
Further, in step (1) and (4), drying process is that 12h~18h is dried under the conditions of 105 DEG C~120 DEG C.
Further, reducing atmosphere is the mixed gas of hydrogen that the volume fraction of ammonia or hydrogen is 10% and nitrogen.
Beneficial effects of the present invention are embodied in：
1. the nickel-base catalyst of the attapulgite load of zinc modification of the present invention is applied in catalytic reforming bio oil and its model
When in thing hydrogen manufacturing, conversion ratio >=90% of raw material, hydrogen yield >=88%, hydrogen selective >=92%, with work can be realized
The high, selectivity of property is high, long lifespan, stability good (>=100h), cheap advantage, disclosure satisfy that catalyzing and reforming biologic oil system
The industrial requirement of hydrogen.
2. the present invention is using Concave-convex clay rod as catalyst carrier, its is cheap and easy to get, reduces the preparation of catalyst
Cost, and with larger ratio surface and higher hydrothermal stability, beneficial to the scattered of active metal.
3. the nickel-base catalyst that the present invention is loaded using zinc come modified attapulgite, zinc is to water gas shift reation and methane weight
Whole reaction has a facilitation, and can be synthesized with Ni formation Ni-Zn, can improve selectivity of the catalyst to hydrogen, anti-sintering
Ability and catalytic life.
4. the preparation method of the nickel-base catalyst of the attapulgite load of zinc modification of the present invention is simple, easy to operate, raw material
It is easy to get, it is with low cost, it is easy to heavy industrialization to use.
5. the nickel-base catalyst of the attapulgite load of zinc modification of the present invention has advantages below：(1) it is molecule to reaction
In C-C keys, C-O keys and c h bond there is extremely strong fracture energy；(2) there is higher high temperature sintering resistant ability and anti-carbon deposit
Ability；(3) there is extremely strong selectivity to the intermediate reaction (such as steam reacting condition and methane reforming reaction) in reforming process；
(4) there is fabulous heat endurance；(5) raw material for being used to prepare catalyst is cheap and easy to get；(6) method for preparing catalyst is simply easy
Operation, preparation process are environmentally safe.
Embodiment
With reference to embodiment, the invention will be further described：
Various raw materials, are such as not specifically noted used in following examples, are commercially available prod well known in the art.
Embodiment 1
The content of Ni in the nickel-base catalyst of the attapulgite load of zinc modification manufactured in the present embodiment is 10wt.%,
Zn content is that 5wt.%, the content of Concave-convex clay rod are 85wt.%, and preparation method is as follows：
(1) 50g Concave-convex clay rods are weighed, are placed in round bottom beaker, are stirred while adding 3mol/L hydrochloric acid
200mL, then carries out water-bath acidifying 3h under high degree of agitation, 60 DEG C of constant temperatures to Concave-convex clay rod；Then stand, topple over
Go out supernatant liquid；The Concave-convex clay rod after acidifying is washed to pH=7 with deionized water again；Then filter, filter cake is placed in baking
12h is dried in case under the conditions of 105 DEG C, afterwards milled processed, then it is 0.18mm to obtain particle diameter with the sieve screening of 60 mesh, 80 mesh
~0.25mm particle；600 DEG C finally are risen to from room temperature with 2 DEG C/min heating rate in tube furnace, temperature 2h is kept
After be cooled to room temperature, obtain modified attapulgite clay；
(2) 2.91g Ni (NO are weighed3)2·6H2O and 1.34g Zn (NO3)2·6H2O is placed in round bottom beaker, is added
50mL deionized water, stirring, after they are completely dissolved, the modified attapulgite that the step of adding 5.00g (1) obtains glues
Soil, then the high degree of agitation 2h under the conditions of 60 DEG C of constant temperature water bath, obtains raw material suspension；
(3) configuration 3mol/L ammonia spirit 500mL is as precipitating reagent, using constant flow pump with 1mL/min drop rate
Precipitating reagent is added in the raw material suspension that step (2) is obtained, pH to 10 is adjusted；Then stirred under the conditions of 60 DEG C of constant temperature water bath
4h, then aging 18h is stood under the same conditions, obtain mix products；
(4) mix products that step (3) is obtained are filtered, filter cake is placed in baking oven to be dried under the conditions of 105 DEG C
12h, afterwards milled processed, then the particle that particle diameter is 0.18mm~0.25mm is obtained with the sieve screening of 60 mesh, 80 mesh；Finally exist
600 DEG C are risen to from room temperature with 2 DEG C/min heating rate in tube furnace, room temperature is cooled to after keeping temperature 2h, is catalyzed
Agent presoma；
(5) catalyst precursor for obtaining step (4) is placed in tube furnace, with 2 DEG C/min heating rate from room temperature
600 DEG C are risen to, H is passed through2And N2Mixed gas (H2Volume fraction is 10%) reductase 12 h, produces the concave convex rod of the zinc modification
Stone (Attapulgite is abbreviated as ATP) supported nickel catalyst, is calculated as 10Ni-5Zn/ATP, numbering 1#.
Embodiment 2
The content of Ni in the nickel-base catalyst of the attapulgite load of zinc modification manufactured in the present embodiment is 10wt.%,
Zn content is that 10wt%, the content of Concave-convex clay rod are 80wt.%, and preparation method is as follows：
(1) 50g Concave-convex clay rods are weighed, are placed in round bottom beaker, are stirred while adding 10mol/L nitric acid
200mL, then carries out water-bath acidifying 6h under high degree of agitation, 80 DEG C of constant temperatures to Concave-convex clay rod；Then it will stand, incline
Pour out supernatant liquid；The Concave-convex clay rod after acidifying is washed to pH=7 with deionized water again；Then filter, filter cake is placed in
18h is dried in baking oven under the conditions of 120 DEG C, afterwards milled processed, then particle diameter is obtained with the sieve screening of 60 mesh, 80 mesh and be
0.18mm~0.25mm particle；500 DEG C finally are risen to from room temperature with 2 DEG C/min heating rate in tube furnace, keeping should
Room temperature is cooled to after temperature 4h, modified attapulgite clay is obtained；
(2) 3.10g Ni (NO are weighed3)2·6H2O and 2.84g Zn (NO3)2·6H2O is placed in round bottom beaker, is added
50mL deionized water, stirring, after they are completely dissolved, the modified attapulgite that the step of adding 5.00g (1) obtains glues
Soil, then the high degree of agitation 4h under the conditions of 80 DEG C of constant temperature water bath, obtains raw material suspension；
(3) configuration 5mol/L ammonia spirit 500mL is as precipitating reagent, using constant flow pump with 5mL/min drop rate
Precipitating reagent is added in the raw material suspension that step (2) is obtained, pH to 9.8 is adjusted；Then stirred under the conditions of 80 DEG C of constant temperature water bath
6h is mixed, then stands aging 24h under the same conditions, mix products are formed；
(4) mix products that step (3) is obtained are filtered, filter cake is placed in baking oven to be dried under the conditions of 120 DEG C
18h, afterwards milled processed, then the particle that particle diameter is 0.18mm~0.25mm is obtained with the sieve screening of 60 mesh, 80 mesh；Finally exist
500 DEG C are risen to from room temperature with 2 DEG C/min heating rate in tube furnace, room temperature is cooled to after keeping temperature 4h, is catalyzed
Agent presoma；
(5) catalyst precursor for obtaining step (4) is placed in tube furnace, with 2 DEG C/min heating rate from room temperature
700 DEG C are risen to, H is passed through2And N2Mixed gas (H2Volume fraction is 10%), to reduce 4h, produce the concave convex rod of the zinc modification
The nickel-base catalyst of stone load, is calculated as 10Ni-10Zn/ATP, numbering 2#.
Embodiment 3
The content of Ni in the nickel-base catalyst of the attapulgite load of zinc modification manufactured in the present embodiment is 15wt.%,
Zn content is that 15wt%, the content of Concave-convex clay rod are 70wt.%, and preparation method is as follows：
(1) 50g Concave-convex clay rods are weighed, are placed in round bottom beaker, are stirred while adding 5mol/L sulfuric acid
200mL, then carries out water-bath acidifying 4h under high degree of agitation, 70 DEG C of constant temperatures to Concave-convex clay rod；Then it will stand, incline
Pour out supernatant liquid；The Concave-convex clay rod after acidifying is washed to pH=7 with deionized water again；Then filter, filter cake is placed in
16h is dried in baking oven under the conditions of 110 DEG C, afterwards milled processed, then particle diameter is obtained with the sieve screening of 60 mesh, 70 mesh and be
0.21mm~0.25mm particle；700 DEG C finally are risen to from room temperature with 2 DEG C/min heating rate in tube furnace, keeping should
Room temperature is cooled to after temperature 3h, modified attapulgite clay is obtained；
(2) 4.79g NiSO is weighed4·6H2O and 4.71g ZnSO4·7H2O is placed in round bottom beaker, adds 50mL's
Deionized water, stirring, after they are completely dissolved, the modified attapulgite clay that the step of adding 5.00g (1) obtains, then
The high degree of agitation 3h under the conditions of 70 DEG C of constant temperature water bath, obtains raw material suspension；
(3) configuration 4mol/L sodium hydroxide solution 500mL is as precipitating reagent, using constant flow pump with 3mL/min dropwise addition
Speed adds precipitating reagent in the raw material suspension that step (2) is obtained, and adjusts pH to 10.2；Then in 70 DEG C of conditions of constant temperature water bath
Lower stirring 5h, then aging 20h is stood under the same conditions, form mix products；
(4) mix products that step (3) is obtained are filtered, filter cake is placed in baking oven to be dried under the conditions of 110 DEG C
15h, afterwards milled processed, then the particle that particle diameter is 0.21mm~0.25mm is obtained with the sieve screening of 60 mesh, 70 mesh；Finally exist
700 DEG C are risen to from room temperature with 2 DEG C/min heating rate in tube furnace, room temperature is cooled to after keeping temperature 3h, is catalyzed
Agent presoma；
(5) catalyst precursor for obtaining step (4) is placed in tube furnace, with 2 DEG C/min heating rate from room temperature
650 DEG C are risen to, H is passed through2And N2Mixed gas (H2Volume fraction is 10%), to reduce 3h, produce the concave convex rod of the zinc modification
The nickel-base catalyst of stone load, is calculated as 15Ni-15Zn/ATP, numbering 3#.
Embodiment 4
Ni contents in the nickel-base catalyst of the attapulgite load of zinc modification manufactured in the present embodiment are 20wt.%, Zn
Content be that 20wt%, the content of Concave-convex clay rod are 60wt.%, preparation method is as follows：
(1) except the acidifying of Concave-convex clay rod select be 5mol/L nitric acid in addition to, the step of other steps and embodiment 2
(1) it is identical, obtain modified attapulgite clay；
(2) 6.76g NiCl is weighed2·6H2O and 7.34g ZnSO4·7H2O is placed in round bottom beaker, adds 50mL's
Deionized water, stirring, after they are completely dissolved, the modified attapulgite clay that the step of adding 5.00g (1) obtains, then
The high degree of agitation 3h under the conditions of 70 DEG C of constant temperature water bath, obtains raw material suspension；
(3) configuration 3mol/L urea liquid 500mL is as precipitating reagent, using constant flow pump with 2mL/min drop rate
Precipitating reagent is added in the raw material suspension that step (2) is obtained, pH to 10 is adjusted；Then stirred under the conditions of 70 DEG C of constant temperature water bath
5h, then aging 22h is stood under the same conditions, form mix products；
(4) mix products that step (3) is obtained are filtered, filter cake is placed in baking oven to be dried under the conditions of 120 DEG C
18h, afterwards milled processed, then the particle that particle diameter is 0.18mm~0.21mm is obtained with the sieve screening of 70 mesh, 80 mesh；Finally exist
650 DEG C are risen to from room temperature with 2 DEG C/min heating rate in tube furnace, room temperature is cooled to after keeping temperature 3.5h, is urged
Agent presoma；
(5) catalyst precursor for obtaining step (4) is placed in tube furnace, with 2 DEG C/min heating rate from room temperature
800 DEG C are risen to, H is passed through2And N2Mixed gas (H2Volume fraction is 10%), to reduce 3.5h, produce the bumps of the zinc modification
The nickel-base catalyst of rod stone load, is calculated as 20Ni-20Zn/ATP, numbering 4#.
Embodiment 5
The content of Ni in the nickel-base catalyst of the attapulgite load of zinc modification manufactured in the present embodiment is 10wt.%,
Zn content is that 10wt%, the content of Concave-convex clay rod are 80wt.%, and preparation method is similar to Example 2, and difference is only
It is that reduction reaction is gases used and H is replaced with ammonia2And N2Mixed gas, the nickel of the attapulgite load of obtained zinc modification
Base catalyst numbering 5#.
Embodiment 6
The catalytic reforming bio oil of the nickel-base catalyst of the attapulgite load of zinc modification and its model thing hydrogen manufacturing test
Above-mentioned 1#~5# catalyst 1g~5g is taken to be placed in fixed bed reactors, the feeding coal of bio oil and its model thing
1g/h~15g/h, raw water carbon mol ratio (S/C) 1~20, reaction temperature is 400 DEG C~700 DEG C.Specific reaction condition and
As a result it see the table below 1.
Table 1
It can be drawn from result above, the nickel-base catalyst of the attapulgite load of zinc modification of the present invention can realize raw material
Conversion ratio >=90%, hydrogen yield >=88%, hydrogen selective >=92%, service life >=100h.
It should be understood that example as described herein and embodiment are not intended to limit the invention, this area only for explanation
Technical staff can make various modifications or change according to it, within the spirit and principles of the invention, any modification for being made,
Equivalent substitution, improvement etc., should be included in the scope of the protection.
Claims (10)
1. a kind of nickel-base catalyst of the attapulgite load of zinc modification, it is characterised in that：Composition includes Concave-convex clay rod, Ni
And Zn, Concave-convex clay rod is carrier, and Ni and Zn are active component, and Ni and Zn are supported on Concave-convex clay rod.
2. the nickel-base catalyst of the attapulgite load of zinc modification as claimed in claim 1, it is characterised in that：Ni content is
10wt.%~20wt.%, Zn content are 5wt.%~20wt.%.
3. the nickel-base catalyst of the attapulgite load of zinc modification as claimed in claim 1 or 2, it is characterised in that：Ni and Zn
It is supported on by chemical precipitation method on Concave-convex clay rod.
4. the nickel-base catalyst of the attapulgite load of zinc modification as claimed any one in claims 1 to 3 is in catalytic reforming
Application in bio oil and its model thing hydrogen manufacturing.
5. the nickel-base catalyst of the attapulgite load of zinc modification as claimed in claim 4 is in catalytic reforming bio oil and its mould
Application in type thing hydrogen manufacturing, it is characterised in that：Catalytic reforming bio oil and its reaction condition of model thing hydrogen manufacturing are：Catalyst is used
1g~5g, feeding coal 1g/h~15g/h of raw material are measured, raw water carbon mol ratio 1~20, reaction temperature is 400 DEG C~700 DEG C.
6. the preparation method of the nickel-base catalyst of the attapulgite load of zinc modification as claimed any one in claims 1 to 3,
It is characterized in that：Comprise the following steps：
(1) Concave-convex clay rod is taken, progress acidification is mixed with inorganic acid, then the Concave-convex clay rod after acidifying is carried out
Washing, filtering, dry, grinding, screening, calcination processing, obtain modified attapulgite clay；
(2) nickel salt and zinc salt are taken, is dissolved in deionized water, modified attapulgite clay is then added, raw material suspension is made；
(3) under agitation, add precipitating reagent into raw material suspension, regulation pH value to 9.8~10.2, then 60 DEG C~
4h~6h is stirred under the conditions of 80 DEG C, then stands aging 18h~24h at the same temperature, mix products are obtained；
(4) mix products filtered, dried, being ground, being sieved, calcination processing, obtain catalyst precursor；
(5) catalyst precursor is placed in reductase 12 h~4h in reducing atmosphere under the conditions of 600 DEG C~800 DEG C, produced described
The nickel-base catalyst of the attapulgite load of zinc modification.
7. the preparation method of the nickel-base catalyst of the attapulgite load of zinc modification as claimed in claim 6, it is characterised in that：
The chemical precipitation agent is one kind in sodium hydroxide, ammoniacal liquor and urea, and concentration is 3mol/L~5mol/L.
8. the preparation method of the nickel-base catalyst of the attapulgite load of zinc modification as claimed in claim 6, it is characterised in that：
Acidification is carried out under the conditions of stirring, 60 DEG C~80 DEG C, time 3h~6h.
9. the preparation method of the nickel-base catalyst of the attapulgite load of zinc modification as claimed in claim 6, it is characterised in that：
The process that is made of raw material suspension is that 2h~4h is stirred under the conditions of 60 DEG C~80 DEG C.
10. the preparation method of the nickel-base catalyst of the attapulgite load of zinc modification as claimed in claim 6, its feature exists
In：In step (1) and (4), calcination process is with 2 DEG C/min heating rate in tube furnace, in 500 DEG C~700 DEG C bars
2h~4h is calcined under part.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710625783.6A CN107233890A (en) | 2017-07-27 | 2017-07-27 | A kind of nickel-base catalyst of attapulgite load of zinc modification and its preparation method and application |
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Cited By (6)
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| CN108187683A (en) * | 2018-01-12 | 2018-06-22 | 安徽理工大学 | Nickel-copper catalyst of attapulgite load that a kind of calcium oxide is modified and its preparation method and application |
| CN111450814A (en) * | 2020-04-29 | 2020-07-28 | 江苏纳欧新材料有限公司 | Method for preparing zinc silicate catalyst by using natural attapulgite and application thereof |
| CN113308261A (en) * | 2021-06-24 | 2021-08-27 | 南京林业大学 | Method for preparing hydrogen-rich gas by biomass pyrolysis catalysis |
| CN113318745A (en) * | 2021-06-24 | 2021-08-31 | 南京林业大学 | Preparation method of hydrogen-rich catalyst for biomass pyrolysis |
| CN114272950A (en) * | 2022-01-04 | 2022-04-05 | 安徽理工大学 | CH (physical channel)4、CO2Catalyst for reforming preparation of synthesis gas and preparation method and application thereof |
| CN114308042A (en) * | 2022-01-04 | 2022-04-12 | 安徽理工大学 | Attapulgite-based ordered microporous zeolite catalyst and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108187683A (en) * | 2018-01-12 | 2018-06-22 | 安徽理工大学 | Nickel-copper catalyst of attapulgite load that a kind of calcium oxide is modified and its preparation method and application |
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| CN113308261A (en) * | 2021-06-24 | 2021-08-27 | 南京林业大学 | Method for preparing hydrogen-rich gas by biomass pyrolysis catalysis |
| CN113318745A (en) * | 2021-06-24 | 2021-08-31 | 南京林业大学 | Preparation method of hydrogen-rich catalyst for biomass pyrolysis |
| CN114272950A (en) * | 2022-01-04 | 2022-04-05 | 安徽理工大学 | CH (physical channel)4、CO2Catalyst for reforming preparation of synthesis gas and preparation method and application thereof |
| CN114308042A (en) * | 2022-01-04 | 2022-04-12 | 安徽理工大学 | Attapulgite-based ordered microporous zeolite catalyst and preparation method and application thereof |
| CN114308042B (en) * | 2022-01-04 | 2023-11-21 | 安徽理工大学 | Attapulgite-based ordered microporous zeolite catalyst and preparation method and application thereof |
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Application publication date: 20171010 |