CN109589983A - A kind of Ni-based methanation catalyst of the modification of combustion method of citric acid preparation and application - Google Patents
A kind of Ni-based methanation catalyst of the modification of combustion method of citric acid preparation and application Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 98
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000009841 combustion method Methods 0.000 title claims abstract description 15
- 238000012986 modification Methods 0.000 title claims description 4
- 230000004048 modification Effects 0.000 title claims description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 title description 9
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 239000001509 sodium citrate Substances 0.000 claims abstract description 18
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 238000002485 combustion reaction Methods 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 239000010453 quartz Substances 0.000 claims abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims abstract 3
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 8
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 7
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 6
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 6
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 6
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical group [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- 239000002351 wastewater Substances 0.000 abstract description 4
- 238000001816 cooling Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 150000002815 nickel Chemical class 0.000 abstract 1
- 238000011156 evaluation Methods 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 239000003245 coal Substances 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- OQUFOZNPBIIJTN-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;sodium Chemical compound [Na].OC(=O)CC(O)(C(O)=O)CC(O)=O OQUFOZNPBIIJTN-UHFFFAOYSA-N 0.000 description 1
- 229910014459 Ca-Ni Inorganic materials 0.000 description 1
- 229910014473 Ca—Ni Inorganic materials 0.000 description 1
- 241000272194 Ciconiiformes Species 0.000 description 1
- 229910019083 Mg-Ni Inorganic materials 0.000 description 1
- 229910019403 Mg—Ni Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910003520 Sr-Ni Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- QDMGKUOANLJICG-UHFFFAOYSA-N [Mg].[N+](=O)(O)[O-] Chemical compound [Mg].[N+](=O)(O)[O-] QDMGKUOANLJICG-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J23/78—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 alkali- or alkaline earth metals
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
柠檬酸盐燃烧法制备改性的镍基甲烷化催化剂的方法，先将催化剂活性组分的前驱体、助剂前驱体、催化剂的载体前驱体分本溶于少量的去离子水，混合；然后再加入配置好的柠檬酸钠溶液，加入过程要不断搅拌，生成的混合物要超声处理30 min再将混合均匀的溶胶转移至石英舟或坩埚中，转移至预热300‑600oC的马弗炉中进行燃烧反应，待冷却至室温后，即制得所需的催化剂。本发明用柠檬酸盐燃烧法制备的甲烷化催化剂，操作简单方便，成本低廉，制备时间短，比表面积大，不产生废水等，特别适合工业化大生产的要求。
The method for preparing the modified nickel-based methanation catalyst by the citrate combustion method is to first dissolve the precursor of the active component of the catalyst, the precursor of the auxiliary agent, and the precursor of the carrier of the catalyst in a small amount of deionized water, and then mix; Then add the prepared sodium citrate solution. Stir continuously during the addition process. The resulting mixture needs to be ultrasonicated for 30 min. Then transfer the well-mixed sol to a quartz boat or crucible, and transfer it to a muffle preheated at 300‑600 o C. The combustion reaction is carried out in the furnace, and the desired catalyst is prepared after cooling to room temperature. The methanation catalyst prepared by the citrate combustion method has the advantages of simple and convenient operation, low cost, short preparation time, large specific surface area, no waste water and the like, and is particularly suitable for the requirements of large-scale industrial production.
Description
Technical field
The present invention relates to the preparation of catalyst and applications, prepare methanation catalyst more particularly to a kind of combustion method of citric acid
The method of agent.
Background technique
Carbon dioxide is also that a kind of cheap penguin quantity is abundant and provides naturally simultaneously as most important greenhouse gases
Source.In recent years, with getting worse for global warming problem and petering out for fossil energy, how carbon dioxide is realized
Effective use have been to be concerned by more and more people.And rich coal resources in China, synthesis gas from coal gasification is carried out to methanation again,
On the one hand the utilization rate that coal can be improved, on the other hand reduces the discharge of carbon dioxide, protects environment.And in coal day
During right gas, technology is very mature, and key is the catalyst of methanation.Currently, the catalyst master of methanation
It will be by the active component of catalyst, auxiliary agent and carrier three parts composition.The active component of catalyst generally selects noble metal or mistake
Metal is crossed, and wherein nickel is cheap because activity is high, is widely used.The carrier of catalyst generally select aluminium oxide,
Zirconium oxide and titanium oxide etc., and wherein aluminium oxide is the carrier generally used.
Methanation catalyst preparation a kind of common method be will the presoma containing silicon source carrier, nickel oxide presoma
With the precursor solution of auxiliary agent, precipitating reagent is added, the predecessor of catalyst is settled out, then using being filtered, washed, do
It is dry, roasting and molding and etc., prepare methanation catalyst.Patent CN102513119A discloses a kind of methanation catalyst
Aluminum nitrate, nickel nitrate, lanthanum nitrate are mixed and K are added by preparation method2CO3It is co-precipitated, is made using aluminium oxide as carrier, metal
Nickel is active component, and lanthana is the methanation catalyst of auxiliary agent.
In the method that traditional precipitation method prepare methanation catalyst, first have to active component, auxiliary agent and carrier
The step of salting liquid carries out co-precipitation or fractional precipitation, and by filtering, repeatedly washs, dry, roasting.Meeting in operating process
A large amount of waste water is generated, environment, and complex process are polluted, it is complex for operation step, it is unfavorable for industrialized large-scale application.And
Sodium citrate combustion method overcomes these disadvantages well.And compared to infusion process, the catalysis of sodium citrate combustion method preparation
Active group of dispersion effect of agent is good, particle is uniform, specific surface area headlight advantage, and catalyst activity is excellent.
Summary of the invention
The shortcomings that in order to make up current traditional technology, the purpose of the present invention is to provide a kind of preparations of sodium citrate combustion method
The method of methanation catalyst, using aluminum nitrate as the raw material of carrier, presoma of the nickel nitrate as active component, nitric acid
Magnesium, calcium nitrate, strontium nitrate and barium nitrate presoma of the one or more as auxiliary agent, sodium citrate is as incendiary agent.Pass through
One step combustion method prepares methanation catalyst, and this method has simple to operate, and low in cost, preparation time is short, compares table
Area is big, does not generate waste water etc., is particularly suitable for the requirement of industrialized production.In order to realize the above object, the present invention is used
Technical solution are as follows: the method that sodium citrate combustion method prepares methanation catalyst, specific step is as follows.
Step 1 presses the presoma of the presoma of the active component of catalyst, the presoma of auxiliary agent and catalyst carrier
It is dissolved in a small amount of deionized water respectively according to the composition and ratio of catalyst, uniformly mixes, wherein the composition of catalyst includes: to account for catalysis
The active component nickel oxide of the 5%-25% of agent total weight, the auxiliary agent that total catalyst weight 1%-10% is accounted in terms of oxide are with remaining
The carrier of catalyst, wherein the auxiliary agent selection MgO, CaO, SrO and BaO etc. are one or more of.
The support precursor of the catalyst is aluminum nitrate, and the carrier of catalyst is aluminium oxide.
The presoma of the active component of the catalyst is nickel nitrate, and the active component of catalyst is elemental nickel.
The auxiliary agent presoma of the catalyst is one or more of magnesium nitrate, calcium nitrate, strontium nitrate and barium nitrate.
The incendiary agent of the catalyst is sodium citrate, and the dosage of incendiary agent is the active group by its molal quantity and catalyst
Divide the ratio between presoma, auxiliary agent presoma and support precursor total moles (1~5): 1.
The solution of configured sodium citrate is added in the solution for the nitrate that step 1 mixes by step 2, drop
Process is added to keep constantly stirring, sonicated 30 min of the mixture of generation obtains transparent colloidal sol.
Step 3, the colloidal sol that step 2 is obtained are transferred to quartz boat or crucible, are transferred to the 300-600 preheated in advanceoC
Muffle furnace in carry out combustion reaction, after being cooled to room temperature, obtain required catalyst.
The methanation catalyst of the present invention prepared using sodium citrate combustion method, compared with traditional method, tool
It has the following advantages:
1. the method for the methanation catalyst of the present invention using the preparation of sodium citrate combustion method, simple to operation, it is suitble to
The application of industrial-scale.
2. the method for the methanation catalyst of the present invention using the preparation of sodium citrate combustion method, utilizes citric acid
Sodium not only releases a large amount of heat as incendiary agent during burning, but also can generate a large amount of gas, and gas exists
A large amount of duct can be generated in catalyst surface in excessive process, be conducive to the specific surface area for expanding catalyst.
3. the method for the methanation catalyst of the present invention using the preparation of sodium citrate combustion method, has environmentally friendly nothing
The characteristics of pollution, does not generate waste water, Environmental Safety.
Detailed description of the invention
Fig. 1 is Mg-Ni/Al2O3The Evaluation results of catalyst.
Fig. 2 is Ca-Ni/Al2O3The Evaluation results of catalyst.
Fig. 3 is Sr-Ni/Al2O3The Evaluation results of catalyst.
Fig. 4 is Ba-Ni/Al2O3The Evaluation results of catalyst.
Case is embodied:
Below by the further thoroughgoing and painstaking description preparation method of the present invention of specific case study on implementation, specific implementation case
Under such as.
Embodiment one
The preparation method of the present embodiment includes the following steps.
Step 1 presses the presoma of the presoma of the active component of catalyst, the presoma of auxiliary agent and catalyst carrier
It is dissolved in a small amount of deionized water respectively according to the composition and ratio of catalyst, uniformly mixes, wherein the composition of catalyst includes: to account for catalysis
The active component nickel oxide of the 5%-25% of agent total weight, the auxiliary agent that total catalyst weight 1%-10% is accounted in terms of oxide are with remaining
The carrier of catalyst, wherein the auxiliary agent selects MgO.The dosage of incendiary agent is by before the active component of its molal quantity and catalyst
Drive the ratio between body, auxiliary agent presoma and support precursor total moles 3:1.
The solution of configured sodium citrate is added in the solution for the nitrate that step 1 mixes by step 2, drop
Process is added to keep constantly stirring, sonicated 30 min of the mixture of generation obtains transparent colloidal sol.
Step 3, the colloidal sol that step 2 is obtained are transferred to quartz boat or crucible, are transferred to the 300-600 preheated in advanceoC
Muffle furnace in carry out combustion reaction, after being cooled to room temperature, obtain required catalyst；The evaluation result of catalyst is shown in figure
1。
Embodiment two
The preparation method of the present embodiment the following steps are included:
Step 1, by the presoma of the presoma of the active component of catalyst, the presoma of auxiliary agent and catalyst carrier according to urging
The composition and ratio of agent is dissolved in a small amount of deionized water respectively, uniformly mixes, and wherein the composition of catalyst includes: that account for catalyst total
The active component nickel oxide of the 5%-25% of weight, accounted in terms of oxide total catalyst weight 1%-10% auxiliary agent and remaining for catalysis
The carrier of agent, wherein the auxiliary agent selects CaO.The dosage of incendiary agent is the active component forerunner by its molal quantity and catalyst
The ratio between body, auxiliary agent presoma and support precursor total moles 3:1.
The solution of configured sodium citrate is added in the solution for the nitrate that step 1 mixes by step 2, drop
Process is added to keep constantly stirring, sonicated 30 min of the mixture of generation obtains transparent colloidal sol.
Step 3, the colloidal sol that step 2 is obtained are transferred to quartz boat or crucible, are transferred to the 300-600 preheated in advanceoC
Muffle furnace in carry out combustion reaction, after being cooled to room temperature, obtain required catalyst；The evaluation result of catalyst is shown in figure
2。
Embodiment three
The preparation method of the present embodiment the following steps are included:
Step 1, by the presoma of the presoma of the active component of catalyst, the presoma of auxiliary agent and catalyst carrier according to urging
The composition and ratio of agent is dissolved in a small amount of deionized water respectively, uniformly mixes, and wherein the composition of catalyst includes: that account for catalyst total
The active component nickel oxide of the 5%-25% of weight, accounted in terms of oxide total catalyst weight 1%-10% auxiliary agent and remaining for catalysis
The carrier of agent, wherein the auxiliary agent selects SrO.The dosage of incendiary agent is the active component forerunner by its molal quantity and catalyst
The ratio between body, auxiliary agent presoma and support precursor total moles 3:1.
The solution of configured sodium citrate is added in the solution for the nitrate that step 1 mixes by step 2, drop
Process is added to keep constantly stirring, sonicated 30 min of the mixture of generation obtains transparent colloidal sol.
Step 3, the colloidal sol that step 2 is obtained are transferred to quartz boat or crucible, are transferred to the 300-600 preheated in advanceoC
Muffle furnace in carry out combustion reaction, after being cooled to room temperature, obtain required catalyst；The evaluation result of catalyst is shown in figure
3。
Example IV
The preparation method of the present embodiment the following steps are included:
Step 1, by the presoma of the presoma of the active component of catalyst, the presoma of auxiliary agent and catalyst carrier according to urging
The composition and ratio of agent is dissolved in a small amount of deionized water respectively, uniformly mixes, and wherein the composition of catalyst includes: that account for catalyst total
The active component nickel oxide of the 5%-25% of weight, accounted in terms of oxide total catalyst weight 1%-10% auxiliary agent and remaining for catalysis
The carrier of agent, wherein the auxiliary agent selects BaO.The dosage of incendiary agent is the active component forerunner by its molal quantity and catalyst
The ratio between body, auxiliary agent presoma and support precursor total moles 3:1.
The solution of configured sodium citrate is added in the solution for the nitrate that step 1 mixes by step 2, drop
Process is added to keep constantly stirring, sonicated 30 min of the mixture of generation obtains transparent colloidal sol.
Step 3, the colloidal sol that step 2 is obtained are transferred to quartz boat or crucible, are transferred to the 300-600 preheated in advanceoC
Muffle furnace in carry out combustion reaction, after being cooled to room temperature, obtain required catalyst；The evaluation result of catalyst is shown in figure
4。
Although implementation method of the invention has been announced as above, it is not limited only in specification and embodiments listed
With it can be fully applied to various fields suitable for the present invention, for those skilled in the art, can be easy
Realize other modification, therefore under without departing substantially from universal defined by claim and equivalency range, the present invention is not
It is limited to specific details and embodiment shown and described herein.
Claims (8)
1. a kind of Ni-based methanation of modification, which is characterized in that its composition includes: the activity for accounting for the 5%-25% of total catalyst weight
Component nickel oxide counts the auxiliary agent for accounting for total catalyst weight 1%-10% using oxide with remaining as the carrier of catalyst, wherein described
Auxiliary agent selects MgO, CaO, SrO and BaO etc. one or more of.
2. the method for the modified nickel-base catalyst of citrate combustion method preparation, which comprises the following steps:
Step 1, by the presoma of the presoma of the active component of catalyst, the presoma of auxiliary agent and catalyst carrier according to urging
The composition and ratio of agent is dissolved in a small amount of deionized water respectively, uniformly mixes, and wherein the composition of catalyst includes: that account for catalyst total
The active component nickel oxide of the 5%-25% of weight, accounted in terms of oxide total catalyst weight 1%-10% auxiliary agent and remaining for catalysis
The carrier of agent, wherein the auxiliary agent selection MgO, CaO, SrO and BaO etc. are one or more of.
3. the support precursor of the catalyst is aluminum nitrate, the carrier of catalyst is aluminium oxide.
4. the presoma of the active component of the catalyst is nickel nitrate, the active component of catalyst is elemental nickel.
5. the auxiliary agent presoma of the catalyst is one or more of magnesium nitrate, calcium nitrate, strontium nitrate and barium nitrate.
6. the incendiary agent of the catalyst is sodium citrate, the dosage of incendiary agent is the active component by its molal quantity and catalyst
The ratio between presoma, auxiliary agent presoma and support precursor total moles (1~5): 1.
7. the solution of configured sodium citrate is added in the solution for the nitrate that step 1 mixes by step 2, it is added dropwise
Process will keep constantly stirring, and sonicated 30 min of the mixture of generation obtains transparent colloidal sol.
8. step 3, the colloidal sol that step 2 is obtained is transferred to quartz boat or crucible, is transferred to the 300-600 preheated in advanceoC's
Combustion reaction is carried out in Muffle furnace, after being cooled to room temperature, obtains required catalyst.
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| CN103537288A (en) * | 2013-10-25 | 2014-01-29 | 中国华能集团清洁能源技术研究院有限公司 | Method for preparing methanation catalyst by adopting urea combustion method |
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