CN111889115A - Deoxygenation catalyst and preparation method and application thereof - Google Patents
Deoxygenation catalyst and preparation method and application thereof Download PDFInfo
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- CN111889115A CN111889115A CN201910365828.XA CN201910365828A CN111889115A CN 111889115 A CN111889115 A CN 111889115A CN 201910365828 A CN201910365828 A CN 201910365828A CN 111889115 A CN111889115 A CN 111889115A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- 238000006392 deoxygenation reaction Methods 0.000 title claims description 4
- 238000002360 preparation method Methods 0.000 title abstract description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000001035 drying Methods 0.000 claims abstract description 43
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 29
- 239000010941 cobalt Substances 0.000 claims abstract description 29
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 27
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 238000004898 kneading Methods 0.000 claims abstract description 10
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000465 moulding Methods 0.000 claims abstract description 7
- VZDYWEUILIUIDF-UHFFFAOYSA-J cerium(4+);disulfate Chemical compound [Ce+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VZDYWEUILIUIDF-UHFFFAOYSA-J 0.000 claims abstract description 4
- 229910000355 cerium(IV) sulfate Inorganic materials 0.000 claims abstract description 4
- 238000011068 loading method Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 37
- 239000007789 gas Substances 0.000 claims description 32
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 claims description 12
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 12
- 238000005470 impregnation Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229940044175 cobalt sulfate Drugs 0.000 claims description 6
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 6
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 5
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 5
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229910000333 cerium(III) sulfate Inorganic materials 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- BZRRQSJJPUGBAA-UHFFFAOYSA-L cobalt(ii) bromide Chemical compound Br[Co]Br BZRRQSJJPUGBAA-UHFFFAOYSA-L 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 150000001869 cobalt compounds Chemical class 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 25
- 239000003245 coal Substances 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 37
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 17
- 229910052760 oxygen Inorganic materials 0.000 description 17
- 239000001301 oxygen Substances 0.000 description 17
- 238000002791 soaking Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 12
- -1 ceryl sulfate Chemical compound 0.000 description 11
- 239000000377 silicon dioxide Substances 0.000 description 11
- 239000000571 coke Substances 0.000 description 9
- 238000004587 chromatography analysis Methods 0.000 description 7
- 239000000523 sample Substances 0.000 description 7
- 229910002651 NO3 Inorganic materials 0.000 description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 238000007084 catalytic combustion reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- XMHIUKTWLZUKEX-UHFFFAOYSA-N hexacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O XMHIUKTWLZUKEX-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- FEBJSGQWYJIENF-UHFFFAOYSA-N nickel niobium Chemical compound [Ni].[Nb] FEBJSGQWYJIENF-UHFFFAOYSA-N 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003568 thioethers Chemical class 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
- C10L2290/02—Combustion or pyrolysis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/20—Capture or disposal of greenhouse gases of methane
Abstract
The invention discloses a deoxidation catalyst and a preparation method thereof, wherein the preparation method of the deoxidation catalyst comprises the following steps: (1) impregnating silicon oxide with mixed liquid containing Nd and nickel, and then drying and roasting at high temperature to prepare modified silicon oxide; (2) loading cobalt on the modified silicon oxide prepared in the step (1), and drying and roasting to prepare cobalt-loaded silicon oxide; (3) and (4) kneading and molding ceric sulfate and the cobalt-loaded silicon oxide prepared in the step (3), and drying and roasting to obtain the deoxidation catalyst. The catalyst is used for deoxidizing the coal bed gas and has the advantages of high activity, low reaction temperature, simple preparation method, low cost and the like.
Description
Technical Field
The invention relates to a deoxidation catalyst, a preparation method and application thereof, in particular to a coal gas layer deoxidation composite catalyst, and a preparation method and application thereof.
Background
The key point of the development and utilization of the coal bed gas is to remove oxygen in the coal bed gas, and the existing coal bed gas deoxidation technology mainly comprises a pressure swing adsorption separation method, a coke combustion method, a catalytic deoxidation method and the like. Chinese patent ZL85103557 discloses a method for separating and enriching methane from coal bed gas by using a pressure swing adsorption method. Generally, the oxygen content of the exhaust gas discharged in the concentration and purification process of methane is also concentrated and improved, and the exhaust gas inevitably contains 5-15% of methane, so that the discharged exhaust gas is in the explosion limit range of methane, and explosion danger exists, so that the application of the technology is limited.
The deoxidation method by using coke combustion (ZL 02113627.0, 200610021720.1) is characterized in that oxygen in methane-rich gas reacts with coke under the high-temperature condition, and part of methane reacts with oxygen to achieve the aim of deoxidation. The advantage is that about 70% of the oxygen reacts with coke and 30% of the oxygen reacts with methane, so that methane losses are smaller. But the disadvantage is that the precious coke resource is consumed, and the coke consumption cost accounts for about 50 percent of the whole operation cost. In addition, the coke deoxidation method has high labor intensity during coke feeding and slag discharging, large environmental dust and difficulty in realizing self-control operation and large-scale production, and the coke contains sulfides in various forms, so that the sulfur content in the gas after oxygen removal is increased.
The technology for researching the supported noble metal catalyst at home and abroad is mature. For example, rare earth cerium component with oxygen storage and release functions is added into a catalyst system for the large-scale ligation of Chinese academy of sciences to prepare the novel supported palladium noble metal catalyst, and the oxygen concentration in produced gas is within 0.1 percent and the oxygen conversion rate is higher than 96 percent after the deoxidation treatment of coal bed gas with the methane concentration of 39.15 percent and the oxygen concentration of 12.6 percent. Since the noble metal catalyst is expensive and has limited resources, the range of application is limited. And the non-noble metal oxide catalyst has low cost and easy availability, so the catalyst is greatly concerned. However, the non-noble metal is limited by activity, and the reaction needs to be carried out at a higher temperature, so that the energy consumption is higher.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a coal bed gas deoxidation catalyst and a preparation method thereof. The catalyst is used for deoxidizing the coal bed gas and has the advantages of high activity, low reaction temperature, simple preparation method, low cost and the like.
A preparation method of a deoxidation catalyst comprises the following steps:
(1) impregnating silicon oxide with mixed liquid containing Nd and nickel, and then drying and roasting at high temperature to prepare modified silicon oxide;
(2) loading cobalt on the modified silicon oxide prepared in the step (1), and drying and roasting to prepare cobalt-loaded silicon oxide;
(3) and (4) kneading and molding ceric sulfate and the cobalt-loaded silicon oxide prepared in the step (3), and drying and roasting to obtain the deoxidation catalyst.
In the method, in the mixed liquid containing Nd and nickel in the step (1), the molar concentrations of metal ions Nd and nickel are the same, generally 0.1-2.5mol/L, preferably 0.5-1.5mol/L, and the mixed liquid is roasted at 700-1000 ℃ for 1-10h after being dried, preferably at 800-900 ℃ for 2-8 h after being dried. The impregnation is preferably carried out by an equal volume impregnation method. The silica can be prepared using commercially available products or according to the prior art. Nd and nickel are derived from corresponding salts, such as nitrate, sulfate, chloride and the like. The mixed liquid of Nd and nickel is used for dipping the silicon oxide and then is roasted at high temperature, and the niobium-nickel composite oxide with the perovskite structure is generated on the inner surface and the outer surface of the silicon oxide, and the composite oxide with the perovskite structure can improve the oxygen concentration shown by the silicon oxide and can inhibit the sintering and inactivation of cobalt.
The above method, the preparation of the cobalt-supported silica in the step (2), can employ conventional techniques, including any method of supporting cobalt on silica. Specifically, the cobalt-containing compound is impregnated and loaded on the molded silicon oxide, or the cobalt-containing compound and the silicon oxide powder are kneaded and molded, and then the obtained product is dried and roasted to obtain the cobalt-loaded silicon oxide. The compound carrying cobalt can be one or more of cobalt nitrate, cobalt sulfate, cobalt bromide and cobalt chloride. The drying time is 1-5h, preferably 2-4h, the drying temperature is 90-150 ℃, preferably 100-130 ℃; the roasting time is 3-8h, preferably 4-6h, and the temperature is 300-600 ℃, preferably 400-500 ℃.
In the above method, the impregnation solution supporting cobalt in step (2) contains at least one of 2, 5-dihydroxy-terephthalic acid and 1,3, 5-benzenetricarboxylic acid, and the mass content of at least one of 2, 5-dihydroxy-terephthalic acid and 1,3, 5-benzenetricarboxylic acid in the impregnation solution is 0.5% to 10%, preferably 2% to 7%. The 2, 5-dihydroxy-terephthalic acid or 1,3, 5-benzene tricarboxylic acid added into the mixed solution has stronger coordination effect with cobalt ions, can improve the dispersion degree of copper on alumina, and further improves the activity of the catalyst.
In the method, a proper amount of peptizing agent, pore-forming agent, metal auxiliary agent and the like can be added in the kneading process in the step (3) according to the requirements.
In the method, the ceryl sulfate in the step (3) is prepared by adopting the prior art. A specific preparation method of ceryl sulfate, such as the preparation of ceryl sulfate by roasting at 300-500 ℃ for 1-10 h.
In the method, before the ceryl sulfate is kneaded in step (3), the cobalt-loaded silica is preferably treated with a water vapor-nitrogen mixed gas with a water vapor volume content of 1% -15%, preferably 1% -5%, at a temperature of 150-. The ceryl sulfate treated by water vapor can improve the hydrophilicity of the surface of the ceryl sulfate, is beneficial to the dispersion of the ceryl sulfate, and further improves the activity.
The catalyst prepared by the method has the weight ratio of silicon oxide to zirconium silicate of 10:1-6:1, and the weight content of cobalt oxide in the catalyst is 5-25%.
Research results show that the mechanism of catalytic combustion of the coal bed gas is that methane is firstly dissociated into CH on the surface of the catalytic combustion catalystxSpecies of which x<4, then carrying out oxidation reaction with the adsorbed oxygen or lattice oxygen. This application will catalyze burning catalyst and have the stronger ceric acyl sulfate of methane activation ability to mix, methane can be activated on ceric acyl sulfate molecular sieve, and activated methane species can overflow to catalytic combustion catalyst around and react, burns more easily fast, is showing the activity that has improved the catalyst, and the composite metal oxide NdCoO who has the perovskite structure that contains in this application catalyst in addition has3-yHas rich oxygen vacancy and strong oxygen adsorption capacity, and is beneficial to the enrichment of oxygen for efficient reaction.
Detailed Description
The action and effect of a deoxygenation catalyst and a preparation method thereof according to the present invention will be further described with reference to the following examples, which should not be construed as limiting the scope of the present invention. In this application,% is volume concentration unless otherwise specified. The ceric acid sulfate referred to in examples and comparative examples was prepared by calcining cerium sulfate at 350 ℃ for 3 hours.
Example 1
Preparation of modified silica: an isovolumetric impregnation method was used to impregnate silica (commercially available, having the following properties: specific surface 335 m)2Per g, the pore volume is 0.86 ml/g) is soaked in Nd nitrate and nickel nitrate aqueous solution, the molar concentration of Nd and nickel metal ions in the solution is 0.5mol/L, and drying and roasting are carried out after soaking, wherein the drying time is 1h, and the drying temperature is 100 ℃; the roasting time is 2 hours, and the temperature is 900 ℃;
preparation of cobalt-loaded silica: soaking a cobalt nitrate solution on the modified silicon oxide by adopting an isometric soaking method, and drying and roasting after soaking, wherein the drying time is 2 hours, and the drying temperature is 130 ℃; the roasting time is 4 hours, and the temperature is 400 ℃;
mixing, kneading and molding cerous sulfate and cobalt-loaded silicon oxide, and drying and roasting to prepare a deoxidation catalyst, wherein the drying time is 4 hours, and the drying temperature is 100 ℃; the roasting time is 6h, and the temperature is 400 ℃. The weight ratio of silicon oxide to zirconium silicate in the catalyst was 8:1, and the weight content of cobalt oxide in the catalyst was 15%.
The catalyst performance is evaluated by taking coal bed methane deoxidation as a probe reaction, and the feed gas comprises the following components: CH (CH)420 vol%，O23vol%, the balance being N2. The reaction temperature is 435 ℃, and the volume space velocity is 14500 h-1After the reaction is stable, detecting O in tail gas at the outlet of the reactor by on-line chromatography2The concentration was 0.86%.
Example 2
Preparation of modified silica: an isovolumetric impregnation method was used to impregnate silica (commercially available, having the following properties: specific surface 335 m)2Pore volume of 0.86 ml/g) was immersed in an aqueous solution of Nd nitrate and nickel nitrate, the molar concentration of Nd and nickel metal ions in the solution was 1.5mol/L, and after immersion, the solution was immersed in an aqueous solution of Nd nitrate and nickel nitrateDrying and roasting, wherein the drying time is 2 hours, and the drying temperature is 100 ℃; the roasting time is 8 hours, and the temperature is 700 ℃;
preparation of cobalt-loaded silica: soaking a cobalt sulfate solution on the modified silicon oxide by adopting an isometric soaking method, drying and roasting after soaking, wherein the drying time is 3 hours, and the drying temperature is 120 ℃; the roasting time is 5 hours, and the temperature is 450 ℃;
mixing, kneading and molding cerous sulfate and cobalt-loaded silicon oxide, and drying and roasting to prepare a deoxidation catalyst, wherein the drying time is 4 hours, and the drying temperature is 100 ℃; the roasting time is 6h, and the temperature is 400 ℃. The weight ratio of silicon oxide to zirconium silicate in the catalyst was 10:1, and the weight content of cobalt oxide in the catalyst was 25%.
The catalyst performance is evaluated by taking coal bed methane deoxidation as a probe reaction, and the feed gas comprises the following components: CH (CH)420 vol%，O23vol%, the balance being N2. The reaction temperature is 435 ℃, and the volume space velocity is 14500 h-1After the reaction is stable, detecting O in tail gas at the outlet of the reactor by on-line chromatography2The concentration was 0.82%.
Example 3
Preparation of modified silica: an isovolumetric impregnation method was used to impregnate silica (commercially available, having the following properties: specific surface 335 m)2Per g, the pore volume is 0.86 ml/g) is soaked in Nd nitrate and nickel nitrate aqueous solution, the molar concentration of Nd and nickel metal ions in the solution is 1mol/L, and drying and roasting are carried out after soaking, wherein the drying time is 0.5h, and the drying temperature is 130 ℃; the roasting time is 5 hours, and the temperature is 800 ℃;
preparation of cobalt-loaded silica: soaking a cobalt bromide solution on the modified silicon oxide by adopting an isometric soaking method, and drying and roasting after soaking, wherein the drying time is 4 hours and the drying temperature is 100 ℃; the roasting time is 4 hours, and the temperature is 500 ℃;
preparation of cobalt-loaded silica: soaking a cobalt sulfate solution on the modified silicon oxide by adopting an isometric soaking method, drying and roasting after soaking, wherein the drying time is 3 hours, and the drying temperature is 120 ℃; the roasting time is 5 hours, and the temperature is 450 ℃;
mixing, kneading and molding cerous sulfate and cobalt-loaded silicon oxide, and drying and roasting to prepare a deoxidation catalyst, wherein the drying time is 4 hours, and the drying temperature is 100 ℃; the roasting time is 6h, and the temperature is 400 ℃. The weight ratio of silicon oxide to zirconium silicate in the catalyst was 7:1, and the weight content of cobalt oxide in the catalyst was 8%.
The catalyst performance is evaluated by taking coal bed methane deoxidation as a probe reaction, and the feed gas comprises the following components: CH (CH)420 vol%，O23vol%, the balance being N2. The reaction temperature is 435 ℃, and the volume space velocity is 14500 h-1After the reaction is stable, detecting O in tail gas at the outlet of the reactor by on-line chromatography2The concentration was 0.66%.
Example 4
The process is carried out in the same manner as in example 1 except that the cobalt sulfate solution contains 6% by mass of 2, 5-dihydroxy-terephthalic acid, and the resulting product is impregnated with alumina, dried, and calcined.
The catalyst performance is evaluated by taking coal bed methane deoxidation as a probe reaction, and the feed gas comprises the following components: CH (CH)420 vol%，O23vol%, the balance being N2. The reaction temperature is 435 ℃, and the volume space velocity is 14500 h-1After the reaction is stable, detecting O in tail gas at the outlet of the reactor by on-line chromatography2The concentration was 0.15%.
Example 5
The same procedure as in example 1 was repeated except that the cobalt sulfate solution contained 3% by mass of 1,3, 5-benzenetricarboxylic acid.
The catalyst performance is evaluated by taking coal bed methane deoxidation as a probe reaction, and the feed gas comprises the following components: CH (CH)420 vol%，O23vol%, the balance being N2. The reaction temperature is 435 ℃, and the volume space velocity is 14500 h-1After the reaction is stable, detecting O in tail gas at the outlet of the reactor by on-line chromatography2The concentration was 0.24%.
Example 6
The difference from example 1 is that before kneading, the commercially available ceryl sulfate was treated with a steam-nitrogen mixture containing 1% by volume of steam at 180 ℃ for 3 min.
Taking coal bed gas deoxidation as probe reactionThe catalyst performance should be evaluated with a feed gas composition of: CH (CH)420 vol%，O23vol%, the balance being N2. The reaction temperature is 435 ℃, and the volume space velocity is 14500 h-1After the reaction is stable, detecting O in tail gas at the outlet of the reactor by on-line chromatography2The concentration was 0.43%.
Example 7
Compared with the example 1, the difference is that before the commercial ceryl sulfate is kneaded, the ceryl sulfate is treated by adopting a water vapor nitrogen mixed gas with the water vapor volume content of 4 percent, the treatment temperature is 120 ℃, and the treatment time is 1-151010 min.
The catalyst performance is evaluated by taking coal bed methane deoxidation as a probe reaction, and the feed gas comprises the following components: CH (CH)420 vol%，O23vol%, the balance being N2. The reaction temperature is 435 ℃, and the volume space velocity is 14500 h-1After the reaction is stable, detecting O in tail gas at the outlet of the reactor by on-line chromatography2The concentration was 0.35%.
Claims (10)
1. A method for preparing a deoxygenation catalyst is characterized by comprising the following steps: the method comprises the following steps:
(1) impregnating silicon oxide with mixed liquid containing Nd and nickel, and then drying and roasting at high temperature to prepare modified silicon oxide;
(2) loading cobalt on the modified silicon oxide prepared in the step (1), and drying and roasting to prepare cobalt-loaded silicon oxide;
(3) and (4) kneading and molding ceric sulfate and the cobalt-loaded silicon oxide prepared in the step (3), and drying and roasting to obtain the deoxidation catalyst.
2. The method of claim 1, wherein: in the mixed liquid containing Nd and nickel in the step (1), the molar concentrations of metal ions Nd and nickel are the same and are both 0.1-2.5mol/, the mixed liquid is dried and then roasted for 1-10h at 700-1000 ℃, and the impregnation adopts an isometric impregnation method.
3. The method of claim 2, wherein: in the mixed liquid containing Nd and nickel in the step (1), the molar concentrations of metal ions Nd and nickel are the same and are both 0.5-1.5mol/L, and the mixed liquid is roasted for 2-8 h at 7800-900 ℃ after being dried.
4. The method of claim 1, wherein: in the step (2), the cobalt-loaded silicon oxide is prepared by impregnating a cobalt-containing compound on the molded silicon oxide or kneading the cobalt-containing compound and silicon oxide powder for molding, and then drying and roasting.
5. The method of claim 4, wherein: the cobalt compound is one or more of cobalt nitrate, cobalt sulfate, cobalt bromide and cobalt chloride.
6. The method of claim 4, wherein: the drying time is 1-5h, and the drying temperature is 90-150 ℃; the roasting time is 3-8h, and the temperature is 300-600 ℃.
7. The method of claim 4, wherein: the impregnation liquid for loading cobalt contains at least one of 2, 5-dihydroxy-terephthalic acid and 1,3, 5-benzene tricarboxylic acid, and the mass content of at least one of 2, 5-dihydroxy-terephthalic acid and 1,3, 5-benzene tricarboxylic acid in the impregnation liquid is 0.5-10%.
8. The method of claim 1, wherein: and (4) adding a peptizing agent, a pore-forming agent or a metal auxiliary agent as required in the kneading process in the step (3).
9. The method of claim 1, wherein: before the cerous sulfate is kneaded in the step (3), the cobalt-loaded silicon oxide is treated by adopting water vapor nitrogen mixed gas with the water vapor volume content of 1-15%, the treatment temperature is 150-.
10. A catalyst prepared by the process of any one of claims 1 to 9, wherein: the weight ratio of the silicon oxide to the ceric sulfate in the catalyst is 10:1-6:1, and the weight content of the cobalt oxide in the catalyst is 5-25%.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5213779A (en) * | 1980-07-31 | 1993-05-25 | Gas Desulfurization Corporation | Process for optimizing the removal of NOX and SOX from gases utilizing lanthanide compounds |
| CN102302931A (en) * | 2011-07-11 | 2012-01-04 | 大连瑞克科技有限公司 | Catalytic combustion deoxidation catalyst for oxygen-containing methane mixed gas, as well as preparation method and application thereof |
| CN102994185A (en) * | 2012-12-11 | 2013-03-27 | 西南化工研究设计院有限公司 | Process of catalytic deoxidation of oxygen-containing coal bed methane and comprehensive utilization of reaction heat |
| CN103920507A (en) * | 2013-01-15 | 2014-07-16 | 南京工业大学 | Catalyst for oxidation of hydrogen chloride to prepare chlorine and application thereof |
| CN106607057A (en) * | 2015-10-26 | 2017-05-03 | 中国石油化工股份有限公司 | Coalbed methane deoxidation catalyst and its preparation method and use |
-
2019
- 2019-05-05 CN CN201910365828.XA patent/CN111889115B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5213779A (en) * | 1980-07-31 | 1993-05-25 | Gas Desulfurization Corporation | Process for optimizing the removal of NOX and SOX from gases utilizing lanthanide compounds |
| CN102302931A (en) * | 2011-07-11 | 2012-01-04 | 大连瑞克科技有限公司 | Catalytic combustion deoxidation catalyst for oxygen-containing methane mixed gas, as well as preparation method and application thereof |
| CN102994185A (en) * | 2012-12-11 | 2013-03-27 | 西南化工研究设计院有限公司 | Process of catalytic deoxidation of oxygen-containing coal bed methane and comprehensive utilization of reaction heat |
| CN103920507A (en) * | 2013-01-15 | 2014-07-16 | 南京工业大学 | Catalyst for oxidation of hydrogen chloride to prepare chlorine and application thereof |
| CN106607057A (en) * | 2015-10-26 | 2017-05-03 | 中国石油化工股份有限公司 | Coalbed methane deoxidation catalyst and its preparation method and use |
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