CN111889113B - Coal gas layer treatment catalyst and preparation method thereof - Google Patents
Coal gas layer treatment catalyst and preparation method thereof Download PDFInfo
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- CN111889113B CN111889113B CN201910365819.0A CN201910365819A CN111889113B CN 111889113 B CN111889113 B CN 111889113B CN 201910365819 A CN201910365819 A CN 201910365819A CN 111889113 B CN111889113 B CN 111889113B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000003034 coal gas Substances 0.000 title description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 45
- 239000011701 zinc Substances 0.000 claims abstract description 45
- -1 ceryl sulfate Chemical compound 0.000 claims abstract description 34
- 239000003245 coal Substances 0.000 claims abstract description 30
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000001035 drying Methods 0.000 claims abstract description 18
- 239000002002 slurry Substances 0.000 claims abstract description 17
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 15
- 238000005507 spraying Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 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 abstract description 7
- 229910000333 cerium(III) sulfate Inorganic materials 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 26
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 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 description 8
- 229910000355 cerium(IV) sulfate Inorganic materials 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 6
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical group [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 229940102001 zinc bromide Drugs 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 229960001939 zinc chloride Drugs 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 28
- 230000000694 effects Effects 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 41
- 229910052760 oxygen Inorganic materials 0.000 description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 239000000523 sample Substances 0.000 description 10
- 239000000571 coke Substances 0.000 description 8
- 238000004587 chromatography analysis Methods 0.000 description 7
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- XMHIUKTWLZUKEX-UHFFFAOYSA-N hexacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O XMHIUKTWLZUKEX-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000007084 catalytic combustion reaction Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000002003 electron diffraction Methods 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 229910002706 AlOOH Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910025794 LaB6 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000005406 washing Methods 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a coal bed gas treatment catalyst, which contains zinc-loaded alumina and ceryl sulfate, wherein the zinc-loaded alumina is wrapped around the ceryl sulfate, the weight ratio of the zinc-loaded alumina to the ceryl sulfate is 8:1-2:1, and the content of zinc in oxide is 5-25 wt% based on the weight of the zinc-loaded alumina; the preparation method of the catalyst comprises the following steps: firstly, uniformly mixing a zinc-containing compound and aluminum hydroxide slurry, then spraying the mixed solution around cerous sulfate, drying and roasting to obtain the coal bed gas 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 coal gas layer treatment catalyst and a preparation method thereof, in particular to a low-temperature high-activity coal gas layer deoxidation catalyst and a preparation method thereof.
Background
China is a large coal producing country, coal bed gas with different concentrations can be produced due to coal production every year, and developing effective coal bed gas utilization technology and reducing direct emission of methane are a component part for building an energy-saving and environment-friendly sustainable development mode and building a low-carbon economic system in China. The method has the advantages that the low-grade energy source coal bed gas is practically and reasonably developed by combining energy conservation and emission reduction and improvement of the requirement on the environment, the low-grade energy source coal bed gas is well converted into available resources, the application range and the scale of the coal bed gas are expanded, the utilization efficiency of the coal bed gas is improved, the dual meanings of energy conservation and environmental protection are realized, the national planning on energy policies is met, the control of the international environmental protection organization on the greenhouse effect is met, the strong support of China on the development and the use of the low-grade energy source is better met, and the domestic rapid development of the coal bed gas industry is promoted.
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 has the advantages of high activity, low reaction temperature, simple preparation method, low cost and the like.
The catalyst contains zinc-loaded alumina and ceryl sulfate, wherein the zinc-loaded alumina is wrapped around the ceryl sulfate, the weight ratio of the zinc-loaded alumina to the ceryl sulfate is 8:1-2:1, preferably 6:1-3:1, and the content of zinc in terms of oxides is 5-25 wt%, preferably 10-20 wt%, based on the weight of the zinc-loaded alumina.
In the catalyst, the thickness of the zinc-loaded alumina wrapped around the ceryl sulfate is 15 μm to 130 μm, preferably 20 μm to 100 μm.
In the catalyst, the cerous sulfate can be spherical or strip-shaped, and is preferably spherical; the cerous acyl sulfate equivalent diameter is 1mm to 8mm, preferably 3mm to 5 mm.
A preparation method of a coal bed methane deoxidation catalyst comprises the following steps: firstly, uniformly mixing a zinc-containing compound and aluminum hydroxide slurry, then spraying the mixed solution around cerous sulfate, drying and roasting to obtain the coal bed gas deoxidation catalyst.
In the above method, the ceryl sulfate may be commercially available or prepared according to 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. The aluminum hydroxide slurry is generally pseudo-boehmite slurry. The pseudoboehmite is also called alumina monohydrate or pseudoboehmite, and the molecular formula is AlOOH & nH 2 O (n = 0.08-0.62). The method for producing the aluminum hydroxide slurry is not particularly limited, and various methods commonly used in the art may be used, and examples thereof include aluminum alkoxide hydrolysis, acid or alkali methods of aluminum salt or aluminate, and NaA1O 2 Introducing CO into the solution 2 The carbonization method of (3). The specific operation method is well known to those skilled in the art and will not be described herein.
In the method, the zinc-containing compound can be one or more of zinc nitrate, zinc sulfate, zinc bromide and zinc chloride.
In the method, the drying time is 1-5h, preferably 2-4h, the drying temperature is 90-150 ℃, preferably 100-; the roasting time is 3-8h, preferably 4-6h, and the temperature is 300-700 ℃, preferably 400-500 ℃.
In the above method, the mixed solution 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 mixed 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 zinc ions, can improve the dispersion degree of zinc on alumina, and further improves the activity of the catalyst.
In the method, before spraying and soaking the mixed solution, the ceryl sulfate is preferably treated by adopting a water vapor nitrogen mixed gas with the water vapor volume content of 0.5-5 percent, and more preferably 1-4 percent, the treatment temperature is 100-. The ceric acyl sulfate treated by the water vapor can improve the hydrophilicity of the surface of the ceric acyl sulfate, is beneficial to spray soaking of mixed liquor, improves the interaction force between the zinc-loaded aluminum oxide and the ceric acyl sulfate, avoids the zinc-loaded aluminum oxide from falling off from the periphery of the ceric acyl sulfate, and improves the stability of the catalyst.
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 catalyst x Species of which x<4, then carrying out oxidation reaction with the adsorbed oxygen or lattice oxygen. This application will catalyze the burning catalyst around ceric acid sulfate, ceric acid sulfate compares the catalytic burning catalyst and has stronger activated methane's effect at low temperature, and the methane substance after the activation diffuses to and reacts in the catalytic burning catalyst coating, burns fast more easily, has showing the activity that has improved the catalyst.
Detailed Description
The function and effect of a coal bed methane deoxidation catalyst and a preparation method thereof are further illustrated with reference to the following examples, but the following examples are not to be construed as limiting the invention. In this application,% is volume concentration unless otherwise specified.
The catalyst of the invention can adopt means such as transmission electron microscope observation, electron diffraction analysis, element composition analysis and the like to confirm the wrapping structure and determine the composition. The determination of the catalyst coating structure specifically adopts the following method: the sample was sufficiently ground in an agate mortar using a high-resolution transmission electron microscope (JEM 2100 LaB6, JEOL Ltd., Japan) with a resolution of 0.23 nm equipped with an X-ray energy dispersive spectrometer (EDX) from EDAX, and then ultrasonically dispersed in absolute ethanol for 20 min. And (3) dripping 2-3 drops of the suspension liquid on a micro-grid carbon film supported by a zinc net, and carrying out TEM observation, electron diffraction analysis and element composition analysis on the sample after the sample is dried. The ceric acid sulfate referred to in examples and comparative examples was prepared by calcining cerium sulfate at 350 ℃ for 3 hours.
Example 1
Preparing aluminum hydroxide slurry by adopting an aluminum isopropoxide hydrolysis method: mixing water and aluminum isopropoxide according to a molar ratio of 120:1, controlling the hydrolysis temperature at 80-85 ℃, hydrolyzing the aluminum isopropoxide for 1.5h, and then aging at 90-95 ℃ for 18h to obtain aluminum hydroxide slurry with the solid content of 21.3 wt%.
Spray soaking process: firstly, uniformly mixing zinc nitrate and aluminum hydroxide slurry, then spraying 500g of ceryl sulfate (a product sold in the market and with the equivalent diameter of 4 mm) in the mixed solution, drying and roasting to prepare the coal bed methane 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 catalyst properties were as follows: the zinc-loaded alumina is wrapped around ceryl sulfate, the weight ratio of the zinc-loaded alumina to the ceryl sulfate is 4:1, and the content of zinc in oxide is 15wt% based on the weight of the zinc-loaded alumina. The thickness of the zinc-loaded alumina wrapped around the ceryl sulfate was 60 μm.
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) 4 20 vol%，O 2 3 vol%, the balance being N 2 . The reaction temperature is 420 ℃, and the volume space velocity is 15000 h -1 After the reaction is stable, detecting O in tail gas at the outlet of the reactor by on-line chromatography 2 The concentration is 0.47%, and O in tail gas at the outlet of the reactor after 300 h operation 2 The concentration was 0.6%.
Example 2
Preparing aluminum hydroxide slurry by adopting an aluminum isopropoxide hydrolysis method: mixing water and aluminum isopropoxide according to a molar ratio of 120:1, controlling the hydrolysis temperature at 80-85 ℃, hydrolyzing the aluminum isopropoxide for 1.5h, and then aging at 90-95 ℃ for 18h to obtain aluminum hydroxide slurry with the solid content of 21.3 wt%.
And (3) spray-dipping process: firstly, uniformly mixing zinc nitrate and aluminum hydroxide slurry, then spraying 500g of ceryl sulfate (a product sold in the market and with the equivalent diameter of 5 mm) in the mixed solution, and drying and roasting to prepare the coal bed methane 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 catalyst properties were as follows: the zinc-loaded alumina is wrapped around ceryl sulfate, the weight ratio of the zinc-loaded alumina to the ceryl sulfate is 3:1, and the content of zinc in oxide is 20wt% based on the weight of the zinc-loaded alumina.
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) 4 20 vol%，O 2 3 vol%, the balance being N 2 . The reaction temperature is 420 ℃, and the volume space velocity is 15000 h -1 After the reaction is stable, detecting O in tail gas at the outlet of the reactor by on-line chromatography 2 The concentration was 0.51%.
Example 3
Preparing aluminum hydroxide slurry by adopting a carbonization method of introducing carbon dioxide gas into sodium metaaluminate solution: will contain 30wt% CO 2 CO of 2 /N 2 Introducing the mixed gas into a sodium metaaluminate solution, carrying out gelling reaction at 30 ℃, controlling the pH of the reaction end point to be 10.5-11.0, aging after the reaction is finished, and washing the mixture by deionized water at 60 ℃ until the pH of the filtrate is 6.5 to obtain aluminum hydroxide slurry with the solid content of 31.2 wt%.
And (3) spray-dipping process: firstly, uniformly mixing zinc nitrate and aluminum hydroxide slurry, then spraying 500g of ceryl sulfate (a product sold in the market and with the equivalent diameter of 3 mm) in the mixed solution, and drying and roasting to prepare the coal bed methane 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 catalyst properties were as follows: the zinc-loaded alumina is wrapped around ceryl sulfate, the weight ratio of the zinc-loaded alumina to the ceryl sulfate is 6:1, and the content of zinc in oxide is 10wt% based on the weight of the zinc-loaded alumina.
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) 4 20 vol%，O 2 3 vol%, the balance being N 2 . The reaction temperature is 420 ℃, and the volume space velocity is 15000 h -1 After the reaction is stable, detecting O in tail gas at the outlet of the reactor by on-line chromatography 2 The concentration was 0.62%.
Example 4
The difference from example 1 is that the mixed solution contains 6% by mass of 2, 5-dihydroxy-terephthalic 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) 4 20 vol%，O 2 3 vol%, the balance being N 2 . The reaction temperature is 420 ℃, and the volume space velocity is 15000 h -1 After the reaction is stable, detecting O in tail gas at the outlet of the reactor by on-line chromatography 2 The concentration was 0.12%.
Example 5
The difference from example 1 is that the mixed solution contains 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) 4 20 vol%，O 2 3 vol%, the balance being N 2 . The reaction temperature is 420 ℃, and the volume space velocity is 15000 h -1 After the reaction is stable, detecting O in tail gas at the outlet of the reactor by on-line chromatography 2 The concentration was 0.05%.
Example 6
The difference from the example 1 is that before spraying and soaking the mixed solution, the ceryl sulfate is treated by adopting a water vapor nitrogen mixed gas with the water vapor volume content of 1 percent, the treatment temperature is 180 ℃, and the treatment time is 3 min.
The catalyst performance is evaluated by taking coal bed methane deoxidation as a probe reaction, and the raw material gas comprises the following components: CH (CH) 4 20 vol%，O 2 3 vol%, the balance being N 2 . The reaction temperature is 420 ℃, and the volume space velocity is 15000 h -1 After the reaction is stable, detecting O in tail gas at the outlet of the reactor by on-line chromatography 2 The concentration is 0.43 percent, and O in tail gas at the outlet of the reactor after 300 hours of operation 2 The concentration was 0.47%.
Example 7
Compared with the example 1, the difference is that before spraying and soaking the mixed solution, the ceric sulfate is treated by adopting the water vapor nitrogen mixed gas with the water vapor volume content of 4 percent, the treatment temperature is 120 ℃, and the treatment time is 10 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) 4 20 vol%，O 2 3 vol%, the balance being N 2 . The reaction temperature is 420 ℃, and the volume space velocity is 15000 h -1 After the reaction is stable, detecting O in tail gas at the outlet of the reactor by on-line chromatography 2 The concentration is 0.48 percent, and O in tail gas at the outlet of the reactor after 300 hours of operation 2 The concentration was 0.53%.
Claims (11)
1. A coal bed gas treatment catalyst, which is characterized in that: the catalyst contains zinc-loaded alumina and ceric sulfate, the zinc-loaded alumina is wrapped around the ceric sulfate, the weight ratio of the zinc-loaded alumina to the ceric sulfate is 8:1-2:1, and the content of zinc in terms of oxide is 5-25 wt% based on the weight of the zinc-loaded alumina; the preparation method of the cerous sulfate comprises the following steps: the cerium sulfate is prepared by roasting at the temperature of 300-500 ℃ for 1-10.
2. The catalyst of claim 1, wherein: the catalyst contains zinc-loaded alumina and ceric sulfate, the zinc-loaded alumina is wrapped around the ceric sulfate, the weight ratio of the zinc-loaded alumina to the ceric sulfate is 6:1-3:1, and the content of zinc in terms of oxides is 10-20 wt% based on the weight of the zinc-loaded alumina.
3. The catalyst of claim 1, wherein: the thickness of the zinc-loaded aluminum oxide wrapped around the ceryl sulfate is 15-130 μm, the ceryl sulfate is spherical or strip-shaped, and the equivalent diameter of the ceryl sulfate is 1-8 mm.
4. The catalyst of claim 3, wherein: the thickness of the zinc-loaded aluminum oxide wrapped around the ceryl sulfate is 20-100 μm, the ceryl sulfate is spherical, and the equivalent diameter of the ceryl sulfate is 3-5 mm.
5. A process for preparing a catalyst as claimed in any one of claims 1 to 4, characterized in that: the method comprises the following steps: firstly, uniformly mixing a zinc-containing compound and aluminum hydroxide slurry, then spraying the mixed solution around cerous sulfate, drying and roasting to obtain the coal bed gas deoxidation catalyst.
6. The method of claim 5, wherein: the aluminum hydroxide slurry is pseudo-boehmite slurry.
7. The method of claim 5, wherein: the zinc-containing compound is one or more of zinc nitrate, zinc sulfate, zinc bromide and zinc chloride.
8. The method of claim 5, wherein: the drying time is 1-5h, and the drying temperature is 90-150 ℃; the roasting time is 3-8h, and the temperature is 300-700 ℃.
9. The method of claim 8, wherein: the drying time is 2-4h, and the drying temperature is 100-130 ℃; the roasting time is 4-6h, and the temperature is 400-500 ℃.
10. The method of claim 5, wherein: the mixed solution contains at least one of 2, 5-dihydroxy-terephthalic acid or 1,3, 5-benzene tricarboxylic acid, and the mass content of at least one of 2, 5-dihydroxy-terephthalic acid or 1,3, 5-benzene tricarboxylic acid in the mixed solution is 0.5-10%.
11. The method of claim 5, wherein: before spraying and soaking the mixed liquid, the ceric sulfate is treated by adopting water vapor nitrogen mixed gas with the water vapor volume content of 0.5-5%, the treatment temperature is 100-.
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Effective date of registration: 20231027 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |