CN104324730B - A kind of catalyst for calcium carbide furnace gas deoxidation and preparation method thereof - Google Patents
A kind of catalyst for calcium carbide furnace gas deoxidation and preparation method thereof Download PDFInfo
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- CN104324730B CN104324730B CN201410543015.2A CN201410543015A CN104324730B CN 104324730 B CN104324730 B CN 104324730B CN 201410543015 A CN201410543015 A CN 201410543015A CN 104324730 B CN104324730 B CN 104324730B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- 239000005997 Calcium carbide Substances 0.000 title claims abstract description 38
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000010949 copper Substances 0.000 claims abstract description 20
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 17
- 229910052802 copper Inorganic materials 0.000 claims abstract description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 239000004480 active ingredient Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000000465 moulding Methods 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 6
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 6
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 6
- 150000003057 platinum Chemical class 0.000 claims description 6
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- JOKPITBUODAHEN-UHFFFAOYSA-N sulfanylideneplatinum Chemical compound [Pt]=S JOKPITBUODAHEN-UHFFFAOYSA-N 0.000 claims description 6
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- CTUFHBVSYAEMLM-UHFFFAOYSA-N acetic acid;platinum Chemical compound [Pt].CC(O)=O.CC(O)=O CTUFHBVSYAEMLM-UHFFFAOYSA-N 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 238000004898 kneading Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 38
- 230000000694 effects Effects 0.000 abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 13
- 239000001301 oxygen Substances 0.000 abstract description 13
- 230000001147 anti-toxic effect Effects 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 20
- 238000006356 dehydrogenation reaction Methods 0.000 description 14
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 229910000510 noble metal Inorganic materials 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 5
- 239000005751 Copper oxide Substances 0.000 description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 description 5
- 229910000431 copper oxide Inorganic materials 0.000 description 5
- 229910052593 corundum Inorganic materials 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 230000001404 mediated effect Effects 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 description 5
- 239000011787 zinc oxide Substances 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- 239000010953 base metal Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000002574 poison Substances 0.000 description 4
- 231100000614 poison Toxicity 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- 230000000295 complement effect Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [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 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 2
- 229940009827 aluminum acetate Drugs 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000007323 disproportionation reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910003446 platinum oxide Inorganic materials 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000004246 zinc acetate Substances 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229910002535 CuZn Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 1
- 229910000070 arsenic hydride Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229960004424 carbon dioxide Drugs 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000005235 decoking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
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- 238000006253 efflorescence Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
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- 206010037844 rash Diseases 0.000 description 1
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- 229910052709 silver Inorganic materials 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
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- 229910052720 vanadium Inorganic materials 0.000 description 1
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Abstract
The invention discloses a kind of catalyst for calcium carbide furnace gas deoxidation, it is made up of active component, coagent and carrier: active component is Cu and Pt, and active ingredient copper, in terms of oxide, weight percentage is 10～50%, and the weight percentage of platinum is 0.1～3%；Coagent is one or more in Zn, Fe, Al, and in terms of oxide, weight percentage is 1～30%；Remaining is carrier.Catalyst of the present invention uses Pt, Cu to be that active component has certain antitoxin performance, deoxy activity height, good stability, deoxidation temperature are low, the oxygen of calcium carbide furnace gas can be taken off to 1.0ppm (1 × 10 6 (v/v)) below, preparation method is simple, is suitable for heavy industrialization application.The present invention discloses the preparation method of this catalyst.
Description
Technical field
The deoxidizing purification that the present invention relates to calcium carbide furnace gas processes, a kind of catalyst for calcium carbide furnace gas deoxidation, with
And preparation method thereof.
Background technology
Carbide is a kind of important basic chemical industry raw material, and chemical name is Acetylenogen., and carbide and water react and prepares acetylene, second
Alkynes is the base stock of synthetic organic chemical manufacturing industry, can synthesize a series of organic compound, carries for industry, agricultural, medicine
For raw material.
In carbide production, carbon material and Calx react, and generate Acetylenogen. (carbide) and CO.Calcium carbide industry is mainly given birth to
Producing device is furnace of calcium carbide, is divided into internal combustion type furnace of calcium carbide and closed type calcium carbide furnace two class.Internal combustion type furnace of calcium carbide and closed type calcium carbide furnace phase
Ratio, energy consumption of unit product is higher, and waste discharge amount is relatively big, 11th Five-Year " period has been forced to eliminate.At present, China's tool
The closed type calcium carbide furnace production technology having independent intellectual property right is the most ripe, and has had the application of certain scale.In carrying out comprehensively
The ripe of combustion furnace of calcium carbide transformation closed type calcium carbide furnace.
Closed type calcium carbide furnace, by installing bell additional, makes furnace of calcium carbide enclose, has completely cut off extraneous air, produced by carbide
The CO (carbon monoxide converter) gas that journey produces is extracted out with air-extractor and is utilized.Simultaneously equipped with auto feed pipe on bell.Closed type calcium carbide furnace is also
It is configured with the devices such as electrode control system, flue gas cleaning, gas burning lime kiln.Compared with the first two type of furnace, closed type calcium carbide furnace by
Without combustion flame on boiler face, carbon material combustible loss and heat-energy losses are little, can burn as gas after the purified process of calcium carbide furnace gas simultaneously
The fuel in limekiln or as organic synthesis raw material, accomplishes that resource makes full use of；Flame and dust, boiler face is not had around furnace of calcium carbide
Device temperature is relatively low, improves work, safe operating conditions；Furnace charge is fed by auto feed pipe, presses the operations such as electrode and adopts
With Automated condtrol, mechanization degree is high, and equipment operation is safer reliably.
Usually constitute from sealed furnace calcium carbide furnace gas out: CO 75～85%, H25～15%, CO21.5～5%, O2
0.5～3%, CH41～2%, N21～10%, tar 1～2%, H2S ＜ 600mg/m3, COS ＜ 300mg/m3, CS2
＞ 3000mg/m3, thiophene ＜ 1mg/m3, mercaptan ＜ 300mg/m3, PH3＜ 300mg/m3, NH3＜ 30mg/m3, NOx
＜ 200mg/m3, separately containing AsH3, the impurity such as HCN.
Chinese Patent Application No. be 201110196752.6 patent application disclose a kind of calcium carbide furnace gas purify concentration CO
Method: by calcium carbide furnace gas dedusting, cooling decoking, temp.-changing adsorption preliminary clearning, supercharging, sulfur-resistant catalytic deoxidization, hydrolysis desulfurization, take off
Acid gas, dearsenization, fine de-sulfur, loss of essence oxygen, dry, pressure-changed adsorption concentrating CO.
In above-mentioned cleaning project, the catalyst for CO deoxidation of deoxidation step domestic current document report mainly includes two
Big class, one is with the catalyst that noble metal is main active component, including Pd/Al2O3(activated carbon), PdMnO/Al2O3、
PdAu(Ag)/Al2O3(TiO2) etc.；Two is non-precious metal catalyst, mainly has CuMnCo/ activated carbon, CuZn/Al2O3(activity
Charcoal), CuOMnO+ auxiliary agent Zn (Ni, Au)/Al2O3Deng.In these catalyst, the noble metal catalyst based on Pt, Pd takes off
Oxygen activity is high, and side reaction is less, but expensive, uses temperature high, is generally used for the removing of micro amount of oxygen, and in high concentration
In CO gas, noble metal catalyst is easily formed carbonyl compound and causes activity decrease.Non-precious metal catalyst is mainly copper, manganese body
System, this kind of dehydrogenation catalyst is cheap, but reactivity is low, when using temperature more than 150 DEG C, when unstripped gas oxygen content
Time high, easy temperature runaway causes copper-based catalysts sintering deactivation, and the side reaction (including disproportionation, methanation etc.) of carbon monoxide is tighter
Weight.And the reducing/regenerating temperature of manganese systems dehydrogenation catalyst is higher, energy consumption is big, and bad mechanical strength, easy efflorescence, is unfavorable for advising greatly
Mould industrial applications.
Chinese invention patent CN1220302A discloses a kind of for synthetic gas deoxidizing catalyst, consisting of CuMnCo/
Activated carbon, can carry out degree of depth deoxidation to the synthesis gas less than 1% oxygen content, and after purification, gas remaining oxygen is less than 1.0ppm.But should
Catalyst low-temperature activity is poor, causes again the sintering of copper-based catalysts during reaction temperature height, reduces service life.Additionally highly concentrated
In degree CO gas, during temperature height, CO dismutation reaction is accelerated, and easily causes catalyst surface carbon deposit, thus causes the catalyst longevity
Life shortens.
Chinese invention patent CN1227139A discloses a kind of deoxidation catalyst in high concentration CO, based on palladium
Catalyst component, the one of Ag, Au, Cr, V prepares for auxiliary agent.This deoxidizer is used for high concentration CO deoxidation, has higher
Activity and selectivity, preferable stability and deoxidation precision.But it uses air speed on the low side, and deoxidation treatment amount is little, use cost
Higher.Additionally this catalyst preparation process is the most troublesome, and carrier needs to carry out presaturation absorbing high temp heat with organic oxygen-containing compound
Processing, energy consumption and pollution are very big, are not suitable for industrial large-scale production.
Summary of the invention
The invention aims to overcome deficiencies of the prior art, it is provided that a kind of for calcium carbide furnace gas deoxidation
Catalyst, is the difunctional dehydrogenation catalyst as active component with noble metal and base metal compounding ingredients, have employed Pt, Cu
For active component, overcome and be that active component reaction temperature is high, poison resistance is low and with base metal activity with single noble metal
The shortcomings such as composition activity is low, side reaction is serious, performance complement.Additionally, present invention also offers the preparation side of described catalyst
Method.
To achieve these goals, the present invention uses following technical proposals:
A kind of catalyst for calcium carbide furnace gas deoxidation, is made up of active component, coagent and carrier, it is characterised in that:
Described active component is Cu and Pt, active ingredient copper, and in terms of oxide, weight percentage is 10～50%, the weight of platinum
Amount percentage composition is 0.1～3%；
Coagent is one or more in Zn, Fe, Al, and in terms of oxide, weight percentage is 1～30%；
Remaining is carrier.
Using Pt, Cu is active component, and its performance complement overcomes with single noble metal for active component reaction temperature
The shortcomings such as height, poison resistance are low and low with base metal active component activity, side reaction is serious.
Pt is to O2There is stronger absorbability, and the easy CO absorption of Cu forms the Metal carbonyl complex of less stable, Pt-
Cu bimetallic active component utilizes it to O2With the absorbability of CO, CO and O in reacting gas can be greatly increased2Contact
Probability and accelerate reaction, thus improve the activity of catalyst.
Experimentation shows 1% platinum catalyst to reuse in 6 times to have the highest reaction conversion ratio and selectivity.
Described active component Cu is selected from any one in Red copper oxide, copper nitrate, Schweinfurt green or copper sulfate；Described activity
Component platinum is selected from any one in platinum sulfide, platinum acetate or platinum nitrate.
Described coagent is selected from any one or a few in the nitrate of Zn, Fe, Al, chloride, acetate.
Described carrier is one or more in silicon dioxide, magnesium oxide or zirconium oxide.
The preparation method of a kind of described catalyst for calcium carbide furnace gas deoxidation, is carried out in accordance with the following steps:
(1) active component Cu and coagent are dissolved in water, are made into mixed solution；
(2) carrier is added the solution that step (1) prepares carry out mediating, extruded moulding, be dried, roasting, before preparing catalyst
Body；
(3) platinum salt is dissolved, make certain density aqueous solution；
(4) catalyst precarsor prepared is immersed in platinum salt solution prepared by step (3), normal temperature dipping 4～8h, it is dried, roasts
Burn, obtain described catalyst.
The preparation method of a kind of described catalyst for calcium carbide furnace gas deoxidation, is carried out in accordance with the following steps:
(1) active component Cu and carrier are mixed in proportion；
(2) by step (1) gained mixture through kneading, extruded moulding, dry, roasting, prepare catalyst precarsor；
(3) platinum salt is dissolved, and make impregnation liquid with the aqueous solution of the salt of coagent；
(4) catalyst precarsor prepared is immersed in mixed solution prepared by step (3), normal temperature dipping 4～8h, it is dried, roasts
Burn, obtain described catalyst.
Described method for preparing catalyst is simple, is suitable for heavy industrialization application.
It is 5000～15000h that described catalyst is applied to unstripped gas air speed-1, catalytic deoxidation reaction temperature is 80～200 DEG C.
Preferably, described catalytic deoxidation reaction temperature is 90～150 DEG C.
Deoxidation treatment amount is big, and reaction temperature is low, air speed 5000～15000h-1Under, reaction temperature 90～150 DEG C can reach very
Good effect.
The oxygen content of deoxidation post-treatment gas is less than 1.0ppm.
Compared with prior art, the invention has the beneficial effects as follows:
(1) have employed Pt, Cu is active component, and its performance complement overcomes with single noble metal for active component reaction temperature
The shortcomings such as height, poison resistance are low and low with base metal active component activity, side reaction is serious.
(2) deoxidation treatment amount is big, and reaction temperature is low；
(3) good stability, poison resistance is strong, and deoxidation precision is high, can be taken off by oxygen to 1.0ppm (1 × 10-6(v/v)) below.
(4) preparation method is simple, is suitable for heavy industrialization application, without reducing/regenerating after first use activation.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the foregoing invention content of the present invention is described in further detail.But should be by this
It is interpreted as that the scope of the above-mentioned theme of the present invention is only limitted to following embodiment.Without departing from the idea case in the present invention described above, root
According to ordinary skill knowledge and customary means, make various replacement and change, all should be included within the scope of the invention.
Embodiment 1
The calcium carbide furnace gas dehydrogenation catalyst of the present embodiment is by (by weight) 30% active component, the coagent of 10% and the load of 60%
Body forms, and active component is to be equivalent to Red copper oxide that copper oxide is 27% and be equivalent to the platinum sulfide that platinum is 3%, coagent
For being equivalent to ferrum oxide in catalyst and iron chloride that zinc oxide content is 10% and zinc nitrate, carrier is silicon dioxide, preparation side
Method is as follows:
(1) Red copper oxide 24.3g, silicon dioxide 60g mix homogeneously are taken；
(2) being mediated by step (1) gained mixture, extruded moulding, be dried 4h at 100 DEG C, at 400 DEG C, roasting 4 is little
Time, prepare catalyst precarsor；
(3) take platinum sulfide 3.49g, iron chloride 14.6g (being equivalent to 6.5g ferrum oxide), zinc nitrate 8.17g (is equivalent to 3.5g oxidation
Zinc), it is configured to dipping solution after adding deionized water dissolving；
(4) catalyst precarsor prepared is immersed in mixed solution prepared by step (3), impregnate 8h under room temperature, at 120 DEG C
Be dried 4h, at 450 DEG C roasting 4h the dehydrogenation catalyst 001 of the implementation case.
Embodiment 2
The calcium carbide furnace gas dehydrogenation catalyst of the present embodiment by the active component of (by weight) 40.1%, the coagent of 20% and
The carrier composition of 39.9%, active component is to be equivalent to Schweinfurt green that copper oxide is 40% and be equivalent to the platinum nitrate that platinum is 0.1%,
Coagent is to be equivalent to aluminium oxide and the aluminum chloride of zinc oxide 20% and zinc chloride in catalyst form, and carrier is zirconium oxide.
(1) take Schweinfurt green 45.5g, aluminum chloride 26.2g (being equivalent to 10g aluminium oxide) and zinc chloride 16.8g (is equivalent to
10g zinc oxide) it is dissolved in deionized water, wiring solution-forming；
(2) taking zirconium oxide 39.9g, the solution that addition step (1) has configured is mediated, and extruded moulding is dried at 120 DEG C
3h, 300 times roastings 5 hours, prepare catalyst precarsor；
(3) take 0.16g platinum nitrate and be configured to solution；
(4) catalyst precarsor prepared is immersed in platinum salt solution prepared by step (3), impregnate 5h under room temperature, at 120 DEG C
Be dried 2h, at 300 DEG C roasting 5h the dehydrogenation catalyst 002 of the implementation case.
Embodiment 3
The calcium carbide furnace gas dehydrogenation catalyst of the present embodiment by the active component of (by weight) 52.1%, the coagent of 30% and
The carrier composition of 17.9%, active component is to be equivalent to Schweinfurt green that copper oxide is 50% and be equivalent to the platinum sulfide that platinum is 2.1%,
Coagent is to be equivalent to aluminium oxide in catalyst, ferrum oxide and the aluminum acetate of zinc oxide 30%, iron acetate and zinc acetate composition,
Carrier is silicon dioxide.
(1) take Schweinfurt green 113.8g, aluminum acetate 40.0g (being equivalent to 10g aluminium oxide), iron acetate 45.7g (is equivalent to
10g ferrum oxide) and zinc acetate 35.9g (being equivalent to 10g zinc oxide) be dissolved in deionized water, wiring solution-forming；
(2) taking silica 1 7.9g, the solution that addition step (1) has configured is mediated, extruded moulding, dry at 120 DEG C
Dry 3h, 400 times roastings 4 hours, prepare catalyst precarsor；
(3) take 2.44g platinum sulfide and be configured to solution；
(4) catalyst precarsor prepared is immersed in platinum salt solution prepared by step (3), impregnate 7h under room temperature, at 100 DEG C
Be dried 3h, at 400 DEG C roasting 4h the dehydrogenation catalyst 003 of the implementation case.
Embodiment 4
The calcium carbide furnace gas dehydrogenation catalyst of the present embodiment is by (by weight) 12% active component, the coagent of 2% and the load of 86%
Body forms, and active component is to be equivalent to Red copper oxide that copper oxide is 10% and be equivalent to the platinum nitrate that platinum oxide is 2%, lives
Property auxiliary agent is the ferric nitrate being equivalent to catalyst 2%, and carrier is zirconium oxide, and preparation method is as follows:
(1) Red copper oxide 10.8g, zirconium oxide 86g mix homogeneously are taken；
(2) being mediated by step (1) gained mixture, extruded moulding, be dried 3h at 120 DEG C, at 400 DEG C, roasting 3 is little
Time, prepare catalyst precarsor；
(3) take platinum nitrate 3.27g, ferric nitrate 6.0g (being equivalent to 2g ferrum oxide), be configured to impregnate molten after adding deionized water dissolving
Liquid；
(4) catalyst precarsor prepared is immersed in mixed solution prepared by step (3), impregnate 6h under room temperature, at 120 DEG C
Be dried 4h, at 500 DEG C roasting 3h the dehydrogenation catalyst 004 of the implementation case.
Embodiment 5
The calcium carbide furnace gas dehydrogenation catalyst of the present embodiment is by (by weight) 51% active component, the coagent of 1% and the load of 48%
Body forms, and active component is to be equivalent to copper sulfate that copper oxide is 50% and be equivalent to the platinum acetate that platinum oxide is 1%, activity
Auxiliary agent is the aluminum nitrate of the aluminium oxide being equivalent to catalyst 1%, and carrier is magnesium oxide, and preparation method is as follows:
(1) copper sulfate 100g, magnesium oxide 48g mix homogeneously are taken；
(2) being mediated by step (1) gained mixture, extruded moulding, be dried 3h at 120 DEG C, at 500 DEG C, roasting 3 is little
Time, prepare catalyst precarsor；
(3) platinum acetate 1.61g is taken, aluminum nitrate 4.2g, it is configured to dipping solution after adding deionized water dissolving；
(4) catalyst precarsor prepared is immersed in mixed solution prepared by step (3), impregnate 4h under room temperature, at 120 DEG C
Be dried 4h, at 400 DEG C roasting 4h the dehydrogenation catalyst 005 of the implementation case.
Embodiment 6
The present embodiment is application and the evaluation to catalyst deoxy activity of the calcium carbide furnace gas dehydrogenation catalyst in embodiment l-5.
Catalyst packing carries out deoxy activity test in fixed bed reactors, and loadings is 50ml.Test procatalyst bed
Layer is passed directly into unstripped gas in air speed 1000h-1, activate 6h at temperature 200 DEG C, then change air speed and temperature according to test condition
Degree directly carries out active testing, and different model catalyst activity test concrete outcome is shown in Table l.Used raw material calcium carbide furnace gas oxygen contains
Amount is 0.5～3%, and hydrogen content is 5～15%, and carbon monoxide content is 75～85%, and nitrogen is l～10%, and remaining is two
Carbonoxide, unstripped gas air speed is 5000～l5000h-1, catalytic deoxidation reaction temperature is 80～200 DEG C.
Table 1 catalyst deoxy activity test result
| Catalyst is numbered | Unstripped gas oxygen content % | Deoxidation temperature DEG C | Unstripped gas air speed h-1 | Tail gas oxygen content ppm |
| 001 | 0.52 | 80 | 5000 | 0.43 |
| 002 | 1.07 | 90 | 10000 | 0.77 |
| 003 | 0.96 | 120 | 15000 | 0.73 |
| 004 | 2.73 | 150 | 10000 | 0.85 |
| 005 | 1.96 | 200 | 8000 | 0.98 |
Claims (3)
1. the preparation method for the catalyst of calcium carbide furnace gas deoxidation, it is characterised in that carry out in accordance with the following steps:
(1) active component Cu and carrier are mixed in proportion；
(2) by step (1) gained mixture through kneading, extruded moulding, dry, roasting, prepare catalyst precarsor；
(3) platinum salt is dissolved, and make impregnation liquid with the aqueous solution of the salt of coagent；
(4) catalyst precarsor prepared is immersed in mixed solution prepared by step (3), normal temperature dipping 4～8h, dry, roasting, obtain described catalyst；
Described catalyst is made up of active component, coagent and carrier, and described active component is Cu and Pt, active ingredient copper, and in terms of oxide, weight percentage is 10 ~ 50%, and the weight percentage of platinum is 0.1 ~ 3%；
Coagent is one or more in Zn, Fe, Al, and in terms of oxide, weight percentage is 1 ~ 30%；
Remaining is carrier；
Described active component Cu is selected from any one in Red copper oxide, copper nitrate, Schweinfurt green or copper sulfate；Described active component platinum is selected from any one in platinum sulfide, platinum acetate or platinum nitrate；
Described carrier is one or more in silicon dioxide, magnesium oxide or zirconium oxide；
Described coagent is selected from any one or a few in the nitrate of Zn, Fe, Al, chloride, acetate.
The preparation method of the catalyst for calcium carbide furnace gas deoxidation the most according to claim 1, it is characterised in that: it is 5000 ~ 15000h that described catalyst is applied to unstripped gas air speed-1, catalytic deoxidation reaction temperature is 80 ~ 200 DEG C.
The preparation method of the catalyst for calcium carbide furnace gas deoxidation the most according to claim 2, it is characterised in that: described catalytic deoxidation reaction temperature is 90 ~ 150 DEG C.
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