CN103846086A - Catalyst for preparing nitric oxides through catalytic ammonia oxidation - Google Patents
Catalyst for preparing nitric oxides through catalytic ammonia oxidation Download PDFInfo
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- CN103846086A CN103846086A CN201410076774.2A CN201410076774A CN103846086A CN 103846086 A CN103846086 A CN 103846086A CN 201410076774 A CN201410076774 A CN 201410076774A CN 103846086 A CN103846086 A CN 103846086A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 99
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 26
- 230000003647 oxidation Effects 0.000 title claims abstract description 18
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 18
- 230000003197 catalytic effect Effects 0.000 title claims description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 169
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 80
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 38
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000002360 preparation method Methods 0.000 claims abstract description 21
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 19
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 19
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 12
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 11
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims abstract description 11
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 9
- 239000010948 rhodium Substances 0.000 claims abstract description 9
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000008021 deposition Effects 0.000 claims abstract description 6
- 230000000694 effects Effects 0.000 claims abstract description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract 3
- 229910052801 chlorine Inorganic materials 0.000 claims abstract 3
- 239000000460 chlorine Substances 0.000 claims abstract 3
- 239000002253 acid Substances 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910000629 Rh alloy Inorganic materials 0.000 claims description 3
- XXVRGGCHZUCJCX-UHFFFAOYSA-N [Cl].[Rh] Chemical compound [Cl].[Rh] XXVRGGCHZUCJCX-UHFFFAOYSA-N 0.000 claims description 3
- 229960000583 acetic acid Drugs 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000007743 anodising Methods 0.000 claims description 2
- 239000012362 glacial acetic acid Substances 0.000 claims description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052753 mercury Inorganic materials 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 claims description 2
- 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 2
- 229910000990 Ni alloy Inorganic materials 0.000 claims 1
- 238000001027 hydrothermal synthesis Methods 0.000 claims 1
- 238000005286 illumination Methods 0.000 claims 1
- 229910001092 metal group alloy Inorganic materials 0.000 claims 1
- 150000002739 metals Chemical class 0.000 claims 1
- 239000002071 nanotube Substances 0.000 claims 1
- PCLURTMBFDTLSK-UHFFFAOYSA-N nickel platinum Chemical compound [Ni].[Pt] PCLURTMBFDTLSK-UHFFFAOYSA-N 0.000 claims 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims 1
- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical compound [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 claims 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 32
- 238000006243 chemical reaction Methods 0.000 abstract description 24
- 230000008569 process Effects 0.000 abstract description 19
- 238000000151 deposition Methods 0.000 abstract description 7
- 230000001699 photocatalysis Effects 0.000 abstract description 7
- 229910045601 alloy Inorganic materials 0.000 abstract description 4
- 239000000956 alloy Substances 0.000 abstract description 4
- 238000011068 loading method Methods 0.000 abstract description 2
- 229910002651 NO3 Inorganic materials 0.000 abstract 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 239000011941 photocatalyst Substances 0.000 abstract 1
- 239000010970 precious metal Substances 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 229910017604 nitric acid Inorganic materials 0.000 description 9
- 229910000510 noble metal Inorganic materials 0.000 description 7
- 239000000243 solution Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000010531 catalytic reduction reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000009940 knitting Methods 0.000 description 3
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910003446 platinum oxide Inorganic materials 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000009991 scouring Methods 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- -1 rhodium ion Chemical class 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- PDNNQADNLPRFPG-UHFFFAOYSA-N N.[O] Chemical compound N.[O] PDNNQADNLPRFPG-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 235000019994 cava Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 208000021760 high fever Diseases 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010278 pulse charging Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
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Abstract
一种用于氨气氧化制备氮氧化物的负载型催化剂的制备。以光催化剂为氨氧化过程催化剂载体，以金属铂、铑、钯的硝酸盐或含氯化合物为前驱体，利用二氧化钛或二氧化锆或氧化钨或氧化钼光催化特性，通过紫外光或可见光照射光催化还原沉积或光催化还原共沉积方法在催化剂载体上负载金属铂、铑、钯或其合金为活性组分，并应用于催化氨氧化过程。所得负载型催化剂比表面积大金属负载量小，反应温度低活性高，可有效减少氨氧化过程贵金属用量，降低催化剂成本。Preparation of a supported catalyst for ammonia oxidation to prepare nitrogen oxides. The photocatalyst is used as the catalyst carrier for the ammonia oxidation process, the nitrate or chlorine-containing compound of metal platinum, rhodium, and palladium is used as the precursor, and the photocatalytic properties of titanium dioxide, zirconium dioxide, tungsten oxide, or molybdenum oxide are used to irradiate with ultraviolet light or visible light. The photocatalytic reduction deposition or photocatalytic reduction co-deposition method loads metal platinum, rhodium, palladium or their alloys on the catalyst carrier as an active component, and is applied to catalyze the ammonia oxidation process. The obtained supported catalyst has large specific surface area, small metal loading capacity, low reaction temperature and high activity, can effectively reduce the amount of precious metal used in the ammoxidation process, and reduce the cost of the catalyst.
Description
Technical field
The present invention relates to a kind of catalytic ammoxidation process and prepare the preparation of the loaded catalyst of nitrogen oxide, in particular for the preparation of the loaded catalyst of ammoxidation process in nitric acid industry.
Background technology
China is the big country of nitric acid production, and 2009 annual capacities have exceeded 9,670,000 tons, occupies global production capacity first.As basic chemical raw materials, nitric acid occupies critical role in national economy, and its production technology adopts ammonia oxidation, and using noble metal platinum as catalyst, its master equation is as follows:
4NH
3+5O
2?=?4NO?+?6H
2O?ΔH=?-907.28?kJ
At present nitric acid industry ammoxidation process is all take platinum or platinum, palladium, rhodium alloy silk screen as catalyst, wherein mainly adopts large-scale oxidation furnace to carry out adiabatic reaction, and operating temperature is 780 ~ 940 ℃, and operating pressure is at 0.1 ~ 1.0MPa.Wherein as follows as the platinum guaze specification of catalyst, platinum filament diameter used is 0.045-0.09mm, and common platinum guaze diameter specifications has 1.1,1.6,2.0,2.4,2.8,3.0m.
The industrial platinum guaze specification of table 1.:
| Wire diameter d(cm) | Empty number n | g（g/cm 2） | S g（cm2/g） | f s(%) |
| 0.006 | 1024 | 0.0389 | 31.0 | 65.3 |
| 0.007 | 1024 | 0.0529 | 26.6 | 60.2 |
| 0.008 | 1024 | 0.0691 | 23.2 | 55.4 |
| 0.009 | 1024 | 0.0875 | 20.7 | 50.7 |
| 0.010 | 1024 | 0.1080 | 18.6 | 46.3 |
| 0.004 | 3600 | 0.0324 | 46.5 | 57.8 |
| 0.005 | 3600 | 0.0506 | 37.2 | 49.0 |
G--------unit cross-sectional area platinum guaze quality
S
gthe contact area of------unit mass platinum guaze
F
sthe free area percentage of------platinum guaze
Platinum guaze catalyst performance advantage main manifestations goes out: ammonia is converted into nitric oxide production high selectivity; Long service life; Recyclable regeneration.But adopt platinum guaze as ammoxidation reaction catalyst, still exist following not enough:
1: catalyst surface utilization rate is low, ammonia and air enter the air speed 90000h of oxidation furnace
-1, the time that mist stops is very short: the free area of platinum guaze has accounted for more than 50%, can cause mist directly from gap, to pass, and the another side area of platinum guaze catalyst does not well use.
2: platinum guaze catalyst bad mechanical strength.Under pyroreaction condition, the strength decreased of platinum silk screen own, simultaneously large airflow scouring impacts platinum guaze, more can cause the vibration of platinum guaze even to subside, and takes away part platinum catalyst simultaneously.
3: ammoxidation process is pyroprocess, and reaction temperature is generally 800-900
oc, at this temperature, catalyst platinum reacts with oxygen following reaction occurs:
Pt?+?O
2?=?PtO
2
Generate volatile platinum oxide and taken away by air-flow, causing the loss of platinum.It is another reason of platinum consumption that airflow scouring causes the mechanical loss of platinum.
4: because reaction is for adiabatic reaction, exceed 880 ℃ when air-flow skewness causes temperature rise, or side reaction occurs while driving igniting or pulse charging:
4NH
3?+?6NO?=?5N
2?+?6H2O?ΔH=?-1810.79?kJ
There is transient state high fever reaction and produce amount of heat, all can cause platinum consumption sharply to increase.
In nitric acid production, platinum consumes minimum double pressurized method and also reaches 0.12g/tNH3 at present, causes platinum consumption to become the cost factor that is only second to raw material ammonia consumption.Reducing platinum consumption, is the key issue of nitric acid industry development.
The method that reduces at present platinum consumption cost is to find alternative catalysts, change platinum guaze knitting skill and use noble metal collecter ring.But non-platinum catalyst activity cycle is short, and ammonia oxidation rate is low, as 15 ~ 20 days oxygenation efficiency of cobalt-containing catalyst are just reduced to 87% from 96%; Palladium need to load on support, and intensity difference cannot substitute platinum; In recent years, the price of raw material ammonia rises steadily simultaneously, and the expense of saving from catalyst can not be offset by raw material ammonia consumption and increase the expense producing, so present nitric acid production producer both at home and abroad is substantially all used platinum group catalyst.
Platinum guaze adopts knitting skill, and GB S201 type platinum guaze is 1024 holes/cm at present
2, wire diameter 0.09mm, reaction contact area 20.7cm
2/ g, far below loaded catalyst form, catalyst utilization ratio is low, improves knitting skill limited with raising catalyst utilization to reducing platinum consumption.Use noble metal collecter ring, platinum oxide occurs to react as follows after being delivered to palldium alloy net by air-flow: 2PdO=2Pd+ O
2, 2Pd+ PtO
2=Pt+2PdO
Reduce deposition forms platinum palladium solid solution on the net at palldium alloy, but this process palldium alloy collecter ring effective area is little, and the rate of recovery only has 50% ~ 80% of platinum loss, adopts the pure palladium net rate of recovery high, but easily caves under the low high temperature of its mechanical strength; And collecter ring method is that to sacrifice palladium metal be cost, although palladium metal does not have platinum expensive, be also a kind of noble metal, also can make cost increase; And mechanical filter method can make SR increase; By marble method recovery platinum complex operation complexity, need to expend a large amount of time and manpower.
In summary, improve ammoxidation reaction conversion ratio and economy, key reduces platinum consumption when being to improve platinum catalyst performance.
Adopt loaded catalyst, there is the carrier of high-specific surface area by employing, can effectively increase the specific area of catalyst, thereby increase the catalyst of ammoxidation process and the contact area of reacting gas, carry high ammonia conversion ratio; Can select the carrier with higher mechanical strength to carry out supported catalyst, effectively improve the mechanical strength of catalyst; Adopt the catalyst of support type to form fixed bed reactors, although the operating process pressure loss increases, the catalyst attrition simultaneously causing due to airflow scouring is effectively contained simultaneously; Loaded catalyst can, on the basis of lower platinum load capacity, effectively provide enough active sites, under compared with low reaction temperatures condition, realizes high conversion ratio, thereby reduces energy consumption of reaction.Meanwhile, low reaction temperature reduces or has avoided the formation of platinum oxide, has removed the operating procedure that reclaims platinum from.
The preparation method of loaded catalyst generally includes infusion process, coprecipitation, galvanoplastic, cladding process etc., but above-mentioned conventional method supported catalyst is difficult to control load amount, be especially difficult to accurate control load process and obtain the monoatomic layer supported catalyst of active component high degree of dispersion.Metal oxide nanostructure is as TiO
2, ZnO
2, WO
3, MoO
3deng having unique light quantum effect, while being subject to light radiation, the electrons in valence band transits to and on conduction band, produces electron-hole pair.This electronics has very strong reducing power, the platinum in solution, palladium, rhodium ion etc. can be reduced into metal and be deposited on carrier surface.In the time that the metal of deposition covers on the surface of carrier completely, reaction stops.Utilize in theory the method for photo catalytic reduction deposition can obtain the coating of atomic thickness, realize the controlled of load capacity.The method depositing by photo catalytic reduction realizes noble metal as the load of platinum, palladium, rhodium, can effectively reduce catalyst loadings, reduces catalyst cost; TiO simultaneously
2, ZrO
2can withstand high temperatures, mechanical strength is high, and not with ammoxidation system in material react, be a kind of desirable ammoxidation process catalyst carrier.
To sum up, the present invention adopts the method for photo catalytic reduction deposition, at titanium dioxide or zirconium dioxide or tungsten oxide or molybdenum oxide carrier surface Supported Pt Nanoparticles, palladium, rhodium catalyst, for ammoxidation process.
Summary of the invention
The object of this invention is to provide a kind of preparation method of the loaded catalyst for ammonia catalytic, preparation method is simple, gained ammoxidation catalyst has high-specific surface area, high mechanical properties, the feature of low noble metal dosage, adopts this catalyst ammoxidation reaction, and reaction temperature reduces, platinum depletion is little, suitable industrial large-scale application.
The key of the technology of the present invention is to adopt loaded catalyst, effectively improve the decentralization of noble metal catalyst, significantly reduce the preparation cost of catalyst, simplify preparation flow, it is relatively gentle that simultaneous reactions process becomes, energy consumption and the platinum consumption of ammoxidation process are reduced, nitric acid production cost.
The technical scheme that realizes above-mentioned purpose is as follows:
1. prepare titanium dioxide that particle diameter is 1nm-10mm or the particle of zirconium dioxide or tungsten oxide or molybdenum oxide by sol-gel process.
2. the powder of titanium dioxide or zirconium dioxide or tungsten oxide or molybdenum oxide being added in autoclave, is titanium dioxide or zirconium dioxide or tungsten oxide or the molybdenum oxide carrier of 1nm-1mm sheet or thread or tubulose for thickness by hydro-thermal legal system.
3. the sheet, thread or tubulose titanium or zirconium or tungsten or the molybdenum that are 0.001mm-10mm with anodizing processing caliber or thickness, obtain titanium dioxide or zirconium dioxide or tungsten oxide or molybdenum oxide that thickness is 1nm-1000nm.Its method is by given shape (sheet or tubulose) first physics polishing (sand papering), then use acetone, carrene, the organic solvent chemical polishings such as absolute ethyl alcohol, again by the Titanium of handling well, zirconium is put into and is contained ammonium sulfate (0.5M), ammonium fluoride (0.5%Wt), hydrogen fluoride (0.5%Wt) or mixed liquor as in the electrolytic cell of electrolyte (200ml) as anode, titanium dioxide after calcining under 800-900 oC 4. or zirconium dioxide or tungsten oxide or molybdenum oxide add and contain platinum, presoma (the chloroplatinic acid of palladium or rhodium, palladium bichloride, the acid of chlorine rhodium) surface plate of solution, add 0.1ml formic acid or acetic acid as hole collecting agent, surface plate is put to Photoreactor, with 500W mercury lamp irradiation 5-10h, obtain load type metal catalyst, under 10-100 oC, dry, obtain institute's controlling catalyst.
5. this catalyst is used for to ammoxidation process, under 600-700 oC condition, ammonia conversion ratio can reach 100%, moves continuously 800 hours catalyst performances unchanged.
The advantage of this technological invention is mainly:
1: Catalyst Production cost, technique is simple.Platinum guaze catalyst 1cm
2need to consume 0.0389g platinum, and adopt load method to prepare platinum catalyst, 1cm
2catalyst only needs load 0.00000126g platinum.Platinum guaze preparation simultaneously needs special machinery, and loaded platinum catalyst preparation technology is simple, only needs simple light source.
2: catalyst performance is higher.Platinum guaze specific surface area of catalyst is 62.3cm
2/ g, and loaded platinum catalyst specific area can reach 10.384 m
2/ g.Platinum guaze Catalyst operating temperature is 780 ~ 940oC, and loaded platinum catalyst operating temperature is 600-700 oC, lower than PtO
2sublimation temperature 850oC.
3: catalyst platinum consumption is little, long service life, stable performance.Loaded platinum catalyst operating temperature is lower than platinum oxidation temperature, continued operation after 800 hours its performance, pattern and load capacity all unchanged.
Below in conjunction with accompanying drawing, embodiments of the invention are described:
Accompanying drawing 1 is catalyst test apparatus (1-1: ammonia, 1-2: oxygen 1-3: nitrogen, 2-1 (2,3): mass flowmenter, 3: reactor, 3-1 (2): temperature controller, 4-1: gas chromatograph, 4-2: computer, 5: tail gas absorption bottle, 6: drying bottle, 7: heating tape)
The scanning electron microscope (SEM) photograph that accompanying drawing 2 is load platinum catalyst;
(a is fresh catalyst to the XRD analysis that accompanying drawing 3 is load platinum catalyst; B is the catalyst after using; ● be K
2ptCl
6◆ for Pt ★ is TiO
2);
The EDS that accompanying drawing 4 is load platinum catalyst analyzes;
(a is fresh catalyst to the XPS analysis that accompanying drawing 5 is load platinum catalyst; B is the catalyst after using;
_for Pt
04f (7/2)
...for Pt
4+4f (5/2)
﹍for Pt
4+4f (7/2)
﹎for Pt
04f (5/2));
Ammoxidation process reaction temperature, reaction time and ammonia conversion ratio test curve that accompanying drawing 6 is load platinum catalyst;
Accompanying drawing 7 is the performance test of load platinum catalyst under air
The continuous runnability test that accompanying drawing 8 is load platinum catalyst
Can find out that from accompanying drawing 3,4,5 platinum simple substance has loaded to the surface of titanium dioxide.Accompanying drawing 6 shows that catalyst catalytic performance after activation certain hour is stablized, and 600
oc left and right ammonia conversion ratio approaches 100%.Accompanying drawing 7 shows that loaded platinum catalyst its catalytic performance under air conditions of preparation is higher than the catalytic performance of platinum guaze catalyst in nitric acid industry production, and reaction temperature can reduce by 100
oc left and right.Accompanying drawing 8 shows in the use procedure of catalyst, and its catalytic performance is stable.
the specific embodiment:
Support type platinum family catalyst and its application thereof below in conjunction with embodiment prepared by the inventive method are described further, but the present invention is not limited only to following embodiment.
embodiment mono-: the preparation of titanium dichloride load platinum catalyst and catalysis characteristics thereof
1. the preparation of titanium dioxide
1. for the preparation method of the catalyst carrier titanium dioxide of oxidation of ammonia gas, employing be sol-gel process:
(1) mix with 40ml butyl titanate and 40ml absolute ethyl alcohol, form solution a, then 20ml pure water is slowly added in solution a, form after gel, leave standstill, ageing 24h, obtains gel, by gel drying.Through grinding, sieve, obtain white solid, bulky grain solid is obtained to the titanium dioxide granule of the different-grain diameters such as 1nm-10mm through row calcining (more than 700 degree, 3-5 hour).
(2) prepare colloidal sol by sol-gel process, adding large particulate matter is core, obtains the particle of titanium hydroxide parcel, by gained particle drying.More than 700 degree, calcining, obtains larger titanium dioxide granule under 3-5 hour.
2. titanium dioxide is prepared in anodic oxidation:
The titanium sheet processing is first used to sand papering, until surfacing is removed grease with absolute ethyl alcohol after smooth, after cleaning with distilled water, then to it through row chemical polishing, polishing fluid is acetone, carrene, absolute ethyl alcohol or their mixed liquor.In electrolytic cell, add 200ml pure water, add 0.5M ammonium sulfate and mass fraction is that the mixed liquor of 0.5% ammonium fluoride or hydrogen fluoride that mass fraction is 0.5% are as electrolyte simultaneously.Obtaining titanium dioxide thickness is 1nm-1000nm.
photo catalytic reduction
The mixture of the titanium dioxide of the 20-40 order size of gained or zirconium dioxide being put into chloroplatinic acid or chloroplatinate or platinum nitrate or above-mentioned solution and acid or glacial acetic acid irradiates 10 hours under ultraviolet lamp, obtains loaded platinum catalyst.From Fig. 1 to Fig. 3, can find out, the surface that platinum has loaded to carrier forms platinum layer.
3. ammoxidation reaction
0.04g catalyst filling, in the quartz ampoule of Ф 4*2, is passed into oxygen and ammonia, and ammonia oxygen is than being 1:15.In from Fig. 5 to Fig. 7, can find out, under the effect of catalyst, reaction only uses 700
oc left and right just can make ammonia transform completely.And the freshly prepd catalyst catalytic performance of the specific activity of the catalyst after pyroreaction is higher.Each driving only needs within 4 hours, to make catalyst catalytic performance reach stable simultaneously.
Claims (6)
1. prepare the preparation method of the catalyst of the support type of nitrogen oxide for ammonia catalytic oxidation for one kind, it is characterized in that: catalyst activity component is elemental metals platinum or palladium or rhodium or platinum-nickel alloys or platinum-rhodium alloy or rhotanium or platinum, palladium, rhodium alloy, catalyst carrier is titanium dioxide or zirconium dioxide or tungsten oxide or molybdenum oxide, and the preparation of catalyst comprises the following steps:
Getting the processed above-mentioned metal oxide of 1g joins on surface plate;
Get 0.02ml platinum, palladium or rhodium presoma chloroplatinic acid or palladium bichloride or the acid of chlorine rhodium joins in surface plate, surface plate is put into Photoreactor, irradiate 5-10h with 500W mercury lamp;
3. catalyst later illumination is washed with pure water, at 60-80
ounder C, dry.
2. a kind of preparation method who prepares the catalyst of the support type of nitrogen oxide for ammonia catalytic oxidation according to claim 1, is characterized in that: presoma is the mixture of chloroplatinic acid or chloroplatinate or platinum nitrate or palladium nitrate or the acid of chlorine palladium or chloropalladate or rhodium nitrate or the acid of chlorine rhodium or chlorine rhodate or above-mentioned solution.
3. a kind of preparation method who prepares the catalyst of the support type of nitrogen oxide for ammonia catalytic oxidation according to claim 1, is characterized in that: titanium dioxide or zirconium dioxide or tungsten oxide or molybdenum oxide are graininess, the particle diameter of carrier is 1 nm-10 mm.
4. a kind of preparation method who prepares the catalyst of the support type of nitrogen oxide for ammonia catalytic oxidation according to claim 1, is characterized in that: prepare by hydro-thermal method titanium dioxide or zirconium dioxide or tungsten oxide or the molybdenum oxide carrier that thickness is 1nm-1mm sheet or thread or tubulose.
5. a kind of preparation method who prepares the catalyst of the support type of nitrogen oxide for ammonia catalytic oxidation according to claim 1, is characterized in that: prepare titanium dioxide that length is 1nm-1000nm or the nano-tube support of zirconium dioxide or tungsten oxide or molybdenum oxide by anodizing.
6. a kind of preparation method who prepares the catalyst of the support type of nitrogen oxide for ammonia catalytic oxidation according to claim 1, it is characterized in that: irradiate take ultraviolet light as light source, take acid or glacial acetic acid as hole trapping agents, the consumption of hole collecting agent is 0.5-1ml, metal simple-substance or the above-mentioned metal alloys of codeposition such as deposition Supported Pt Nanoparticles, palladium or rhodium.
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| CN104056623A (en) * | 2014-06-23 | 2014-09-24 | 中海油太原贵金属有限公司 | Preparation method of nonwoven catalyst for nitric acid production |
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| CN105561902A (en) * | 2015-07-09 | 2016-05-11 | 四川大学 | Manufacturing method of metal plate type microchannel reactor |
| CN105797718B (en) * | 2016-03-18 | 2018-04-24 | 厦门大学 | A kind of preparation method of atomically dispersed palladium catalyst of large load |
| CN105797718A (en) * | 2016-03-18 | 2016-07-27 | 厦门大学 | A kind of preparation method of atomically dispersed palladium catalyst of large load |
| CN107790127A (en) * | 2017-11-13 | 2018-03-13 | 盐城工学院 | A kind of Pt Ag/WO3Plasma photocatalysis agent and its preparation method and application |
| CN107790127B (en) * | 2017-11-13 | 2018-11-30 | 盐城工学院 | A kind of Pt-Ag/WO3Plasma photocatalysis agent and its preparation method and application |
| CN109453770A (en) * | 2018-10-30 | 2019-03-12 | 中海油太原贵金属有限公司 | A kind of catalyst of the ammoxidation nitrogen oxides of oxide carried platinum |
| CN115805072A (en) * | 2021-09-13 | 2023-03-17 | 中国科学院理化技术研究所 | Supported AgPt alloy photocatalyst and preparation method and application thereof |
| CN115805072B (en) * | 2021-09-13 | 2024-05-07 | 中国科学院理化技术研究所 | A supported AgPt alloy photocatalyst and its preparation method and application |
| CN114735721A (en) * | 2022-03-22 | 2022-07-12 | 山东新和成氨基酸有限公司 | Method for preparing hydrocyanic acid by using efficient catalyst |
| CN114735721B (en) * | 2022-03-22 | 2023-12-12 | 山东新和成氨基酸有限公司 | Method for preparing hydrocyanic acid by high-efficiency catalyst |
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Application publication date: 20140611 |