CN101199938B - Method of carbon monoxide shift catalyst prepared by pillared clay - Google Patents
Method of carbon monoxide shift catalyst prepared by pillared clay Download PDFInfo
- Publication number
- CN101199938B CN101199938B CN2007100664623A CN200710066462A CN101199938B CN 101199938 B CN101199938 B CN 101199938B CN 2007100664623 A CN2007100664623 A CN 2007100664623A CN 200710066462 A CN200710066462 A CN 200710066462A CN 101199938 B CN101199938 B CN 101199938B
- Authority
- CN
- China
- Prior art keywords
- aging
- catalyst
- pillared
- temperature
- carbon monoxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- 239000004927 clay Substances 0.000 title claims abstract description 21
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 230000032683 aging Effects 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 9
- 239000013049 sediment Substances 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000005859 coupling reaction Methods 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 39
- 238000003756 stirring Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 230000009466 transformation Effects 0.000 claims description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 11
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 150000002500 ions Chemical class 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 239000002734 clay mineral Substances 0.000 claims description 6
- 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 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 230000008878 coupling Effects 0.000 claims description 5
- 238000010168 coupling process Methods 0.000 claims description 5
- 238000013467 fragmentation Methods 0.000 claims description 5
- 238000006062 fragmentation reaction Methods 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 4
- 239000011229 interlayer Substances 0.000 claims description 4
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 4
- 239000002114 nanocomposite Substances 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000005342 ion exchange Methods 0.000 claims description 3
- 239000010410 layer Substances 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 2
- 239000000440 bentonite Substances 0.000 abstract description 8
- 229910000278 bentonite Inorganic materials 0.000 abstract description 8
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 abstract description 8
- 150000003839 salts Chemical class 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract 1
- 239000012299 nitrogen atmosphere Substances 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 235000012216 bentonite Nutrition 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- 239000011651 chromium Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 238000000247 postprecipitation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910001566 austenite Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
Disclosed is a carbon monoxide conversion catalyst preparing method by pillared clay. The pillared liquid is made from the reaction of Fe3+ soluble salt and alkali in the nitrogen atmosphere. After aging, the pillared liquid takes exchange coupling reaction by adding the bentonite at the temperature from 40 DEG C to 90 DEG C; after the aging and precipitating, filtering, washing the sediments, and drying at the temperature of 80 DEG C to 140 DEG C, the catalyst for high concentration (40 percent to 100 percent) carbon monoxide conversion is obtained, and the conversion rate of the CO is from 70 percent to 99 percent.
Description
One, technical field: the present invention relates to a kind of CO steam transformation catalyst technology of preparing, belong to the chemical preparation technical field.
Two, background technology
The CO conversion is the reaction of extensive use on the chemical industry, is mainly used in the industry such as synthetic ammonia hydrogen manufacturing and regulates synthesis gas and make process.The CO catalyst for water-gas shift reaction is the key technology material of its reaction, generally be to form with iron oxide load chromium, cupric oxide zinc supported or aluminium or chromium, molybdenum oxide load molybdenum isoreactivity component, generally such industrial catalyst cost cost height, and poisonous and cause environmental pollution in production and the use, the useful life of catalyst is shorter simultaneously.
The patent of CO steam transformation catalyst has following: as disclosing a kind of preparation method of iron chromium mo-series carbon monoxide transformation catalyst among the Chinese patent CN90101486.9, it is that inorganic salts with the iron of solubility, chromium, molybdenum carry out co-precipitation in alkaline solution, washs roasting then and beats sheet and form; Disclose among the CN95121834.4 a kind of Cr iron-series type height (in) intermediate temp conversion catalyst,, ferric sulfate ferrous with sulfonium acid or be primary raw material with ferrous sulfate, potassium chlorate (sodium chlorate), sulfuric acid is with CeO
2(CeO), active A l
2O
3And KOH etc. be auxiliary agent, adopts solution neutralization precipitation method new technology, and acquisition is with active phase γ-Fe
2O
3Catalyst body for main body; Disclose a kind of novel nano-Cr iron-series catalyst for high-temp conversion of CO and preparation method thereof among the CN01138010.1, the preparation technology that it adopts coprecipitation and wet-mixing to combine substitutes chromium oxide with multiple metal oxide auxiliary agent synergy.This type of catalyst progressively is eliminated, though being used widely industrial of Chrome-free is applicable in the lower conversion gas of CO content owing to the toxicity that contains in its production of chromium and the use.Column clay is a kind of typical layer column type porous material, be a kind of based on clay mineral interlayer chemism, introduce in the clay interlamination region as column-supporting agent having difference in functionality group guest species by modes such as ion-exchanges, the class aperture with molecule rank pillar is big, the novel nano composite of distribution rule thereby form.Column clay generally is used for water treatment, also have and be used for catalytic action on a small quantity, as disclosing consisting of of a kind of catalyst by preparing low-carbon mixed alcohol by synthetic gas: Mo:20-40% among the Chinese patent CN01130481.2, Ni:4-10%, Mn:0.1-5.0%, K:5-15%, S:20-40%, column clay: 20-40%.The catalyst of NOx in a kind of waste gas stream of purifying motor vehicle is disclosed among the CN200580008583.1, it is characterized in that this catalyst comprise be selected from column clay, terre verte, hectorite, with and composition thereof modified clay mineral matter, all these clay minerals by aluminium, silicon or titanium (oxide) as shore supports.Column clay is all or part of class new material that is substituted and be fixed on its interlayer by some specific ion or ion cluster of exchangeable ion in the clay mineral interlamination region, be a kind of permeability material with certain hole, can be after its specific area of while is pillared up to 450～500m
2Therefore the material of/g is used for catalyst or adsorbent has its corresponding advantage, shows from the interrelated data retrieval, has not yet to see with column clay directly as the relevant report of CO transformation catalyst.
Three, summary of the invention
1. goal of the invention:, the invention provides a kind of technology with preparing carbon monoxide transfer catalyst from pillared clay in order to solve in the existing technology not about the vacancy of high-concentration carbon monoxide (40%～100%) transformation catalyst exploitation.
2. Fa Ming technical scheme: the technical scheme that technical solution problem of the present invention is adopted is: adopt a kind of natural clay after modification, come the substitute goods traditional catalyst, comprise system Fe
3+Pillared liquid, pillared liquid and bentonite reaction, precipitation, filtration, sediment washing, oven dry obtain the carbon monoxide transformation catalyst several steps, and concrete technical process is as follows: (1) is the Fe of 0.1～0.3mol/L with concentration
3+Soluble-salt solution as in ferric nitrate or the iron chloride any one, is to stir under 5～30 ℃ the room temperature in temperature, (divides 10 times) in the time of stirring to add a kind of in sodium carbonate or the NaOH alkalescence thing in batches, makes content and the Fe of OH-
3+The ratio of content reaches 5: 1～between 1: 1, and when adding alkali, in solution, feed nitrogen continuously, continue at room temperature to stir 2.0h then, thereby obtain the transparent pillared liquid of brown, after the pillared liquid that obtains at room temperature left standstill aging 12h, (2) in aging pillared liquid, drop into after fragmentation is sieved granularity less than the bentonite of 2 μ m, make Fe
3+Ion mol quantity and natural montmorillonite mass ratio reach 10mmol/g, and the preferred chemical component weight percentage of natural clay is formed: SiO
266.36%, Al
2O
314.28%, Fe
2O
3+ FeO1.29%, MgO4.08%, CaO2.06%, Na
2O0.05%, K
2O0.18%, H
2O
++ H
2O
-10.63%.Be continuous stirring 12h in 40 ℃～90 ℃ the water bath with thermostatic control in temperature then, continuing in temperature is 40 ℃～90 ℃ the aging 24h of water bath with thermostatic control, makes Fe
3+With Ca in bentonite exchange, coupling, precipitation, filtration after (3) are aging, sediment is with each 3000ml water washing 6 times, dries 3h and can get CO conversion catalyst in temperature is 80 ℃～140 ℃ air dry oven.The preferred chemical component weight percentage of column clay CO transformation catalyst is formed after the modification: SiO
256.57%, Al
2O
312.25%, Fe
2O
3+ FeO15.85%, MgO3.48%, CaO1.76%, Na
2O0.04%, K
2O0.15%, H
2O
++ H
2O
-9.06%.Column clay is a kind of typical layer column type porous material, be a kind of based on clay mineral interlayer chemism, introduce in the clay interlamination region as column-supporting agent having difference in functionality group guest species by modes such as ion-exchanges, class aperture with molecule rank pillar is big, the novel nano composite of distribution rule thereby form, for being used as the CO transformation catalyst, Fe is loaded between argillic horizon, make wherein Fe
2O
3The content of+FeO reaches more than 15%, specific area 400m
2More than/the g,, can also screen size be that 2～200 μ m use as carrier simultaneously, make as sphere after also can being shaped and use according to experimental results show that it can satisfy the requirement of carbon monoxide transformation catalyst.Unsetting column clay had both reduced the cost of Catalyst Production as transformation catalyst, had avoided the pollution of other catalyst to environment again.Simultaneously also filled up the blank that is used for high-concentration carbon monoxide (40%～100%) transformation catalyst, its CO interconversion rate reaches 70%～99%.
3. good effect of the present invention is: high-concentration carbon monoxide (40%～100%) transformation catalyst can be widely used for its comprehensive utilization in producers such as system methyl alcohol, phosphorus production, has the low temperature active height, the distinguishing feature of anti-high carbonomonoxide concentration.Adopt natural clay lower as feedstock production carbon monoxide transformation catalyst cost, produce and use environmental pollution little, this technology is practical.
Four, the specific embodiment
Embodiment 1:
Be dissolved in the 16.67L water and stirring at room temperature with the 1.21kg ferric nitrate, at this moment Fe in the solution
3+Concentration be 0.18mol/L, add 265g natrium carbonicum calcinatum powder in the time of stirring in batches, this moment OH
-Content and Fe
3+The ratio of content reaches 1: 1, and when adding sodium carbonate in solution the uninterrupted nitrogen that feeds, continue at room temperature to stir 2.0h then, thereby obtain the transparent pillared liquid of brown, behind the at room temperature aging 12h of pillared liquid that obtains, input granularity after fragmentation is sieved makes Fe less than the bentonite of 2 μ m
3+The mass ratio of ion mol number and natural montmorillonite reaches 10mmol/g, is continuous stirring 12h in 40 ℃ the water bath with thermostatic control in temperature then, and in temperature is aging 24h in 40 ℃ the water bath with thermostatic control, make Fe
3+With Ca in bentonite exchange, coupling, aging postprecipitation, filtration, sediment is with each 3000ml water washing 6 times, dries 3h and can obtain CO conversion catalyst in temperature is 80 ℃ air dry oven.The content of iron (comprising di-iron trioxide and ferrous oxide) is 14.3% in the synthetic rear catalyst, and its specific area is 466m
2/ g.The catalyst that makes with above-mentioned condition is in fixed bed reactors, and reduction temperature is 300 ℃, through reduction in 2 hours, feeds and purifies the back yellow phosphoric tail gas, and the air speed of reaction is gas flow (m
3/ h) with catalyst volume (m
3) than being 2000/h, the reaction gas to steam ratio is 0.5, the CO rate of change of reaction reaches 99%.
Embodiment 2:
Be dissolved in the 16.67L water and stirring at room temperature with 1.70kg iron chloride, at this moment Fe in the solution
3+Concentration be 0.3mol/L, add 1325g natrium carbonicum calcinatum powder in the time of stirring in batches, this moment OH
-Content and Fe
3+The ratio of content reaches 2.5: 1, and when adding sodium carbonate in solution the uninterrupted nitrogen that feeds, continue at room temperature to stir 2.0h then, thereby obtain the transparent pillared liquid of brown, behind the at room temperature aging 12h of pillared liquid that obtains, input granularity after fragmentation is sieved makes Fe less than 1.5 μ m bentonites
3+Ion mol amount reaches 10mmol/g with the mass ratio of natural montmorillonite, is the uninterrupted 12h of stirring in 60 ℃ the water bath with thermostatic control in temperature then, and is aging 24h in 60 ℃ the water bath with thermostatic control in temperature, makes Fe3
+ withCa in bentonite exchange, coupling, are filtered at aging after precipitation, and filtrate is with each 3000ml water washing 6 times, dry in temperature is 120 ℃ air dry oven and can get CO conversion catalyst.The content of iron (comprising di-iron trioxide and ferrous oxide) is 15.8% in the synthetic rear catalyst, and its specific area is 485m
2/ g.
In fixed bed reactors, 350 ℃ of reduction temperatures feed and purify the back yellow phosphoric tail gas through reduction in 2 hours with the catalyst that makes in the above-mentioned condition, and reaction velocity is gas flow (m
3/ h) with catalyst volume (m
3) than being 3000/h, the reaction gas to steam ratio is 0.6, the CO rate of change of reaction reaches 75%.
Embodiment 3:
Be dissolved in the 16.67L water and stirring at room temperature with 1.70kg iron chloride, at this moment Fe in the solution
3+Concentration be 0.3mol/L, add the 2kg sodium hydroxide powder in the time of stirring in batches, this moment OH
-Content and Fe
3+The ratio of content reaches 5: 1, and when adding sodium carbonate in solution the uninterrupted nitrogen that feeds, continue at room temperature to stir 2.0h then, thereby obtain the transparent pillared liquid of brown, behind the at room temperature aging 12h of pillared liquid that obtains, input granularity after fragmentation is sieved makes Fe less than 1.5 μ m bentonites
3+Ion mol number and natural montmorillonite mass ratio reach 10mmol/g, are the uninterrupted 12h of stirring in 80 ℃ the water bath with thermostatic control in temperature then, and are 80 ℃ the aging 24h of water bath with thermostatic control in temperature, make Fe
3+With Ca in bentonite exchange, coupling, aging postprecipitation, filtration, filtrate is with each 3000ml water washing 6 times, dries in temperature is 100 ℃ air dry oven and can get CO conversion catalyst.The content of iron (comprising di-iron trioxide and ferrous oxide) is 13.6% in the synthetic rear catalyst, and its specific area is 444m
2/ g.In fixed bed reactors, 400 ℃ of reduction temperatures feed and purify the back yellow phosphoric tail gas through reduction in 2 hours with the catalyst that makes in the above-mentioned condition, and reaction velocity is gas flow (m
3/ h) with catalyst volume (m
3) than being 4000/h, the reaction gas to steam ratio is 0.7, the CO rate of change of reaction reaches 90%.
Claims (1)
1. the method with preparing carbon monoxide transfer catalyst from pillared clay comprises system Fe
3+Pillared liquid, pillared liquid and natural montmorillonite reaction, precipitation are aging, filtration, sediment washing, dry the carbon monoxide transformation catalyst several steps, it is characterized in that:
1.1 system Fe
3+Pillared liquid, aging is the Fe of 0.1～0.3mol/L with concentration
3+Soluble-salt solution, described Fe
3+Soluble-salt is any one in ferric nitrate or the iron chloride, in temperature is to stir under 5～30 ℃ the temperature, adds a kind of in sodium carbonate or the NaOH for 10 times in the same time-division of stirring, and makes content and the Fe of OH-
3+The ratio of content reaches 5: 1～between 1: 1, and when adding alkali, in solution, feed nitrogen continuously, and continue at room temperature to stir 2h, thereby obtain the transparent pillared liquid of brown, the pillared liquid that obtains is at room temperature left standstill aging 12h;
1.2 the reaction of pillared liquid and natural montmorillonite, precipitation are aging, in the pillared liquid after aging, drop into after fragmentation is sieved granularity less than the natural montmorillonite of 2 μ m, make Fe
3+Ion molal quantity and natural montmorillonite mass ratio reach 10mmol/g, and the chemical component weight percentage of natural montmorillonite consists of SiO
266.36%, Al
2O
314.28%, Fe
2O
3+ FeO1.29%, MgO4.08%, CaO2.06%, Na
2O0.05%, K
2O0.18%, H
2O
++ H
2O
-10.63%, be continuous stirring 12h in 40 ℃～90 ℃ the water bath with thermostatic control in temperature, continuing in temperature is 40 ℃～90 ℃ the aging 24h of water bath with thermostatic control, makes Fe
3+With the Ca exchange in the natural montmorillonite, coupling;
1.3 sediment filtration, washing, oven dry obtain carbon monoxide transformation catalyst, pillared natural montmorillonite sediment after aging filters, sediment is with each 3000ml water washing 6 times, column clay after temperature is that oven dry 3h gets modification in 80 ℃～140 ℃ the air dry oven, be CO conversion catalyst, this CO transformation catalyst chemical component weight percentage consists of: SiO
256.57%, Al
2O
312.25%, Fe
2O
3+ FeO15.85%, MgO3.48%, CaO1.76%, Na
2O0.04%, K
2O0.15%, H
2O
++ H
2O
-9.06%, it is a kind of typical layer column type porous material, be a kind of based on clay mineral interlayer chemism, introduce in the clay interlamination region as column-supporting agent having difference in functionality group guest species by ion-exchange method, class aperture with molecule rank pillar is big, the nano composite material of distribution rule thereby form, for being used as the CO transformation catalyst, Fe
3+Load between argillic horizon, make wherein Fe
2O
3The content of+FeO reaches more than 15%, specific area 400m
2More than/the g, make the two active adduction, form that the class aperture with molecule rank pillar is big, the nano composite material of distribution rule, can be used as concentration and be 40%～100% carbon monoxide transformation catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100664623A CN101199938B (en) | 2007-12-17 | 2007-12-17 | Method of carbon monoxide shift catalyst prepared by pillared clay |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100664623A CN101199938B (en) | 2007-12-17 | 2007-12-17 | Method of carbon monoxide shift catalyst prepared by pillared clay |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101199938A CN101199938A (en) | 2008-06-18 |
| CN101199938B true CN101199938B (en) | 2010-12-01 |
Family
ID=39515408
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007100664623A Expired - Fee Related CN101199938B (en) | 2007-12-17 | 2007-12-17 | Method of carbon monoxide shift catalyst prepared by pillared clay |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101199938B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115254088B (en) * | 2022-08-30 | 2023-11-21 | 华东理工大学 | Catalyst for producing alkyl diphenylamine and preparation method and application thereof |
-
2007
- 2007-12-17 CN CN2007100664623A patent/CN101199938B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN101199938A (en) | 2008-06-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2237882B1 (en) | Iron-based water gas shift catalyst | |
| CN101190415B (en) | Method of producing a catalyst used for synthesizing dimethylether from a synthesis gas containing carbon dioxide | |
| CN103079695A (en) | Modified zinc ferrite catalyst and method of preparation and use | |
| CN103663529A (en) | Method for preparing nano-calcium carbonate slurry by using waste gypsum as calcium source, product and application | |
| CN105214599B (en) | Sulphur arsenic adsorbent and preparation method thereof | |
| EP0100512A2 (en) | Reaction mass, method for the manufacture thereof and use thereof | |
| KR20210001642A (en) | Method of Preparing Layered Double Hydroxide Based Adsorbent and Method of Removing Heavy Metals in Water Using the Same Prepared thereby | |
| CN105582877B (en) | Room temperature desulfurating and dearsenic agent and preparation method thereof | |
| CN103769234A (en) | Protective agent for sulfur tolerant shift catalyst and preparation method thereof | |
| CN103769116A (en) | Sulfur tolerant shift catalyst and preparation method | |
| US4910004A (en) | Process for selective reduction of nitrogen oxides contained in oxygenated gaseous effluents | |
| CN102824849A (en) | Method for reducing NOx emission in FCC (Fluid Catalytic Cracking) regeneration process | |
| Ma et al. | Application of engineered natural ores to intermediate‐and high‐temperature CO2 capture and conversion | |
| Ai et al. | Immobilization of β-FeOOH nanomaterials on the basalt fiber as a novel porous composite to effectively remove phosphate from aqueous solution | |
| CN101717247B (en) | Novel material for processing water into small molecular group water and preparation method and application thereof | |
| CN101199938B (en) | Method of carbon monoxide shift catalyst prepared by pillared clay | |
| JPH06122519A (en) | Hydrated amorphous ferric oxide particle powder and its production | |
| CN101856617B (en) | Method for preparing iron-based chrome-free high-temperature water gas conversion catalyst in hydrogen-rich atmosphere | |
| CN102489150B (en) | Preparation method for load type iron-based sulfureted hydrogen removal agent under room temperature | |
| CN105749855A (en) | Liquid-phase dechlorinating agent and preparation method and application thereof | |
| CN104560250B (en) | Cleanser and preparation method thereof | |
| Li et al. | Clean removal of silicon (IV) and vanadium (V) from high concentration chromium (VI) solutions in the chromate production processes | |
| CN101239307A (en) | Method for preparing carbon monoxide translating catalyst | |
| CN108854476A (en) | Protective agent of methanol synthesis catalyst and its preparation method and application | |
| CN101259416A (en) | Method for preparing carbon monoxide transfer catalyst from pillared clay |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20101201 Termination date: 20121217 |