CN1546232A - Fe-Mo catalyst for preparing formaldehyde through methanol oxidation and preparation process thereof - Google Patents
Fe-Mo catalyst for preparing formaldehyde through methanol oxidation and preparation process thereof Download PDFInfo
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- CN1546232A CN1546232A CNA2003101065698A CN200310106569A CN1546232A CN 1546232 A CN1546232 A CN 1546232A CN A2003101065698 A CNA2003101065698 A CN A2003101065698A CN 200310106569 A CN200310106569 A CN 200310106569A CN 1546232 A CN1546232 A CN 1546232A
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- catalyst
- methanol oxidation
- formaldehyde
- catalyzer
- iron
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- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims description 63
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims description 54
- 230000003647 oxidation Effects 0.000 title claims description 16
- 238000007254 oxidation reaction Methods 0.000 title claims description 16
- 238000002360 preparation method Methods 0.000 title claims description 12
- 229910017116 Fe—Mo Inorganic materials 0.000 title 1
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims abstract 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 16
- 239000011651 chromium Substances 0.000 claims description 15
- 238000000975 co-precipitation Methods 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 238000001556 precipitation Methods 0.000 claims description 11
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 10
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical group [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 7
- 239000012018 catalyst precursor Substances 0.000 claims description 6
- 238000007493 shaping process Methods 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- 235000021355 Stearic acid Nutrition 0.000 claims description 5
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 5
- 239000008117 stearic acid Substances 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 4
- 229940010552 ammonium molybdate Drugs 0.000 claims description 4
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 4
- 239000011609 ammonium molybdate Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- FRVCGRDGKAINSV-UHFFFAOYSA-L iron(2+);octadecanoate Chemical compound [Fe+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O FRVCGRDGKAINSV-UHFFFAOYSA-L 0.000 claims description 3
- 229920000609 methyl cellulose Polymers 0.000 claims description 3
- 239000001923 methylcellulose Substances 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 2
- 108010038629 Molybdoferredoxin Proteins 0.000 claims 1
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- HBELESVMOSDEOV-UHFFFAOYSA-N [Fe].[Mo] Chemical compound [Fe].[Mo] HBELESVMOSDEOV-UHFFFAOYSA-N 0.000 claims 1
- 239000000654 additive Substances 0.000 claims 1
- 230000000996 additive effect Effects 0.000 claims 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 abstract 1
- RKFLTKXKVVFHFH-UHFFFAOYSA-N formaldehyde;iron Chemical compound [Fe].O=C RKFLTKXKVVFHFH-UHFFFAOYSA-N 0.000 abstract 1
- DSMZRNNAYQIMOM-UHFFFAOYSA-N iron molybdenum Chemical compound [Fe].[Fe].[Mo] DSMZRNNAYQIMOM-UHFFFAOYSA-N 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 241000219782 Sesbania Species 0.000 description 6
- 238000004062 sedimentation Methods 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000012452 mother liquor Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000000748 compression moulding Methods 0.000 description 3
- 230000001143 conditioned effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 241000370738 Chlorion Species 0.000 description 2
- 102100023618 Neutrophil cytosol factor 2 Human genes 0.000 description 2
- 101710120095 Neutrophil cytosol factor 2 Proteins 0.000 description 2
- 102100023617 Neutrophil cytosol factor 4 Human genes 0.000 description 2
- 101710120087 Neutrophil cytosol factor 4 Proteins 0.000 description 2
- 238000010835 comparative analysis Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- HZNPCLUBXJLRAA-UHFFFAOYSA-N iron;oxomolybdenum Chemical compound [Fe].[Mo]=O HZNPCLUBXJLRAA-UHFFFAOYSA-N 0.000 description 2
- 230000001404 mediated effect Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- 230000003245 working effect Effects 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction 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
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- KWUUWVQMAVOYKS-UHFFFAOYSA-N iron molybdenum Chemical compound [Fe].[Fe][Mo][Mo] KWUUWVQMAVOYKS-UHFFFAOYSA-N 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000047 product Substances 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
- -1 weaving Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Abstract
The invention refers to a kind of formaldehyde iron phase catalyst made up by oxidizing in industrial alcohol and the manufacturing method. Oxide of chromium and vanadium are added into the iron-molybdenum catalyst system, forms the four-component catalyst system; the shape of the catalyst is designed as a hollow cylinder ring structure, it has low catalyst bed resistance in using, the catalyst has a high alcohol converting rate and high yield of formaldehyde, the heat stability of catalyst is good and the lifespan is long.
Description
Technical field:
The invention belongs to organic chemical industry's catalyst field, be specifically related to a kind of industrial methanol oxidation system formaldehyde iron-molybdic catalyst and preparation method thereof.
Background technology:
Formaldehyde is important basic Organic Chemicals, has become the Chemicals of scale operation and consumption, is widely used in chemical industry, medicine, weaving, wood working and petroleum industry.The modern industry Formaldehyde Production, mainly adopting with methyl alcohol is that the oxidation style of raw material prepares technology.And the iron-molybdenum oxide catalyzer with the advantage on its aspect of performance, has obtained development and use widely after nineteen fifty-two is used for methanol oxidation system formaldehyde industrial production.
The patent of external disclosed preparation iron-molybdic catalyst is a lot, is 3,408,309 as U.S. Patent Publication No., is two component iron-molybdenum oxide catalyzer open day October 29 nineteen sixty-eight.Afterwards people for the physical strength of improving iron-molybdic catalyst, improve activity of such catalysts and work-ing life, in iron-molybdic catalyst, add various metal oxide auxiliary agents again.U.S. Patent Publication No. 3,846,341, open day on November 5th, 1974 described catalyzer, be the methanol oxidation system formaldehyde iron-molybdic catalyst that adopts gel method to prepare, and add a spot of tungsten and cobalt/cobalt oxide auxiliary agent, improve the performance of catalyzer; When adopting this legal system to be equipped with catalyzer,, make the catalyzer each component comparison difficulty that is uniformly dispersed, be difficult for realizing because what generate is gel.U.S. Patent Publication No. 3,978,136, open day on August 31st, 1976, be to be raw material with Iron(III) chloride hexahydrate and ammonium paramolybdate, adopt coprecipitation method prepare iron-molybdic catalyst gained slurry through wash clean after, with TiO
2Add in the slurry, stir, prepare the ideal catalyzer; Because chloride ion-containing in the raw material in washing process, with the chlorion washes clean, consume a large amount of water, otherwise chlorion can bring adverse influence to the performance of catalyzer.U.S. Patent Publication No. 4,829,042, open day on May 9th, 1989, described catalyzer is made up of iron molybdate and molybdenum oxide, its preparation method is: under certain precipitation temperature and violent stirring, the nitrate aqueous solution of iron is joined in the ammonium salt aqueous solution of molybdenum, and throw out gained siccative and non-agglomerating, hangs down the Fe of specific surface after washing, oven dry
2O
3Mechanically mixing requires the specific surface of the ferric oxide of adding had better not surpass 3m
2/ g; By weight, non-sintering Fe
2O
3Addition account for Fe
2O
320%～50% best with Mo-Fe catalyzer total amount.In this catalyst system that makes by co-precipitation, the Mo/Fe mol ratio is 2～4, and an amount of non-sintering Fe is arranged
2O
3Do not combine with molybdenum.Chinese patent CN1100667A, open day March 29 nineteen ninety-five, described catalyzer is as active constituent with molybdenum, and form through prepared by co-precipitation with structural promoter metal oxide (as elements such as Fe, Cr, Co), catalyzer can be two components (Mo, Fe), three components (Mo, Fe, Co or Cr) or four components (Mo, Fe, Co, Cr).This catalyzer is tested in micro-reactor, is getting rid of heat effect, and under 340 ℃～380 ℃ conditions, methanol conversion is 99%～100%, and the formaldehyde yield is 95.6%～98.8%.Yet there are no Industrial products and use report.
Summary of the invention:
The objective of the invention is to propose methanol oxidation system formaldehyde iron-molybdic catalyst that a kind of industrial production uses and preparation method thereof, this catalyzer has lower catalytic bed resistance in industry is used, and having high methanol conversion and formaldehyde yield, the better heat stability and the work-ing life of catalyzer are longer.This catalyzer adopts the method preparation of co-precipitation, adds the oxide compound of chromium and vanadium in iron molybdenum two component oxide systems, obtains the catalyzer of four component systems.(Mo+V)/(Fe+Cr) mol ratio of methanol oxidation making formaldehyde catalyst of the present invention is between 1.8～5.0, and best (Mo+V)/(Fe+Cr) mol ratio is 2.0～3.0; The weight percent that the amount of added chromic oxide accounts for whole catalyzer is 2%～30%, and it is 0.5%-5% that Vanadium Pentoxide in FLAKES accounts for catalyst weight per-cent.
According to the present invention, the auxiliary agent vanadium is to join in the ammonium molybdate solution with ammonium meta-vanadate, forms mixing solutions; Auxiliary agent chromium is that the form with chromic oxide joins in the catalyst system, before coprecipitation reaction, ammonium meta-vanadate, the chromic oxide of metering is joined in the ammonium molybdate solution, is mixed with the mixing solutions of three components, and the pH value of mixing solutions is transferred to 1.0～3.0.Under violent stirring, iron nitrate solution is slowly joined in the mixing solutions as precipitation agent, and whole coprecipitation reaction should be finished in 60 minutes, in the coprecipitation reaction process, the pH value of keeping suspension with ammoniacal liquor is 1.0～3.0, till precipitin reaction finishes.Can guarantee that like this active substance molybdenum is precipitated out to greatest extent from solution, chromic oxide is disperseed to greatest extent, the complex catalyst precursor thing of preparing is easy to sedimentation, washing.The catalyzer that obtains after drying, moulding, the roasting has suitable structure and crystal grain.
According to the present invention, the catalyzer face shaping of preparing is the hollow cylinder ring structure, and physical dimension is: outer diameter D: 4～6mm; Inner diameter d: 1～3mm; Length H:3～6mm, outer diameter D/inner diameter d=2.0～4.5.Its forming method can be compression moulding or extrusion forming.
The detailed preparation process of catalyzer of the present invention is described below:
Be dissolved in four hydration Ammonium Heptamolybdates and ammonium meta-vanadate in the deionized water jointly, be mixed with the solution that concentration is 10%～25% (weight percent concentration), the pH value to 1.0 of regulator solution～3.0, and be heated to certain temperature (30 ℃～80 ℃), the chromic oxide (2%～30%) of required adding is poured in the mixing solutions of ammonium molybdate and ammonium meta-vanadate, under violent stirring, slowly the adding concentration expressed in percentage by weight is 5%～15% iron nitrate aqueous solution, keeping the pH value of suspension with ammoniacal liquor is 1.0～3.0, till precipitin reaction finishes, precipitin reaction was finished in 60 minutes, and continued to stir 1～3 hour; Sedimentation is then removed supernatant liquid with siphonage, uses deionised water three times; The throw out that filtration is obtained toasted 24 hours at 80 ℃, 150 ℃～180 ℃ bakings 6～8 hours.The complex catalyst precursor thing of preparing is carried out granulation or mills; in this process, add the forming agent that accounts for catalyst weight 1%-20%; as: a kind of shaping assistant in stearic acid, iron stearate, sesbania powder, methylcellulose gum, aluminum solutions glue or the silicon sol, add-on is preferably 2%-15%.Then with material compression moulding or extrusion forming.Physical dimension is: outer diameter D=4～6mm; Inner diameter d=1～3mm; Length H=3～6mm, outer diameter D/inner diameter d=2.0～4.5.
Compression moulding: after the complex catalyst precursor thing drying that precipitin reaction is obtained, mill, in its process, add an amount of water, be a granulated into the small-particle of 1.6～2.0mm, oven dry, add the stearic acid or the iron stearate that account for catalyst weight 1%～8%, mix, be pressed into required shape then.
Extrusion forming: be the siccative that the complex catalyst precursor thing drying that precipitin reaction obtains is obtained, add the tackiness agent that accounts for catalyst weight 5%～20%, as: sesbania powder, methylcellulose gum, aluminium colloidal sol, silicon sol any one, add water and mediate, extrude into required shape then.
In 24 hours, maturing temperature slowly is promoted to 380 ℃～450 ℃ by room temperature at last, and this roasting temperature 2～4 hours.
Embodiment:
The present invention will be further described below in conjunction with embodiment.
Embodiment 1
Under violent stirring, to 2660ml, concentration is 15% (weight concentration), pH value is (wherein V/ (Mo+V) mol ratio is 0.014) in～2.5 the Ammonium Heptamolybdate and ammonium metavanadate aqueous solution, the chromic oxide that adds 16.0 grams earlier, slowly add 3000ml, concentration again and be 10% iron nitrate aqueous solution, when coprecipitation reaction suspension pH value is 1.8, till extremely precipitation finishes with this required pH value of ammoniacal liquor conditioned reaction, 27 minutes precipitin reaction times spent.After precipitation finishes, continue to stir 2 hours; Stop to stir, sedimentation is removed supernatant liquid with siphonage, uses deionized water wash again three times; Filter to precipitate then and separate with mother liquor; Filter cake was 80 ℃ of bakings 24 hours, and 150 ℃～180 ℃ are toasted a few hours, and the siccative that obtains is stand-by.(Mo+V)/(Fe+Cr) atomic ratio of catalyzer is 2.6, and Cr/ (Fe+Cr) atomic ratio is 0.12, and V/ (Mo+V) atomic ratio is 0.014.
Embodiment 1-1
Get the above-mentioned catalyzer siccative of 150 grams, adding water, to be a granulated into diameter be 1.6～2.0mm small-particle, 100 ℃ of oven dry; The siccative that obtains adds 6 gram stearic acid, mixes; Be pressed into φ 4.5 * 1.0, length is 4.5 hollow cylinder; 430 ℃ of roasting temperatures 3 hours, obtain sample NCF-1-1 at last.
Embodiment 1-2
Get the above-mentioned catalyzer siccative of 150 grams, add 15 gram sesbania powder, mix, add water and mediate; Extrude into afterwards φ 4.5 * 1.0, length is 4.5 hollow cylinder; Under 100 ℃ of temperature, dry,, obtain sample NCF-1-2 430 ℃ of roasting temperatures 3 hours.
Embodiment 2
Get the above-mentioned catalyzer siccative of 150 grams, adding water, to be a granulated into diameter be 1.6～2.0mm small-particle, 100 ℃ of oven dry; Add 6 gram stearic acid, mix; Be pressed into the sheet base of φ 4.5 * 4.5,, obtain sample NCF-2 430 ℃ of roasting temperatures 3 hours.
Embodiment 3:
Under violent stirring, to 2660ml, concentration is 15% (weight concentration), pH value is in～2.5 the Ammonium Heptamolybdate aqueous solution, slowly adding 3500ml, concentration are 10% iron nitrate aqueous solution, when coprecipitation reaction suspension pH value is 1.8, till extremely precipitation finishes with this required pH value of ammoniacal liquor conditioned reaction, 30 minutes precipitin reaction times spent.After precipitation finishes, continue to stir 2 hours; Stop to stir, sedimentation is removed supernatant liquid with siphonage, uses deionized water wash again three times; Filter to precipitate then and separate with mother liquor; Filter cake was 80 ℃ of bakings 24 hours, and 150 ℃～180 ℃ were toasted 6 hours; The Mo/Fe atomic ratio of catalyzer is about 2.6.Add the sesbania powder that accounts for catalyst weight 8%, mix, add water and mediate; Extrude into afterwards φ 4.5 * 1.0, length is 4.5 hollow cylinder; Under 100 ℃ of temperature, dry,, obtain sample NCF-3 400 ℃ of roasting temperatures 2 hours.
Embodiment 4:
Under violent stirring, to 2660ml, concentration is 15% (weight concentration), pH value is in～2.5 the Ammonium Heptamolybdate aqueous solution, the chromic oxide that adds 16.0 grams earlier, slowly add 3000ml, concentration after a while and be 10% iron nitrate aqueous solution, when coprecipitation reaction suspension pH value is 1.8, till extremely precipitation finishes with this required pH value of ammoniacal liquor conditioned reaction, 28 minutes precipitin reaction times spent.After precipitation finishes, continue to stir 2 hours; Stop to stir, sedimentation is removed supernatant liquid with siphonage, uses deionized water wash again three times; Filter to precipitate then and separate with mother liquor; Filter cake was 80 ℃ of bakings 24 hours, and 150 ℃～180 ℃ were toasted 6 hours; The Mo/ of catalyzer (Fe+Cr) atomic ratio is about 2.6, and Cr/ (Fe+Cr) atomic ratio is 0.13.Add the sesbania powder that accounts for catalyst weight 8%, mediated 40 minutes, extrude into φ 4.5 * 1.0mm then, length is the hollow cylinder of 4.5mm.430 ℃ of roasting temperatures 3 hours, obtain sample NCF-4.
Embodiment 5:
Under violent stirring, to 2660ml, concentration is 15% (weight concentration), in the mixed aqueous solution (wherein V/ (Mo+V) atomic ratio is 0.014) of pH value for～2.5 Ammonium Heptamolybdate and ammonium meta-vanadate, slowly adding 3500ml, concentration are 10% iron nitrate aqueous solution, when coprecipitation reaction suspension pH value is 1.8, keep this pH value till precipitation finishes with ammoniacal liquor, 28 minutes precipitin reaction times spent.After precipitation finishes, continue to stir 2 hours; Stop to stir, sedimentation is removed supernatant liquid with siphonage, uses deionized water wash again three times; Filter to precipitate then and separate with mother liquor; Filter cake was 80 ℃ of bakings 24 hours, and 150 ℃～180 ℃ were toasted 6 hours; (Mo+V)/Fe atomic ratio of catalyzer is about 2.6, and V/ (Mo+V) atomic ratio is about 0.015.The sesbania powder of adding 8% was mediated 40 minutes, extruded into φ 4.5 * 1.0mm then, and length is the hollow cylinder of 4.5mm; 420 ℃ of roasting temperatures 2 hours, obtain sample NCF-5.Active testing: as reference, active comparative evaluation the results are shown in following table with the advanced commercial catalysts of external certain company.
Embodiment 6: with NCF-1-2 type catalyzer under 450 ℃ of temperature heat-resisting 20 hours, obtaining catalyst sample was NCF-1-2
*
Active testing: as reference, active comparative evaluation the results are shown in following table (the catalyzed reaction hot(test)-spot temperature is at 350 ℃～365 ℃) with the advanced commercial catalysts of external certain company.
| Sample | Methyl alcohol/(methyl alcohol+air)/% | Air speed/h -1 | Inlet temperature/℃ | Methanol conversion/% | Formaldehyde yield/% |
| ??NCF-1-1 | ????6 | ??20000 | ????240 | ????98.2 | ????93.4 |
| ??NCF-1-2 | ????6 | ??20000 | ????240 | ????99.3 | ????94.6 |
| ??NCF-2 | ????6 | ??20000 | ????240 | ????97.8 | ????91.6 |
| ??NCF-3 | ????6 | ??20000 | ????240 | ????98.1 | ????92.3 |
| ??NCF-4 | ????6 | ??20000 | ????240 | ????97.4 | ????93.0 |
| ??NCF-5 | ????6 | ??20000 | ????240 | ????98.3 | ????93.8 |
| ??NCF-1-2 * | ????6 | ??20000 | ????240 | ????98.5 | ????94.4 |
| Reference | ????6 | ??20000 | ????240 | ????98.2 | ????92.1 |
Claims (8)
1, a kind of catalyzer of methanol oxidation system formaldehyde, it is characterized in that its main component is iron molybdate and molybdic oxide, and the oxides additive of interpolation chromium and vanadium, the molybdenum-iron mol ratio is 1.8: 1 to 5: 1, it is 2%-30% that the chromic oxide that adds accounts for catalyst weight per-cent, and it is 0.5%-5% that Vanadium Pentoxide in FLAKES accounts for catalyst weight per-cent.
2, a kind of Preparation of catalysts method of methanol oxidation system formaldehyde, adopt the method for co-precipitation to be prepared from, it is characterized in that the auxiliary agent vanadium is is that form with chromic oxide joins in the catalyst system with ammonium meta-vanadate form, chromium, before precipitin reaction, ammonium meta-vanadate, chromic oxide are joined in the ammonium molybdate solution, be mixed with the mixing solutions of three components, under violent stirring, iron nitrate solution is slowly joined in the mixing solutions as precipitation agent, and whole coprecipitation reaction was finished in 60 minutes; Before carrying out co-precipitation, need transfer to 1.0～3.0 with the pH value of the ammonium salt aqueous solution of molybdenum and vanadium; In the coprecipitation reaction process, the pH value of keeping suspension with ammoniacal liquor is 1.0～3.0, till precipitin reaction finishes; With the washing of the complex catalyst precursor thing that obtains, filter, filter throw out baking, the granulation that obtains or mill, moulding, work in-process obtain catalyst prod through roasting.
3, a kind of Preparation of catalysts method of methanol oxidation system formaldehyde as claimed in claim 2, it is characterized in that the complex catalyst precursor thing that obtains is with deionised water, filtration, to obtain filtering throw out 80 ℃ of bakings 24 hours, 150 ℃～180 ℃ bakings 4～8 hours; To the oven dry material carry out granulation or mill, moulding, work in-process obtain catalyst prod 380 ℃～450 ℃ following roastings 2～4 hours.
4, according to claim 1 or 4 described methanol oxidation making formaldehyde catalysts, it is characterized in that the catalyzer face shaping is the hollow cylinder ring structure, physical dimension is: outer diameter D=4～6mm, inner diameter d=1～3mm, height H=3～6mm, outer diameter D/inner diameter d=2.0～4.5.
5, the preparation method of methanol oxidation making formaldehyde catalyst according to claim 2, the profile that it is characterized in that catalyzer is to be pressed into annular.
6, the preparation method of methanol oxidation making formaldehyde catalyst according to claim 2, the profile that it is characterized in that catalyzer extrude to circularize.
7, methanol oxidation making formaldehyde catalyst according to claim 1 is characterized in that when shaping of catalyst, needs to add the shaping assistant that accounts for catalyst weight 1%～20%.
8, methanol oxidation making formaldehyde catalyst according to claim 7 is characterized in that shaping assistant is a kind of in stearic acid, iron stearate, sesbania powder, methylcellulose gum, aluminium colloidal sol, the silicon sol, and add-on is 2%～15%.
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Address after: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699 Patentee after: SINOPEC NANJING CHEMICAL RESEARCH INSTITUTE Co.,Ltd. Address before: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699 Patentee before: RESEARCH INSTITUTE OF NANJING CHEMICAL INDUSTRIAL Group |
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