CN103508863B - A kind of method preparing anhydrous formaldehyde - Google Patents

A kind of method preparing anhydrous formaldehyde Download PDF

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CN103508863B
CN103508863B CN201210224986.1A CN201210224986A CN103508863B CN 103508863 B CN103508863 B CN 103508863B CN 201210224986 A CN201210224986 A CN 201210224986A CN 103508863 B CN103508863 B CN 103508863B
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cerium
active metal
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oxide
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CN103508863A (en
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王峰
王业红
徐杰
张晓辰
陈贵夫
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Dalian Institute of Chemical Physics of CAS
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
    • C07C45/512—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being a free hydroxyl group
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
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    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides

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Abstract

The present invention relates to a kind of method preparing anhydrous formaldehyde.The method adopts cerium catalyst based, is made up of main active metal, cerium oxide and promotor.Detailed process is: adopt fixed-bed reactor, methanol feed concentration is 10% ~ 70%(volumeter), Feed space velocities is 15 ~ 80ml/ (gs), reacts under 200 ° of C ~ 900 ° C, and methanol conversion is 65% ~ 95%, formaldehyde yield 50% ~ 90%.The involved in the present invention method preparing anhydrous formaldehyde, catalyst preparing is simple, and stability is high, and reaction conditions is comparatively gentle, need not at high temperature carry out, the transformation efficiency of methyl alcohol and the yield of formaldehyde all higher.

Description

A kind of method preparing anhydrous formaldehyde
Technical field
The present invention relates to a kind of method preparing anhydrous formaldehyde, be specifically related to methyl alcohol anaerobic dehydrogenation and prepare anhydrous formaldehyde.
Background technology
Formaldehyde is a kind of important Organic Chemicals, is mainly used to produce the material such as resol, melamine resin, also can be used to produce the Chemicals such as urotropine, BDO, is also synthetic dyestuff, agricultural chemicals, the meticulous important source material with specialty chemicals etc.
Industrial production formaldehyde many employings methanol oxidation method.By Theoretical Calculation, its product is the mixture (molar ratio 1:1) of formaldehyde and water.Vapour pressure due to formalin is lower and formaldehyde and water form azeotrope, and it is high that isolation andpurification prepares anhydrous formaldehyde energy consumption.But synthetic resins and prepare the production processes such as urotropine, need anhydrous formaldehyde, its demand increases gradually.Therefore, that develops less energy-consumption has application prospect by the route of methyl alcohol direct dehydrogenation formaldehyde.
The formaldehyde that methyl alcohol anaerobic dehydrogenation technique obtains is easy to be separated with byproduct hydrogen gas, and anhydrous generation, avoid the lock out operation of formalin, and by product is hydrogen, capable of circulation for the synthesis of methyl alcohol; Meanwhile, this reaction there will not be methanol oxidation to generate the problem of formic acid etching apparatus, thus is conducive to the stable of formaldehyde solution and purification.
In recent years, prepare the emphasis of formaldehyde mainly in the exploitation of raw catalyst under research methyl alcohol oxygen free condition, comprise a few class such as metal and oxide catalyst, an alkali metal salt and molecular sieve catalyst.CN102274722A discloses V 2o 3and loading type V 2o 3preparation method, methanol conversion is higher than 99%, and formaldehyde selectivity reaches 90%.A kind of method that CN101961650A discloses even co-precipitation prepares Zirconium-base catalyst and catalysis methanol anaerobic dehydrogenation, and formaldehyde yield reaches 60%.Dai Weilin etc. (CN1390639A, CN1537673A, CN1544147A) disclose a series of preparation method being applied to the carried silver catalyst of methyl alcohol direct dehydrogenation, and the yield of formaldehyde is higher than 75%.Patent CN101147872A is that raw material is prepared industrial sodium carbonate catalysis and prepared anhydrous formaldehyde with industrial sodium bicarbonate, and yield is 45%.
The subject matter that above route exists is: catalyst activity and stability lower, temperature of reaction high (generally higher than 600 ° of C), reaction preference difference etc.Therefore, develop efficient, stable catalyzer, under the prerequisite ensureing higher product yield, reduce temperature of reaction to greatest extent and have great importance, this industrialization also preparing anhydrous formaldehyde for the anaerobic dehydrogenation of methyl alcohol lays the foundation.
Summary of the invention
The object of the invention is design and prepare new catalytic material, and for preparing the process of formaldehyde under methyl alcohol oxygen free condition, under realizing mild conditions, high yield prepares the object of formaldehyde.The preparation of this process used catalyst is simple and stability is high, and reaction conditions is comparatively gentle, and transformation efficiency and selectivity are all higher, and by product is less.
The anhydrous formaldehyde of the present invention's design is prepared by following scheme.Its process is be raw material with methyl alcohol, and rare gas element does carrier gas, reacts in fixed-bed reactor, fill in crystal reaction tube cerium catalyst based after be placed in fixed-bed reactor, temperature of reaction is 200 ° of C ~ 900 ° C.Wherein, described cerium is catalyst based, in mass fraction, has following composition: 1 ~ 20 part of main active metal, the cerium oxide of 100 parts and 0 ~ 20 part of promotor; Described main active metal is: one or two or more kinds in nickel, copper, silver, gold, platinum, palladium, ruthenium, rhodium; Described cerium oxide is: cerous oxide, cerium dioxide or the oxide compound CeO between cerous oxide and cerium dioxide xone or more in (X:1.5 ~ 2); Described promotor is: one or two or more kinds in manganese, iron, zinc, zirconium, titanium, calcium, barium, magnesium.The catalyst based preparation process of described cerium is as follows: be immersed in by cerium oxide in the soluble salt solutions containing main active metal or in the soluble salt of main active metal and the soluble salt solutions of promotor, leave standstill, dry, 300 ° of C ~ 700 ° C roastings more than 1 hour, under 300 ° of C ~ 500 ° C hydrogen atmospheres more than reductase 12 hour, obtain finished product; Or by cerium oxide and main active metal or by the precursor mechanically mixing of cerium oxide and main active metal and promotor, 300 ° of C ~ 700 ° C roastings more than 1 hour, under 300 ° of C ~ 500 ° hydrogen atmospheres more than reductase 12 hour, obtain finished product.Preferably main active metal is one or more in nickel, copper, platinum, palladium, ruthenium; Best main active metal is one or more in nickel, platinum, palladium; Preferably cerium oxide is cerium dioxide or the oxide compound CeO between cerous oxide and cerium dioxide xone or more in (X:1.5 ~ 2); Best cerium oxide is cerium dioxide; Preferably promotor is one or more in manganese, iron, zinc, calcium, magnesium; Best promotor is one or more in iron, zinc, magnesium.
In described crystal reaction tube, loading catalyst thickness of bed layer is 5mm ~ 60mm, methanol feed concentration 10% ~ 70%(volumeter), Feed space velocities is 15 ~ 80ml/ (gs).In described preferably crystal reaction tube, loading catalyst thickness of bed layer is 7mm ~ 40mm, and methanol feeding preferred concentration is 20% ~ 60%(volumeter), preferably Feed space velocities is 20 ~ 60ml/ (gs), and preferably temperature of reaction is 250 ° of C ~ 800 ° C.In the crystal reaction tube of described the best, loading catalyst thickness of bed layer is 10mm ~ 30mm, and methanol feeding optimum concn is 35% ~ 45%(volumeter), best Feed space velocities is 25 ~ 50ml/ (gs), and best temperature of reaction is 300 ° of C ~ 450 ° C.Described rare gas element is one or two or more kinds in nitrogen, argon gas, helium.
Methanol dehydrogenation is gas-solid-phase catalytic reaction, in reaction process, first methyl alcohol be adsorbed in the catalyst based surface of cerium, adsorptive and then the generation product that reacts, active sites is the band defective Ce-O-Ce oxo bridge and main active metal that in high-temperature calcination process, hydroxyls dehydrate produces.With the Ce of Lacking oxygen n+can be used as Lewis acid (L acid) centers catalyse reaction.Because L acid site has the ability accepting electron pair, thus reduce the interaction of oxygen and hydrogen in methanol hydroxylethyl, effectively activate hydroxyl.The catalyst based middle main active metal (nickel, copper, silver, gold, platinum, palladium, ruthenium, rhodium) of cerium, can activate the c h bond in methanol molecules effectively, and the two synergy effectively catalysis methanol removes hydrogen.Adding of promotor interacts with main active metal, the electronic state of modulation main active centre metal, change the density of d orbital electron, more be conducive to the electronics receiving c h bond, to sum up, the catalyst based selectivity preparing reactive behavior and the product of doing well in the reaction of anhydrous formaldehyde at methanol dehydrogenation of cerium.
The present invention, compared with the anhydrous formaldehyde preparation technology of announcement, has following several advantage: 1, reaction conditions is comparatively gentle, and reaction need not at high temperature be carried out, and less than 500 degree can be reacted; 2, the transformation efficiency of methyl alcohol and the selectivity of formaldehyde all higher; 3, this reaction adopts oxide compound or carried oxide catalyzed reaction, and material is easy to get, and preparation is simple, and stability is high.
Embodiment
In order to be further elaborated to the present invention, provide several concrete case study on implementation below, but the invention is not restricted to these embodiments.
Embodiment 1
Take 100g ceric ammonium nitrate in air atmosphere, 500 ° of C roasting 5h, obtain cerium oxide.Be immersed in the mixing solutions of Palladous chloride and zinc chloride, dry, 350 ° of C roastings 1 hour, reduce 3 hours under 400 ° of C hydrogen atmospheres, obtained main active metal (Pd): cerium oxide: promotor (Zn)=20:100:5(mass ratio) cerium catalyst based, sieving after being pressed into sheet, it is particles filled in crystal reaction tube to get 20-40 object, filling thickness 5mm bed, at ambient pressure, nitrogen gas does carrier gas, 10%(volumeter) methyl alcohol by micro pump sample introduction, react under 250 ° of C, Feed space velocities is 35ml/ (gs), gas-chromatography on-line checkingi methanol conversion is 85%, formaldehyde yield 55%.
Embodiment 2
Take 100g cerous nitrate in air atmosphere, 500 ° of C roasting 5h, obtain cerium oxide.Be immersed in the mixing solutions of hydrochloro-auric acid and iron(ic) chloride, dry, 450 ° of C roastings 3 hours, reductase 12 hour under 450 ° of C hydrogen atmospheres, obtained main active metal (Au): cerium oxide: promotor (Fe)=15:100:15(mass ratio) cerium catalyst based, sieving after being pressed into sheet, it is particles filled in crystal reaction tube to get 20-40 object, filling thickness 5mm bed, at ambient pressure, argon gas does carrier gas, 20%(volumeter) methyl alcohol by micro pump sample introduction, react under 450 ° of C, Feed space velocities is 35ml/ (gs), gas-chromatography on-line checkingi methanol conversion is 65%, formaldehyde yield 56%.
Embodiment 3
Taking 50g cerous nitrate is dissolved in 4L water, adopts the ammoniacal liquor of 25wt% as precipitation agent, regulation system pH=9.5, and by gained precipitation and centrifugal separation, dry, 500 ° of C roasting 3h, obtain cerium oxide.Be immersed in the aqueous solution of nickelous nitrate, dry, 300 ° of C roastings 4 hours, reduce 4 hours under 450 ° of C hydrogen atmospheres, obtained main active metal (Ni): cerium oxide: promotor=15:100:0(mass ratio) cerium catalyst based, sieving after being pressed into sheet, it is particles filled in crystal reaction tube to get 20-40 object, filling thickness 25mm bed, at ambient pressure, nitrogen gas does carrier gas, 10%(volumeter) methyl alcohol by micro pump sample introduction, react under 600 ° of C, Feed space velocities is 60ml/ (gs), gas-chromatography on-line checkingi methanol conversion is 74%, formaldehyde yield 50%.
Embodiment 4
Taking 50g cerous nitrate is dissolved in 4L water, adopts the sodium hydroxide solution of 10wt% as precipitation agent, regulation system pH=11.5, and by gained precipitation and centrifugal separation, dry, 500 ° of C roasting 3h, obtain cerium oxide.Be immersed in the mixed aqueous solution of Platinic chloride and zinc nitrate, leave standstill, dry, 400 ° of C roastings 2 hours, reductase 12 hour under 400 ° of C hydrogen atmospheres, obtained main active metal (Pt): cerium oxide: promotor (Zn)=10:100:5(mass ratio) cerium catalyst based, sieving after being pressed into sheet, it is particles filled in crystal reaction tube to get 20-40 object, filling thickness 36mm bed, at ambient pressure, nitrogen gas does carrier gas, 60%(volumeter) methyl alcohol by micro pump sample introduction, react under 550 ° of C, Feed space velocities is 25ml/ (gs), gas-chromatography on-line checkingi methanol conversion is 90%, formaldehyde yield 85%.
Embodiment 5
Taking 50g ceric ammonium nitrate is dissolved in 4L water, adopts the aqueous sodium carbonate of 25wt% as precipitation agent, regulation system pH=10, and by gained precipitation and centrifugal separation, dry, 500 ° of C roasting 3h, obtain cerium oxide.Be immersed in the mixed aqueous solution of cupric nitrate and Manganous chloride tetrahydrate, leave standstill, dry, 300 ° of C roastings 1 hour, reduce 5 hours under 400 ° of C hydrogen atmospheres, obtained main active metal (Cu): cerium oxide: promotor (Mn)=5:100:20(mass ratio) cerium catalyst based, sieving after being pressed into sheet, it is particles filled in crystal reaction tube to get 20-40 object, filling thickness 43mm bed, at ambient pressure, argon gas does carrier gas, 35%(volumeter) methyl alcohol by micro pump sample introduction, react under 350 ° of C, Feed space velocities is 45ml/ (gs), gas-chromatography on-line checkingi methanol conversion is 95%, formaldehyde yield 70%.
Embodiment 6
Take 100g ceric ammonium nitrate in air atmosphere, 500 ° of C roasting 5h, obtain cerium oxide.Be immersed in palladium chloride aqueous solution, leave standstill, dry, 400 ° of C roastings 1 hour, reductase 12 hour under 400 ° of C hydrogen atmospheres, obtained main active metal (Pd): cerium oxide: promotor=10:100:0(mass ratio) cerium catalyst based, sieving after being pressed into sheet, it is particles filled in crystal reaction tube to get 20-40 object, filling thickness 15mm bed, at ambient pressure, argon gas does carrier gas, 50%(volumeter) methyl alcohol by micro pump sample introduction, react under 700 ° of C, Feed space velocities is 50ml/ (gs), gas-chromatography on-line checkingi methanol conversion is 78%, formaldehyde yield 66%.
Embodiment 7
Take 50g cerous nitrate respectively and 36g cetyl trimethylammonium bromide is dissolved in 5L water, stir, until dissolve completely.Adopt the ammoniacal liquor of 25wt% as precipitation agent, dropwise add above-mentioned system, until pH=10.0.This mixture is put into synthesis reactor, crystallization 3d under 100 ° of C, after crystallization, centrifugal, washing, dry, roasting 3h under 500 ° of C, obtains cerium oxide.Be immersed in the mixed aqueous solution of nickelous nitrate and zinc chloride, leave standstill, dry, 300 ° of C roastings 5 hours, reduce 3 hours under 450 ° of C hydrogen atmospheres, obtained main active metal (Ni): cerium oxide: promotor (Zn)=15:100:10(mass ratio) cerium catalyst based, sieving after being pressed into sheet, it is particles filled in crystal reaction tube to get 20-40 object, filling thickness 23mm bed, at ambient pressure, helium atmosphere does carrier gas, 45%(volumeter) methyl alcohol by micro pump sample introduction, react under 400 ° of C, Feed space velocities is 65ml/ (gs), gas-chromatography on-line checkingi methanol conversion is 95%, formaldehyde yield 90%.
Embodiment 8
Take 100g cerous nitrate under the mixed atmosphere of air and nitrogen, 500 ° of C roasting 5h, obtain cerium oxide.Be immersed in the mixing solutions of hydrochloro-auric acid and iron(ic) chloride, leave standstill, dry, 300 ° of C roastings 1 hour, reductase 12 hour under 450 ° of C hydrogen atmospheres, obtained main active metal (Au): cerium oxide: promotor (Fe)=15:100:15(mass ratio) cerium catalyst based, sieving after being pressed into sheet, it is particles filled in crystal reaction tube to get 20-40 object, filling thickness 30mm bed, at ambient pressure, helium atmosphere does carrier gas, 20%(volumeter) methyl alcohol by micro pump sample introduction, react under 350 ° of C, Feed space velocities is 15ml/ (gs), gas-chromatography on-line checkingi methanol conversion is 87%, formaldehyde yield 56%.
Embodiment 9
Taking 50g cerous nitrate is dissolved in 4L water, adopts the potassium hydroxide aqueous solution of 15wt% as precipitation agent, regulation system pH=11, and by gained precipitation and centrifugal separation, dry, 500 ° of C roasting 3h, obtain cerium oxide.Be immersed in the mixed aqueous solution of rhodium chloride and magnesium chloride, leave standstill, dry, 300 ° of C roastings 1 hour, reductase 12 hour under 500 ° of C hydrogen atmospheres, obtained main active metal (Rh): cerium oxide: promotor (Mg)=8:100:5(mass ratio) cerium catalyst based, sieving after being pressed into sheet, it is particles filled in crystal reaction tube to get 20-40 object, filling thickness 20mm bed, at ambient pressure, nitrogen gas does carrier gas, 35%(volumeter) methyl alcohol by micro pump sample introduction, react under 400 ° of C, Feed space velocities is 35ml/ (gs), gas-chromatography on-line checkingi methanol conversion is 66%, formaldehyde yield 53%.
Embodiment 10
Taking 50g ceric ammonium nitrate is dissolved in 5L water, adopts the wet chemical of 25wt% as precipitation agent, regulation system pH=10, and by gained precipitation and centrifugal separation, dry, 500 ° of C roasting 3h, obtain cerium oxide.Be immersed in the mixed aqueous solution of ruthenium chloride and bariumchloride, leave standstill, dry, 450 ° of C roastings 1 hour, reduce 3 hours under 450 ° of C hydrogen atmospheres, obtained main active metal (Ru): cerium oxide: promotor (Ba)=10:100:5(mass ratio) cerium catalyst based, sieving after being pressed into sheet, it is particles filled in crystal reaction tube to get 20-40 object, filling thickness 5mm bed, at ambient pressure, argon gas does carrier gas, 60%(volumeter) methyl alcohol by micro pump sample introduction, react under 600 ° of C, Feed space velocities is 80ml/ (gs), gas-chromatography on-line checkingi methanol conversion is 78%, formaldehyde yield 67%.
Embodiment 11
Get 50g cerous nitrate, 20g nickelous nitrate mechanically mixing, in air atmosphere, 500 ° of C roasting 5h, reduce 3 hours under 400 ° of C hydrogen atmospheres, obtained main active metal (Ni): cerium oxide: promotor (Zn)=21:100:0(mass ratio) cerium catalyst based, sieving after being pressed into sheet, it is particles filled in crystal reaction tube to get 20-40 object, filling thickness 10mm bed, at ambient pressure, nitrogen gas does carrier gas, 25%(volumeter) methyl alcohol by micro pump sample introduction, react under 350 ° of C, Feed space velocities is 45ml/ (gs), gas-chromatography on-line checkingi methanol conversion is 75%, formaldehyde yield 65%.
Embodiment 12
Get 50g cerous nitrate, 20g nickelous nitrate, 5g magnesium hydroxide mechanically mixing, in air atmosphere, 500 ° of C roasting 5h, reductase 12 hour under 500 ° of C hydrogen atmospheres, obtained main active metal (Ni): cerium oxide: promotor (Mg)=21:100:8(mass ratio) cerium catalyst based, sieving after being pressed into sheet, it is particles filled in crystal reaction tube to get 20-40 object, filling thickness 10mm bed, at ambient pressure, nitrogen gas does carrier gas, 25%(volumeter) methyl alcohol by micro pump sample introduction, react under 350 ° of C, Feed space velocities is 45ml/ (gs), gas-chromatography on-line checkingi methanol conversion is 75%, formaldehyde yield 65%.
Comparative example 1
Take Ag-SiO 2-MgO fills 5mm bed, and at ambient pressure, nitrogen gas does carrier gas, 10%(volumeter) methyl alcohol by micro pump sample introduction, react under 250 ° of C, Feed space velocities is 35ml/ (gs), gas-chromatography on-line checkingi methanol conversion is 65%, formaldehyde yield 60%.
Comparative example 2
Take Na 2cO 3fill 5mm bed, at ambient pressure, argon gas does carrier gas, 20%(volumeter) methyl alcohol by micro pump sample introduction, react under 450 ° of C, Feed space velocities is 35ml/ (gs), and gas-chromatography on-line checkingi methanol conversion is 55%, formaldehyde yield 436%.
Comparative example 3
Take Na-ZSM-5 and fill 25mm bed, at ambient pressure, nitrogen gas does carrier gas, 10%(volumeter) methyl alcohol by micro pump sample introduction, react under 600 ° of C, Feed space velocities is 60ml/ (gs), gas-chromatography on-line checkingi methanol conversion is 53%, formaldehyde yield 45%.
Comparative example 4
Take Cu-ZnO and fill 36mm bed, at ambient pressure, nitrogen gas does carrier gas, 60%(volumeter) methyl alcohol by micro pump sample introduction, react under 550 ° of C, Feed space velocities is 25ml/ (gs), gas-chromatography on-line checkingi methanol conversion is 15%, formaldehyde yield 9.5%.

Claims (9)

1. prepare a method for anhydrous formaldehyde, it is characterized in that:
Be raw material with methyl alcohol, rare gas element does carrier gas, reacts in fixed-bed reactor, fill in crystal reaction tube cerium catalyst based after be placed in fixed-bed reactor, temperature of reaction is 200 DEG C ~ 900 DEG C;
Described cerium is catalyst based, in mass fraction, has following composition: 1 ~ 20 part of main active metal, the cerium oxide of 100 parts and 0 ~ 20 part of promotor.
2., according to described in claim 1, it is characterized in that:
Described main active metal is: one or two or more kinds in nickel, copper, silver, gold, platinum, palladium, ruthenium, rhodium;
Described cerium oxide is: cerous oxide, cerium dioxide or the oxide compound CeO between cerous oxide and cerium dioxide xone or more in (X:1.5 ~ 2);
Described promotor is: one or two or more kinds in manganese, iron, zinc, zirconium, titanium, calcium, barium, magnesium.
3., according to described in claim 2, it is characterized in that:
The catalyst based preparation process of described cerium is as follows: be immersed in by cerium oxide in the soluble salt solutions containing main active metal or in the soluble salt of main active metal and the soluble salt solutions of promotor, leave standstill, dry, 300 DEG C ~ 700 DEG C roastings more than 1 hour, under 300 DEG C ~ 500 DEG C hydrogen atmospheres more than reductase 12 hour, obtain finished product;
Or by cerium oxide and main active metal or by the precursor mechanically mixing of cerium oxide and main active metal and promotor, 300 DEG C ~ 700 DEG C roastings more than 1 hour, under 300 DEG C ~ 500 ° hydrogen atmospheres more than reductase 12 hour, obtain finished product.
4., according to described in Claims 2 or 3, it is characterized in that:
Preferably main active metal is one or more in nickel, copper, platinum, palladium, ruthenium; Preferably cerium oxide is cerium dioxide or the oxide compound CeO between cerous oxide and cerium dioxide xone or more in (X:1.5 ~ 2);
Preferably promotor is one or more in manganese, iron, zinc, calcium, magnesium.
5. according to described in claim 4, it is characterized in that: best main active metal is one or more in nickel, platinum, palladium; Best cerium oxide is cerium dioxide; Best promotor is one or more in iron, zinc, magnesium.
6., according to described in claim 1, it is characterized in that:
In described crystal reaction tube, loading catalyst thickness of bed layer is 5mm ~ 60mm, methanol feed concentration 10% ~ 70% (volumeter), and Feed space velocities is 15 ~ 80ml/ (gs).
7., according to described in claim 1 or 6, it is characterized in that:
In described preferably crystal reaction tube, loading catalyst thickness of bed layer is 7mm ~ 40mm, methanol feeding preferred concentration is 20% ~ 60% (volumeter), preferably Feed space velocities is 20 ~ 60ml/ (gs), and preferably temperature of reaction is 250 DEG C ~ 800 DEG C.
8., according to described in claim 1 or 6, it is characterized in that:
In the crystal reaction tube of described the best, loading catalyst thickness of bed layer is 10mm ~ 30mm, methanol feeding optimum concn is 35% ~ 45% (volumeter), best Feed space velocities is 25 ~ 50ml/ (gs), and best temperature of reaction is 300 DEG C ~ 450 DEG C.
9., according to described in claim 1, it is characterized in that:
Described rare gas element is one or two or more kinds in nitrogen, argon gas, helium.
CN201210224986.1A 2012-06-29 2012-06-29 A kind of method preparing anhydrous formaldehyde Expired - Fee Related CN103508863B (en)

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Publication number Priority date Publication date Assignee Title
CN105085211B (en) * 2014-05-16 2017-09-05 陈建安 A kind of manufacture method of formaldehyde, glycolaldehyde and ethylene glycol
CN105170145A (en) * 2014-06-20 2015-12-23 中国科学院大连化学物理研究所 Catalyst for anoxic dehydrogenation of methanol, and application thereof
CN105601487B (en) * 2016-03-10 2018-06-05 衡水市银河化工有限责任公司 The preparation method of anhydrous formaldehyde
CN108002994B (en) * 2016-10-31 2021-03-30 中国科学院大连化学物理研究所 Method for preparing high-carbon ketone
CN107162884A (en) * 2017-07-07 2017-09-15 册亨荣畅化工科技发展有限公司 The technique that a kind of methanol dehydrogenation produces anhydrous formaldehyde
CN109422638B (en) * 2017-08-31 2021-11-23 中国科学院大连化学物理研究所 Method for preparing ketone compound by ABE fermentation liquor conversion
CN111217687A (en) * 2018-11-27 2020-06-02 中国科学院大连化学物理研究所 Method for preparing anhydrous formaldehyde
CN110893350A (en) * 2019-12-10 2020-03-20 北京世天科技股份有限公司 Preparation and application of noble metal catalyst-loaded molecular sieve

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1248491A (en) * 1999-08-09 2000-03-29 中国石油化工集团公司 Novel load silver catalyst and preparation process thereof
US20040220429A1 (en) * 2002-02-20 2004-11-04 Regents Of The University Of California Process and catalyst for production of formaldehyde from dimethyl ether
CN1792443A (en) * 2004-12-22 2006-06-28 舒德化学催化剂意大利有限责任公司 Catalysts for oxidation of methanol to formaldehyde
CN102430407A (en) * 2011-03-10 2012-05-02 中国科学院福建物质结构研究所 Loaded copper catalyst for preparing anhydrous methanal by direct dehydrogenation of methanol, and preparation method for loaded copper catalyst

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1248491A (en) * 1999-08-09 2000-03-29 中国石油化工集团公司 Novel load silver catalyst and preparation process thereof
US20040220429A1 (en) * 2002-02-20 2004-11-04 Regents Of The University Of California Process and catalyst for production of formaldehyde from dimethyl ether
CN1792443A (en) * 2004-12-22 2006-06-28 舒德化学催化剂意大利有限责任公司 Catalysts for oxidation of methanol to formaldehyde
CN102430407A (en) * 2011-03-10 2012-05-02 中国科学院福建物质结构研究所 Loaded copper catalyst for preparing anhydrous methanal by direct dehydrogenation of methanol, and preparation method for loaded copper catalyst

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Activity and Characterization by XPS, HR-TEM, Raman Spectroscopy, and BET Surface Area of CuO/CeO2-TiO2 Catalysts;Maria Suzana P. Francisco等;《J. Phys. Chem. B》;20100910;第105卷(第43期);摘要以及Figure8 *

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