CN109806881A - A kind of iron-molybdic catalyst and preparation method thereof for prepn. of formaldehyde by oxidation of methanol - Google Patents
A kind of iron-molybdic catalyst and preparation method thereof for prepn. of formaldehyde by oxidation of methanol Download PDFInfo
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Abstract
The present invention provides a kind of iron-molybdic catalyst and preparation method thereof of prepn. of formaldehyde by oxidation of methanol, the catalyst is using iron-molybdenum as main active component, mischmetal is auxiliary agent, and the main active component is iron molybdate and molybdenum trioxide, and auxiliary agent is the rare earth oxide based on lanthanum and cerium；Wherein molybdenum-iron molar ratio is 1.8~3.5:1, and the rare earth oxide based on lanthanum and cerium accounts for the 0.1~5.0% of catalyst gross mass.Preparation method is the dispersion that L-arginine, cetyl trimethylammonium bromide, polyvinylpyrrolidone and other activating agents are added in ammonium molybdate and ferric nitrate precipitation process and promotes metal.Have high methanol conversion and formaldehyde yield, stability preferable in catalyst use process of the present invention.
Description
Technical field
The present invention relates to organic chemical industry fields, concretely relate to a kind of iron molybdenum catalysis for prepn. of formaldehyde by oxidation of methanol
Agent and preparation method thereof.
Background technique
With the fast development of auto industry, construction industry and adnornment industry, need of the formaldehyde as traditional large industrial chemicals
It asks and increasingly increases.Modern Formaldehyde Production mainly uses methanol oxidizing process to prepare, and technique is mainly silver-colored method and iron molybdenum method.In recent years,
With the rapid growth of formaldehyde demand, iron molybdenum method technique and catalyst are rapid due to the superiority development in terms of its reactivity worth.
Since nineteen fifty-two iron-molybdic catalyst is for prepn. of formaldehyde by oxidation of methanol industrialized production, a variety of iron have been developed both at home and abroad
Molybdenum catalyst and preparation method.Nineteen sixty-eight, American invention a kind of iron molybdenum two-component catalyst, publication number are 3408309.To change
It is added on the basis of iron molybdenum two-component catalyst in the activity of kind catalyst and the mechanical strength of stability and catalyst, people
Its metal oxide develops a series of iron-molybdic catalysts as auxiliary agent.1974, United States Patent (USP) (3846341) disclosed one
Kind improves catalyst performance wherein joined a small amount of tungsten and cobalt using the iron-molybdic catalyst of gel method preparation.1976,
United States Patent (USP) (3978136) is disclosed again using Iron(III) chloride hexahydrate and ammonium paramolybdate as raw material, using coprecipitation preparation
After slurry obtained by catalyst is cleaned, TiO2 is added and stirs evenly, has prepared ideal catalyst.1977, Italy
Societa ' Italiana Resime S.I.R.P.A company develops a kind of prepn. of formaldehyde by oxidation of methanol catalyst, with molybdate
It is that raw material co-precipitation is made with iron salt solutions.Sediment after drying impregnates a kind of decomposable bismuth salt aqueous solution, then does again
Dry and roasting obtains finished catalyst.The KH series of Perstorp Formox company, Sweden and the exploitation of rope company, Top, Denmark is urged
Agent and FK catalyst series have obtained good industrial application.China is slow using iron molybdenum method production formaldehyde technical progress,
The research and development of catalyst relatively lag behind, but also develop multiple catalysts in recent years.Research Institute of Nanjing Chemical Industry Group has invented a kind of industry
With Fe-Mo catalyst for preparing formaldehyde through methanol oxidation and preparation method thereof (publication number 1546232A).Catalyst removes iron molybdenum main component
Outside, the oxide for being also added into auxiliary agent chromium and vanadium forms four component catalyst systems.A kind of more metallic irons have been invented by Tsinghua University
Molybdenum catalyst (CN103933998A), be added on the basis of two kinds of existing iron, molybdenum elements nickel, bismuth, praseodymium, cobalt, cerium,
The oxides such as vanadium, chromium improve the product yield of target and the stability of catalyst as auxiliary agent.Ministry of Chemical Industry's Beijing chemical industry
A kind of prepn. of formaldehyde by oxidation of methanol catalyst (CN1100667) has been invented by research institute.The catalyst is helped by active component molybdenum with structure
Agent oxide is co-precipitated, and can be two components, three components or four components.The Southwest Research & Design Institute of Chemical Industry, Chinese Academy of Sciences Jilin
Chemical activator research institute, China Petroleum Tianjin Branch Company, Zhengzhou Polytechnical College, Shenyang Institute of Chemical Technology, Science and Technology Ltd., Asus
It does a lot of work in terms of the research and development of iron-molybdic catalyst.
Summary of the invention
The iron-molybdic catalyst and preparation method thereof that the object of the present invention is to provide a kind of for prepn. of formaldehyde by oxidation of methanol.
A kind of iron-molybdic catalyst for prepn. of formaldehyde by oxidation of methanol, the main component of the catalyst are iron molybdate and three oxidations
Molybdenum, auxiliary agent are the rare earth oxide based on lanthanum and cerium；Molybdenum-iron molar ratio is 1.8~3.3:1, the rare-earth oxidation based on lanthanum and cerium
Object accounts for the 0.1~5% of catalyst total amount.
A kind of preparation method for Fe-Mo catalyst for preparing formaldehyde through methanol oxidation, specifically: in ammonium molybdate, ferric nitrate and mix
It closes in rare earth compound precipitation process and activating agent is added；The activating agent is L-arginine, cetyl trimethylammonium bromide
(CTAB), the one or more of polyvinylpyrrolidone (PVP) isoreactivity agent.
The preparation method one, comprises the concrete steps that:
(1), ammonium molybdate and iron nitrate solution are prepared respectively according to molybdenum-iron molar ratio, weigh suitable mixed rare earth compound
Soluble-salt and L-arginine, citric acid, cetyl trimethylammonium bromide (CTAB), polyvinylpyrrolidone (PVP) etc. are living
The one or more of property agent are dissolved in iron nitrate solution or ammonium molybdate solution；
(2), deionized water is added in a stirring kettle, solution pH value is modulated 1.0-3.0 with nitric acid.Under vigorous stirring
The solution such as ammonium molybdate and ferric nitrate are instilled simultaneously, titrating and maintaining the pH value of suspension with ammonium hydroxide in precipitation process is 1.0~3.0,
And the temperature of suspension is controlled at 20~80 DEG C；
(3), after titrating, suspension is spent after aging aging 1 hour under the conditions of maintaining 60~80 DEG C of temperature
Ionized water washs filter 23；
(4), the sediment obtained after washing filtering is dried 12 hours under the conditions of 80~120 DEG C, 180 DEG C of drying 4 are small
When, after drying object grinding, molding, 350~550 DEG C of roastings obtain finished catalyst in 3 hours.
Wherein, rare earth compound can be soluble-salt, be also possible to oxide or carbonate.
Molybdenum-iron molar ratio in step (1) are as follows: 1.8~3.5:1, the quality of rare earth compound soluble-salt is with rare earth oxide
Meter accounts for the 0.1~5.0% of catalyst gross mass；The dosage of activating agent is account for catalyst gross mass 0.1~5.0%.
Preparation method two, the specific steps are as follows:
(1), ammonium molybdate and iron nitrate solution are prepared respectively according to molybdenum-iron molar ratio, weigh suitable activating agent and be dissolved in nitric acid
In ferrous solution or ammonium molybdate solution；
(2), deionized water is added in a stirring kettle, solution pH value is modulated 1.0~3.0 with nitric acid, by mischmetal oxygen
Compound or carbonate powder are added in solution, instill the solution such as ammonium molybdate and ferric nitrate, titration precipitating simultaneously under vigorous stirring
Maintaining the pH value of suspension with ammonium hydroxide in the process is 1.0~3.0, and controls the temperature of suspension at 20~80 DEG C；
(3), after titrating, suspension is spent after aging aging 1 hour under the conditions of maintaining 60~80 DEG C of temperature
Ionized water washs filter 23；
(4), the sediment obtained after washing filtering is dried 12 hours under the conditions of 80~120 DEG C, 180 DEG C of drying 4 are small
When, after drying object grinding, molding, 350~550 DEG C of roastings obtain finished catalyst in 3 hours.
Wherein, rare earth compound can be soluble-salt, be also possible to oxide or carbonate.
Molybdenum-iron molar ratio in step (1) are as follows: 1.8~3.5:1, the matter of mixed rare-earth oxide or carbonate in step (2)
Amount accounts for the 0.1~5.0% of catalyst gross mass in terms of rare earth oxide；The dosage of activating agent is account for catalyst gross mass 0.1
~5.0%.
The present invention has the advantages that due to the addition of activating agent in the addition and preparation process of rare earth oxide auxiliary agent, this
The catalyst activity component high degree of dispersion of invention, active height, thermal stability are good in prepn. of formaldehyde by oxidation of methanol reaction process
With the service life it is long the features such as.
Detailed description of the invention
Fig. 1 1000 hours stability experiment results of catalyst of the present invention.
Specific embodiment
Following embodiment will be further described the present invention, but not thereby limiting the invention.
Comparative example 1
It weighs 38.8g ammonium molybdate and 39.9g ferric nitrate is dissolved in respectively in 200ml water, add in the beaker of a 1000ml
Enter 150ml deionized water, after nitric acid tune pH value to 1.0-3.0, strong stirring solution always, the molybdic acid that then will be prepared
Ammonium and iron nitrate solution instill simultaneously, and maintaining the pH value of suspension with ammonium hydroxide in titration process is 1.0-3.0, and controls suspension
The temperature of liquid terminates rear suspension liquid in 60 DEG C of titration and is stirred continuously, and keeps 60 DEG C of agings 1 hour, then, centrifugation, washing 3
It is secondary；It is dried under the conditions of 80-120 DEG C of sediment 12 hours, 180 DEG C dry 4 hours, after drying object grinding, compression molding, 420 DEG C
Roasting obtains finished catalyst A in 3 hours.
Embodiment 1
It weighs 38.8g ammonium molybdate and 39.9g ferric nitrate is dissolved in respectively in 200ml water, then weigh 2g polyvinylpyrrolidone
(PVP) it is dissolved in ammonium molybdate solution；150ml deionized water is added in the beaker of a 1000ml, extremely with nitric acid tune pH value
After 1.0-3.0, the solution that mischmetal carbonate powder of the 0.5g mainly containing lanthanum and cerium is added to strong stirring always is weighed
In, it then by the ammonium molybdate prepared and iron nitrate solution while instilling, the pH value for maintaining suspension with ammonium hydroxide in titration process is
1.0-3.0, and the temperature for controlling suspension terminates rear suspension liquid in 60 DEG C of titration and is stirred continuously, and keeps 60 DEG C of agings 1 hour,
Then, centrifugation is washed 3 times；It is dried under the conditions of 80-120 DEG C of sediment 12 hours, 180 DEG C dry 4 hours, and drying object is ground
After mill, compression molding, 420 DEG C of half product roastings obtain finished catalyst B for 3 hours, and 520 DEG C of half product obtain for roasting 3 hours
To finished catalyst C.
Embodiment 2
It weighs 56.4g ammonium molybdate and 39.8g ferric nitrate is dissolved in respectively in 200ml water, then weigh 2g cetyl trimethyl
Ammonium bromide (CTAB) is dissolved in ammonium molybdate solution；150ml deionized water is added in the beaker of a 1000ml, with nitric acid tune PH
Value is added to the molten of strong stirring always to mischmetal carbonate powder of the 2.0g mainly containing lanthanum and cerium after 1.0-3.0, is weighed
It in liquid, then by the ammonium molybdate prepared and iron nitrate solution while instilling, maintains the pH value of suspension in titration process with ammonium hydroxide
It is 1.0-3.0, and the temperature for controlling suspension terminates rear suspension liquid in 60 DEG C of titration and is stirred continuously, and keeps 60 DEG C of agings 1 small
When, then, centrifugation is washed 3 times；It is dried under the conditions of 80-120 DEG C of sediment 12 hours, 180 DEG C dry 4 hours, drying
After object grinding, compression molding, 420 DEG C of roastings obtain finished catalyst D in 3 hours.
Embodiment 3
It weighs 32g ammonium molybdate and 39.9g ferric nitrate is dissolved in respectively in 200ml water, then weigh 1g L-arginine and be added to nitre
It is dissolved completely in sour ferrous solution, weighs mixed rare earth nitrates of the 2g mainly containing lanthanum and cerium and be dissolved in ammonium molybdate solution, at one
150ml deionized water is added in the beaker of 1000ml, after nitric acid tune pH value to 1.0-3.0, strong stirring solution always,
Then it by the ammonium molybdate prepared and iron nitrate solution while instilling, the pH value for maintaining suspension with ammonium hydroxide in titration process is
1.0-3.0, and the temperature for controlling suspension terminates rear suspension liquid in 60 DEG C of titration and is stirred continuously, and keeps 60 DEG C of agings 1 hour,
Then, centrifugation is washed 3 times；It is dried under the conditions of 80-120 DEG C of sediment 12 hours, 180 DEG C dry 4 hours, and drying object is ground
After mill, compression molding, 420 DEG C of roastings obtain finished catalyst E in 3 hours.
Embodiment 4
Catalyst performance test is carried out in self-control lab scale reaction unit.Reactor diameter 14mm, catalyst loading 2.5g, instead
Answer pressure for normal pressure, 270~300 DEG C of reaction temperature, air speed 20000h-1, oxygen content is 10% in unstripped gas, and methanol content is
6%.
Product uses Shimadzu GC-2014 on-line chromatographic analysis, GDX-403 packed column, TCD detector, hydrogen as carrier gas.Instead
The data in result are answered to have ignored the carbon monoxide in product and carbon dioxide.Specific evaluation results are shown in Table 1, and wherein reference is
Industrial import catalyst.
Using catalyst B as representative, loading amount 2.5g, reaction pressure is normal pressure, 275~300 DEG C of reaction temperature, air speed
10000h-1, oxygen content is 10% in unstripped gas, methanol content 6%.The stability experiment knot of reaction continuous operation 1000 hours
Fruit sees Fig. 1.
Table 1
Claims (8)
1. a kind of iron-molybdic catalyst for prepn. of formaldehyde by oxidation of methanol, which is characterized in that the catalyst is using iron-molybdenum as chief active
Component, mischmetal are auxiliary agent, and the main active component is iron molybdate and molybdenum trioxide, and auxiliary agent is dilute based on lanthanum and cerium
Native oxide；Wherein molybdenum-iron molar ratio is 1.8~3.5:1, and the rare earth oxide based on lanthanum and cerium accounts for the 0.1 of catalyst gross mass
~5.0%.
2. a kind of preparation method for the iron-molybdic catalyst of prepn. of formaldehyde by oxidation of methanol as described in claim 1, it is characterised in that
This method is that activating agent is added in ammonium molybdate, ferric nitrate and mixed rare earth compound precipitation process；The activating agent is L- essence
One or more of propylhomoserin, citric acid, cetyl trimethylammonium bromide, polyvinylpyrrolidone and other activating agents.
3. the preparation method for the iron-molybdic catalyst of prepn. of formaldehyde by oxidation of methanol according to claim 2, it is characterised in that its
Preparation method one, the specific steps are as follows:
(1), ammonium molybdate and iron nitrate solution are prepared respectively according to molybdenum-iron molar ratio, it is solvable to weigh suitable mixed rare earth compound
Property salt and activating agent are dissolved in iron nitrate solution or ammonium molybdate solution；
(2), deionized water is added in a stirring kettle, solution pH value is modulated 1.0~3.0 with nitric acid；Under vigorous stirring simultaneously
Ammonium molybdate and iron nitrate solution are instilled, titrating and maintaining the pH value of suspension with ammonium hydroxide in precipitation process is 1.0~3.0, and is controlled
The temperature of suspension is at 20~80 DEG C；
(3), after titrating, suspension uses deionization aging 1 hour under the conditions of maintaining 60~80 DEG C of temperature after aging
Water washing filter 23；
(4), the sediment obtained after washing filtering is dried 12 hours under the conditions of 80~120 DEG C, 180 DEG C dry 4 hours, dry
After dry grinding, molding, 350~550 DEG C of roastings obtain finished catalyst in 3 hours.
4. the preparation method for the iron-molybdic catalyst of prepn. of formaldehyde by oxidation of methanol according to claim 2, it is characterised in that its
Preparation method two, the specific steps are as follows:
(1), ammonium molybdate and iron nitrate solution are prepared respectively according to molybdenum-iron molar ratio, weighing suitable activating agent, to be dissolved in ferric nitrate molten
In liquid or ammonium molybdate solution；
(2), deionized water is added in a stirring kettle, solution pH value is modulated 1.0~3.0 with nitric acid, by mixed rare-earth oxide
Or carbonate powder is added in solution, instills the solution such as ammonium molybdate and ferric nitrate simultaneously under vigorous stirring, titrates precipitation process
The middle pH value that suspension is maintained with ammonium hydroxide is 1.0~3.0, and controls the temperature of suspension at 20~80 DEG C；
(3), after titrating, suspension uses deionization aging 1 hour under the conditions of maintaining 60~80 DEG C of temperature after aging
Water washing filter 23；
(4), the sediment obtained after washing filtering is dried 12 hours under the conditions of 80~120 DEG C, 180 DEG C dry 4 hours, dry
After dry grinding, molding, 350~550 DEG C of roastings obtain finished catalyst in 3 hours.
5. the preparation method according to Claims 2 or 3 for the iron-molybdic catalyst of prepn. of formaldehyde by oxidation of methanol, it is characterised in that
Mixed rare earth compound is soluble-salt, specially nitrate, oxide or carbonate.
6. the preparation method according to Claims 2 or 3 for the iron-molybdic catalyst of prepn. of formaldehyde by oxidation of methanol, it is characterised in that
Mixed rare earth compound is nitrate.
7. the preparation method for the iron-molybdic catalyst of prepn. of formaldehyde by oxidation of methanol according to claim 3, it is characterised in that step
Suddenly molybdenum-iron molar ratio in (1) are as follows: the quality of 1.8~3.5:1, rare earth compound soluble-salt account for catalyst in terms of rare earth oxide
The 0.1~5.0% of gross mass；The dosage of activating agent is account for catalyst gross mass 0.1~5.0%.
8. the preparation method for the iron-molybdic catalyst of prepn. of formaldehyde by oxidation of methanol according to claim 4, it is characterised in that step
Suddenly molybdenum-iron molar ratio in (1) are as follows: 1.8~3.5:1, the quality of mixed rare-earth oxide or carbonate is with rare earth oxygen in step (2)
Compound meter accounts for the 0.1~5.0% of catalyst gross mass；The dosage of activating agent is account for catalyst gross mass 0.1~5.0%.
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Cited By (3)
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|---|---|---|---|---|
| CN114345362A (en) * | 2020-10-12 | 2022-04-15 | 中石化南京化工研究院有限公司 | Iron-molybdenum-based catalyst for preparing formaldehyde by methanol oxidation and preparation method thereof |
| CN114618507A (en) * | 2020-12-11 | 2022-06-14 | 中国科学院大连化学物理研究所 | Iron-molybdenum catalyst for preparing formaldehyde through methanol oxidation assisted by ink-jet printing, and preparation and application thereof |
| CN115504929A (en) * | 2022-10-26 | 2022-12-23 | 安徽国星生物化学有限公司 | Synthetic method of 2-methylpyridine |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114345362A (en) * | 2020-10-12 | 2022-04-15 | 中石化南京化工研究院有限公司 | Iron-molybdenum-based catalyst for preparing formaldehyde by methanol oxidation and preparation method thereof |
| CN114618507A (en) * | 2020-12-11 | 2022-06-14 | 中国科学院大连化学物理研究所 | Iron-molybdenum catalyst for preparing formaldehyde through methanol oxidation assisted by ink-jet printing, and preparation and application thereof |
| CN115504929A (en) * | 2022-10-26 | 2022-12-23 | 安徽国星生物化学有限公司 | Synthetic method of 2-methylpyridine |
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