CN102240554B - Pollution-free preparation process for catalyst used in preparation of formaldehyde through methanol oxidation by iron-molybdenum method - Google Patents
Pollution-free preparation process for catalyst used in preparation of formaldehyde through methanol oxidation by iron-molybdenum method Download PDFInfo
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Abstract
Disclosed is a pollution-free preparation process for a catalyst used in preparation of formaldehyde through methanol oxidation by the iron-molybdenum method. The process comprises the following steps: dissolving polyhydric alcohol in water to form a base solution; beating the obtained base solution with molybdic acid to obtain a slurry; preheating the slurry to a temperature of 20 to 100 DEG C; allowing air to enter into a storage tank containing carbonyl iron to obtain air saturated by carbonyl iron; allowing the saturated air to enter into the preheated slurry; ageing the reacted slurry at a temperature of 20 to 100 DEG C for 1 to 24 h after carbonyl iron is volatilized completely, and filtering the slurry to obtain a filter cake; carrying out drying at a temperature of 80 to 200 DEG C, crushing, molding and roasting at a temperature of 350 to 500 DEG C on the filter cake to obtain the catalyst; repeatedly cycling the air from the storage tank containing carbonyl iron until the content of carbonyl iron in the air is less than 1.0 g/m<3>, and discharging the air after absorption by the base solution reaches the standard; merging the filtrate and absorption liquid generated in the above steps and returning the merged liquid for cyclic utilization after having used the liquid to readjust the concentration and volume of polyhydric alcohol, thereby enabling no discharge of three wastes (waste gas, waste water and industrial residue) in the whole process. The catalyst prepared by the process has high activity and good intensity and meets requirements for preparing formaldehyde through methanol oxidation by the iron-molybdenum method.
Description
Technical field
The invention belongs to organic chemical industry's catalyst field, more particularly a kind of pollution-free preparation method of catalyst of iron molybdenum method prepn. of formaldehyde by oxidation of methanol.
Background technology
In the modern industry, the production of formaldehyde is adopts methyl alcohol to be raw material, to make by air oxidation, and main flow technique can be divided into argent as " silver-colored method " technique of catalyst with iron and molybdenum oxides " iron molybdenum method " technique as catalyst by the catalyst difference of using.Because " iron molybdenum method " prepn. of formaldehyde by oxidation of methanol technique has: 1) technical process is brief; 2) catalyst long service life; 3) product yield is high, is the highest technology of formaldehyde yield; 4) high, the Functionality, quality and appealing design of product design can satisfy the demand of polyformaldehyde; 5) energy consumes low; 6) thermal efficiency is high; 7) safety, environmental protection without outstanding advantages such as " three wastes " dischargings, meet the large policy environment of " energy-saving and emission-reduction ", have obtained great development in the world in recent years scope, become the main flow direction of technical development.
The patent of the iron-molybdic catalyst of the disclosed preparation prepn. of formaldehyde by oxidation of methanol of recent domestic is a lot, but in general, basic preparation technology can be divided into two classes: (1) gel method, such as FR1604707, GB1282949, US3846341 etc.; (2) coprecipitation is such as US3978136, US4420421, US4829042, CN110066 and CN100413584 etc.Although above method can make enough iron-molybdic catalysts of good prepn. of formaldehyde by oxidation of methanol of active enough height, intensity, all has a common shortcoming: a large amount of waste water or dusty gas discharging.
Summary of the invention
The object of the present invention is to provide a kind of pollution-free preparation method of catalyst of iron molybdenum method prepn. of formaldehyde by oxidation of methanol.Make iron-molybdic catalyst active enough high, intensity is enough good, can satisfy the requirement that has iron molybdenum method prepn. of formaldehyde by oxidation of methanol technique now.
Realize the technical scheme of the object of the invention:
A kind of preparation method of catalyst of iron molybdenum method prepn. of formaldehyde by oxidation of methanol is characterized in that: without " three wastes " discharging, be pollution-free method in the preparation process; The chemical composition of said catalyst take catalyst quality as benchmark is MoO
380.0～85.0%, surplus is Fe
2O
3The preparation process of catalyst is as follows successively:
1), polyalcohol is soluble in water as end liquid, polyalcohol is 1: 300～1: 20 with the ratio of the amount of substance of water in the end liquid;
2), with step 1) end liquid of gained and molybdic acid making beating make slurries, molybdic acid gross mass and end liquid mass ratio are 1: 30～1: 40 in the slurries;
3), slurries are preheated to 20～100 ℃, preferred 45～95 ℃;
4), pass into air to containing in the carbonyl iron basin, obtain by the saturated air of carbonyl iron;
5), passed into step 3 with above-mentioned by the saturated air of carbonyl iron) in the slurries of preheating;
6), after carbonyl iron is evaporated completely, reacted slurries in 20～100 ℃ of lower aging 1～24h, are then filtered, get filter cake;
7), filter cake through 80～200 ℃ of dryings, shatter, moulding, namely get formaldehyde catalyst in 350～500 ℃, preferred 380～450 ℃ of roastings;
8), go out step 5) air through the blower fan iterative cycles, to carbonyl iron content less than 1.0g/m3 after, with above-mentioned steps 1) end liquid of gained absorbs can be to airborne release after up to standard;
9), step 6) in filtrate and step 8) in absorption liquid merge, return step 2 behind readjustment polyalcohol concentration and the volume) recycling, whole process is discharged without " three wastes ".
Among the preparation method of the present invention, described polyalcohol is ethylene glycol, propane diols, glycerine or butanediol.
Among the preparation method of the present invention, described carbonyl iron is iron pentacarbonyl, di-iron enneacarbonyl or tri-iron dodecacarbonyl.
Among the preparation method of the present invention, step 9) recycling behind the filtrate readjustment polyalcohol concentration described in and the volume, to add step 1) after added polynary alcohol and water reaches the polyalcohol concentration and volume of liquid of the initial end, return to and add molybdic acid making beating slurrying liquid, thereby realize the filtrate cycle utilization, whole process is discharged without " three wastes ".
Characteristics of the present invention are:
1, the preparation process of whole catalyst is pollution-free method without " three wastes " discharging;
2, the catalyst that makes is enough iron-molybdic catalysts of good prepn. of formaldehyde by oxidation of methanol of active enough height, intensity, can satisfy the requirement of existing " iron molybdenum method " prepn. of formaldehyde by oxidation of methanol technique;
The catalyst activity evaluation method:
The catalyst activity property testing adopts the stainless steel fixed-bed tube reactor that is immersed in the molten salt bath, caliber Φ 20 * 2.0mm, the long 90cm of reactor.By electrical immersion heater heating and melting salt bath, temperature is controlled by adjuster.
Appreciation condition is: system pressure is normal pressure, 230 ℃ of reaction temperatures, air air speed 14000h
-1, import methyl alcohol volume content 6.67%, catalyst amount 20g.With gc analysis reactor outlet liquid and gas component content.
The specific embodiment
Following embodiment is catalyst preparation example of the present invention, and described embodiment only is used for explanation the present invention rather than is used for restriction the present invention.
Embodiment 1
The preparation of the catalyst of iron molybdenum method prepn. of formaldehyde by oxidation of methanol, the chemical composition of said catalyst take catalyst quality as benchmark is MoO
380.0～85.0%, surplus is Fe
2O
3The preparation process of catalyst is as follows successively:
1), polyalcohol is soluble in water as end liquid, polyalcohol is 1: 300～1: 20 with the ratio of the amount of substance of water in the end liquid;
2), with step 1) end liquid of gained and molybdic acid making beating make slurries, molybdic acid gross mass and end liquid mass ratio are 1: 30～1: 40 in the slurries;
3), slurries are preheated to 20～100 ℃, preferred 45～95 ℃;
4), pass into air to containing in the carbonyl iron basin, obtain by the saturated air of carbonyl iron;
5), passed into step 3 with above-mentioned by the saturated air of carbonyl iron) in the slurries of preheating;
6), after carbonyl iron is evaporated completely, reacted slurries in 20～100 ℃ of lower aging 1～24h, are then filtered, get filter cake;
7), filter cake through 80～200 ℃ of dryings, shatter, moulding, namely get formaldehyde catalyst in 350～500 ℃, preferred 380～450 ℃ of roastings;
8), go out step 5) air through the blower fan iterative cycles, to carbonyl iron content less than 1.0g/m3 after, with above-mentioned steps 1) end liquid of gained absorbs can be to airborne release after up to standard;
9), step 6) in filtrate and step 8) in absorption liquid merge, return step 2 behind readjustment polyalcohol concentration and the volume) recycling, whole process is discharged without " three wastes ".
Wherein, described polyalcohol is ethylene glycol, propane diols, glycerine or butanediol; Described carbonyl iron is iron pentacarbonyl, di-iron enneacarbonyl or tri-iron dodecacarbonyl; Step 9) recycling behind the filtrate readjustment polyalcohol concentration described in and the volume, to add step 1) after added polynary alcohol and water reaches the polyalcohol concentration and volume of liquid of the initial end, return to and add molybdic acid making beating slurrying liquid, thereby realize the filtrate cycle utilization, whole process is discharged without " three wastes ".
Embodiment 2
The preparation of the catalyst of iron molybdenum method prepn. of formaldehyde by oxidation of methanol
1, getting 5mol ethylene glycol is dissolved in the 5400g deionized water and namely gets end liquid;
2, adding the molybdic acid that contains molybdenum trioxide 1mol in the liquid of the above-mentioned end fully pulls an oar;
3, slurries are preheated to 90 ℃;
4, the speed with 0.5L/min passes into air in the iron pentacarbonyl basin that contains the 0.2mol di-iron trioxide, obtains by the saturated air of carbonyl iron;
5, passed into step 3 with above-mentioned by the saturated air of carbonyl iron) in the slurries of preheating;
6, after iron pentacarbonyl is evaporated completely, reacted slurries in 90 ℃ of lower aging 12h, are then filtered, get filter cake;
7, filter cake through 80 ℃ of dryings, shatter, compression molding, 450 ℃ of roastings namely get formaldehyde catalyst;
8, go out step 5) air through the blower fan iterative cycles, to carbonyl iron content less than 1.0g/m
3After, with above-mentioned steps 1) end liquid of gained absorbs backward airborne release up to standard;
9, filtrate and step 8 step 6)) in absorption liquid merge, return step 2 behind readjustment polyalcohol concentration and the volume) recycling, whole process is discharged without " three wastes ".
This routine prepared catalyst forms and character the results are shown in Table 1.
Embodiment 3
The preparation of the catalyst of iron molybdenum method prepn. of formaldehyde by oxidation of methanol
1, getting the 3mol propane diols is dissolved in the 5400g deionized water and namely gets end liquid;
2, adding the molybdic acid that contains molybdenum trioxide 0.5mol in the liquid of the above-mentioned end fully pulls an oar;
3, slurries are preheated to 20 ℃;
4, the speed with 0.5L/min passes into air in the iron pentacarbonyl basin that contains the 0.1mol di-iron trioxide, obtains by the saturated air of carbonyl iron;
5, passed into step 3 with above-mentioned by the saturated air of carbonyl iron) in the slurries of preheating;
6, after iron pentacarbonyl is evaporated completely, reacted slurries in 20 ℃ of lower aging 24h, are then filtered, get filter cake;
7, filter cake through 90 ℃ of dryings, shatter, compression molding, 350 ℃ of roastings namely get formaldehyde catalyst;
8, go out step 5) air through the blower fan iterative cycles, to carbonyl iron content less than 1.0g/m
3After, with above-mentioned steps 1) end liquid of gained absorbs backward airborne release up to standard;
9, filtrate and step 8 step 6)) in absorption liquid through merging, returning step 2 behind readjustment polyalcohol concentration and the volume) recycling, whole process is discharged without " three wastes ".
This routine prepared catalyst forms and character the results are shown in Table 1.
Embodiment 4
The preparation of the catalyst of iron molybdenum method prepn. of formaldehyde by oxidation of methanol
1, getting the 15mol glycerine is dissolved in the 5400g deionized water and namely gets end liquid;
2, adding the molybdic acid that contains molybdenum trioxide 2mol in the liquid of the above-mentioned end fully pulls an oar;
3, slurries are preheated to 100 ℃;
4, the speed with 2.0L/min passes into air in the di-iron enneacarbonyl basin that contains the 0.4mol di-iron trioxide, obtains by the saturated air of carbonyl iron;
5, passed into step 3 with above-mentioned by the saturated air of carbonyl iron) in the slurries of preheating;
6, after carbonyl iron is evaporated completely, reacted slurries in 100 ℃ of lower aging 1h, are then filtered, get filter cake;
7, filter cake through 120 ℃ of dryings, shatter, compression molding, 380 ℃ of roastings namely get formaldehyde catalyst;
8, go out step 5) air through the blower fan iterative cycles, to carbonyl iron content less than 1.0g/m3 after, with above-mentioned steps 1) end liquid of gained absorbs backward airborne release up to standard;
9, filtrate and step 8 step 6)) in absorption liquid through merging, returning step 2 behind readjustment polyalcohol concentration and the volume) recycling, whole process is discharged without " three wastes ".
This routine prepared catalyst forms and character the results are shown in Table 1.
Embodiment 5
The preparation of the catalyst of iron molybdenum method prepn. of formaldehyde by oxidation of methanol
1, gets the 5mol butanediol and namely get end liquid in the 5400g deionized water;
2, adding the molybdic acid that contains molybdenum trioxide 1mol in the liquid of the above-mentioned end fully pulls an oar;
3, slurries are preheated to 95 ℃;
4, the speed with 0.5L/min passes into air in the iron pentacarbonyl basin that contains the 0.2mol di-iron trioxide, obtains by the saturated air of carbonyl iron;
5, passed into step 3 with above-mentioned by the saturated air of carbonyl iron) in the slurries of preheating;
6, after iron pentacarbonyl is evaporated completely, reacted slurries in 95 ℃ of lower aging 8h, are then filtered, get filter cake;
7, filter cake through 80 ℃ of dryings, shatter, compression molding, 350 ℃ of roastings namely get formaldehyde catalyst;
8, go out step 5) air through the blower fan iterative cycles, to carbonyl iron content less than 1.0g/m3 after, with above-mentioned steps 1) end liquid of gained absorbs backward airborne release up to standard;
9, filtrate and step 8 step 6)) in absorption liquid through merging, returning step 2 behind readjustment polyalcohol concentration and the volume) recycling, whole process is discharged without " three wastes ".
This routine prepared catalyst forms and character the results are shown in Table 1.
Embodiment 6
The preparation of the catalyst of iron molybdenum method prepn. of formaldehyde by oxidation of methanol
1, getting 1mol ethylene glycol is dissolved in the 5400g deionized water and namely gets end liquid;
2, adding the molybdic acid that contains molybdenum trioxide 1mol in the liquid of the above-mentioned end fully pulls an oar;
3, slurries are preheated to 100 ℃;
4, the speed with 0.5L/min passes into air in the iron pentacarbonyl basin that contains the 0.2mol di-iron trioxide, obtains by the saturated air of carbonyl iron;
5, passed into step 3 with above-mentioned by the saturated air of carbonyl iron) in the slurries of preheating;
6, after iron pentacarbonyl is evaporated completely, reacted slurries in 90 ℃ of lower aging 10b, are then filtered, get filter cake;
7, filter cake through 200 ℃ of dryings, shatter, compression molding, 500 ℃ of roastings namely get formaldehyde catalyst;
8, go out step 5) air through the blower fan iterative cycles, to carbonyl iron content less than 1.0g/m3 after, with above-mentioned steps 1) end liquid of gained absorbs backward airborne release up to standard;
9, filtrate and step 8 step 6)) in absorption liquid through merging, returning step 2 behind readjustment polyalcohol concentration and the volume) recycling, whole process is discharged without " three wastes ".
This routine prepared catalyst forms and character the results are shown in Table 1.
Embodiment 7
The preparation of the catalyst of iron molybdenum method prepn. of formaldehyde by oxidation of methanol
1, getting the 10mol propane diols is dissolved in the 5400g deionized water and namely gets end liquid;
2, adding the molybdic acid that contains molybdenum trioxide 5mol in the liquid of the above-mentioned end fully pulls an oar;
3, slurries are preheated to 50 ℃;
4, the speed with 1.0L/min passes into air in the di-iron enneacarbonyl basin that contains the 1.0mol di-iron trioxide, obtains by the saturated air of carbonyl iron;
5, passed into step 3 with above-mentioned by the saturated air of carbonyl iron) in the slurries of preheating;
6, after carbonyl iron is evaporated completely, reacted slurries in 90 ℃ of lower aging 6h, are then filtered, get filter cake;
7, filter cake through 80 ℃ of dryings, shatter, compression molding, 400 ℃ of roastings namely get formaldehyde catalyst;
8, go out step 5) air through the blower fan iterative cycles, to carbonyl iron content less than 1.0g/m3 after, with above-mentioned steps 1) end liquid of gained absorbs can be to airborne release after up to standard;
9, filtrate and step 8 step 6)) in absorption liquid through merging, returning step 2 behind readjustment polyalcohol concentration and the volume) recycling, whole process is discharged without " three wastes ".
This routine prepared catalyst forms and character the results are shown in Table 1.
Embodiment 8
The preparation of the catalyst of iron molybdenum method prepn. of formaldehyde by oxidation of methanol
1, getting the 5mol glycerine is dissolved in the 5400g deionized water and namely gets end liquid;
2, adding the molybdic acid that contains molybdenum trioxide 1mol in the liquid of the above-mentioned end fully pulls an oar;
3, slurries are preheated to 45 ℃;
4, the speed with 0.2L/min passes into air in the tri-iron dodecacarbonyl basin that contains the 0.2mol di-iron trioxide, obtains by the saturated air of carbonyl iron;
5, passed into step 3 with above-mentioned by the saturated air of carbonyl iron) in the slurries of preheating;
6, after carbonyl iron is evaporated completely, reacted slurries in 65 ℃ of lower aging 18h, are then filtered, get filter cake;
7, filter cake through 80 ℃ of dryings, shatter, compression molding, 480 ℃ of roastings namely get formaldehyde catalyst;
8, go out step 5) air through the blower fan iterative cycles, to carbonyl iron content less than 1.0g/m3 after, with above-mentioned steps 1) end liquid of gained absorbs can be to airborne release after up to standard;
9, filtrate and step 8 step 6)) in absorption liquid through merging, returning step 2 behind readjustment polyalcohol concentration and the volume) recycling, whole process is discharged without " three wastes ".
This routine prepared catalyst forms and character the results are shown in Table 1.
Embodiment 9
The preparation of the catalyst of iron molybdenum method prepn. of formaldehyde by oxidation of methanol
Press embodiment 2, recycling 10 times of end liquid; All the other step operations are identical with embodiment 2 with condition.
This routine prepared catalyst forms and character the results are shown in Table 1.
Embodiment 10
Press embodiment 2, recycling 50 times of end liquid; All the other operations are identical with embodiment 2 with condition.
This routine prepared catalyst forms and character the results are shown in Table 1.
Each embodiment catalyst of table 1 forms and the character result
Claims (6)
1. the preparation method of the catalyst of an iron molybdenum method prepn. of formaldehyde by oxidation of methanol is characterized in that: without " three wastes " discharging, be pollution-free method in the preparation process; The chemical composition of said catalyst take catalyst quality as benchmark is MoO
380.0～85.0%, surplus is Fe
2O
3The preparation process of catalyst is as follows successively:
1), polyalcohol is soluble in water as end liquid, polyalcohol is 1 ﹕, 300～1 ﹕ 20 with the ratio of the amount of substance of water in the end liquid;
2), the end liquid of step 1) gained and molybdic acid making beating are made slurries, molybdic acid gross mass and end liquid mass ratio are 1 ﹕, 28～1 ﹕ 36 in the slurries;
3), slurries are preheated to 20～100 ℃;
4), pass into air to containing in the carbonyl iron basin, obtain by the saturated air of carbonyl iron;
5), passed in the slurries of step 3) preheating by the saturated air of carbonyl iron above-mentioned;
6), after carbonyl iron is evaporated completely, reacted slurries in 20～100 ℃ of lower aging 1～24h, are then filtered, get filter cake;
7), filter cake through 80～200 ℃ of dryings, shatter, moulding, namely get catalyst in 350～500 ℃ of roastings;
8), the air that goes out step 5) is through the blower fan iterative cycles, to carbonyl iron content less than 1.0g/m
3After, absorb backward airborne release up to standard with the end liquid of above-mentioned step 1) gained;
9), the filtrate in the step 6) and the absorption liquid in the step 8) merges, return step 2 behind readjustment polyalcohol concentration and the volume) recycling, whole process is discharged without " three wastes ".
2. press the preparation method of the catalyst of a kind of iron molybdenum method prepn. of formaldehyde by oxidation of methanol claimed in claim 1, it is characterized in that: described polyalcohol is ethylene glycol, propane diols, glycerine or butanediol.
3. press the preparation method of the catalyst of a kind of iron molybdenum method prepn. of formaldehyde by oxidation of methanol claimed in claim 1, it is characterized in that: described carbonyl iron is iron pentacarbonyl, di-iron enneacarbonyl or tri-iron dodecacarbonyl.
4. press the preparation method of the catalyst of a kind of iron molybdenum method prepn. of formaldehyde by oxidation of methanol claimed in claim 1, it is characterized in that: the slurries described in the step 3) are preheated to 45～95 ℃.
5. by the preparation method of the catalyst of a kind of iron molybdenum method prepn. of formaldehyde by oxidation of methanol claimed in claim 1, it is characterized in that: the filter cake described in the step 7) through 80～200 ℃ of dryings, shatter, moulding, namely get catalyst in 380～450 ℃ of roastings.
6. press the preparation method of the catalyst of a kind of iron molybdenum method prepn. of formaldehyde by oxidation of methanol claimed in claim 1, it is characterized in that: recycling behind the filtrate readjustment polyalcohol concentration described in the step 9) and the volume, after the added polynary alcohol and water of interpolation step 1) reaches the polyalcohol concentration and volume of liquid of the initial end, return to and add molybdic acid making beating slurrying liquid, thereby realize the filtrate cycle utilization, whole process is discharged without " three wastes ".
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| CN103831109B (en) * | 2014-03-13 | 2015-12-09 | 华烁科技股份有限公司 | A kind of pollution-free preparation process of wide temperature coal preparing natural gas methanation catalyst |
| CN104193605A (en) * | 2014-08-13 | 2014-12-10 | 山东滨州新天阳化工有限责任公司 | Environment-friendly formaldehyde preparation process |
| CN104193604A (en) * | 2014-08-13 | 2014-12-10 | 山东滨州新天阳化工有限责任公司 | Formaldehyde preparation process |
| CN107473976B (en) * | 2016-06-08 | 2019-07-12 | 中国科学院大连化学物理研究所 | A kind of preparation method of N- methoxyl methyl aminated compounds |
| CN106397147A (en) * | 2016-08-19 | 2017-02-15 | 新疆天智辰业化工有限公司 | Technology for producing formaldehyde through iron-molybdenum method |
| CN110893344B (en) * | 2018-09-13 | 2021-04-27 | 中国科学院大连化学物理研究所 | Iron-molybdenum catalyst for preparing formaldehyde by methanol oxidation, preparation and application thereof |
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| US4003850A (en) * | 1971-10-04 | 1977-01-18 | United States Steel Corporation | Novel iron oxide catalysts |
| CN1546232A (en) * | 2003-12-09 | 2004-11-17 | 南化集团研究院 | Fe-Mo catalyst for preparing formaldehyde through methanol oxidation and preparation process thereof |
| CN101327433A (en) * | 2008-07-30 | 2008-12-24 | 中国科学院山西煤炭化学研究所 | Nano metallic carbide catalyst and preparation and use |
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