CN102240554A - 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 methanol oxidation system formaldehyde.
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 technology can be divided into argent as " silver-colored method " technology of catalyst with iron and molybdenum oxides " iron molybdenum method " technology as catalyst by the catalyst difference of using.Because " iron molybdenum method " methanol oxidation system formaldehyde technology has: 1) technical process is brief; 2) catalyst long service life; 3) product yield height is the highest technology of formaldehyde yield; 4) product design height, Functionality, quality and appealing design can satisfy the demand of polyformaldehyde; 5) energy consumes low; 6) thermal efficiency height; 7) safety, environmental protection do not have outstanding advantages such as " three wastes " discharging, meet the big 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 domestic and international in recent years disclosed preparation methanol oxidation system formaldehyde is a lot, but in general, basic preparation technology can be divided into two classes: (1) gel method, as FR1604707, GB1282949, US3846341 etc.; (2) coprecipitation is as US3978136, US4420421, US4829042, CN110066 and CN100413584 etc.Though above method can make the iron-molybdic catalyst of the methanol oxidation system formaldehyde that activity is enough high, intensity is enough good, 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 methanol oxidation system formaldehyde.Make iron-molybdic catalyst active enough high, intensity is enough good, can satisfy the requirement that has iron molybdenum method methanol oxidation system formaldehyde technology now.
Realize the technical scheme of the object of the invention:
A kind of Preparation of catalysts method of iron molybdenum method methanol oxidation system formaldehyde is characterized in that: do not have " three wastes " discharging in the preparation process, be pollution-free method; Said catalyst is that the chemical composition of benchmark is MoO with the catalyst quality
380.0～85.0%, surplus is Fe
2O
3The Preparation of catalysts steps in sequence is as follows:
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, the molybdic acid gross mass is 1: 30～1: 40 with the ratio of end liquid quality in the slurries;
3), slurries are preheated to 20～100 ℃, preferred 45～95 ℃;
4), in containing the carbonyl iron basin bubbling air, obtain by the saturated air of carbonyl iron;
5), fed in the slurries of step 3) preheating by the saturated air of carbonyl iron above-mentioned;
6), treat that carbonyl iron is evaporated completely after, reacted slurries in 20～100 ℃ of down aging 1～24h, are filtered then, filter cake;
7), filter cake is through 80～200 ℃ of dryings, powder essence, moulding, promptly gets formaldehyde catalyst in 350～500 ℃, preferred 380～450 ℃ of roastings;
8), the air that goes out step 5) circulates repeatedly through blower fan, to carbonyl iron content less than 1.0g/m3 after, absorbing with the end liquid of above-mentioned step 1) gained can be to airborne release after up to standard;
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 does not have " three wastes " discharging.
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, recycling behind filtrate readjustment polyalcohol concentration described in the step 9) and the volume, be after the added polynary alcohol and water of interpolation step 1) reaches the polyalcohol concentration and volume of liquid of the initial end, return and add molybdic acid making beating slurrying liquid, thereby realize the filtrate cycle utilization, whole process does not have " three wastes " discharging.
Characteristics of the present invention are:
1, whole Preparation of catalysts process does not have " three wastes " discharging, is pollution-free method;
The iron-molybdic catalyst of the methanol oxidation system formaldehyde that the catalyst that 2, makes is active enough height, intensity is enough good can satisfy the requirement of existing " iron molybdenum method " methanol oxidation system formaldehyde technology;
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 a 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 a catalyst preparation example of the present invention, and described embodiment only is used to the present invention is described rather than be used to limit the present invention.
Embodiment 1
The Preparation of catalysts of iron molybdenum method methanol oxidation system formaldehyde, said catalyst is that the chemical composition of benchmark is MoO with the catalyst quality
380.0～85.0%, surplus is Fe
2O
3The Preparation of catalysts steps in sequence is as follows:
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, the molybdic acid gross mass is 1: 30～1: 40 with the ratio of end liquid quality in the slurries;
3), slurries are preheated to 20～100 ℃, preferred 45～95 ℃;
4), in containing the carbonyl iron basin bubbling air, obtain by the saturated air of carbonyl iron;
5), fed in the slurries of step 3) preheating by the saturated air of carbonyl iron above-mentioned;
6), treat that carbonyl iron is evaporated completely after, reacted slurries in 20～100 ℃ of down aging 1～24h, are filtered then, filter cake;
7), filter cake is through 80～200 ℃ of dryings, powder essence, moulding, promptly gets formaldehyde catalyst in 350～500 ℃, preferred 380～450 ℃ of roastings;
8), the air that goes out step 5) circulates repeatedly through blower fan, to carbonyl iron content less than 1.0g/m3 after, absorbing with the end liquid of above-mentioned step 1) gained can be to airborne release after up to standard;
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 does not have " three wastes " discharging.
Wherein, described polyalcohol is ethylene glycol, propane diols, glycerine or butanediol; Described carbonyl iron is iron pentacarbonyl, di-iron enneacarbonyl or tri-iron dodecacarbonyl; Recycling behind filtrate readjustment polyalcohol concentration described in the step 9) and the volume, be after the added polynary alcohol and water of interpolation step 1) reaches the polyalcohol concentration and volume of liquid of the initial end, return and add molybdic acid making beating slurrying liquid, thereby realize the filtrate cycle utilization, whole process does not have " three wastes " discharging.
Embodiment 2
The Preparation of catalysts of iron molybdenum method methanol oxidation system formaldehyde
1, getting 5mol ethylene glycol is dissolved in the 5400g deionized water and promptly gets end liquid;
2, the molybdic acid that adds trioxygen-containing molybdenum 1mol in liquid of the above-mentioned end is fully pulled an oar;
3, slurries are preheated to 90 ℃;
4, with speed bubbling air in the iron pentacarbonyl basin that contains the 0.2mol di-iron trioxide of 0.5L/min, obtain by the saturated air of carbonyl iron;
5, fed in the slurries of step 3) preheating by the saturated air of carbonyl iron above-mentioned;
6, treat that iron pentacarbonyl is evaporated completely after, reacted slurries in 90 ℃ of down aging 12h, are filtered then, filter cake;
7, filter cake promptly gets formaldehyde catalyst through 80 ℃ of dryings, powder essence, compression molding, 450 ℃ of roastings;
8, the air that goes out step 5) circulates repeatedly through blower fan, to carbonyl iron content less than 1.0g/m
3After, up to standard back with the end liquid absorption of above-mentioned step 1) gained to airborne release;
9, return step 2 behind filtrate in the step 6) and the absorption liquid in step 8) merging, readjustment polyalcohol concentration and the volume) recycling, whole process does not have " three wastes " discharging.
This routine prepared catalyst forms and character the results are shown in Table 1.
Embodiment 3
The Preparation of catalysts of iron molybdenum method methanol oxidation system formaldehyde
1, getting the 3mol propane diols is dissolved in the 5400g deionized water and promptly gets end liquid;
2, the molybdic acid that adds trioxygen-containing molybdenum 0.5mol in liquid of the above-mentioned end is fully pulled an oar;
3, slurries are preheated to 20 ℃;
4, with speed bubbling air in the iron pentacarbonyl basin that contains the 0.1mol di-iron trioxide of 0.5L/min, obtain by the saturated air of carbonyl iron;
5, fed in the slurries of step 3) preheating by the saturated air of carbonyl iron above-mentioned;
6, treat that iron pentacarbonyl is evaporated completely after, reacted slurries in 20 ℃ of down aging 24h, are filtered then, filter cake;
7, filter cake promptly gets formaldehyde catalyst through 90 ℃ of dryings, powder essence, compression molding, 350 ℃ of roastings;
8, the air that goes out step 5) circulates repeatedly through blower fan, to carbonyl iron content less than 1.0g/m
3After, up to standard back with the end liquid absorption of above-mentioned step 1) gained to airborne release;
9, filtrate in the step 6) and the absorption liquid in the step 8) return step 2 after merging, adjusting back polyalcohol concentration and volume) recycling, whole process does not have " three wastes " discharging.
This routine prepared catalyst forms and character the results are shown in Table 1.
Embodiment 4
The Preparation of catalysts of iron molybdenum method methanol oxidation system formaldehyde
1, getting the 15mol glycerine is dissolved in the 5400g deionized water and promptly gets end liquid;
2, the molybdic acid that adds trioxygen-containing molybdenum 2mol in liquid of the above-mentioned end is fully pulled an oar;
3, slurries are preheated to 100 ℃;
4, with speed bubbling air in the di-iron enneacarbonyl basin that contains the 0.4mol di-iron trioxide of 2.0L/min, obtain by the saturated air of carbonyl iron;
5, fed in the slurries of step 3) preheating by the saturated air of carbonyl iron above-mentioned;
6, treat that carbonyl iron is evaporated completely after, reacted slurries in 100 ℃ of down aging 1h, are filtered then, filter cake;
7, filter cake promptly gets formaldehyde catalyst through 120 ℃ of dryings, powder essence, compression molding, 380 ℃ of roastings;
8, the air that goes out step 5) circulates repeatedly through blower fan, to carbonyl iron content less than 1.0g/m3 after, absorb back up to standard to airborne release with the end liquid of above-mentioned step 1) gained;
9, filtrate in the step 6) and the absorption liquid in the step 8) return step 2 after merging, adjusting back polyalcohol concentration and volume) recycling, whole process does not have " three wastes " discharging.
This routine prepared catalyst forms and character the results are shown in Table 1.
Embodiment 5
The Preparation of catalysts of iron molybdenum method methanol oxidation system formaldehyde
1, gets the 5mol butanediol and promptly get end liquid in the 5400g deionized water;
2, the molybdic acid that adds trioxygen-containing molybdenum 1mol in liquid of the above-mentioned end is fully pulled an oar;
3, slurries are preheated to 95 ℃;
4, with speed bubbling air in the iron pentacarbonyl basin that contains the 0.2mol di-iron trioxide of 0.5L/min, obtain by the saturated air of carbonyl iron;
5, fed in the slurries of step 3) preheating by the saturated air of carbonyl iron above-mentioned;
6, treat that iron pentacarbonyl is evaporated completely after, reacted slurries in 95 ℃ of down aging 8h, are filtered then, filter cake;
7, filter cake promptly gets formaldehyde catalyst through 80 ℃ of dryings, powder essence, compression molding, 350 ℃ of roastings;
8, the air that goes out step 5) circulates repeatedly through blower fan, to carbonyl iron content less than 1.0g/m3 after, absorb back up to standard to airborne release with the end liquid of above-mentioned step 1) gained;
9, filtrate in the step 6) and the absorption liquid in the step 8) return step 2 after merging, adjusting back polyalcohol concentration and volume) recycling, whole process does not have " three wastes " discharging.
This routine prepared catalyst forms and character the results are shown in Table 1.
Embodiment 6
The Preparation of catalysts of iron molybdenum method methanol oxidation system formaldehyde
1, getting 1mol ethylene glycol is dissolved in the 5400g deionized water and promptly gets end liquid;
2, the molybdic acid that adds trioxygen-containing molybdenum 1mol in liquid of the above-mentioned end is fully pulled an oar;
3, slurries are preheated to 100 ℃;
4, with speed bubbling air in the iron pentacarbonyl basin that contains the 0.2mol di-iron trioxide of 0.5L/min, obtain by the saturated air of carbonyl iron;
5, fed in the slurries of step 3) preheating by the saturated air of carbonyl iron above-mentioned;
6, treat that iron pentacarbonyl is evaporated completely after, reacted slurries in 90 ℃ of down aging 10b, are filtered then, filter cake;
7, filter cake promptly gets formaldehyde catalyst through 200 ℃ of dryings, powder essence, compression molding, 500 ℃ of roastings;
8, the air that goes out step 5) circulates repeatedly through blower fan, to carbonyl iron content less than 1.0g/m3 after, absorb back up to standard to airborne release with the end liquid of above-mentioned step 1) gained;
9, filtrate in the step 6) and the absorption liquid in the step 8) return step 2 after merging, adjusting back polyalcohol concentration and volume) recycling, whole process does not have " three wastes " discharging.
This routine prepared catalyst forms and character the results are shown in Table 1.
Embodiment 7
The Preparation of catalysts of iron molybdenum method methanol oxidation system formaldehyde
1, getting the 10mol propane diols is dissolved in the 5400g deionized water and promptly gets end liquid;
2, the molybdic acid that adds trioxygen-containing molybdenum 5mol in liquid of the above-mentioned end is fully pulled an oar;
3, slurries are preheated to 50 ℃;
4, with speed bubbling air in the di-iron enneacarbonyl basin that contains the 1.0mol di-iron trioxide of 1.0L/min, obtain by the saturated air of carbonyl iron;
5, fed in the slurries of step 3) preheating by the saturated air of carbonyl iron above-mentioned;
6, treat that carbonyl iron is evaporated completely after, reacted slurries in 90 ℃ of down aging 6h, are filtered then, filter cake;
7, filter cake promptly gets formaldehyde catalyst through 80 ℃ of dryings, powder essence, compression molding, 400 ℃ of roastings;
8, the air that goes out step 5) circulates repeatedly through blower fan, to carbonyl iron content less than 1.0g/m3 after, absorbing with the end liquid of above-mentioned step 1) gained can be to airborne release after up to standard;
9, filtrate in the step 6) and the absorption liquid in the step 8) return step 2 after merging, adjusting back polyalcohol concentration and volume) recycling, whole process does not have " three wastes " discharging.
This routine prepared catalyst forms and character the results are shown in Table 1.
Embodiment 8
The Preparation of catalysts of iron molybdenum method methanol oxidation system formaldehyde
1, getting the 5mol glycerine is dissolved in the 5400g deionized water and promptly gets end liquid;
2, the molybdic acid that adds trioxygen-containing molybdenum 1mol in liquid of the above-mentioned end is fully pulled an oar;
3, slurries are preheated to 45 ℃;
4, with speed bubbling air in the tri-iron dodecacarbonyl basin that contains the 0.2mol di-iron trioxide of 0.2L/min, obtain by the saturated air of carbonyl iron;
5, fed in the slurries of step 3) preheating by the saturated air of carbonyl iron above-mentioned;
6, treat that carbonyl iron is evaporated completely after, reacted slurries in 65 ℃ of down aging 18h, are filtered then, filter cake;
7, filter cake promptly gets formaldehyde catalyst through 80 ℃ of dryings, powder essence, compression molding, 480 ℃ of roastings;
8, the air that goes out step 5) circulates repeatedly through blower fan, to carbonyl iron content less than 1.0g/m3 after, absorbing with the end liquid of above-mentioned step 1) gained can be to airborne release after up to standard;
9, filtrate in the step 6) and the absorption liquid in the step 8) return step 2 after merging, adjusting back polyalcohol concentration and volume) recycling, whole process does not have " three wastes " discharging.
This routine prepared catalyst forms and character the results are shown in Table 1.
Embodiment 9
The Preparation of catalysts of iron molybdenum method methanol oxidation system formaldehyde
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 is formed and the character result
Claims (6)
1. the Preparation of catalysts method of an iron molybdenum method methanol oxidation system formaldehyde is characterized in that: do not have " three wastes " discharging in the preparation process, be pollution-free method; Said catalyst is that the chemical composition of benchmark is MoO with the catalyst quality
380.0～85.0%, surplus is Fe
2O
3The Preparation of catalysts steps in sequence is as follows:
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, the molybdic acid gross mass is 1: 28～1: 36 with the ratio of end liquid quality in the slurries;
3), slurries are preheated to 20～100 ℃;
4), in containing the carbonyl iron basin bubbling air, obtain by the saturated air of carbonyl iron;
5), fed in the slurries of step 3) preheating by the saturated air of carbonyl iron above-mentioned;
6), treat that carbonyl iron is evaporated completely after, reacted slurries in 20～100 ℃ of down aging 1～24h, are filtered then, filter cake;
7), filter cake is through 80～200 ℃ of dryings, powder essence, moulding, promptly gets formaldehyde catalyst in 350～500 ℃ of roastings;
8), the air that goes out step 5) circulates repeatedly through blower fan, to carbonyl iron content less than 1.0g/m
3After, up to standard back with the end liquid absorption of above-mentioned step 1) gained to airborne release;
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 does not have " three wastes " discharging.
2. by the Preparation of catalysts method of the described a kind of iron molybdenum method methanol oxidation system formaldehyde of claim 1, it is characterized in that: described polyalcohol is ethylene glycol, propane diols, glycerine or butanediol.
3. by the Preparation of catalysts method of the described a kind of iron molybdenum method methanol oxidation system formaldehyde of claim 1, it is characterized in that: described carbonyl iron is iron pentacarbonyl, di-iron enneacarbonyl or tri-iron dodecacarbonyl.
4. by the Preparation of catalysts method of the described a kind of iron molybdenum method methanol oxidation system formaldehyde of claim 1, it is characterized in that: the slurries described in the step 3) are preheated to 45～95 ℃;
5. by the Preparation of catalysts method of the described a kind of iron molybdenum method methanol oxidation system formaldehyde of claim 1, it is characterized in that: the filter cake described in the step 7) promptly gets formaldehyde catalyst through 80～200 ℃ of dryings, powder essence, moulding in 380～450 ℃ of roastings;
6. press the Preparation of catalysts method of the described a kind of iron molybdenum method methanol oxidation system formaldehyde of claim 1, it is characterized in that: recycling behind filtrate readjustment polyalcohol concentration described in the step 9) and the volume, be after the added polynary alcohol and water of interpolation step 1) reaches the polyalcohol concentration and volume of liquid of the initial end, return and add molybdic acid making beating slurrying liquid, thereby realize the filtrate cycle utilization, whole process does not have " three wastes " discharging.
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| CN103831109A (en) * | 2014-03-13 | 2014-06-04 | 华烁科技股份有限公司 | Pollution-free preparation process for wide-temperature coal-based natural gas methanation catalyst |
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| 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 |
| 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 |
| CN107473976A (en) * | 2016-06-08 | 2017-12-15 | 中国科学院大连化学物理研究所 | A kind of preparation method of N methoxyl methyls aminated compounds |
| CN110893344A (en) * | 2018-09-13 | 2020-03-20 | 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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| CN103831109A (en) * | 2014-03-13 | 2014-06-04 | 华烁科技股份有限公司 | Pollution-free preparation process for wide-temperature coal-based natural gas methanation catalyst |
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| 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 |
| CN110893344A (en) * | 2018-09-13 | 2020-03-20 | 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 |
| 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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