CN107056593A - A kind of production method and system of ultra-large formaldehyde - Google Patents
A kind of production method and system of ultra-large formaldehyde Download PDFInfo
- Publication number
- CN107056593A CN107056593A CN201710088438.3A CN201710088438A CN107056593A CN 107056593 A CN107056593 A CN 107056593A CN 201710088438 A CN201710088438 A CN 201710088438A CN 107056593 A CN107056593 A CN 107056593A
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- Prior art keywords
- absorption tower
- methanol
- formaldehyde
- production method
- absorber portion
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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
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
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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
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of production method and system of ultra-large formaldehyde, aforementioned production method is：The methanol steam that will be come out from evaporator, water vapour, the gaseous mixture of formaldehyde vapor and air is incorporated a part of water vapour again, through superheater, enter oxidator after filter, in oxidator in the presence of silver catalyst, in temperature be 590 625 DEG C, oxygen methanol molar ratio is reaction generation formaldehyde and other accessory substances under conditions of 0.33 0.37, the reaction generation gas of high temperature absorbs through the first absorption tower and second absorption tower dealcoholysis successively, product is produced from the bottom on the first absorption tower, the liquid supplement that partially absorbs of second absorption tower bottom extraction is returned in evaporator, the tail gas of the hydrogen containing high content after dealcoholysis enters in exhaust gas treating device through the recovery waste heat that burns.In the production method for the ultra-large formaldehyde that the present invention is provided, pass through the setting of relatively low oxygen methanol molar ratio and relatively low reaction temperature so that the ratio of dehydrogenation reaction is close to 48 50%.
Description
Technical field
The present invention relates to Formaldehyde Production technical field, more particularly to a kind of production method and system of ultra-large formaldehyde.
Background technology
At present, domestic and international prepn. of formaldehyde mainly has two kinds of Yin Fa and iron molybdenum method.The advantage of silver-colored method is to invest small, power
Consumption is low, has the disadvantage that methanol unit consumption is high, methanol content is high in formaldehyde, concentration of formaldehyde is low (37% or so), list covering device ability compared with
Small maximum is also with regard to 120,000 tons of devices.To the improved technique of conventional silver method such as circulation of tail gas method, flue gas round-robin method, both approaches
Although concentration of formaldehyde can be improved, fail effectively to reduce product methanol content, if by improving reaction temperature and oxygen-methanol ratio
To reduce the methanol content in product, necessarily increase side reaction, methanol unit consumption increases.Because adding tail gas or flue gas recirculation
Blower fan, causes power consumption to increase.The advantage of iron molybdenum method is that methanol unit consumption is low, and methanol content is low in formaldehyde, and concentration of formaldehyde is adjustable
(37~55%), automaticity is high, and list covering device ability is big；Have the disadvantage that product acid number is higher, investment is big, power consumption is high,
Cost is high, is only applicable to the field using high-concentration formaldehyde as raw material such as polyformaldehyde, paraformaldehyde.
The action for administering haze with China is promoted, and is used as the PM2.5 for the diesel combustion contribution for constituting one of haze arch-criminal
Occupy considerable proportion, and the PM2.5 keys for reducing diesel combustion contribution are exactly to improve the quality of diesel oil, and improve diesel quality
It is to reduce Diesel Emissions PM2.5 strength means that means, exactly addition, which improve diesel quality polymethoxy dimethyl ether PODE,.And want
Accomplish this point, 1.5 hundred million tons of Chinese Diesel consumption figure, the amount of addition 10% is exactly 15,000,000 tons of scale, and the PODE that to start
The dynamic then ten thousand tons of production capacities of 10-30 of device, and 10 ton energy generation devices, it is necessary to the formaldehyde of supporting 25 ton, and domestic silver-colored method
Device conventional equipment will 3 sets of 8-10, ten thousand tons of matched with devices, construction wastes very much, it is more likely that by external ten thousand tons of iron molybdenums of 24-28
Formaldehyde device replaces.So we must break through original technology framework, design ultra-large silver-colored subtraction unit, substitute into
Mouthful, the construction cost of device is reduced, is easy to the Rapid Expansion of PODE industries, contributes oneself a strength.
The content of the invention
The above mentioned problem existed for existing Formaldehyde Production, now provides a kind of production method of ultra-large formaldehyde and is
System, it is desirable to provide a kind of flow is short, unit equipment invests small, byproduct steam to overheat high-pressure water vapor, and maximum productivity can
Up to 320,000 tons of ultra-large silver-colored formaldehyde production method and system.
Concrete technical scheme is as follows：
The first aspect of the invention is to provide a kind of production method of ultra-large formaldehyde, has the feature that, will
The gaseous mixture of the methanol steam, water vapour, formaldehyde vapor and the air that are come out from evaporator is incorporated a part of water vapour again, through overheat
After device, filter enter oxidator, in oxidator in the presence of silver catalyst, in temperature be 590-625 DEG C, oxygen-methanol
Mol ratio is reaction generation formaldehyde and other accessory substances under conditions of 0.33-0.37, and the reaction of high temperature generates gas successively through first
Absorption tower and second absorption tower dealcoholysis are absorbed, and product is produced from the bottom on the first absorption tower, and second absorption tower bottom is produced
Partially absorb liquid supplement to return in evaporator, to realize extraction at the top of the cyclic process of dealcoholysis-recycling, second absorption tower
The tail gas of the hydrogen containing high content enters through the recovery waste heat that burns in exhaust gas treating device, and the water vapour of generation overheats to obtain through flue gas
Obtain high pressure superheater water vapour.
Above-mentioned production method, also has the feature that, injects and evaporates after methanol feedstock is preheated through methanol heater
The top of device.
Above-mentioned production method, is also had the feature that, the part that the second absorber portion in the first absorption tower is produced is inhaled
The top that liquid is pumped into the first absorption tower through methanol heater is received, to preheat methanol feedstock using the absorbing liquid of high temperature.
Above-mentioned production method, also has the feature that, second absorbs the part that pars infrasegmentalis is produced in second absorption tower
Absorbing liquid is pumped into the bottom of the second absorber portion in the first absorption tower, with dealcoholysis again, meets the product demand of various concentrations.
The second aspect of the invention is to provide a kind of production system of utilization aforementioned production method, with such spy
Levy, including evaporator, superheater, filter, oxidator, the first absorption tower, second absorption tower, liquid seal trough, vent gas treatment tower, steam
Send out the top of device and one end of superheater to connect, the other end of superheater and one end of filter are connected, the other end of filter
With the top links of oxidator, the bottom of oxidator is connected with the bottom on the first absorption tower, the top on the first absorption tower and second
The bottom connection on absorption tower, the top of second absorption tower is connected with liquid seal trough, and liquid seal trough is connected with the bottom of vent gas treatment tower.
Above-mentioned production system, also has the feature that, in addition to methanol heater, the bottom and top of methanol heater
Portion is corresponded respectively by pipeline to be connected with the bottom and top of evaporator.
Above-mentioned production system, also has the feature that, second absorption tower is divided into dealcoholysis section, first from bottom to up
The bottom of the second absorber portion is inhaled with first in absorber portion, the second absorber portion, the 3rd absorber portion and valve plate section, second absorption tower
Receive the bottom connection of the second absorber portion in tower.
Above-mentioned production system, also has the feature that, the bottom and top of the second absorber portion are equal in the first absorption tower
It is connected with methanol heater.
Above-mentioned production method, also has the feature that, silver catalyst is that multilayer different type is knitted silver in oxidator
Net.
The beneficial effect of such scheme is：
In the production method for the ultra-large formaldehyde that the present invention is provided, by relatively low oxygen-methanol molar ratio and relatively low
Reaction temperature setting so that the ratio of dehydrogenation reaction is incidentally produced close to 48-50%, and then during methanol oxidation generation formaldehyde
Water just reduce；The setting of relatively low oxygen-methanol molar ratio and relatively low reaction temperature greatly reduces dispensing steam simultaneously
Addition.Formaldehyde extraction concentration is 37-67% in the production method that the present invention is provided, can interior various concentrations that meet in a big way
Product demand, and alcohol extraction Han Liang≤0.5%.
Brief description of the drawings
Fig. 1 is the structural representation of the production system of ultra-large formaldehyde provided in embodiments of the invention.
In accompanying drawing：1st, evaporator；2nd, superheater；3rd, filter；4th, oxidator；5th, the first absorption tower；6th, second absorption tower；
7th, liquid seal trough；8th, vent gas treatment tower；9th, drum；10th, methanol heater.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Site preparation is described, it is clear that described embodiment is only a part of embodiment of the invention, rather than whole embodiments.It is based on
Embodiment in the present invention, those of ordinary skill in the art obtained on the premise of creative work is not made it is all its
His embodiment, belongs to the scope of protection of the invention.
It should be noted that in the case where not conflicting, the embodiment in the present invention and the feature in embodiment can phases
Mutually combination.
The invention will be further described with specific embodiment below in conjunction with the accompanying drawings, but not as limiting to the invention.
Fig. 1 is the structural representation of the production system of ultra-large formaldehyde provided in embodiments of the invention.Such as Fig. 1 institutes
Show, the production system of the ultra-large formaldehyde provided in embodiments of the invention, including：Evaporator 1, superheater 2, filter 3,
Oxidator 4, the first absorption tower 5, second absorption tower 6, liquid seal trough 7, vent gas treatment tower 8, top and the superheater 2 of evaporator 1
One end is connected, and the other end of superheater 2 is connected with one end of filter 3, the other end of filter 3 and the top chain of oxidator 4
Connect, the bottom of oxidator 4 is connected with the bottom on the first absorption tower 5, the top on the first absorption tower 5 and the lower end of second absorption tower 6
Connection, the top of second absorption tower 6 is connected with liquid seal trough 7, and liquid seal trough 7 is connected with the lower end of vent gas treatment tower 8.
Specifically, second absorption tower 6 includes dealcoholysis section, the first absorber portion, the second absorber portion, the 3rd absorber portion and valve tower
The bottom of second absorber portion is connected with the bottom of the second absorber portion in the first absorption tower 5 in plate section, second absorption tower 6；Oxidator 4
Middle reaction heat is reclaimed by the heat exchange coil of the bottom of oxidator 4, above-mentioned heat exchange coil include from top to down preheating section, superheat section,
Evaporator section, the two ends of evaporator section are connected with drum 9, and drum 9 is that superheater 2 provides steam；The bottom of methanol heater 10 and
Top is corresponded respectively by pipeline to be connected with the bottom and top of evaporator 1, also, the second absorption in the first absorption tower 5
The bottom and top of section are connected with methanol heater 10；Silver catalyst is that multilayer different type is knitted silver-colored net in oxidator 4.
The production technology of the production system of the ultra-large formaldehyde provided in embodiments of the invention is：Methanol feedstock is by first
Alcohol heater 10 injects the top of evaporator 1 after preheating, air is driven into the bottom of evaporator 1 by roots blower, with preheating
Methanol feedstock afterwards is inversely contacted, then with being entrained with dilute formaldehyde of methanol, water (by the second absorption pars infrasegmentalis of second absorption tower 6
Extraction) mixing, quaternary gaseous mixture is formed, after overheating through superheater 2 and be incorporated a part of water vapour, oxygen is entered after filter 3
Change device 4, in oxidator 4 in the presence of silver catalyst, in temperature be 590-625 DEG C, oxygen-methanol molar ratio be 0.33-
Reaction generation formaldehyde and other accessory substances under conditions of 0.37, the reaction of high temperature generate gas successively through the first absorption tower 5 and second
The dealcoholysis of absorption tower 6 is absorbed, and product is produced from the bottom on the first absorption tower 5, and the liquid that partially absorbs of the bottom of second absorption tower 6 extraction is mended
Fill and return in evaporator 1, to realize the hydrogen containing high content in the cyclic process of dealcoholysis-recycling, second absorption tower 6 after dealcoholysis
The tail gas of gas enters in exhaust gas treating device 8 after liquid seal trough 7, through the recovery waste heat that burns, the water vapour of generation through flue gas overheat from
And high pressure superheater water vapour is obtained, above-mentioned high pressure superheater water vapour can inject drum 9, can also make through pipeline for other production systems
With.
In embodiments of the invention, the liquid that partially absorbs that can produce the second absorber portion in the first absorption tower 5 flows through methanol
The tube side of heater 10 is pumped into the top on the first absorption tower 5, is added using the absorbing liquid using cyclic process high temperature herein as methanol
Hot device 10 provides heat preheating methanol feedstock.
In embodiments of the invention, the second absorber portion in second absorption tower 6 can also be produced according to the concentration requirement of product
Partially absorb the bottom that liquid pump enters the second absorber portion in the first absorption tower 5, with dealcoholysis again.
Preferred embodiments of the present invention are the foregoing is only, embodiments of the present invention and protection model is not thereby limited
Enclose, to those skilled in the art, should can appreciate that made by all utilization description of the invention and diagramatic content
Scheme obtained by equivalent substitution and obvious change, should be included in protection scope of the present invention.
Claims (9)
1. a kind of production method of ultra-large formaldehyde, it is characterised in that by the methanol steam come out from evaporator, water vapour,
The gaseous mixture of formaldehyde vapor and air is incorporated a part of water vapour again, oxidator is entered after superheater, filter, in the oxygen
Change in device in the presence of silver catalyst, in temperature be 590-625 DEG C, oxygen-methanol molar ratio be under conditions of 0.33-0.37 it is anti-
Formaldehyde and other accessory substances should be generated, the reaction generation gas of high temperature absorbs through the first absorption tower and second absorption tower dealcoholysis successively,
Product is produced from the bottom on first absorption tower, and the liquid supplement that partially absorbs that the second absorption tower bottom is produced is returned to
In the evaporator, to realize the tail gas of the hydrogen of extraction at the top of the cyclic process of dealcoholysis-recycling, the second absorption tower
Into in exhaust gas treating device through the recovery waste heat that burns, the water vapour of generation overheats to obtain high pressure superheater water vapour through flue gas.
2. production method according to claim 1, it is characterised in that injected after methanol feedstock is preheated through methanol heater
The top of the evaporator.
3. production method according to claim 2, it is characterised in that produce the second absorber portion in first absorption tower
Partially absorb the top that liquid is pumped into first absorption tower through the methanol preheater, with using high temperature the absorbing liquid it is pre-
The heat methanol feedstock.
4. production method according to claim 3, it is characterised in that the second absorber portion is produced in the second absorption tower
The bottom that liquid pump enters the second absorber portion in first absorption tower is partially absorbed, with dealcoholysis again.
5. the production system of a kind of production method according to claim any one of 1-4, it is characterised in that including evaporation
Device, superheater, filter, oxidator, the first absorption tower, second absorption tower, liquid seal trough, vent gas treatment tower, the evaporator
Top is connected with one end of the superheater, and the other end of the superheater is connected with one end of the filter, the filtering
The other end of device is connected with the top of the oxidator, and the bottom of the oxidator is connected with the bottom on first absorption tower,
The top on first absorption tower is connected with the bottom of the second absorption tower, the top of the second absorption tower and the fluid-tight
Groove is connected, and the liquid seal trough is connected with the bottom of the vent gas treatment tower.
6. production system according to claim 5, it is characterised in that also including methanol heater, the methanol heater
Bottom and top corresponded and be connected with the bottom and top of the evaporator respectively by pipeline.
7. production system according to claim 5, it is characterised in that the second absorption tower is divided into taking off from bottom to up
Alcohol section, the first absorber portion, the second absorber portion, the 3rd absorber portion and valve plate section, the bottom of second absorber portion with it is described
The bottom connection of second absorber portion in first absorption tower.
8. production system according to claim 6, it is characterised in that in first absorption tower bottom of the second absorber portion
It is connected with top with the methanol heater.
9. the production system according to claim any one of 5-8, it is characterised in that silver catalyst is many in the oxidator
The silver-colored net of layer different type knitting.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710088438.3A CN107056593A (en) | 2017-02-17 | 2017-02-17 | A kind of production method and system of ultra-large formaldehyde |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710088438.3A CN107056593A (en) | 2017-02-17 | 2017-02-17 | A kind of production method and system of ultra-large formaldehyde |
Publications (1)
| Publication Number | Publication Date |
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| CN107056593A true CN107056593A (en) | 2017-08-18 |
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ID=59622758
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710088438.3A Pending CN107056593A (en) | 2017-02-17 | 2017-02-17 | A kind of production method and system of ultra-large formaldehyde |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107501060A (en) * | 2017-08-24 | 2017-12-22 | 开封龙宇化工有限公司 | A kind of concentrated formaldehyde production technology |
| CN109232217A (en) * | 2018-11-08 | 2019-01-18 | 山东明化新材料有限公司 | A kind of flue gas recirculation prepn. of formaldehyde and its device |
| CN109574820A (en) * | 2018-12-10 | 2019-04-05 | 安徽金禾实业股份有限公司 | A kind of production method of formaldehyde |
| CN110041183A (en) * | 2019-05-15 | 2019-07-23 | 宜都市多邦化工有限公司 | The recycling system and method for dilute formaldehyde in a kind of production of paraformaldehyde |
| CN112479845A (en) * | 2020-11-09 | 2021-03-12 | 潍坊惠丰化工有限公司 | High-concentration formaldehyde production device and production process |
| CN112920029A (en) * | 2021-02-03 | 2021-06-08 | 安徽金禾实业股份有限公司 | Device and method for extracting and refining methanol from formaldehyde |
| WO2024166931A1 (en) * | 2023-02-08 | 2024-08-15 | 三菱瓦斯化学株式会社 | Formaldehyde absorption system, absorption method, and method for designing absorption system |
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| CN107501060A (en) * | 2017-08-24 | 2017-12-22 | 开封龙宇化工有限公司 | A kind of concentrated formaldehyde production technology |
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| CN112920029A (en) * | 2021-02-03 | 2021-06-08 | 安徽金禾实业股份有限公司 | Device and method for extracting and refining methanol from formaldehyde |
| WO2024166931A1 (en) * | 2023-02-08 | 2024-08-15 | 三菱瓦斯化学株式会社 | Formaldehyde absorption system, absorption method, and method for designing absorption system |
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