CN108395422A - A kind of the synthesis extracting process and device of metaformaldehyde - Google Patents
A kind of the synthesis extracting process and device of metaformaldehyde Download PDFInfo
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- CN108395422A CN108395422A CN201810465540.5A CN201810465540A CN108395422A CN 108395422 A CN108395422 A CN 108395422A CN 201810465540 A CN201810465540 A CN 201810465540A CN 108395422 A CN108395422 A CN 108395422A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D323/00—Heterocyclic compounds containing more than two oxygen atoms as the only ring hetero atoms
- C07D323/04—Six-membered rings
- C07D323/06—Trioxane
Abstract
The invention discloses the synthesis extracting process and device of a kind of metaformaldehyde, it is suitable for using commercially available cheap formaldehyde as Material synthesis metaformaldehyde：Including sequentially connected reactor, extraction tower, knockout tower and metaformaldehyde finished product pipeline, the formalin after concentration is reacted in the reactor as raw material, and product enters after extracting, detaching in metaformaldehyde finished product pipeline successively.Formalin after concentration is sent into reactor to react, liquid after reaction is sent into extraction tower, it is inversely extracted with the extractant being added from lower part, bottom of tower obtains dilute formalin containing formaldehyde, it is sent into dilute formaldehyde recovery unit, tower top obtains the extract liquor containing metaformaldehyde and extractant, which enters knockout tower and detached, high-purity metaformaldehyde is obtained by knockout tower bottom, recovered overhead extractant recycles.The configuration of the present invention is simple, small investment, low energy consumption.
Description
Technical field
The present invention relates to the synthesis extracting process and device of a kind of metaformaldehyde, it is suitable for commercially available cheap formaldehyde being original
Expect synthesizing triformol.
Background technology
Metaformaldehyde is a kind of solid polymer of the low polymerization degree of stabilization of formaldehyde, and property is stablized relatively, easily stored,
And it under certain condition can be using depolymerization as formaldehyde monomers.Therefore, metaformaldehyde can substitute formaldehyde and participate in using formaldehyde as raw material
Nearly all reaction.Meanwhile metaformaldehyde is also the important compound in methanol downstream, it can be with synthesis clean fuel and high-performance
Material.With the development of China's economic, the demand to metaformaldehyde is in increase trend.And China's Gas Resource is abundant, coal first
Alcohol technology is very ripe, but the development and utilization of Downstream Products of Methanol is insufficient.High yield metaformaldehyde synthesis technology
Exploitation and its subsequent product deep processing be Development of Coal Chemical Industry needs, by meet fine chemical product the market demand and
The development of coal chemical industry is pushed to generate great reality and strategic importance.
Currently, industrial more commonly used metaformaldehyde synthesis technology is using sulfuric acid as catalyst synthesizing triformol, this
Technique there are formaldehyde conversions low, high energy consumption, the problems such as byproduct is more, etching apparatus is serious.
Invention content
The technical problem to be solved by the present invention is to be directed to the deficiencies in the prior art, and provide a kind of metaformaldehyde
Synthesis extraction equipment, the apparatus structure is simple, and small investment, low energy consumption.
The present invention also provides a kind of synthesis extracting process of metaformaldehyde, the formalin after concentration is sent into anti-by this method
Device is answered to be reacted, the liquid after reaction is sent into extraction tower, is inversely extracted with the extractant being added from lower part, bottom of tower obtains
Dilute formalin containing formaldehyde is sent into dilute formaldehyde recovery unit, and tower top obtains the extract liquor containing metaformaldehyde and extractant,
The extract liquor enters knockout tower and is detached, and high-purity metaformaldehyde, recovered overhead extractant cycle are obtained by knockout tower bottom
It utilizes.
To achieve the goals above, the present invention adopts the following technical scheme that：
A kind of synthesis extraction equipment of metaformaldehyde, including sequentially connected reactor, extraction tower, knockout tower and trimerization first
Aldehyde finished product pipeline, the formalin after concentration are reacted in the reactor as raw material, and product is laggard through extracting, detaching successively
Enter in metaformaldehyde finished product pipeline, it is characterised in that：
The reactor is equipped with import I and outlet I：Import I is connected with the device for providing raw material；
The extraction tower, top is equipped with liquid outlet I, top is equipped with inlet I, lower part is equipped with inlet II, bottom is set
There is liquid outlet II：Inlet I is connected with the outlet I of reactor, and liquid outlet II is connected with dilute formaldehyde recovery line, inlet II with
The device for being capable of providing extractant is connected；
The knockout tower, tower top is equipped with gas outlet, top is equipped with inlet IV, middle part is equipped with inlet III, bottom is set
There is liquid outlet III：Inlet III is connected with the liquid outlet I of extraction tower, and liquid outlet III is connected with metaformaldehyde finished product pipeline, goes out
Gas port is connected with condenser, return tank, reflux pump in turn, and the outlet of reflux pump is divided into two-way：All the way with the inlet of extraction tower
II is connected, and another way is connected to flow back with inlet IV.
In above-mentioned technical proposal, the condenser is equipped with import II and outlet II：The gas outlet of import II and knockout tower
It is connected, outlet II is connected with return tank.
In above-mentioned technical proposal, the return tank is equipped with import III and outlet III：Import III and condenser go out
Mouth II is connected, and outlet III is connected with reflux pump.
In above-mentioned technical proposal, the reflux pump is equipped with import IV and outlet IV：The outlet of import IV and return tank
III is connected, and IV points of outlet is two-way, is connected all the way with the inlet II of extraction tower, the inlet IV phases of another way and knockout tower
Even.
In above-mentioned technical proposal, the reactor is fixed bed reactors, and built with catalyst, which is big
The D006 of any one in hole resin cation, superpower acid resin, preferably Kai Rui environmental protective chemical industries limited liability company production
Type acid resin catalyst, D008 type high temperature resistant acidic resin catalysts.
In above-mentioned technical proposal, the extraction tower, built with extractant, extractant is esters extractant, ketone extraction
Take any one in agent, ether extration agent, alcohol kind of extractants, phenols extractant, two kinds or more with arbitrary proportion mixes and
At mixture.
In above-mentioned technical proposal, the extraction tower, tower is interior to be filled with internals, and internals are any one in filler, column plate
Kind；
In above-mentioned technical proposal, the knockout tower, tower is interior to be filled with internals, and internals are any one in filler, column plate
Kind.
In above-mentioned technical proposal, the knockout tower, tower lower part (boiling evaporator section again) is equipped with reboiler.
The present invention also provides a kind of synthesis extracting process of metaformaldehyde, include the following steps：
(1) polymerisation：Using the formalin after concentration as raw material, raw material under the catalytic action of catalyst, in temperature
Degree is 75 DEG C -120 DEG C, and pressure carries out polymerisation under conditions of being 0-0.5MPa and generates metaformaldehyde；
(2) it extracts：The product that step (1) obtains under the action of extractant, temperature be 50-75 DEG C, pressure 0-
It is extracted under conditions of 1MPa, respectively obtains dilute formalin containing formaldehyde and the extraction containing metaformaldehyde and extractant
Liquid；Dilute formalin recycling containing formaldehyde；
(3) rectifying detaches：The extract liquor containing metaformaldehyde and extractant that step (2) obtains is 60-125 in temperature
DEG C, pressure carry out rectifying separation under conditions of being 0-1MPa, obtain the metaformaldehyde of liquid and gaseous extractant, the three of liquid
Polyformaldehyde harvests；Gaseous extractant forms the extractant of liquid, the extractant reflux of liquid and/or cycle profit by condensation
With.
In above-mentioned technical proposal, synthesis extracting process specifically includes following steps：
(1) polymerisation：Using the formalin after concentration as raw material, raw material is sent to through import I in reactor, at it
Polymerisation is carried out under the catalytic action of interior catalyst, the obtained product after reaction send followed by outlet I, inlet I
Enter into extraction tower；
Formalin after the concentration, the wherein a concentration of 55wt%-85wt% of formaldehyde, Feed space velocities 0.2-
0.8h-1；
The reactor, in temperature be 75 DEG C -120 DEG C, pressure 0-0.5MPa；
The reactor, the interior catalyst loaded are macropore cation resin, superpower acid resin, preferably triumphant auspicious ring
It is D006 types acid resin catalyst or D008 type high temperature resistant acidic resin catalysts to protect Science and Technology Ltd.'s production.
(2) it extracts：Step (1) obtain product entered in extraction tower from the inlet I on top, extractant from lower part into
Liquid mouth II is entered in extraction tower, and the two inversely contacts to be extracted；The bottom of tower of extraction tower obtains dilute first containing formaldehyde
Aldehyde solution through liquid outlet II outflows and is sent into dilute formaldehyde recovery line；The tower top of extraction tower is obtained containing metaformaldehyde and extraction
The extract liquor for taking agent is sent to followed by liquid outlet I, inlet III in knockout tower；
The extraction tower, in temperature be 50-75 DEG C, pressure 0-1MPa；
The extraction tower, in extractant be esters extractant, ketone extractant, ether extration agent, alcohols extraction
Any one in agent, phenols extractant, two kinds or more the mixtures mixed with arbitrary proportion；
The mass ratio that the extractant obtains product with step (1) is 3~6:1.
(3) rectifying detaches：The extract liquor containing metaformaldehyde and extractant that step (2) obtains, occurs in knockout tower
Rectifying detaches, and the bottom of tower of knockout tower obtains the metaformaldehyde of liquid, through liquid outlet III outflows and is sent into metaformaldehyde finished product pipeline
Middle harvesting；The tower top of knockout tower obtains gaseous extractant, is sent in condenser followed by gas outlet, import II；Gaseous state
Extractant it is condensed formed liquid extractant after be sent in return tank；Fluid extractant in return tank is in reflux pump
Under effect, a part is returned in extraction tower by inlet II and is recycled, and another part returns to knockout tower by inlet IV
In flow back；
The knockout tower, tower top temperature are 60-80 DEG C, pressure 0-1MPa；Column bottom temperature is 75-125 DEG C, and pressure is
0-1MPa；
The reflux, reflux ratio 0.5-1.0:1.
The advantages of technical solution of the present invention, is：Formalin after concentration is sent into reactor and reacted by this method,
Liquid after reaction is sent into extraction tower, is inversely extracted with the extractant being added from lower part, bottom of tower is obtained containing the dilute of formaldehyde
Formalin is sent into dilute formaldehyde recovery unit, and tower top obtains the extract liquor containing metaformaldehyde and extractant, which enters
Extract liquor knockout tower is detached, and obtains high-purity metaformaldehyde by rectifying column bottom, recovered overhead extractant recycles.It should
Apparatus structure is simple, and small investment, low energy consumption.
Description of the drawings
Fig. 1：The flow chart of the synthesis extracting process of metaformaldehyde of the present invention；
Fig. 2：The structural schematic diagram of the synthesis extraction equipment of metaformaldehyde of the present invention；
Wherein：1, reactor, 2, extraction tower, 3, knockout tower, 4, condenser, 5, return tank, 6, reflux pump, 7, reboiler.
Specific implementation mode
The specific implementation mode of technical solution of the present invention is described in detail below, but the present invention is not limited in being described below
Hold：
The main innovation point of the method for the present invention is：Formalin after concentration is sent into reactor and reacted by this method,
Liquid after reaction is sent into extraction tower, is inversely extracted with the extractant being added from lower part, bottom of tower is obtained containing the dilute of formaldehyde
Formalin is sent into dilute formaldehyde recovery unit, and tower top obtains the extract liquor containing metaformaldehyde and extractant, which enters
Knockout tower is detached, and by rectifying, bottom of tower obtains high-purity metaformaldehyde, and recovered overhead extractant recycles.This method
Have the advantages that significant equipment investment is few, simple for process, low energy consumption with device.
The present invention provides a kind of synthesis extraction equipment of metaformaldehyde, including sequentially connected reactor 1, extraction tower 2, point
From tower 3 and metaformaldehyde finished product pipeline, the formalin after concentration is reacted in the reactor as raw material, and product passes through successively
Enter in metaformaldehyde finished product pipeline after extraction, separation, as shown in Figure 2：
The reactor is equipped with import I and outlet I：Import I is connected with the device for providing raw material；
The extraction tower, top is equipped with liquid outlet I, top is equipped with inlet I, lower part is equipped with inlet II, bottom is set
There is liquid outlet II：Inlet I is connected with the outlet I of reactor, and liquid outlet II is connected with dilute formaldehyde recovery line, inlet II with
The device for being capable of providing extractant is connected；
The knockout tower, tower top is equipped with gas outlet, top is equipped with inlet IV, middle part is equipped with inlet III, bottom is set
There is liquid outlet III：Inlet III is connected with the liquid outlet I of extraction tower, and liquid outlet III is connected with metaformaldehyde finished product pipeline, goes out
Gas port is connected with condenser 4；
The condenser 4 is equipped with import II and outlet II：Import II is connected with the gas outlet of knockout tower, and outlet II connects
It is connected to return tank 5；
The return tank 5 is equipped with import III and outlet III：Import III is connected with the outlet II of condenser, outlet
III is connected with reflux pump 6；
The reflux pump 6 is equipped with import IV and outlet IV：Import IV is connected with the outlet III of return tank, IV points of outlet
For two-way, it is connected all the way with the inlet II of extraction tower, another way is connected with the inlet IV of knockout tower；
The knockout tower, tower lower part (boiling evaporator section again) are equipped with reboiler 7.
Preferably, the reactor is fixed bed reactors, and built with catalyst, which is macroporous cation
The D006 types of any one in resin, superpower acid resin, further preferably Kai Rui environmental protective chemical industries limited liability company production
Acid resin catalyst, D008 type high temperature resistant acidic resin catalysts.
Preferably, the extraction tower, built with extractant, extractant is esters extractant, ketone extractant, ether
Any one in kind of extractants, alcohol kind of extractants, phenols extractant, two kinds or more the mixing mixed with arbitrary proportion
Object.
Preferably, the extraction tower, tower is interior to be filled with internals, and internals are any one in filler, column plate；
Preferably, the knockout tower, tower is interior to be filled with internals, and internals are any one in filler, column plate.
The present invention also provides a kind of synthesis extracting process of metaformaldehyde, flow chart is as shown in Figure 1：
(1) polymerisation：Using the formalin after concentration as raw material, raw material is sent to through import I in reactor, at it
Polymerisation is carried out under the catalytic action of interior catalyst, the obtained product after reaction send followed by outlet I, inlet I
Enter into extraction tower；
(2) it extracts：Step (1) obtain product entered in extraction tower from the inlet I on top, extractant from lower part into
Liquid mouth II is entered in extraction tower, and the two inversely contacts to be extracted；The bottom of tower of extraction tower obtains dilute first containing formaldehyde
Aldehyde solution through liquid outlet II outflows and is sent into dilute formaldehyde recovery line；The tower top of extraction tower is obtained containing metaformaldehyde and extraction
The extract liquor for taking agent is sent to followed by liquid outlet I, inlet III in knockout tower；
(3) rectifying detaches：The extract liquor containing metaformaldehyde and extractant that step (2) obtains, occurs in knockout tower
Rectifying detaches, and the bottom of tower of knockout tower obtains the metaformaldehyde of liquid, through liquid outlet III outflows and is sent into metaformaldehyde finished product pipeline
Middle harvesting；The tower top of knockout tower obtains gaseous extractant, is sent in condenser followed by gas outlet, import II；Gaseous state
Extractant it is condensed formed liquid extractant after be sent in return tank；Fluid extractant in return tank is in reflux pump
Under effect, a part is returned in extraction tower by inlet II and is recycled, and another part returns to knockout tower by inlet IV
In flow back.
The method of the present invention is described in detail with reference to embodiment：
Embodiment 1：
A kind of synthetic method of metaformaldehyde, includes the following steps：
(1) a concentration of 65% formalin of 1000kg/h is added to fixed bed reactors 1 (wherein from import I
The catalyst of filling is D006, and air speed is 0.35h-1) in, it is reacted under 105 DEG C, the reaction condition of 0.2MPa；It is anti-from fixed bed
The outlet I of device is answered to obtain the formalin containing metaformaldehyde of 1000kg/h, wherein 520kg/h containing metaformaldehyde, formaldehyde
130kg/h；
(2) product that step (1) obtains is entered from the inlet I on 2 top of extraction tower in extraction tower, and from extraction tower 2
At 65 DEG C counter-current extraction occurs for the extractant toluene for the 1560kg/h that the inlet II of lower part is added under the conditions of 0.1MPa；From extraction
The liquid outlet I at 2 top of tower is taken to obtain the extract liquor of 2080kg/h, wherein 520kg/h containing metaformaldehyde, toluene 1560kg/h, from
Inlet III enters knockout tower 3；Dilute formalin of 480kg/h is obtained from the liquid outlet II of 2 bottom of extraction tower, wherein
130kg/h containing formaldehyde is sent into dilute aldehyde recovery line.
(3) the 2080kg/h extract liquors that the tower top of step (2) extraction tower obtains are sent in knockout tower 3, in bottom of tower temperature
Degree is 120 DEG C, and tower top temperature is 70 DEG C, rectifying separation under conditions of pressure is 0.1MPa；Liquid outlet from 3 bottom of knockout tower
III obtains the metaformaldehyde of 520kg/h, is sent in metaformaldehyde finished product pipeline；It is obtained from the gas outlet at 3 top of knockout tower
The toluene of 1560kg/h is sent to followed by gas outlet, import II in condenser；Toluene within the condenser after condensation according to
Secondary to flow through return tank, reflux pump, a part is returned in extraction tower by inlet II and is recycled；Another part is by inlet IV
Back to (the reflux ratio 0.75 that flowed back in knockout tower:1).
The metaformaldehyde that the present embodiment is produced, formaldehyde conversion per pass are 80%, and total conversion 100%, metaformaldehyde is received
Rate is 99.77%.
Embodiment 2：
A kind of metaformaldehyde synthetic method, other process conditions and method are same as Example 1, only its initial feed
For 70% concentrated formaldehyde of 500kg/h, extractant is the benzene of 1400kg/h, and the operating condition of extraction tower 2 is：75 DEG C of tower body temperature,
Tower pressure is normal pressure；The operating condition of extract liquor knockout tower 3 is：130 DEG C of column bottom temperature, 85 DEG C, pressure 0.2MPa of tower top temperature,
The metaformaldehyde of 280kg/h is finally obtained, formaldehyde total conversion is 100%, yield 99.45%.
Examples detailed above is technical concept and technical characterstic to illustrate the invention, can not limit the present invention's with this
Protection domain.The equivalent transformation or modification that all essence according to the present invention is done, should all cover in protection scope of the present invention
Within.
Claims (10)
1. a kind of synthesis extracting process of metaformaldehyde, which is characterized in that include the following steps：
(1) polymerisation：Using the formalin after concentration as raw material, raw material is under the catalytic action of catalyst, in temperature
75 DEG C -120 DEG C, pressure carries out polymerisation under conditions of being 0-0.5MPa and generates metaformaldehyde；
(2) it extracts：The product that step (1) obtains is under the action of extractant, temperature is 50-75 DEG C, pressure is 0-1MPa's
Under the conditions of extracted, respectively obtain dilute formalin containing formaldehyde and the extract liquor containing metaformaldehyde and extractant；Contain
There is dilute formalin of formaldehyde to recycle；
(3) rectifying detaches：The extract liquor containing metaformaldehyde and extractant that step (2) obtains is 60-125 DEG C, presses in temperature
Power carries out rectifying separation under conditions of being 0-1MPa, obtains the metaformaldehyde of liquid and gaseous extractant, the trimerization first of liquid
Aldehyde harvests；Gaseous extractant forms the extractant of liquid by condensation, and the extractant of liquid is flowed back and/or recycled.
2. according to the method described in claim 1, it is characterized in that, specifically including following steps：
(1) polymerisation：Using the formalin after concentration as raw material, raw material is sent to through import I in reactor, in it
Polymerisation is carried out under the catalytic action of catalyst, the obtained product after reaction is sent to followed by outlet I, inlet I
In extraction tower；
(2) it extracts：Step (1) obtains that product is entered from the inlet I on top in extraction tower, extractant is from the inlet of lower part
II is entered in extraction tower, and the two inversely contacts to be extracted；It is molten that the bottom of tower of extraction tower obtains dilute formaldehyde containing formaldehyde
Liquid through liquid outlet II outflows and is sent into dilute formaldehyde recovery line；The tower top of extraction tower is obtained containing metaformaldehyde and extractant
Extract liquor, be sent in knockout tower followed by liquid outlet I, inlet III；
(3) rectifying detaches：The extract liquor containing metaformaldehyde and extractant that step (2) obtains, occurs rectifying in knockout tower
Separation, the bottom of tower of knockout tower obtain the metaformaldehyde of liquid, through being adopted in liquid outlet III outflows and feeding metaformaldehyde finished product pipeline
It receives；The tower top of knockout tower obtains gaseous extractant, is sent in condenser followed by gas outlet, import II；Gaseous extraction
It is sent in return tank after taking the condensed extractant for forming liquid of agent；The effect of fluid extractant in return tank in reflux pump
Under, a part by inlet II back to recycling in extraction tower, another part by inlet IV back in knockout tower into
Row reflux.
3. according to the method described in claim 2, it is characterized in that, in step (1), the formalin after the concentration,
A concentration of 55wt%-85wt% of middle formaldehyde, Feed space velocities 0.2-0.8h-1；The reactor, in temperature be 75
DEG C -120 DEG C, pressure 0-0.5MPa；The reactor, the interior catalyst loaded are macropore cation resin, super acids
Resin.
4. according to the method described in claim 2, it is characterized in that, in step (2), the extractant is obtained with step (1)
The mass ratio of product is 3~6:1；The extraction tower, in temperature be 50-75 DEG C, pressure 0-1MPa；The extraction
Tower, in extractant be esters extractant, ketone extractant, ether extration agent, alcohol kind of extractants, appointing in phenols extractant
Meaning is a kind of, two kinds or more the mixtures mixed with arbitrary proportion.
5. according to the method described in claim 2, it is characterized in that, in step (3), the knockout tower, tower top temperature 60-
80 DEG C, pressure 0-1MPa, column bottom temperature are 75-125 DEG C, pressure 0-1MPa；The reflux, reflux ratio 0.5-1.0:1.
6. a kind of synthesis extraction equipment of metaformaldehyde, including sequentially connected reactor (1), extraction tower (2), knockout tower (3)
With metaformaldehyde finished product pipeline, the formalin after concentration is reacted in the reactor as raw material, product successively through extraction,
Enter in metaformaldehyde finished product pipeline after separation, it is characterised in that：
The reactor is equipped with import I and outlet I：Import I is connected with the device for providing raw material；
The extraction tower, top is equipped with liquid outlet I, top is equipped with inlet I, lower part is equipped with inlet II, bottom is equipped with out
Liquid mouth II：Inlet I is connected with the outlet I of reactor, and liquid outlet II is connected with dilute formaldehyde recovery line, inlet II with can
The device for providing extractant is connected；
The knockout tower, tower top is equipped with gas outlet, top is equipped with inlet IV, middle part is equipped with inlet III, bottom is equipped with out
Liquid mouth III：Inlet III is connected with the liquid outlet I of extraction tower, and liquid outlet III is connected with metaformaldehyde finished product pipeline, gas outlet
It is connected with condenser (4)；
The condenser (4) is equipped with import II and outlet II：Import II is connected with the gas outlet of knockout tower, exports II connections
There is return tank；
The return tank (5) is equipped with import III and outlet III：Import III is connected with the outlet II of condenser, exports III
It is connected with reflux pump；
The reflux pump (6) is equipped with import IV and outlet IV：Import IV is connected with the outlet III of return tank, and IV points of outlet is
Two-way is connected with the inlet II of extraction tower all the way, and another way is connected with the inlet IV of knockout tower.
7. device according to claim 6, it is characterised in that：The reactor is fixed bed reactors, built with
Catalyst；The extraction tower, built with extractant.
8. device according to claim 7, it is characterised in that：The catalyst is macropore cation resin, super acids
Any one in resin；The extractant is esters extractant, ketone extractant, ether extration agent, alcohol kind of extractants, phenol
Any one in kind of extractants, two kinds or more the mixtures mixed with arbitrary proportion.
9. device according to claim 6, it is characterised in that：The extraction tower, tower is interior to be filled with internals, and internals are to fill out
Material, any one in column plate；The knockout tower, tower is interior to be filled with internals, and internals are any one in filler, column plate.
10. device according to claim 6, it is characterised in that：The knockout tower, tower lower part are equipped with reboiler (7).
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| CN109180636A (en) * | 2018-11-08 | 2019-01-11 | 凯瑞环保科技股份有限公司 | It is a kind of to extract the device and method that synthesizing triformol is coupled with catalysis technique |
| CN109369607A (en) * | 2018-11-15 | 2019-02-22 | 凯瑞环保科技股份有限公司 | A kind of device and method of azeotropic catalysis reaction synthesizing triformol |
| CN110156747A (en) * | 2019-04-16 | 2019-08-23 | 天津大学 | A kind of partition wall reactive distillation manufacturing technique method and device for metaformaldehyde |
| CN110256399A (en) * | 2019-07-29 | 2019-09-20 | 凯瑞环保科技股份有限公司 | A kind of device and method that methylal oxidation produces metaformaldehyde |
| CN110437045A (en) * | 2019-08-26 | 2019-11-12 | 江苏道尔顿石化科技有限公司 | A kind of no alkali cleaning method preparation high-purity metaformaldehyde separating technology |
| CN110467595A (en) * | 2019-08-26 | 2019-11-19 | 江苏道尔顿石化科技有限公司 | A kind of no sulfuric acid process metaformaldehyde synthesizer and its synthesis route |
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| CN109180636A (en) * | 2018-11-08 | 2019-01-11 | 凯瑞环保科技股份有限公司 | It is a kind of to extract the device and method that synthesizing triformol is coupled with catalysis technique |
| CN109180636B (en) * | 2018-11-08 | 2023-08-08 | 凯瑞环保科技股份有限公司 | Device and method for synthesizing trioxymethylene by coupling extraction and catalysis technology |
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