CN107353188A - A kind of method for preparing anhydrous gaseous formaldehyde - Google Patents
A kind of method for preparing anhydrous gaseous formaldehyde Download PDFInfo
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- CN107353188A CN107353188A CN201610306090.6A CN201610306090A CN107353188A CN 107353188 A CN107353188 A CN 107353188A CN 201610306090 A CN201610306090 A CN 201610306090A CN 107353188 A CN107353188 A CN 107353188A
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- formaldehyde
- alcohol
- anhydrous gaseous
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- methanol
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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
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/38—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group
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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
- C07C45/783—Separation; Purification; Stabilisation; Use of additives by gas-liquid treatment, e.g. by gas-liquid absorption
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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
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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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
- C07C45/85—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to a chemical modification
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of method for preparing anhydrous gaseous formaldehyde, methods described sequentially includes：(1) carry out formaldehyde and prepare reaction；(2) formaldehyde in alcohol absorption step (1) is used to prepare the product reacted；And (3) by the product heats in previous step to 125 to 180 DEG C to discharge anhydrous gaseous formaldehyde.By the present invention, anhydrous gaseous formaldehyde can be directly obtained, and technique is simple, flow is short, and more other anhydrous gaseous formaldehyde preparation method energy consumptions are greatly reduced, and avoid the participation of extra water, so as to which wastewater discharge is also greatly decreased.
Description
Technical field
The present invention relates to a kind of method for preparing anhydrous gaseous formaldehyde, and in particular to by using alcohol as condensation
Agent prepares the formaldehyde in the product of reaction to absorb formaldehyde, then heats absorbent so as to discharge no aqueous vapor
The method of phase formaldehyde.
Background technology
Formaldehyde is a kind of important Organic Ingredients in chemical field, and its property is active, mainly as production agriculture
The raw material of the materials such as medicine glyphosate, phenolic resin, Lauxite, polyacetal resin, melamine resin and centre
Body, it is widely used in coating and field of pesticides.
The method of industrial production formaldehyde is very ripe at present, uses methanol oxidizing process mostly, i.e., in silver, copper etc.
In the presence of metallic catalyst Oxidation of Methanol is to generate the method for formaldehyde, here, in the oxidizing gas of generation
All using water come spray-absorption formaldehyde in absorption, so as to finally give 37%-40% formalin.
But required in the production process of many products using anhydrous formaldehyde, such as resinae, special agricultural chemicals
Class etc., and demand is larger.Obtain anhydrous formaldehyde, it is necessary to which presently commercially available formalin is entered
Row distillation operation, this will not only put into more considerable equipment, operating cost, and formaldehyde can also be with water shape
Into azeotropic mixture, the difficulty of separation is further increased.Or, it is desirable to it can also be adopted in anhydrous reaction
With paraformaldehyde, still, the preparation process of paraformaldehyde is also required to formalin being concentrated by evaporation, dried
Deng can equally consume substantial amounts of energy, this is not economic and environment-friendly enough.It also proposed in recent years in catalyst
In the presence of make methanol direct dehydrogenation generation formaldehyde and hydrogen method, the method reaction after do not generate water, can
Directly obtain anhydrous formaldehyde.However, the problem of methods described is present is catalyst easily poisoning and inactivation, circulation
Utilization rate is poor, thus also only resides within laboratory demonstration and improved stage, there is not yet large-scale production
Report.
Therefore, according to the current method by producing formaldehyde by methanol oxidation, a kind of new production nothing is developed
The technique of water beetle aldehyde has very big value and application prospect.
The content of the invention
[technical problem]
This invention address that a kind of method for preparing anhydrous gaseous formaldehyde of exploitation, methods described can directly obtain nothing
Water gaseous formaldehyde, and technique is simple, flow is short, and more other anhydrous gaseous formaldehyde preparation method energy consumptions are significantly
Reduce, avoid the participation of extra water, so as to which wastewater discharge is also greatly decreased.
[technical scheme]
According to an aspect of the invention, there is provided a kind of method for preparing anhydrous gaseous formaldehyde, methods described
Sequentially include：(1) carry out formaldehyde and prepare reaction；(2) formaldehyde in alcohol absorption step (1) is used to prepare instead
The product answered；And the gains in previous step are heated to 125 to 180 DEG C to discharge nothing by (3)
Water gaseous formaldehyde.
According to an embodiment of the invention, wherein, the formaldehyde prepares reaction and not limited particularly,
As long as it is the process that formaldehyde is generated by chemically reacting, for example, it may include methanol oxidizing process, day
Right gas oxidizing process, methanol dehydrogenation method etc..Preferably, formaldehyde preparation process of the invention is methanol oxidizing process,
The process of generation formaldehyde is aoxidized by methanol, its main reaction process is as shown in following formula 1.
[formula 1]
CH3OH+1/2O2→H2O+HCHO
Also, during the oxidation generation formaldehyde by methanol, used catalyst is this area
Catalysis oxidation methanol is to be made the custom catalystses of formaldehyde, for example, copper, silver catalyst, but the present invention is not
It is only limitted to this.
It is above-described first when the formaldehyde prepares reaction in addition, according to an embodiment of the invention
During alcohol oxidizing process, because the product in the methanol oxidizing process includes water, so the preparation of the present invention is without aqueous vapor
The method of phase formaldehyde is still further comprised between step (2) and (3) by the suction of gained in step (2)
Thing is received to be evaporated under reduced pressure with dewatered process.
According to another implementation of the invention, the formaldehyde prepares reaction and can also be natural gas oxidizing process
Or methanol dehydrogenation method etc..Wherein, the main reaction such as following formula of the natural gas oxidizing process (namely for methane oxidizing process)
Shown in 2.
[formula 2]
CH4+O2→H2O+HCHO
Also, in the natural gas oxidizing process, used catalyst is this area catalytically oxidizing natural gas
(methane) be made formaldehyde custom catalystses, for example, MoO3/SiO2、V2O5/SiO2、Cr2O3/SiO2、
Fe-Mo-Co、Mo/ZrO2Deng catalyst, but the present invention is not limited to this.It is further, since described natural
Product in gas oxidizing process also includes water, so the present invention's prepares the method for anhydrous gaseous formaldehyde in step (2)
(3) can also further comprise the absorbent of gained in step (2) being evaporated under reduced pressure between to remove moisture
Process.
Wherein, the main reaction of the methanol dehydrogenation method is as shown in following formula 3.
[formula 3]
CH3OH→H2+HCHO
Also, in the methanol dehydrogenation method, used catalyst is this area catalysis methanol direct dehydrogenation
So that the custom catalystses of formaldehyde are made, for example, Ag/SiO2-ZnO、Ag/SiO2The catalyst such as-MgO, but
The present invention is not limited to this.In addition, although the main reaction of the methanol dehydrogenation method does not produce water, but according to
Need, the method for preparing anhydrous gaseous formaldehyde of the invention also can be between step (2) and (3) further
Including the absorbent of gained in step (2) is evaporated under reduced pressure with dewatered process.
In the present invention, the product that the formaldehyde prepares reaction be gas phase, and it refers to chemically reacting from passing through
Generate the derived gas-phase product mixture for including formaldehyde, the gas-phase product mixture in the reactor of formaldehyde
May contain unreacted raw material (such as methanol, oxygen, CO), reaction product (for example, formaldehyde,
Water, hydrogen etc.) and other foreign gases and/or side reaction product gas etc., wherein the formaldehyde included can
To generate hemiacetal with alcohol in procedure described above (2), so as to be dissolved in alcohol, meanwhile, alcohol is again
The good solvent of formaldehyde, thus the alcohol not still condensing agent of formaldehyde, or the solvent of formaldehyde.
Therefore, according to an embodiment of the invention, the alcohol can be selected from saturation unitary, binary,
One or more in more polynary aliphatic alcohol and polyethylene glycol, poly- propyl alcohol etc..In addition, it is optional, when
When the alcohol is aliphatic alcohol, one or more hydrogen on its alkyl chain part can also be by other substituent institutes
Substitution, the substituent can be, for example, methyl, hydroxymethyl, cyclohexyl etc..
Preferably, the alcohol can be one kind or more in cyclohexanol, nonyl alcohol, polyethylene glycol and glycerine
Kind.By using alcohol enumerated above, formaldehyde can be quickly dissolved and absorbed.
Preferably, the alcohol can be the polyethylene glycol that weight average molecular weight is 200 to 400.In addition, formaldehyde
Maximum level in the polyethylene glycol that the weight average molecular weight is 200 to 400 is 50wt%, herein,
The maximum level refers to the concept of the amount for the whole formaldehyde that can enter in the polyethylene glycol phase, i.e., at this
With the amount of whole formaldehyde existing for hemiacetal state and free state in polyethylene glycol.
Wherein, in step (2), the mol ratio that the alcohol prepares the formaldehyde in product with step (1) is
0.1-3:1, preferably 0.5-1.5:1, more preferably 1:1.
Wherein, the temperature conditionss when gas-phase product is absorbed by alcohol are 10-100 DEG C, preferably 30-80 DEG C,
More preferably 60 DEG C.At this temperature, alcohol can effectively dissolve the formaldehyde in the gas-phase product and be formed therewith
Hemiacetal.
In the present invention, the reactor for implementing the step (2) does not limit particularly, as long as it is can
Realize the reactor of the abundant exchange of gas-liquid, the example may include, but be not limited to, spray column etc. all
Plate column and packed tower etc..
According to an embodiment of the invention, the pressure of the vacuum distillation between the step (2) and (3)
Power condition is 100-10mmHg, preferably 40-10mmHg, more preferably 20mmHg, and the decompression
The temperature conditionss of distillation are 40 to 80 DEG C, preferably 50-70 DEG C, more preferably 68 DEG C.In this temperature and pressure
Under the conditions of, water that can to greatest extent in removing step (2) in the absorbent of gained, it is ensured that the present invention is most
The water content of anhydrous formaldehyde made from end minimizes, simultaneously because the decomposition bar for the hemiacetal that the present invention is formed
Part is more than 125 DEG C, therefore will not also cause the decomposition of hemiacetal in alcohol, avoids the loss of formaldehyde.
In the present invention, the reactor for implementing the vacuum distillation does not limit particularly, as long as it is can be real
The reactor being now evaporated under reduced pressure, the example may include, but be not limited to, thin film evaporation tower etc. all be applicable
Plate column and packed tower.It by the vacuum distillation process according to the present invention, can contain the dehydrate of generation
Water reaches 0.001-0.01wt%, preferably 0.001wt%.
According to an embodiment of the invention, the temperature conditionss of the process of step (3) are preferably 130-170 DEG C,
More preferably 140-160 DEG C；And pressure condition is normal pressure to 0.5MPa, preferably normal pressure to 0.4MPa,
More preferably normal pressure is to 0.2MPa.Under the conditions of this temperature and pressure, no water beetle can be obtained with stability and high efficiency
Aldehyde.
In the present invention, the reactor of implementation steps (3) does not limit particularly, as long as it is achievable
The reactor of temperature control heating, the example may include, but be not limited to, the tower knot such as plate column and packed tower
Structure, while reactor can also be used.
In the yield of the formaldehyde of preparation in accordance with the present invention, i.e. step (3) amount of the formaldehyde of release with
It is more than 92% that formaldehyde of the present invention, which prepares the ratio between amount of whole formaldehyde in the gas-phase product reacted,.
[beneficial effect]
, can be on the basis of the formaldehyde prepration process of routine by improving post-processing approach and straight according to the present invention
Anhydrous gaseous formaldehyde is obtained to obtain, the post-processing approach technique is simple, flow is short, water-soluble compared with formaldehyde is first made
Liquid and then rectifying and the post-processing approach energy consumption that obtains anhydrous formaldehyde or paraformaldehyde is greatly reduced, cost advantage
Significantly, and the participation of extra water is avoided, it is green so as to which wastewater discharge is also greatly decreased.
Brief description of the drawings
Fig. 1 schematically illustrates the post processing of the formaldehyde preparation process according to an embodiment of the invention
Technological process.
Reference
1st, methanol oxidizing tower
2nd, heat exchanger
3rd, spray absorber
4th, the top showerhead of spray column 3
5th, the offgas duct of spray column 3
6th, thin film evaporation tower
7th, the tower top pipeline of thin film evaporation tower 6
8th, it is pyrolyzed tower
9th, it is pyrolyzed the tower top pipeline of tower 8
Embodiment
Hereinafter, it will be described with reference to the accompanying drawings the preferred embodiment of the present invention.Although will be attached with reference to being illustrated in
Embodiment in figure describes the present invention, but it should be noted that embodiment provided by the present invention is only
As illustrating, and it is not intended to be limiting technical spirit and core element and the operation of the present invention.Do not departing from
On the premise of the technical spirit and scope of the present invention, illustrative embodiments of the invention can change in a variety of manners
Become.
As shown in figure 1, after the oxidized catalysis oxidation of tower 1 of methanol, the gas-phase product containing formaldehyde of generation from
Tower top is discharged, after carrying out heat exchange in the heat exchanger 2 so that temperature is changed into 10-100 DEG C, into spray column
3 bottom, meanwhile, use with the mol ratio of the formaldehyde included in gas-phase product as 0.1-3:1 cyclohexanol,
Nonyl alcohol, polyethylene glycol and/or glycerine etc. spray from the top showerhead 4 of spray column 3, and gas phase counter current contacting,
Do not discharged in gas phase by offgas duct 5 of the gas that above-described alcohol absorbs through tower top.Formaldehyde and a small amount of water warp
Alcohol absorbs, and a part of formaldehyde generation hemiacetal.
Afterwards, the absorbent obtained by said process is discharged by spray column bottom, into the top of thin film evaporation tower 6,
It is 100-10mmHg, preferably 40-10mmHg, more preferably 20mmHg in pressure, temperature is 40 to 80 DEG C
Under conditions of run thin film evaporation tower 6, the water in absorbent is discharged from tower top pipeline 7, thin film evaporation tower 6
Bottom of towe for water content 0.001-0.01wt% dehydrate.Herein, it is aqueous in dehydrate to ensure
Amount is low as far as possible, can be used in series multiple thin film evaporation towers and/or plate column, packed tower.
Afterwards, the dehydrate discharged by the bottom of towe of thin film evaporation tower 6 enters the top of pyrolysis tower 8, in pressure
For normal pressure to 0.5MPa, temperature is run the pyrolysis tower under conditions of being 125 to 180 DEG C, is pyrolyzed out
Formaldehyde gas is discharged by tower top pipeline 9, is final products, water content 1-0.1wt%.Bottom of towe is then liquid
The alcohol of phase, spray column 3 is returned by the road, is sprayed again by its top showerhead 4, recycled so as to realize.
Embodiment
Embodiment 1
The preparation that formaldehyde is carried out using methanol oxidizing process is reacted, and the gas that content of formaldehyde is 30% afterwards is from methanol
Column overhead discharge is aoxidized, temperature is down to after 60 DEG C, enters spray tower bottom with 330kg/h flow, together
When polyethylene glycol (weight average molecular weight 300) with 1000kg/h flows from spray column top spray, so as to
It is 16wt% to content of formaldehyde, content water is 5.4wt% formaldehyde absorption thing.The absorbent is through pump afterwards
Squeeze into thin film evaporation tower, be dehydrated, contained under conditions of 68 DEG C of temperature, vacuum 25mm mercury column
Water is 0.005wt% dehydrate.The dehydrate is passed through pyrolysis tower with 1100kg/h speed,
155 DEG C are pyrolyzed with heating under normal pressure, so as to obtain the formaldehyde gas that water content is 0.3wt%, yield 96%.
Calculation formula：The amount for the formaldehyde that formaldehyde yield=pyrolysis obtains/formaldehyde is prepared in the gas-phase product of reaction
The amount * 100% of formaldehyde
Embodiment 2
The preparation that formaldehyde is carried out using methanol oxidizing process is reacted, and the gas that content of formaldehyde is 30% afterwards is from methanol
Column overhead discharge is aoxidized, temperature is down to after 60 DEG C, enters spray tower bottom with 330kg/h flow, together
When glycerine with 320kg/h flows from spray column top spray, be 36.9wt% so as to obtain content of formaldehyde,
Content water is 14wt% formaldehyde absorption thing.The absorbent is squeezed into thin film evaporation tower through pump afterwards, in temperature
68 DEG C are spent, is dehydrated under conditions of vacuum 25mm mercury column, obtains the dehydrate that water content is 0.006wt%.
The dehydrate is passed through pyrolysis tower with 420kg/h speed, pyrolysis is heated under 155 DEG C and normal pressure, from
And the formaldehyde gas that water content is 0.4wt% is obtained, yield 92%.
Claims (10)
1. a kind of method for preparing anhydrous gaseous formaldehyde, methods described sequentially include：
(1) carry out formaldehyde and prepare reaction；
(2) formaldehyde in alcohol absorption step (1) is used to prepare the product reacted；And
(3) gains in previous step are heated to 125 to 180 DEG C to discharge anhydrous gaseous formaldehyde.
2. according to the method for claim 1, wherein, in step (1), the formaldehyde prepares reaction and uses methanol oxidizing process, natural gas oxidizing process or methanol dehydrogenation method；Optionally, between step (2) and (3), methods described, which still further comprises, is evaporated under reduced pressure the absorbent of gained in step (2) with dewatered process.
3. according to the method for claim 2, wherein, the pressure of the vacuum distillation is 100-10mmHg, preferably 40-10mmHg, more preferably 20mmHg.
4. according to the method for claim 2, wherein, the temperature of the vacuum distillation is 40 to 80 DEG C, preferably 50-70 DEG C, more preferably 68 DEG C.
5. method according to claim 1 or 2, wherein, the alcohol employed in step (2) is the one or more in saturation unitary, binary and more polynary aliphatic alcohol and polyethylene glycol.
6. according to the method for claim 5, wherein, the alcohol is the one or more in cyclohexanol, nonyl alcohol, polyethylene glycol and glycerine, it is preferable that the alcohol is the polyethylene glycol that weight average molecular weight is 200 to 400.
7. method according to claim 1 or 2, wherein, in step (2), the mol ratio that the alcohol prepares the formaldehyde in product with step (1) is 0.1-3:1, preferably 0.5-1.5:1, more preferably 1:1.
8. method according to claim 1 or 2, wherein, in step (2), the temperature when product is absorbed by the alcohol is 10-100 DEG C, preferably 30-80 DEG C, more preferably 60 DEG C.
9. method according to claim 1 or 2, wherein, the heating-up temperature in step (3) is preferably 130-170 DEG C, more preferably 140-160 DEG C.
10. method according to claim 1 or 2, wherein, the pressure in step (3) is normal pressure to 0.5MPa, preferably normal pressure to 0.4MPa, more preferably normal pressure to 0.2MPa.
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| CN201610306090.6A CN107353188A (en) | 2016-05-10 | 2016-05-10 | A kind of method for preparing anhydrous gaseous formaldehyde |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111440057A (en) * | 2020-05-27 | 2020-07-24 | 无锡赫利邦化工科技有限公司 | Preparation method for producing anhydrous formaldehyde by extractive distillation |
| CN111943822A (en) * | 2020-09-22 | 2020-11-17 | 凯瑞环保科技股份有限公司 | Device and method for producing high-concentration formaldehyde by using methanol |
| CN112521255A (en) * | 2019-09-19 | 2021-03-19 | 山东辰信新能源有限公司 | Preparation method of polyoxymethylene dimethyl ether and mixture thereof |
| WO2021052328A1 (en) * | 2019-09-19 | 2021-03-25 | 山东辰信新能源有限公司 | Preparation method for polyoxymethylene dimethyl ether and mixture thereof |
| CN112574013A (en) * | 2019-09-27 | 2021-03-30 | 山东辰信新能源有限公司 | Preparation method of polymethoxy dimethyl ether (DMMn) |
| CN112898134A (en) * | 2021-04-05 | 2021-06-04 | 山东辰信新能源有限公司 | Dehydration and catalytic synthesis method and device for polymethoxy dimethyl ether |
| CN114057543A (en) * | 2020-07-29 | 2022-02-18 | 山东辰信新能源有限公司 | Recovery method of ineffective carrier in DMMn synthesis process |
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| US3423368A (en) * | 1965-10-14 | 1969-01-21 | Hary E Cier | Extractive recovery of formaldehyde |
| CN103339094A (en) * | 2011-01-26 | 2013-10-02 | 宝理塑料株式会社 | Method for producing hemiformal concentrate and method for producing formaldehyde gas |
| CN104710292A (en) * | 2015-03-24 | 2015-06-17 | 江苏凯茂石化科技有限公司 | Method for refining anhydrous pure formaldehyde gas and process device |
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| US3423368A (en) * | 1965-10-14 | 1969-01-21 | Hary E Cier | Extractive recovery of formaldehyde |
| CN103339094A (en) * | 2011-01-26 | 2013-10-02 | 宝理塑料株式会社 | Method for producing hemiformal concentrate and method for producing formaldehyde gas |
| CN104710292A (en) * | 2015-03-24 | 2015-06-17 | 江苏凯茂石化科技有限公司 | Method for refining anhydrous pure formaldehyde gas and process device |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112521255A (en) * | 2019-09-19 | 2021-03-19 | 山东辰信新能源有限公司 | Preparation method of polyoxymethylene dimethyl ether and mixture thereof |
| WO2021052328A1 (en) * | 2019-09-19 | 2021-03-25 | 山东辰信新能源有限公司 | Preparation method for polyoxymethylene dimethyl ether and mixture thereof |
| CN112521255B (en) * | 2019-09-19 | 2023-07-14 | 山东辰信新能源有限公司 | Preparation method of polyoxymethylene dimethyl ether and mixture thereof |
| CN112574013A (en) * | 2019-09-27 | 2021-03-30 | 山东辰信新能源有限公司 | Preparation method of polymethoxy dimethyl ether (DMMn) |
| CN111440057A (en) * | 2020-05-27 | 2020-07-24 | 无锡赫利邦化工科技有限公司 | Preparation method for producing anhydrous formaldehyde by extractive distillation |
| CN114057543A (en) * | 2020-07-29 | 2022-02-18 | 山东辰信新能源有限公司 | Recovery method of ineffective carrier in DMMn synthesis process |
| CN114057543B (en) * | 2020-07-29 | 2023-09-15 | 山东辰信新能源有限公司 | Recovery method of failure carrier in DMMn synthesis process |
| CN111943822A (en) * | 2020-09-22 | 2020-11-17 | 凯瑞环保科技股份有限公司 | Device and method for producing high-concentration formaldehyde by using methanol |
| CN112898134A (en) * | 2021-04-05 | 2021-06-04 | 山东辰信新能源有限公司 | Dehydration and catalytic synthesis method and device for polymethoxy dimethyl ether |
| CN112898134B (en) * | 2021-04-05 | 2023-09-12 | 山东辰信新能源有限公司 | Dehydration and catalytic synthesis method and device for polymethoxy dimethyl ether |
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