CN105949061A - Process and device for recovering dimethyl carbonate by steam permeation method - Google Patents
Process and device for recovering dimethyl carbonate by steam permeation method Download PDFInfo
- Publication number
- CN105949061A CN105949061A CN201610391089.8A CN201610391089A CN105949061A CN 105949061 A CN105949061 A CN 105949061A CN 201610391089 A CN201610391089 A CN 201610391089A CN 105949061 A CN105949061 A CN 105949061A
- Authority
- CN
- China
- Prior art keywords
- dimethyl carbonate
- water
- methanol
- membrane separator
- permeable membrane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 238000000034 method Methods 0.000 title claims abstract description 38
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 180
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 152
- 239000012528 membrane Substances 0.000 claims abstract description 139
- 238000004821 distillation Methods 0.000 claims abstract description 74
- 238000000605 extraction Methods 0.000 claims abstract description 68
- 239000007788 liquid Substances 0.000 claims abstract description 60
- 238000000895 extractive distillation Methods 0.000 claims abstract description 29
- 238000011084 recovery Methods 0.000 claims abstract description 5
- 239000007921 spray Substances 0.000 claims abstract description 3
- 230000035515 penetration Effects 0.000 claims description 68
- 239000012466 permeate Substances 0.000 claims description 27
- 239000006200 vaporizer Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000012535 impurity Substances 0.000 claims description 16
- 239000000284 extract Substances 0.000 claims description 15
- 238000009834 vaporization Methods 0.000 claims description 15
- 230000008016 vaporization Effects 0.000 claims description 15
- 239000010410 layer Substances 0.000 claims description 14
- 238000009833 condensation Methods 0.000 claims description 10
- 230000005494 condensation Effects 0.000 claims description 10
- 239000000470 constituent Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 6
- 229920000620 organic polymer Polymers 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012044 organic layer Substances 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- 238000005832 oxidative carbonylation reaction Methods 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 239000004408 titanium dioxide Substances 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 25
- 239000006227 byproduct Substances 0.000 abstract description 6
- GUNDKLAGHABJDI-UHFFFAOYSA-N dimethyl carbonate;methanol Chemical compound OC.COC(=O)OC GUNDKLAGHABJDI-UHFFFAOYSA-N 0.000 abstract description 5
- 239000005416 organic matter Substances 0.000 abstract description 2
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 24
- 239000012530 fluid Substances 0.000 description 13
- 230000000149 penetrating effect Effects 0.000 description 12
- 238000000429 assembly Methods 0.000 description 6
- 230000000712 assembly Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- -1 Dimethyl carbonate-methanol Chemical compound 0.000 description 5
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 5
- 230000006315 carbonylation Effects 0.000 description 5
- 238000005810 carbonylation reaction Methods 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
- 239000002808 molecular sieve Substances 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 150000002148 esters Chemical group 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UCVQOIPQDBZRMG-UHFFFAOYSA-N [C].COC(C=1C(C(=O)OC)=CC=CC1)=O Chemical compound [C].COC(C=1C(C(=O)OC)=CC=CC1)=O UCVQOIPQDBZRMG-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 231100000004 severe toxicity Toxicity 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- QNLVXLJTOLHAMA-UHFFFAOYSA-N N=NC=NN.N=NC=NN.C(O)(O)=O Chemical compound N=NC=NN.N=NC=NN.C(O)(O)=O QNLVXLJTOLHAMA-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000003747 fuel oil additive Substances 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005373 pervaporation Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 230000035943 smell Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/08—Purification; Separation; Stabilisation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a process and a device for recovering dimethyl carbonate by a vapor permeation method, wherein the specific process comprises the following steps: and (3) removing partial by-products from the reaction liquid after primary distillation, and allowing the methanol-dimethyl carbonate azeotrope to enter from the middle part of the extractive distillation tower and contact with spray water at the top of the extractive distillation tower for extraction and separation. Separating the liquid at the bottom of the extraction tower into methanol by a vapor permeation membrane separator, and returning the water and the trace dimethyl carbonate to the top of the extraction tower after heat exchange; after the distillate at the top of the extraction tower is separated by the separator, the water layer at the bottom of the separator returns to the extraction tower, the organic matter layer at the upper part of the separator is further heated and enters a steam permeable membrane separator to separate high-concentration dimethyl carbonate, the dimethyl carbonate enters a dimethyl carbonate storage tank after being condensed by a condenser, and the permeating water returns to the top of the extraction tower after heat exchange. The invention has the advantages of simple process, high safety coefficient, less equipment investment, high energy utilization rate and high recovery rate.
Description
Technical field
The present invention relates to a kind of technique reclaiming dimethyl carbonate and device, particularly relate to a kind of vapor permeation and reclaim carbon
The technique of dimethyl phthalate and device, belong to vapor permeable membrane application.
Background technology
Dimethyl carbonate is called for short DMC, is a kind of water white transparency, slightly abnormal smells from the patient, micro-sweet liquid, can be formed with water under room temperature
Azeotropic mixture, is a kind of important organic synthesis intermediate.DMC can replace the phosgene of severe toxicity to make carbonyl agent, is also a kind of simultaneously
Novel fuel oil additive and green solvent.The physics special due to it and chemical property, few with in application process producing
Environment is produced and pollutes, be described as " green " Organic chemical products, " the new foundation stone " of organic synthesis, at home and abroad draw attention.
The production method of dimethyl carbonate mainly has phosgenation and the big class of non-phosgene two.Phosgenation with the phosgene of severe toxicity is
Raw material, the general enterprise only producing phosgene produces DMC nearby and it is necessary to use careful safety measure.Meanwhile, because of phosgene
In containing chlorine, in finished product, the content of chlorine is higher, limits application and the development of DMC.Non-phosgene is divided into again ester-interchange method and first
Alcohol oxidation carbonylation method, has the advantages such as yield is high, corrosion-free, nontoxic, commonly used by some developing countries.
Due to thermodynamic (al) restriction, obtained by general rectification in the production process of dimethyl carbonate is methanol and carbonic acid
The azeotropic mixture of dimethyl ester, dimethyl carbonate can not be kept completely separate out by common rectificating method at all, it is impossible to obtains more high-purity
The DMC of degree.Typically requiring and carry out extracting rectifying or variable-pressure rectification etc. on the basis of conventional distillation again, separation process is the most multiple
Miscellaneous, equipment investment is higher, and observable index is relatively big, the requirement of serious non-compliance " green production ".
Be difficult to separate for traditional separation method or indissociable nearly boiling point, constant boiling point organic mixture solution point
From, pervaporation membrane, as emerging membrane separation technique, is comparatively ideal selection.Its principle is with in organic mixture each group
Point steam pressure difference is motive force, utilizes what the difference of each component dissolubility in film and diffusion velocity caused to diffuse through film
Speed difference realize the process that separates, its prominent advantage is high efficiency, low energy consumption can to realize distillation, extract and absorption etc.
The separation task that traditional method has been difficult to.
Summary of the invention
The present invention proposes a kind of vapor permeation and reclaims technique and the device of dimethyl carbonate, its object is to safely,
Efficiently, energy-conservation recovery dimethyl carbonate.Water vapour penetration technology utilizes and is existed by each component in separation liquid (or steam) mixture
The character that in film, dissolving (absorption) is different from diffusion rate reaches the purpose separated, and separation process is not limited by component VLE
System, it is possible to realize distill with low energy consumption, extract, separation task that traditional method such as absorption has been difficult to, replacement conventional carbon
Dimethyl phthalate recovery technology has broad application prospects.It is simple that the method has technical process, and safety coefficient is high, equipment investment
Few, capacity usage ratio is high, the feature that the response rate is high.
According to the first aspect of the invention:
A kind of vapor permeation reclaims the technique of dimethyl carbonate, comprises the steps:
A), the dimethyl carbonate feed liquid prepared by ester-interchange method or oxidative carbonylation of methanol method is adopted use water as
Carry out extractive distillation for extract, realize separating to unreacted methanol and dimethyl carbonate;
B), to the heavy constituent obtained after extractive distillation sending in the first vapor permeable membrane and separate, per-meate side obtains methanol, cuts
Side is stayed to obtain water;
C), to the light component obtained after extractive distillation sending in the second vapor permeable membrane and separate, per-meate side obtains water, retains
Side obtains dimethyl carbonate.
In one embodiment, before reaction feed liquid is carried out extractive distillation, by the way of distillation, heavy constituent is removed miscellaneous
Matter.
In one embodiment, for the light component obtained in step c, after needing to be first passed through condensation, layering, will
Upper organic layer is sent in the second vapor permeable membrane and is separated;The lower aqueous layer that layering obtains returns the charging of extractive distillation.
In one embodiment, during extractive distillation, reaction feed liquid is to feed at the middle part of extraction distillation column.
In one embodiment, in step b, heavy constituent needed heating vaporization, temperature before entering the first vapor permeable membrane
Spend preferably 100~150 DEG C.
In one embodiment, in step c, light component is sent into before separating in the second vapor permeable membrane to be needed into one
Step heating, temperature preferably 100~150 DEG C.
In one embodiment, step b retains the water that in the water and/or step c that side obtains, per-meate side obtains be back to
Spray as extract during extractive distillation.
In one embodiment, the liquid of the heavy constituent sending into the first vapor permeable membrane consist of water 85~96%, methanol 4
~15%, dimethyl carbonate < 5%.
In one embodiment, the liquid of the light component sending into the second vapor permeable membrane consist of dimethyl carbonate 85~
97%, water 0.1~10%, methanol < 5%.
In one embodiment, the first vapor permeable membrane is preferential Organic substance film thoroughly;Second vapor permeable membrane is preferential saturating
Moisture film;Membrane material is the combination of one or more in molecular screen membrane, amorphous silica film or organic polymer films.
In one embodiment, in step b and/or step c, the side gauge that retains of vapor permeable membrane can be 0~1
MPa, the absolute pressure of per-meate side can be 0~10000 Pa.
According to the second aspect of the invention:
A kind of vapor permeation reclaims the device of dimethyl carbonate, includes extraction distillation column, the top of described extraction distillation column
Portion arranges filler, and the middle part of extraction distillation column is reaction feed liquid port;The bottom of extraction distillation column and the first vapor permeable membrane
The feed liquid port of separator connects;The top of extraction distillation column is connected with the feed liquid port of the second water vapour penetration membrane separator.
In one embodiment, also include primary distillation tower, the outlet of primary distillation tower and the reaction feed liquid port of extraction distillation column
Connect.
Also including layering tank, the top of extraction distillation column is connected with the feed liquid port of layering tank, and the top of layering tank is again
Being connected with the feed liquid port of the second water vapour penetration membrane separator, the bottom of layering tank is connected to the charging aperture of extraction distillation column.
In one embodiment, the per-meate side of the first water vapour penetration membrane separator is connected with methanol tank;Second steam oozes
The side that retains of permeable membrane separator is connected with dimethyl carbonate storage tank.
In one embodiment, the first water vapour penetration membrane separator retain side and/or the second water vapour penetration membrane separator
Per-meate side be connected with the top of extraction distillation column.
In one embodiment, the film that the first water vapour penetration membrane separator is used is preferential Organic substance film thoroughly;Second steams
The film that vapour permeable membrane separator is used is preferential water permeable membrane;First water vapour penetration membrane separator and/or the second vapor permeable membrane
The membrane material of separator is the combination of one or more in molecular screen membrane, amorphous silica film or organic polymer films.
In one embodiment, the first water vapour penetration membrane separator and the second water vapour penetration membrane separator can be by 1
~100 vapor permeation membrane component series, parallel or series-parallel connection mode combine.
In one embodiment, the bottom of extraction distillation column is by the first vaporizer and the first water vapour penetration membrane separator
Feed liquid port connect;Also including the second vaporizer, it is for carrying out the feed liquid entering the second water vapour penetration membrane separator
Heating.
Beneficial effect
Compared with traditional separating technology, the present invention reclaims dimethyl carbonate by water vapour penetration membrane separator, is not limited by azeotropic
System, it is possible to obtain the dimethyl carbonate product of higher purity, simple to operate, the response rate is high.By adding water, simply extract
Take distillation and can reach dimethyl carbonate and methanol separates largely, make follow-up steam infiltration processing pressure reduce.Enter
In the feed liquid of the second water vapour penetration membrane separator containing a small amount of methanol advantageously in film to dimethyl carbonate and the separation of water
And the stable operation of film.The feed liquid entered in the first water vapour penetration membrane separator contains only a small amount of methanol, enters the second steam
Feed liquid in permeable membrane separator contains only a small amount of water so that the process load of vapor permeable membrane is less, and membrane area is less.
Accompanying drawing explanation
Fig. 1 is the process chart reclaiming dimethyl carbonate in embodiment;
Wherein, 1, primary distillation tower;2, extractive distillation column;3, the first pump;4, the first vaporizer;5, the first water vapour penetration membrane separator;
6, the first condenser;7, methanol tank;8, the first vacuum pump;9, the second condenser, 10, layering tank, the 11, second pump, 12, second
Vaporizer, the 13, second water vapour penetration membrane separator;14, the 3rd condenser;15, the second vacuum pump;16, surge tank;17, the 4th
Condenser;18, dimethyl carbonate storage tank.
Detailed description of the invention
Heretofore described percentage ratio is in the case of without special instruction, all referring to mass percent.
Being primarily directed to by ester-interchange method and methanol oxidation of the technique of recovery dimethyl carbonate provided by the present invention
Carbonylation method prepares the reaction feed liquid obtained in dimethyl carbonate, mainly can be containing the dimethyl carbonate, the most anti-generated in feed liquid
The methanol that should complete, water, byproduct of reaction impurity etc., obtained by general rectification is the azeotropic of methanol and dimethyl carbonate
Thing, dimethyl carbonate can not be kept completely separate out by common rectificating method at all, it is impossible to obtains the DMC of higher degree.
Using device as shown in Figure 1, the method for the present invention, mainly first passing through adds water in reaction feed liquid extracts
Take rectification, by the higher intersolubility of water and methanol, break the methanol and dimethyl carbonate formed in substance system straight run distillation
Azeotropic mixture, the dimethyl carbonate of water, methanol and trace enters the bottom of extractive distillation and distillates, and dimethyl carbonate and a small amount of water
Separate out from separator upper part, by the way of extractive distillation, achieve the initial gross separation of methanol and dimethyl carbonate.
It follows that for bottoms material, carry out methanol by the first water vapour penetration membrane separator and separate with water, used
Film be preferential Organic substance film thoroughly, make crossover of methanol film layer, retain the water that side obtains and return in extraction tower, returning of water can be improved
By rate.In a typical embodiment, enter the first water vapour penetration membrane separator consist of water 85~96%, methanol 4~
15%, dimethyl carbonate < 5%.
After distillating the separation of steam separated device for tower top, the organic matter layer on separator top sends into the second water vapour penetration
Membrane separator carries out water and separates with dimethyl carbonate, and the film used is preferential water permeable membrane, makes water pass through film layer, retains side and obtain
To dimethyl carbonate finished product, per-meate side water can also be back in extraction distillation column as extract;A typical enforcement
In mode, enter the first water vapour penetration membrane separator consist of dimethyl carbonate 85~97%, water 0.1~10%, methanol is less than
5%.After having obtained dimethyl carbonate finished product trapped fluid, its storage tank is passed through nitrogen and protects.
In one embodiment, preferably by the mode of predistillation, pre-treatment is carried out for reaction mass, permissible
Get rid of the heavy constituent in a part of reaction system, be re-fed into the light component distilled out in extractive distillation step processing, it is possible to
Make the product purity finally given higher.
In one embodiment, for the light component produced by extractive distillation tower top, it is overheated to be directly over
Send into the second water vapour penetration membrane separator and separate after device heating, owing to extractive distillation process at relatively high temperatures still can be by
A part of water is brought in overhead components, in another embodiment, and can be to the light component warp produced by extractive distillation tower top
After crossing condensation, layered shaping, the organic layer on its top is carried out overheated rear feeding water vapour penetration membrance separation, by the water layer bottom it
It is back to the charging of extractive distillation column, Water circulation can be made.
In some embodiments, the first water vapour penetration membrane separator and the second water vapour penetration membrane separator can be by
1~100 vapor permeation membrane component series, parallel or series-parallel connection mode combine.
In some embodiments, the membrane material of the first water vapour penetration membrane separator and the second water vapour penetration membrane separator is
The combination of one or more in molecular screen membrane, amorphous silica film or organic polymer films.
In practical operation, the first water vapour penetration membrane separator and the second water vapour penetration membrane separator retain side gauge pressure model
Enclosing can be 0~1 MPa, and the absolute pressure of per-meate side can be 0~10000 Pa.Extraction tower bottom liquid enters the first water vapour penetration
Before membrane separator, need to be heated to 100~150 DEG C;Extraction tower overhead-liquid enter the second water vapour penetration membrane separator it
Before, needing to be heated to 100~150 DEG C, it is vacuum draw that penetrating fluid enters the mode of condenser.
According to above-mentioned method, device of the present invention as shown in Figure 1: primary distillation tower 1 is for carrying out reaction feed liquid
Predistillation, removes heavy constituent, and tower top is connected with the middle part charging aperture of extractive distillation column 2, for light component is sent into extraction essence
Evaporating in step, the top of extractive distillation column 2 is provided with water and adds entrance, for addition water in tower as extract, and logical at the bottom of tower
Crossing the first pump 3 to be connected with the first vaporizer 4, for tower bottom liquid carries out heating vaporization, the outlet of the first vaporizer 4 is again with first
The entrance of water vapour penetration membrane separator 5 connects, for heavy constituent at the bottom of tower (mainly methanol, water, trace carbon dimethyl phthalate) point
From, the per-meate side of the first water vapour penetration membrane separator 5 is connected with the first condenser 6, methanol tank the 7, first vacuum pump 8 in turn,
The methanol that per-meate side is obtained can be condensed, collect.And the tower top of extractive distillation column 2 by after the second condenser 9 with point
Layer tank 10 connects, and the effect of layering tank 10 is that the light component to the tower top through condensation carries out layered shaping, and the water layer of bottom returns
Return extraction distillation column 2 reuse again, and the azeotropic nitride layer on upper strata is re-fed into the second water vapour penetration membrane separator 13 and separates, therefore
The bottom of layering tank 10 is connected with the middle part charging aperture of extractive distillation column 2, and the top of layering tank 10 is by the second pump 11 and second
Vaporizer 12 connects, and vaporizer for carrying out heating vaporization to feed liquid, and the outlet of the second vaporizer 12 is oozed with the second steam again
Permeable membrane separator 13 connects, for light component (mainly water and dimethyl carbonate) is separated, and the second water vapour penetration membrane separator
Being connected with the 3rd condenser the 14, second vacuum pump 15, surge tank 16 in 13 per-meate side in turn, surge tank 16 is used for receiving per-meate side
Water, the entrance retaining side of surge tank 16 and the first water vapour penetration membrane separator 5 top with extractive distillation column 2 again is connected,
For by Water circulation;Second water vapour penetration membrane separator 13 retain after side carries out heat exchange connection by the 4th condenser 17,
It is connected with dimethyl carbonate storage tank 18 again.
Embodiment 1
The reactant liquor using ester exchange reaction to prepare in dimethyl carbonate is added primary distillation tower 1, is part by-product at the bottom of tower, tower top
For dimethyl carbonate-methanol azeotropic mixture, and trace impurity, azeotropic temperature about 63 DEG C.Dimethyl carbonate-methanol azeotropic mixture enters
After extraction distillation column 2 and water carry out extract and separate, it is about the water of 95%, the methanol of 5% at the bottom of extraction distillation column 2 tower and is less than 0.05%
Dimethyl carbonate and trace impurity mixture.Controlling flow is that 90kg/h water-methanol-dimethyl carbonate enters the first vaporizer
4, enter into after vaporization and carried out dealcoholysis by the first water vapour penetration membrane separator 5 that 4 MFI molecular screen membrane assemblies are in series and divide
From.In first water vapour penetration membrane separator 5, feeding temperature is 120 DEG C, film retain side gauge pressure 0.23MPa, per-meate side absolute pressure
10000Pa.Crossover of methanol vapor permeable membrane in feed liquid enters methanol tank 7, infiltration after penetrating fluid the first condenser 6 condenses
Liquid methanol content is 97.5%;Feed liquid water content to 98.7%, returns to extraction distillation column 2 top by membrance separation concentration.Extraction
After distillation column 2 overhead components layered tank 10 separates, the water layer of layering tank 10 bottom is back to extraction distillation column 2 charging aperture, point
Layer tank 10 top is the dimethyl carbonate of 96.8%, the water of 2.5% and the methanol less than 0.5% and the mixture of impurity.Control flow
Enter the second vaporizer 12 for 90kg/h water-methanol-dimethyl carbonate, enter into after vaporization by 4 NaA molecular sieve membrane component string
The second water vapour penetration membrane separator 13 that connection is constituted carries out dehydration and separates.In second water vapour penetration membrane separator 13, temperature is 120
DEG C, film retain side gauge pressure 0.24MPa, per-meate side absolute pressure 5000Pa.Water in feed liquid condenses through the 3rd through vapor permeable membrane
Entering surge tank 16 after device 14 condensation and return to extraction distillation column 2 top, penetrating fluid water content is 98.7%;Feed liquid carbonic acid diformazan
Ester content to 98.4%, returns to extraction distillation column 2 top by membrance separation concentration.
Embodiment 2
Enter adding extraction distillation column 2 after the reactant liquor using ester exchange reaction to prepare in dimethyl carbonate heating vaporization with water
After row extract and separate, it is the water of 92%, the methanol of 5% and the dimethyl carbonate less than 3% and trace impurity at the bottom of extraction distillation column 2 tower
Mixture.Controlling flow is that 90kg/h water-methanol-dimethyl carbonate enters the first vaporizer 4, enters into by 4 MFI after vaporization
Molecular screen membrane assembly the first water vapour penetration membrane separator 5 in series carries out dealcoholysis separation.First water vapour penetration membrane separator 5
Middle feeding temperature is 120 DEG C, film retain side gauge pressure 0.23MPa, per-meate side absolute pressure 10000Pa.Crossover of methanol in feed liquid steams
Vapour permeable membrane enters methanol tank 7 after penetrating fluid the first condenser 6 condenses, and penetrating fluid methanol content is 93.4%;Feed liquid is aqueous
Amount, by membrance separation concentration to 96.3%, returns to extraction distillation column 2 top.10 points of the layered tank of extraction distillation column 2 overhead components
From rear, the water layer of layering tank 10 bottom is back to extraction distillation column 2 charging aperture, and layering tank 10 top is the carbonic acid diformazan of 94.2%
Ester, the water of 2.2% and the methanol less than 1.5% and the mixture of impurity.Controlling flow is 90kg/h water-methanol-dimethyl carbonate
Enter the second vaporizer 12, after vaporization, enter into the second water vapour penetration membrance separation in series by 4 NaA molecular sieve membrane assemblies
Device 13 carries out dehydration and separates.In second water vapour penetration membrane separator 13, temperature is 120 DEG C, film retain side gauge pressure 0.24MPa, ooze
Side absolute pressure 5000Pa thoroughly.Water in feed liquid enters surge tank 16 through vapor permeable membrane after the 3rd condenser 14 condensation and returns to
Extraction distillation column 2 top, penetrating fluid water content is 95.6%;Feed liquid DMC addition by membrance separation concentration to 96.6%,
Return to extraction distillation column 2 top.
Embodiment 3
The reactant liquor using methanol carbonylation to prepare in dimethyl carbonate is added primary distillation tower 1, is part by-product at the bottom of tower, tower
Top is dimethyl carbonate-methanol azeotropic mixture, and trace impurity, azeotropic temperature 63 DEG C.Dimethyl carbonate-methanol azeotropic mixture enters
After extraction distillation column 2 and water carry out extract and separate, it is about the water of 94%, the methanol of 6% at the bottom of extraction distillation column 2 tower and is less than 0.05%
Dimethyl carbonate ternary and trace impurity mixture.Controlling flow is that 180kg/h water-methanol-dimethyl carbonate enters first
Vaporizer 4, enters into the first water vapour penetration membrane separator 5 by 6 MFI molecular screen membrane assemblies are in series and takes off after vaporization
Alcohol separates.In first water vapour penetration membrane separator 5, feeding temperature is 120 DEG C, film retain side gauge pressure 0.23MPa, per-meate side is exhausted
Pressure 2000Pa.Crossover of methanol vapor permeable membrane in feed liquid enters methanol tank 7 after penetrating fluid the first condenser 6 condenses, and oozes
Transparent liquid methanol content is 97.6%;Feed liquid water content to 98.4%, returns to extraction distillation column 2 top by membrance separation concentration.Extraction
After taking the separation of distillation column 2 overhead components layered tank 10, the water layer of layering tank 10 bottom is back to extraction distillation column 2 charging aperture,
Layering tank 10 top is about the dimethyl carbonate of 97%, the water of 2.5% and the methanol less than 0.5% and mixtures of impurities.Control flow
Enter the second vaporizer 12 for 180kg/h water-methanol-dimethyl carbonate, enter into after vaporization by 6 NaA molecular sieve membrane modules
Second water vapour penetration membrane separator 13 in series carries out dehydration and separates.In second water vapour penetration membrane separator 13, temperature is
120 DEG C, film retain side gauge pressure 0.24MPa, per-meate side absolute pressure 2000Pa.Water in feed liquid passes through the condensed device of vapor permeable membrane
Entering surge tank 16 after 14 condensations and return to extraction distillation column 2 top, penetrating fluid water content is 98.2%;Feed liquid dimethyl carbonate
Content to 97.9%, returns to extraction distillation column 2 top by membrance separation concentration.
Embodiment 4
The reactant liquor using methanol carbonylation to prepare in dimethyl carbonate is added primary distillation tower 1, is part by-product at the bottom of tower, tower
Top is dimethyl carbonate-methanol azeotropic mixture, and trace impurity, azeotropic temperature 63 DEG C.Dimethyl carbonate-methanol azeotropic mixture enters
After extraction distillation column 2 and water carry out extract and separate, it is about the water of 95%, the methanol of 5% at the bottom of extraction distillation column 2 tower and is less than 0.05%
Dimethyl carbonate and the mixture of trace impurity.Controlling flow is that 250kg/h water-methanol-dimethyl carbonate enters the first steaming
Send out device 4, enter into the first water vapour penetration membrane separator 5 by 8 MFI molecular screen membrane assemblies are in series after vaporization and carry out dealcoholysis
Separate.In first water vapour penetration membrane separator 5, feeding temperature is 100 DEG C, film retain side gauge pressure 0.12MPa, per-meate side absolute pressure
1000Pa.Crossover of methanol vapor permeable membrane in feed liquid enters methanol tank 7, penetrating fluid methanol after the first condenser 6 condensation
Content is 99.2%;Feed liquid water content to 99.8%, returns to extraction distillation column 2 top by membrance separation concentration.Extraction distillation column 2
After overhead components layered tank 10 separates, the water layer of layering tank 10 bottom is back to extraction distillation column 2 charging aperture, on layering tank 10
Portion is about the dimethyl carbonate of 97%, the water of 2.5% and the methanol of 0.5% and trace impurity mixture.Control flow is 250kg/h
Water-methanol-dimethyl carbonate enters the second vaporizer 12, enters into by 8 NaA molecular sieve membrane assemblies in series after vaporization
Second water vapour penetration membrane separator 13 carries out dehydration and separates.In second water vapour penetration membrane separator 13, feeding temperature is 100 DEG C, film
Retain side gauge pressure 0.13MPa, per-meate side absolute pressure 1000Pa.After water in feed liquid condenses through vapor permeable membrane condensed device 14
Entering surge tank 16 and return to extraction distillation column 2 top, penetrating fluid water content is 99.7%;Feed liquid DMC addition is passed through
Membrance separation concentration, to 99.7%, returns to extraction distillation column 2 top.
Embodiment 5
The reactant liquor using methanol carbonylation to prepare in dimethyl carbonate is added primary distillation tower 1, is part by-product at the bottom of tower, tower
Top is dimethyl carbonate-methanol azeotropic mixture, and trace impurity, azeotropic temperature 63 DEG C.Dimethyl carbonate-methanol azeotropic mixture enters
After extraction distillation column 2 and water carry out extract and separate, it is about the water of 94%, the methanol of 5% at the bottom of extraction distillation column 2 tower and is less than 0.05%
Dimethyl carbonate and the mixture of trace impurity.Controlling flow is that 250kg/h water-methanol-dimethyl carbonate enters the first steaming
Send out device 4, enter into the first water vapour penetration membrane separator 5 by 8 MFI molecular screen membrane assemblies are in series after vaporization and carry out dealcoholysis
Separate.In first water vapour penetration membrane separator 5, feeding temperature is 100 DEG C, film retain side gauge pressure 0.12MPa, per-meate side absolute pressure
1000Pa.Crossover of methanol vapor permeable membrane in feed liquid enters methanol tank 7, penetrating fluid methanol after the first condenser 6 condensation
Content is 98.5%;Feed liquid water content to 98.9%, returns to extraction distillation column 2 top by membrance separation concentration.Extraction distillation column 2
Overhead components is about the dimethyl carbonate of 93%, the water of 5.5% and the methanol of 0.5% and trace impurity mixture, controls its flow and is
250kg/h water-methanol-dimethyl carbonate is directly entered the second vaporizer 12, enters into by 8 NaA molecular sieve membrane groups after vaporization
Part the second water vapour penetration membrane separator 13 in series carries out dehydration and separates.Charging temperature in second water vapour penetration membrane separator 13
Degree is 100 DEG C, film retain side gauge pressure 0.13MPa, per-meate side absolute pressure 1000Pa.Water in feed liquid passes through vapor permeable membrane through cold
Entering surge tank 16 after condenser 14 condensation and return to extraction distillation column 2 top, penetrating fluid water content is 98.8%;Feed liquid carbonic acid two
Methyl ester content to 99.1%, returns to extraction distillation column 2 top by membrance separation concentration.
Claims (9)
1. the technique that a vapor permeation reclaims dimethyl carbonate, it is characterised in that comprise the steps:
A), the dimethyl carbonate feed liquid prepared by ester-interchange method or oxidative carbonylation of methanol method is adopted use water as
Carry out extractive distillation for extract, realize separating to unreacted methanol and dimethyl carbonate;
B), to the heavy constituent obtained after extractive distillation sending in the first vapor permeable membrane and separate, per-meate side obtains methanol, cuts
Side is stayed to obtain water;
C), to the light component obtained after extractive distillation sending in the second vapor permeable membrane and separate, per-meate side obtains water, retains
Side obtains dimethyl carbonate.
The technique that vapor permeation the most according to claim 1 reclaims dimethyl carbonate, it is characterised in that to reaction feed liquid
Before carrying out extractive distillation, by the way of distillation, remove heavy constituent impurity;For the light component obtained in step c, need by
After it first passes through condensation, layering, upper organic layer is sent in the second vapor permeable membrane and separate;The lower floor that layering obtains
Water layer returns the charging of extractive distillation;During extractive distillation, reaction feed liquid is to feed at the middle part of extraction distillation column.
The technique that vapor permeation the most according to claim 1 reclaims dimethyl carbonate, it is characterised in that in step b, weight
Component needed heating vaporization, temperature preferably 100~150 DEG C before entering the first vapor permeable membrane;In step c, light component is sent
Enter and need before the second vapor permeable membrane separates to heat further, temperature preferably 100~150 DEG C.
The technique that vapor permeation the most according to claim 1 reclaims dimethyl carbonate, it is characterised in that cut in step b
The water that in the water and/or step c that side obtains, per-meate side obtains is stayed to spray as extract during being back to extractive distillation;
Send into the first vapor permeable membrane heavy constituent consist of water 85~96%, methanol 4~15%, dimethyl carbonate < 5%;Send into second
The light component of vapor permeable membrane consist of dimethyl carbonate 85~97%, water 0.1~10%, methanol < 5%.
The technique that vapor permeation the most according to claim 1 reclaims dimethyl carbonate, it is characterised in that the first steam oozes
Permeable membrane is preferential Organic substance film thoroughly;Second vapor permeable membrane is preferential water permeable membrane;Membrane material is molecular screen membrane, amorphous titanium dioxide
The combination of one or more in silicon fiml or organic polymer films;In step b and/or step c, vapor permeable membrane retain side table
Pressure scope can be 0~1 MPa, and the absolute pressure of per-meate side can be 0~10000 Pa.
6. the device of a vapor permeation recovery dimethyl carbonate, it is characterised in that include extraction distillation column (2), described
The top of extraction distillation column (2) filler is set, the middle part of extraction distillation column (2) is reaction feed liquid port;Extraction distillation column
(2) bottom is connected with the feed liquid port of the first water vapour penetration membrane separator (5);The top of extraction distillation column (2) is steamed with second
The feed liquid port of vapour permeable membrane separator (13) connects.
Vapor permeation the most according to claim 6 reclaims the device of dimethyl carbonate, it is characterised in that at the beginning of also including
Evaporating tower (1), the outlet of primary distillation tower (1) is connected with the reaction feed liquid port of extraction distillation column (2);Also include layering tank (10),
The top of extraction distillation column (2) is connected with the feed liquid port of layering tank (10), and the top of layering tank (10) is oozed with the second steam again
The feed liquid port of permeable membrane separator (13) connects, and the bottom of layering tank (10) is connected to the charging aperture of extraction distillation column (2).
Vapor permeation the most according to claim 6 reclaims the device of dimethyl carbonate, it is characterised in that the first steam oozes
The per-meate side of permeable membrane separator (5) is connected with methanol tank (7);Second water vapour penetration membrane separator (13) retain side and carbonic acid
Dimethyl ester storage tank (18) connects;First water vapour penetration membrane separator (5) retain side and/or the second water vapour penetration membrane separator
(13) per-meate side is connected with the top of extraction distillation column (2).
Vapor permeation the most according to claim 6 reclaims the device of dimethyl carbonate, it is characterised in that the first steam oozes
The film that permeable membrane separator (5) is used is preferential Organic substance film thoroughly;The film that second water vapour penetration membrane separator (13) is used is
Preferential water permeable membrane;The membrane material of the first water vapour penetration membrane separator (5) and/or the second water vapour penetration membrane separator (13) is molecule
The combination of one or more in sieve membrane, amorphous silica film or organic polymer films;First water vapour penetration membrane separator
And the second water vapour penetration membrane separator (13) can be by 1~100 vapor permeation membrane component series, parallel or series-parallel connection (5)
Mode combines;The bottom of extraction distillation column (2) is by the first vaporizer (4) and the first water vapour penetration membrane separator (5)
Feed liquid port connect;Also including the second vaporizer (12), it is for entering the second water vapour penetration membrane separator (13)
Feed liquid heats.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610391089.8A CN105949061A (en) | 2016-06-06 | 2016-06-06 | Process and device for recovering dimethyl carbonate by steam permeation method |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610391089.8A CN105949061A (en) | 2016-06-06 | 2016-06-06 | Process and device for recovering dimethyl carbonate by steam permeation method |
Publications (1)
Publication Number | Publication Date |
---|---|
CN105949061A true CN105949061A (en) | 2016-09-21 |
Family
ID=56907703
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610391089.8A Pending CN105949061A (en) | 2016-06-06 | 2016-06-06 | Process and device for recovering dimethyl carbonate by steam permeation method |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN105949061A (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108440306A (en) * | 2018-05-24 | 2018-08-24 | 梁小朝 | A kind of device and method of the green production of tetramethyl ammonium carbonate |
CN108939592A (en) * | 2018-09-29 | 2018-12-07 | 天津中福环保科技股份有限公司 | A kind of dangerous waste process field medium-high viscosity solvent recovery unit, its skid structure and method |
CN109534999A (en) * | 2018-11-30 | 2019-03-29 | 太原理工大学 | A kind of synthesis technology and device of dimethyl carbonate |
CN111100004A (en) * | 2019-12-30 | 2020-05-05 | 江苏奥克化学有限公司 | Method and integrated device for refining dimethyl carbonate |
CN115572215A (en) * | 2022-10-24 | 2023-01-06 | 浙江汇甬新材料有限公司 | Separation method of methanol and dimethyl carbonate azeotrope by membrane separation coupled rectification |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1218031A (en) * | 1997-11-24 | 1999-06-02 | 化学工业部西南化工研究设计院 | Process for separating dimethyl carbonate by water extraction rectification |
-
2016
- 2016-06-06 CN CN201610391089.8A patent/CN105949061A/en active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1218031A (en) * | 1997-11-24 | 1999-06-02 | 化学工业部西南化工研究设计院 | Process for separating dimethyl carbonate by water extraction rectification |
Non-Patent Citations (3)
Title |
---|
MASAKAZU KONDO ET AL.: "Permeation mechanism through zeolite NaA and T-type membranes for practical dehydration of organic solvents", 《JOURNAL OF MEMBRANE SCIENCE》 * |
WOOYOUNG WON ET AL.: "Pervaporation with chitosan membranes: separation of dimethyl carbonate/methanol/water mixtures", 《JOURNAL OF MEMBRANE SCIENCE》 * |
李洪亮等: "蒸汽渗透技术及其应用", 《膜科学与技术》 * |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108440306A (en) * | 2018-05-24 | 2018-08-24 | 梁小朝 | A kind of device and method of the green production of tetramethyl ammonium carbonate |
CN108440306B (en) * | 2018-05-24 | 2023-11-03 | 柏川新材料科技(宁波)有限公司 | Green production equipment and method of tetramethyl ammonium carbonate |
CN108939592A (en) * | 2018-09-29 | 2018-12-07 | 天津中福环保科技股份有限公司 | A kind of dangerous waste process field medium-high viscosity solvent recovery unit, its skid structure and method |
CN109534999A (en) * | 2018-11-30 | 2019-03-29 | 太原理工大学 | A kind of synthesis technology and device of dimethyl carbonate |
CN109534999B (en) * | 2018-11-30 | 2021-08-10 | 潞安化工集团有限公司 | Synthesis process and device of dimethyl carbonate |
CN111100004A (en) * | 2019-12-30 | 2020-05-05 | 江苏奥克化学有限公司 | Method and integrated device for refining dimethyl carbonate |
CN111100004B (en) * | 2019-12-30 | 2022-07-08 | 江苏奥克化学有限公司 | Method and integrated device for refining dimethyl carbonate |
CN115572215A (en) * | 2022-10-24 | 2023-01-06 | 浙江汇甬新材料有限公司 | Separation method of methanol and dimethyl carbonate azeotrope by membrane separation coupled rectification |
CN115572215B (en) * | 2022-10-24 | 2024-04-30 | 浙江汇甬新材料有限公司 | Separation method of methanol and dimethyl carbonate azeotrope through coupling and rectification of membrane separation |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN105949061A (en) | Process and device for recovering dimethyl carbonate by steam permeation method | |
TWI421121B (en) | Low-energy extractive distillation process for dehydration of aqueous ethanol | |
CN105418368B (en) | A kind of technique and device for producing high straight alcohol | |
CN101143803B (en) | Method for separating dimethyl carbonate and methanol azeotrope | |
CN101372442B (en) | Apparatus and method for separating tert-butanol and water using batch fractionating and pervaporation | |
US9138678B2 (en) | Membrane-augmented distillation with compression and condensation to separate solvents from water | |
KR20100068488A (en) | Method for dewatering a mixture of mostly ethanol and water | |
CN103071307A (en) | Rectification-steam penetration-coupled organic solvent dewatering method and device | |
CN103449967B (en) | Process and device for increasing yield of acetone-hydrogenation isopropanol production | |
CN110938047B (en) | Tetrahydrofuran-benzene-water mixture separation process and device | |
CN104370698B (en) | The technique of a kind of infiltration evaporation-compression rectification integrated purification methylcarbonate and methyl alcohol | |
CN107628930A (en) | A kind of heat pump separation of extractive distillation methanol, the energy saving technique of isopropyl alcohol and water | |
CN108059597A (en) | Method and device for producing ethyl acetate by integrating reactive distillation and pervaporation | |
CN106542975B (en) | The method of continuous production high-purity triethylene glycol | |
CN106117120B (en) | A kind of technique and device of rectifying-Steam soak coupled method recycling pyridine | |
CN104370699B (en) | The technique of the integrated separating dimethyl carbonate of a kind of infiltration evaporation-atmospheric distillation and methyl alcohol | |
CN104610018B (en) | Method for separating ethanol fermentation liquid | |
CN104926655A (en) | Technology and device for diethyl oxalate synthesis through vapor permeation dehydration process | |
CN103772202A (en) | Method for separating methanol-dimethyl carbonate azeotropic liquid | |
CN102887816B (en) | Method for preparing dichloropropanol with chemical reaction-pervaporation coupling method | |
CN103613480B (en) | Device and method for recycling low-concentration organic solvent | |
CN100408531C (en) | Process for producing high concentration tert-butyl alcohol by permeation vaporization method and products therefrom | |
CN109231635A (en) | A kind of dichloroethanes/ethane nitrile wastewater New Process for Treatment | |
CN106883209B (en) | A kind of preparation process of dioxolanes | |
CN103772144B (en) | Method for separating acetone-butanol-ethanol fermentation liquor by pervaporation-rectification coupling |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160921 |
|
RJ01 | Rejection of invention patent application after publication |