CN113461246A - Method for recovering glycerol monomethyl ether and glycerol from epichlorohydrin wastewater - Google Patents
Method for recovering glycerol monomethyl ether and glycerol from epichlorohydrin wastewater Download PDFInfo
- Publication number
- CN113461246A CN113461246A CN202110929843.XA CN202110929843A CN113461246A CN 113461246 A CN113461246 A CN 113461246A CN 202110929843 A CN202110929843 A CN 202110929843A CN 113461246 A CN113461246 A CN 113461246A
- Authority
- CN
- China
- Prior art keywords
- membrane
- glycerol
- concentration
- monomethyl ether
- wastewater
- 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
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title claims abstract description 223
- 238000000034 method Methods 0.000 title claims abstract description 78
- 239000002351 wastewater Substances 0.000 title claims abstract description 68
- PSJBSUHYCGQTHZ-UHFFFAOYSA-N 3-Methoxy-1,2-propanediol Chemical compound COCC(O)CO PSJBSUHYCGQTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 63
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000012528 membrane Substances 0.000 claims abstract description 115
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 86
- 239000013505 freshwater Substances 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 29
- 238000000926 separation method Methods 0.000 claims abstract description 26
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000018044 dehydration Effects 0.000 claims abstract description 15
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 15
- 238000011033 desalting Methods 0.000 claims abstract description 8
- 235000011187 glycerol Nutrition 0.000 claims description 72
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 41
- 238000000909 electrodialysis Methods 0.000 claims description 37
- 239000011780 sodium chloride Substances 0.000 claims description 19
- 238000010612 desalination reaction Methods 0.000 claims description 17
- 238000010992 reflux Methods 0.000 claims description 13
- 238000009279 wet oxidation reaction Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 8
- 230000008020 evaporation Effects 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 238000007670 refining Methods 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 16
- 239000006227 byproduct Substances 0.000 abstract description 8
- 238000000746 purification Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 description 20
- 239000000047 product Substances 0.000 description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- 238000005265 energy consumption Methods 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- 238000004064 recycling Methods 0.000 description 8
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 238000003918 potentiometric titration Methods 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- OWXJKYNZGFSVRC-NSCUHMNNSA-N (e)-1-chloroprop-1-ene Chemical compound C\C=C\Cl OWXJKYNZGFSVRC-NSCUHMNNSA-N 0.000 description 1
- JQQJROWLUNBRMP-UHFFFAOYSA-N 1-chloro-1-methoxypropan-1-ol Chemical compound CCC(O)(Cl)OC JQQJROWLUNBRMP-UHFFFAOYSA-N 0.000 description 1
- OOJRTGIXWIUBGG-UHFFFAOYSA-N 2-methylpropane-1,2,3-triol Chemical compound OCC(O)(C)CO OOJRTGIXWIUBGG-UHFFFAOYSA-N 0.000 description 1
- SSZWWUDQMAHNAQ-UHFFFAOYSA-N 3-chloropropane-1,2-diol Chemical compound OCC(O)CCl SSZWWUDQMAHNAQ-UHFFFAOYSA-N 0.000 description 1
- 241000237536 Mytilus edulis Species 0.000 description 1
- 241000183024 Populus tremula Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007791 dehumidification Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 235000020638 mussel Nutrition 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/40—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation
- C07C41/42—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation by distillation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
Abstract
The invention provides a method for recovering glycerol monomethyl ether and glycerol from epichlorohydrin wastewater, which comprises the following steps: (1) desalting the epoxy chloropropane wastewater to obtain desalted fresh water; (2) the desalted fresh water is subjected to membrane concentration to obtain membrane concentrated water; (3) and the membrane concentrated water is subjected to secondary concentration and dehydration in sequence to obtain dehydrated materials, and the dehydrated materials are refined and separated to respectively obtain glycerol and glycerol monomethyl ether. The method realizes the separation and purification of the byproducts of the glycerol monomethyl ether and the glycerol in the water layer, and solves the difficult problems of resource recovery and comprehensive utilization of the epichlorohydrin byproduct.
Description
Technical Field
The invention relates to the technical field of resource recovery, in particular to a method for recovering glycerol monomethyl ether and glycerol from epichlorohydrin wastewater.
Background
Epichlorohydrin is a basic organic chemical raw material with wide application, is an intermediate for synthesizing glycerol, and is also a main raw material for synthesizing products such as epoxy resin, chlorohydrin rubber and the like. The prior production process of epoxy chloropropane comprises a chlorohydrin method, a glycerol method and a hydrogen peroxide oxidation method. The chlorohydrin method has the disadvantages of large amount of saline wastewater, high treatment cost and serious environmental pollution, and belongs to a restricted process. The glycerol process is subject to a supply of raw materials and cannot meet the ever-increasing market demand.
The hydrogen peroxide oxidation method adopts chloropropene as a raw material and hydrogen peroxide as an oxidant, and prepares epoxy chloropropane by catalytic epoxidation, and has the advantages of wide raw material source, high atom utilization rate and clean process route, thus becoming a focus of attention of researchers.
The method adopts a titanium silicalite molecular sieve as a catalyst to catalyze epoxy chloropropane by a hydrogen peroxide method, and generates wastewater in the post-treatment process, wherein the wastewater contains glycerol with a certain concentration and a glycerol monomethyl ether byproduct, and in addition, contains sodium chloride salt. The glycerol has wide application, can be used as intermediates of various chemical products, the glycerol monomethyl ether can be used as a solvent of agricultural chemical products, the byproducts are easy to dissolve in water and obviously cause resource waste if not recycled, the manufacturing cost of epoxy chloropropane by a hydrogen peroxide method is increased, but because the water layer has high salt content, the salt concentration is increased and separated out along with the increase of the material concentration in the process of distilling and recycling the glycerol and the glycerol monomethyl ether, the heat transfer efficiency of a heat exchanger is reduced, the separation energy consumption is improved, the coking of the heat exchanger is caused, the blocking risk of a circulating pump is increased, and the stable operation of a production device is seriously influenced.
CN106630083A and CN106630007A disclose methods for converting 3-chloro-1, 2-propanediol in epoxidized wastewater into glycerol and converting monochloropropanediol monomethyl ether into glycerol monomethyl ether by using an alkaline aqueous solution or a solid strong base catalyst to realize the non-toxicity and harmless treatment of the wastewater. The patent aims at improving the biodegradability of the wastewater and does not relate to the recovery of glycerol and glycerol monomethyl ether.
CN206705802U discloses a device for treating wastewater from epichlorohydrin production based on membrane separation technology, which can remove organic and inorganic impurities in wastewater better by performing adsorption and membrane filtration treatment on epichlorohydrin burning wastewater, and the treated wastewater can be concentrated and recovered to obtain salt with higher purity, but no mention is made about resource utilization of organic matters in water layer.
CN105621764B discloses a treatment process of epichlorohydrin production wastewater, which realizes resource utilization of salt in the wastewater by wet oxidation and photocatalytic oxidation technologies. However, the technology can not recover organic matters in the water layer, and the wet oxidation process has high temperature and high pressure, high requirement on equipment materials and large investment.
Aiming at the problems existing in the process of processing the epichlorohydrin byproduct in the prior technical scheme, the development of a recycling method of the epichlorohydrin wastewater is urgently needed.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for recovering glycerol monomethyl ether and glycerol from epichlorohydrin wastewater, which can effectively separate salt and organic matters in the wastewater, separate and purify byproducts of epichlorohydrin such as glycerol and glycerol monomethyl ether, realize resource recovery and comprehensive utilization, and has a wide application prospect.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for recovering glycerol monomethyl ether and glycerol from epichlorohydrin wastewater, which comprises the following steps:
(1) desalting the epoxy chloropropane wastewater to obtain desalted fresh water;
(2) the desalted fresh water is subjected to membrane concentration to obtain membrane concentrated water;
(3) and the membrane concentrated water is subjected to secondary concentration and dehydration in sequence to obtain dehydrated materials, and the dehydrated materials are refined and separated to respectively obtain glycerol and glycerol monomethyl ether.
The method for recovering the glycerol monomethyl ether and the glycerol from the epichlorohydrin wastewater provided by the invention realizes the concentration and recovery of organic substances in the epichlorohydrin wastewater, realizes the long-service life of the membrane by adopting a mode of combining membrane concentration and secondary concentration, greatly reduces the energy consumption, can realize the recovery of the glycerol and the glycerol monomethyl ether by a relatively economic technical means, and improves the utilization rate of resources. And the desalination treatment is firstly carried out and then the membrane concentration is carried out, thereby reducing the influence of the salinity in the wastewater on the service life of the membrane and prolonging the service life of the membrane in the membrane concentration.
Preferably, the desalting of step (1) comprises electrodialysis desalting.
Preferably, the electrodialysis membrane is any one of a homogeneous membrane, a heterogeneous membrane or an alloy membrane.
Preferably, the electrodialysis desalination operation temperature is 5 ~ 35 ℃, for example can be 5 ℃, 9 ℃, 12 ℃, 15 ℃, 19 ℃, 22 ℃, 25 ℃, 29 ℃, 32 ℃ or 35 ℃, but not limited to the values, in this range other values are also applicable.
Preferably, the electrodialysis desalination adopts a three-stage electrodialysis operation mode.
Preferably, the concentration chamber for electrodialysis desalination is provided with initial water with conductivity of 10-100 μ s/cm, such as 10 μ s/cm, 20 μ s/cm, 30 μ s/cm, 40 μ s/cm, 50 μ s/cm, 60 μ s/cm, 70 μ s/cm, 80 μ s/cm, 90 μ s/cm or 100 μ s/cm, but not limited to the values listed, and other values not listed in the range are also applicable.
Preferably, the electrodialysis desalination electrode compartment is provided with brine.
Preferably, the brine is a sodium chloride solution, and the mass concentration of the sodium chloride solution is 3 to 6 wt%, for example, 3 wt%, 4 wt%, 5 wt%, or 6 wt%, but not limited to the above-mentioned values, and other values not listed in this range are also applicable.
Preferably, the voltage for the electrodialysis desalination is 10-20V, for example, 10V, 11V, 12V, 13V, 14V, 15V, 16V, 17V, 18V, 19V or 20V, but is not limited to the values listed, and other values not listed in this range are also applicable.
Preferably, the electric current for the electrodialysis desalination is 1 to 3A, and may be, for example, 1A, 1.2A, 1.5A, 2.0A, 2.2A, 2.5A, 2.8A or 3.0A, but is not limited to the values listed, and other values not listed in the range are also applicable.
Preferably, the electrodialysis desalted concentrated water is subjected to wet oxidation treatment.
Preferably, the membrane for membrane concentration in step (2) is a permeable membrane.
Preferably, the membrane-concentrated membrane comprises a membrane of the dupont XC series, the delameyer pro series, or the delameyer DTRO series.
The film of the present invention may be selected from any one of Dellam Metro DTMO-02, DuPont XC70, or Dellam Mero pro10, for example.
Because the organic matter is concentrated, the special membrane is selected, the reverse osmosis membrane screens water and macromolecular organic matter under the action of pressure, no phase change occurs in the concentration process, and the energy consumption is obviously reduced; the membrane has better tolerance to organic components and salts, and can be suitable for concentrating organic matters.
Preferably, the operation pressure of the membrane concentration in step (2) is 2 to 8MPa, for example, 2MPa, 3MPa, 4MPa, 5MPa, 6MPa, 7MPa or 8MPa, etc., but is not limited to the values listed, and other values not listed in the range are also applicable.
Preferably, the membrane concentration temperature is 5 to 45 ℃, for example, can be 5 ℃, 10 ℃, 14 ℃, 19 ℃, 23 ℃, 28 ℃, 32 ℃, 37 ℃, 41 ℃ or 45 ℃, but not limited to the cited value, in this range other values are also applicable.
The invention aims at two special components of glycerol and glycerol monomethyl ether, particularly prefers the operation temperature and has better mulching film concentration effect.
Preferably, the secondary concentration of step (3) comprises multi-effect evaporative concentration.
Preferably, the absolute pressure of the secondary concentration is 15 to 50kPa, and for example, 15kPa, 20kPa, 22kPa, 25kPa, 30kPa, 32kPa, 35kPa, 40kPa, 42kPa, 45kPa, 48kPa, or 50kPa, etc., may be mentioned, but the present invention is not limited to the mentioned values, and other values not mentioned in the range are also applicable.
Preferably, the secondary concentration kettle temperature is 70 ~ 100 ℃, for example can be 70 ℃, 72 ℃, 74 ℃, 75 ℃, 78 ℃, 80 ℃, 82 ℃, 85 ℃, 88 ℃, 90 ℃, 95 ℃ or 100 ℃ and so on, but not limited to the number, in this range other values are also applicable.
Preferably, the form of dehydration in step (3) comprises fractional dehydration.
Preferably, the dehydration kettle temperature is 60 ~ 150 ℃, for example can be 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 120 ℃, 130 ℃, 140 ℃ or 150 ℃, but not limited to the number, in the range of other values are also applicable.
The absolute pressure of the dehydration is preferably 0.1 to 10kPa, and may be, for example, 0.5kPa, 1.6kPa, 2.7kPa, 3.7kPa, 4.8kPa, 5.8kPa, 6.9kPa, 7.9kPa, 9kPa, or 10kPa, but is not limited to the values listed, and other values not listed in this range are also applicable.
The reflux ratio of the dehydration is preferably 1 to 10:1, and may be, for example, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
Preferably, the COD in the effluent after dehydration is less than or equal to 500ppm, such as 100ppm, 200ppm, 300ppm, 400ppm or 500ppm, but not limited to the values recited, and other values not recited in the range are also applicable.
Preferably, the dewatered material has a water content of 0.2 wt.% or less, and may be, for example, 0.01 wt.%, 0.04 wt.%, 0.06 wt.%, 0.08 wt.%, 0.1 wt.%, 0.12 wt.%, 0.14 wt.%, 0.16 wt.%, 0.18 wt.%, or 0.2 wt.%, and the like, but is not limited to the recited values, and other values not recited in this range are equally applicable.
Preferably, the refining separation mode of the step (3) comprises rectification separation.
Preferably, the absolute pressure of the rectification separation is 0.5 to 10kPa, and may be, for example, 0.5kPa, 1.6kPa, 2.7kPa, 3.7kPa, 4.8kPa, 5.8kPa, 6.9kPa, 7.9kPa, 9kPa, or 10kPa, but is not limited to the values listed, and other values not listed in this range are also applicable.
Preferably, the reflux ratio of the rectification separation is 1 to 10:1, and may be, for example, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1, but is not limited to the values listed, and other values not listed in the range are also applicable.
Preferably, the temperature of the distillation separation is 150 to 180 ℃, for example, 150 ℃, 155 ℃, 160 ℃, 162 ℃, 170 ℃, 175 ℃, 178 ℃ or 180 ℃, but not limited to the values listed, and other values not listed in the range are also applicable.
Preferably, the epichlorohydrin wastewater contains glycerol and glycerol monomethyl ether.
Preferably, the mass concentration of glycerol in the epichlorohydrin wastewater is 0.1 to 5 wt%, and for example, may be 0.1 wt%, 0.7 wt%, 1.2 wt%, 1.8 wt%, 2.3 wt%, 2.9 wt%, 3.4 wt%, 4 wt%, 4.5 wt%, or 5 wt%, but is not limited to the values listed, and other values not listed in this range are also applicable.
Preferably, the mass concentration of the glycerol monomethyl ether in the epichlorohydrin wastewater is 0.1 to 10 wt%, for example, 0.1 wt%, 1.2 wt%, 2.3 wt%, 3.4 wt%, 4.5 wt%, 5.6 wt%, 6.7 wt%, 7.8 wt%, 8.9 wt%, or 10 wt%, but not limited to the above-mentioned values, and other values not listed in this range are also applicable.
From the above, the content of glycerol and glycerol monomethyl ether in the epichlorohydrin wastewater is very low, but the yield of the annual epichlorohydrin is high, even the low-content glycerol and glycerol monomethyl ether have higher recovery value under the condition of larger yield, but the purification and concentration of the low-content substances are difficult in the actual production process, a large amount of energy consumption is consumed by a simple rectification process, and the economic benefit is poor.
Preferably, the epichlorohydrin wastewater also contains sodium chloride.
Preferably, the mass concentration of sodium chloride in the epichlorohydrin wastewater is 0.1 to 5.0 wt%, for example, 0.1 wt%, 0.7 wt%, 1.2 wt%, 1.8 wt%, 2.3 wt%, 2.9 wt%, 3.4 wt%, 4 wt%, 4.5 wt%, or 5.0 wt%, etc., but not limited to the recited values, and other values not recited in this range are also applicable.
Although the epichlorohydrin wastewater only contains a small amount of salt, the epichlorohydrin wastewater has a large influence on the service life of the membrane, so that the service life and the concentration effect of the membrane are remarkably improved by desalting and then concentrating the membrane.
As a preferable technical scheme of the invention, the method comprises the following steps:
(1) performing electrodialysis desalination on the epoxy chloropropane wastewater, wherein the operation temperature of the electrodialysis desalination is 5-35 ℃ to obtain desalted fresh water, and performing wet oxidation treatment on the concentrated water desalted by the electrodialysis;
(2) concentrating the desalted fresh water by using a membrane, wherein the operation pressure of the membrane concentration is 2-8 MPa, the temperature is 5-45 ℃, and membrane concentrated water is obtained, and the membrane concentrated by using the membrane comprises membranes of Dupont XC series, Dellam Merr pro series or Dellam Merr DTRO series;
(3) the membrane concentrated water is sequentially subjected to multi-effect evaporation concentration and rectification dehydration to obtain effluent with COD (chemical oxygen demand) less than or equal to 500ppm and a dehydrated material with water content less than or equal to 0.2 wt%, the dehydrated material is subjected to rectification separation, absolute pressure of the rectification separation is 0.5-10 kPa, reflux ratio is 1-10: 1, and glycerin and glycerol monomethyl ether are respectively obtained.
According to the invention, a special membrane is selected to carry out membrane concentration on organic small molecular substances, so that compared with pure rectification concentration, the energy consumption is obviously reduced, and the operating pressure and the operating temperature in the membrane concentration process are combined, so that the membrane concentration method has good interception and concentration effects on glycerol and glycerol monomethyl ether, and the economic benefit of the epichlorohydrin process can be improved.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) according to the method for recovering the monomethyl ether of glycerol and the glycerol from the epichlorohydrin wastewater, provided by the invention, the salt and the target product are efficiently separated preferably in an electrodialysis mode, so that on one hand, the influence of the salt in the wastewater on the membrane concentration osmotic pressure is reduced, the membrane concentration multiple is improved, on the other hand, the influence of the salt on a heat exchanger and a circulating pump is reduced, and the stable operation of a subsequent concentration and rectification device is ensured;
(2) according to the method for recovering the glycerol monomethyl ether and the glycerol from the epichlorohydrin wastewater, provided by the invention, the organic matters in the water are concentrated by adopting a membrane concentration mode, water and macromolecular organic matters are screened by a reverse osmosis membrane under the action of pressure, no phase change is generated in the concentration process, and the energy consumption is obviously reduced;
(3) the method for recovering the glycerol monomethyl ether and the glycerol from the epichlorohydrin wastewater provided by the invention realizes separation and purification of the by-products of the glycerol monomethyl ether and the glycerol in the water layer, and solves the problems of resource recovery and comprehensive utilization of the by-products in the water layer, wherein the recovery rate of the glycerol monomethyl ether is more than or equal to 80%, preferably more than or equal to 90%, the mass concentration can reach more than 95 wt%, the recovery rate of the glycerol is more than or equal to 80%, the mass concentration can reach more than 90 wt%, the COD (chemical oxygen demand) in the recovered water resource is less than or equal to 500ppm, and the recovered water resource can be directly discharged into a garden pipe network.
Drawings
FIG. 1 is a flow chart of a method for recovering glycerol monomethyl ether and glycerol from epichlorohydrin wastewater provided by the invention.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
The invention provides a method for recovering glycerol monomethyl ether and glycerol from epichlorohydrin wastewater, wherein the flow of the method is shown in figure 1, and concretely, the method comprises the following steps:
(1) performing electrodialysis desalination on the epoxy chloropropane wastewater, wherein the operation temperature of the electrodialysis desalination is 5-35 ℃ to obtain desalted fresh water, and performing wet oxidation treatment on the concentrated water desalted by the electrodialysis;
(2) concentrating the desalted fresh water by using a membrane, wherein the operation pressure of the membrane concentration is 2-8 MPa, the temperature is 5-45 ℃, and membrane concentrated water is obtained, and the membrane concentrated by using the membrane comprises membranes of Dupont XC series, Dellam Merr pro series or Dellam Merr DTRO series; membrane concentrated fresh water is recycled to the epoxy chloropropane separation procedure;
(3) the membrane concentrated water is sequentially subjected to multiple-effect evaporation concentration and rectification dehydration, the evaporated water is circulated to the step (1) and placed in a concentration chamber or used as circulating condensed water for recycling, so that effluent with COD (chemical oxygen demand) less than or equal to 500ppm and dehydrated materials with water content less than or equal to 0.2 wt% are obtained, the dehydrated water reaches the standard and is discharged to a park pipe network, the dehydrated materials are subjected to rectification separation, the absolute pressure of the rectification separation is 0.5-10 kPa, the reflux ratio is 1-10: 1, and tower bottom material-glycerol and tower top material-glycerol monomethyl ether are respectively obtained.
Example 1
The embodiment provides a method for recovering glycerol monomethyl ether and glycerol from epichlorohydrin wastewater, wherein the mass concentration of the glycerol monomethyl ether, the mass concentration of the glycerol, the mass concentration of the sodium chloride and the mass concentration of the water in the epichlorohydrin wastewater are respectively 1.7 wt%, 0.9 wt%, 2.2 wt% and 95.2 wt%.
Specifically, the method comprises the following steps:
(1) the electrodialysis adopts 10 groups of homogeneous membranes provided by the blue company, the membrane stack adopts 10 groups of homogeneous membranes, epoxy chloropropane wastewater with initial conductivity of 37ms/cm is put into a dilute chamber for electrodialysis desalination, concentrated effluent is put into a concentrated chamber with the conductivity of 10 mus/cm, 4 wt% NaCl salt water is put into a polar chamber, a three-stage electrodialysis operation mode is adopted, the voltage is set to be 15V, the current is set to be 2.2A, the operation temperature is controlled to be 25-35 ℃, the operation is stopped when the operation is carried out until the conductivity of concentrated water in the concentrated chamber reaches 195ms/cm, and the operation is stopped when the conductivity of fresh water in the dilute chamber reaches 410 mus/cm, so as to obtain desalted fresh water, and the electrodialysis desalted concentrated water is subjected to wet oxidation treatment and is recycled;
(2) membrane concentration is carried out on the desalted fresh water, wherein the membrane element is Delang Meier DTROMO-02, the operating pressure of the membrane concentration is 3.8-8 MPa, and the temperature is 25-35 ℃, so that membrane concentrated water is obtained; membrane concentrated fresh water is recycled to the epoxy chloropropane separation procedure;
(3) carrying out triple-effect evaporation concentration on the membrane concentrated water, wherein the absolute pressure is 15-65 kPa, and the kettle temperature is 70-100 ℃, so as to obtain a concentrated material and evaporated water, and circulating the evaporated water to a concentration chamber in the step (1) or recycling the evaporated water as circulating condensed water;
rectifying and dehydrating the concentrated material, wherein the number of dehydrated theoretical plates is 20, the absolute pressure is 5kPa, the kettle temperature is 60-130 ℃, and the reflux ratio is 1, so that concentrated effluent with the COD of 424ppm and dehydrated material with the water content of 0.08 wt% are obtained; the dehydrated effluent reaches the standard and is discharged into a park pipe network.
And (3) rectifying and separating the dehydrated material, wherein the number of theoretical plates for rectifying and separating is 35, the kettle temperature is 150-180 ℃, the absolute pressure for rectifying and separating is 1kPa, and the reflux ratio is 3:1, so that a monomethyl glycerol ether product and a glycerol product are respectively obtained.
The composition of each stream in this example is shown in table 1.
TABLE 1
As can be seen from table 1, the method for recovering monomethyl ether and glycerol from epichlorohydrin wastewater provided in this embodiment effectively realizes concentration and rectification separation of monomethyl ether and glycerol, thereby significantly improving the recovery effects of the monomethyl ether and glycerol, and simultaneously realizes recycling of water resources therein, the COD content of the dehydrated water is only 424ppm, and sodium chloride is not detected.
Example 2
The embodiment provides a method for recovering glycerol monomethyl ether and glycerol from epichlorohydrin wastewater, which is based on the embodiment 1, an electrodialysis membrane stack adopts 10 groups of heterogeneous membranes, the current is 1.1A, other conditions are not changed, the operation is finished, the conductivity of concentrated water in a concentrated chamber is 173ms/cm, the conductivity of fresh water in a fresh chamber is 410 mus/cm, at the moment, the mass concentration of the glycerol monomethyl ether in the concentrated water is 0.12 wt%, the mass concentration of the glycerol is 0.24 wt%, the mass concentration of sodium chloride is 15.2 wt%, the TOC1940ppm is subjected to dehumidification type oxidation treatment and resource utilization, the mass concentration of the glycerol monomethyl ether in the fresh water is 1.90 wt%, the mass concentration of the glycerol is 0.98 wt%, the mass concentration of the sodium chloride is 0.02 wt%, and the rest is the same as the embodiment 1.
Example 3
The embodiment provides a method for recovering glycerol monomethyl ether and glycerol from epichlorohydrin wastewater, which is implemented by adopting DuPont XC70 as a membrane concentration membrane element on the basis of embodiment 1, wherein the operating pressure is 2.0-4.5 MPa, the temperature is 25-35 ℃, and the mass concentration of the glycerol monomethyl ether, the mass concentration of the glycerol and the mass concentration of the sodium chloride in membrane-concentrated fresh water are respectively 0.02 wt%, 0.08 wt% and 0.004 wt%, respectively, and the membrane-concentrated fresh water is reused in an epichlorohydrin separation process, and the mass concentration of the glycerol monomethyl ether, the mass concentration of the glycerol and the mass concentration of the sodium chloride in the membrane-concentrated water are respectively 4.59 wt%, 2.27 wt% and 0.04 wt%.
Example 4
In this embodiment, on the basis of example 1, delayer pro10 is adopted as a membrane concentration membrane element, and the membrane concentration fresh water with the mass concentration of 0.04 wt% of glycerol monomethyl ether, the mass concentration of glycerol of 0.13 wt% and the mass concentration of sodium chloride of 0.008 wt% are reused in the epichlorohydrin separation process, and the membrane concentration concentrated water with the mass concentration of glycerol monomethyl ether of 10.22 wt%, the mass concentration of glycerol of 4.80 wt% and the mass concentration of sodium chloride of 0.07 wt% is obtained.
Example 5
The embodiment provides a method for recycling glycerol monomethyl ether and glycerol from epichlorohydrin wastewater, which is implemented by adopting MVR evaporation under the conditions of absolute pressure of 50-60 kPa and kettle temperature of 75-85 ℃ under the condition that other conditions are not changed on the basis of embodiment 1, wherein 50ppm of undetected COD (chemical oxygen demand) of glycerol monomethyl ether and glycerol in evaporated water is removed to step (1), and part of glycerol monomethyl ether and glycerol is recycled as circulating condensed water, and the mass concentration of glycerol monomethyl ether in a concentrated material is 58.38 wt%, the mass concentration of glycerol is 27.53 wt%, and the mass concentration of sodium chloride is 0.47 wt%.
Example 6
This embodiment provides a method for recovering glycerol monomethyl ether and glycerol from epichlorohydrin wastewater, where the mass concentration of glycerol monomethyl ether, the mass concentration of glycerol, the mass concentration of sodium chloride, and the mass concentration of water in the epichlorohydrin wastewater are 0.5 wt%, 1.8 wt%, 1.5 wt%, and 96.2 wt%, respectively.
Specifically, the method comprises the following steps:
(1) the electrodialysis adopts EX-3BT provided by blue company, the membrane stack adopts 12 groups of homogeneous membranes, epoxy chloropropane wastewater with initial conductivity of 25.7 is put into a thin chamber for electrodialysis desalination, the concentrated effluent conductivity of the thick chamber is 50 mus/cm, 6 wt% NaCl salt water is put into a polar chamber, a three-stage electrodialysis operation mode is adopted, the voltage is set to be 20V, the current is 1.0A, the operation temperature is controlled to be 15-25 ℃, the operation is stopped when the operation is carried out until the concentrated water conductivity of the thick chamber reaches 177ms/cm, and the fresh water conductivity of the thin chamber reaches 620 mus/cm, desalted fresh water is obtained, and the concentrated water desalted by the electrodialysis is subjected to wet oxidation treatment and is recycled;
(2) membrane concentration is carried out on the desalted fresh water, wherein a membrane element is Delnam pro10, the operating pressure of the membrane concentration is 3.0-5.3 MPa, and the temperature is 10-25 ℃, so that membrane concentrated water is obtained; membrane concentrated fresh water is recycled to the epoxy chloropropane separation procedure;
(3) carrying out four-effect evaporation concentration on the membrane concentrated water, wherein the absolute pressure is 35-45 kPa, and the kettle temperature is 80-90 ℃, so as to obtain a concentrated material and evaporated water, and circulating the evaporated water to a concentration chamber in the step (1) or recycling the evaporated water as circulating condensed water;
rectifying and dehydrating the concentrated material, wherein 25 dehydrated theoretical plates are provided, the absolute pressure is 10kPa, the kettle temperature is 60-130 ℃, and the reflux ratio is 1.2, so that a dehydrated material with the water content of only 0.06 wt% and dehydrated effluent with COD of 392ppm are obtained, and the dehydrated effluent is discharged to a garden pipe network;
and (3) rectifying and separating the dehydrated material, wherein the number of theoretical plates for rectifying and separating is 30, the kettle temperature is 160-180 ℃, the absolute pressure for rectifying and separating is 10kPa, and the reflux ratio is 10:1, so that a glycerol product and a glycerol monomethyl ether product are respectively obtained.
Example 7
The embodiment provides a method for recovering glycerol monomethyl ether and glycerol from epichlorohydrin wastewater, wherein the mass concentration of the glycerol monomethyl ether, the mass concentration of the glycerol, the mass concentration of the sodium chloride and the mass concentration of the water in the epichlorohydrin wastewater are respectively 1.1 wt%, 1.0 wt%, 3.0 wt% and 94.9 wt%.
Specifically, the method comprises the following steps:
(1) the electrodialysis adopts EX-3BT provided by blue company, the membrane stack adopts 12 groups of homogeneous membranes, epichlorohydrin wastewater with initial conductivity of 49.5ms/cm is put into a dilute chamber for electrodialysis desalination, concentrated effluent is put into a concentrated chamber with the conductivity of 100 mus/cm, 3 wt% NaCl salt water is put into a polar chamber, a three-stage electrodialysis operation mode is adopted, the voltage is set to be 10V, the current is set to be 3A, the operation temperature is controlled to be 5-10 ℃, the operation is stopped when the concentrated water is operated to reach the conductivity of 183ms/cm of the concentrated water in the concentrated chamber, and the operation is stopped when the fresh water conductivity of the dilute chamber is 390 mus/cm, desalted fresh water is obtained, and the electrodialysis desalted concentrated water is subjected to wet oxidation treatment and is recycled;
(2) membrane concentration is carried out on the desalted fresh water, the membrane element is XC70, the operating pressure of the membrane concentration is 2-3.5 MPa, and the temperature is 5-15 ℃, so that membrane concentrated water is obtained; membrane concentrated fresh water is recycled to the epoxy chloropropane separation procedure;
(3) carrying out triple-effect evaporation concentration on the membrane concentrated water, wherein the absolute pressure is 15-60 kPa, and the kettle temperature is 75-80 ℃, so as to obtain a concentrated material and evaporated water, and circulating the evaporated water to a concentration chamber in the step (1) or recycling the evaporated water as circulating condensed water;
rectifying and dehydrating the concentrated material, wherein the number of dehydrated theoretical plates is 20, the absolute pressure is 5-15 kPa, the kettle temperature is 60-120 ℃, and the reflux ratio is 1.3, so as to obtain dehydrated material with the COD of dehydrated effluent less than or equal to 500ppm and the water content less than or equal to 0.2 wt%; and the dehydrated effluent is discharged to a pipe network of a park.
And (3) rectifying and separating the dehydrated material, wherein the number of theoretical plates for rectifying and separating is 25, the kettle temperature is 160-180 ℃, the absolute pressure for rectifying and separating is 1kPa, and the reflux ratio is 3:1, so that a glycerol product and a glycerol monomethyl ether product are respectively obtained.
The compositions and yields of the final glycerol monomethyl ether and glycerol products of examples 1-7 are shown in Table 2.
TABLE 2
As can be seen from Table 2, the method for recovering the glycerol monomethyl ether and the glycerol from the epichlorohydrin wastewater provided by the invention can realize the technical effects that the recovery rate of the glycerol monomethyl ether is more than or equal to 80%, preferably more than or equal to 90%, and the recovery rate of the glycerol is more than or equal to 80%.
Examples 8 to 10
Embodiments 8 to 10 provide methods for recovering glycerol monomethyl ether and glycerol from epichlorohydrin wastewater, and based on embodiment 1, different vacuum degrees and reflux ratios of rectification are adjusted, and experimental data are shown in table 3.
TABLE 3
Examples 11 to 12 and comparative example 1
Examples 11 to 12 and comparative example 1 provide methods for recovering monomethyl ether of glycerin and glycerin from epichlorohydrin wastewater, only a membrane concentrated by a membrane is adjusted based on example 4, a common dupont sea membrane is used in comparative example 1, and experimental data are shown in table 4.
TABLE 4
Therefore, the special selection of the membrane can obviously improve the yield of the final glycerol monomethyl ether and glycerol, and compared with the common Dupont sea mussel membrane, the membrane has better tolerance and higher product quality yield.
Comparative example 2
This comparative example provides a process for recovering monomethyl ether of glycerin and glycerin from epichlorohydrin wastewater, which is the same as in example 1 except that the membrane concentration in step (2) is not performed and the triple effect evaporation concentration is performed directly.
The ASPEN comparison is used to calculate the common energy consumption, including heat loss and the like, of example 1 and comparative example 2, wherein the energy consumption of 1 ton of produced water in example 1 is 5kwh, and the energy consumption of 1 ton of concentrated water in comparative example 2 is 0.5 ton of steam and 20 kwh.
The temperature, pressure, dissolved oxygen and pH parameters of the above examples fluctuate during long-term operation, and therefore only control is performed within specific ranges.
Detecting COD content by oxidation-reduction potentiometric titration, detecting TOC content by combustion oxidation-non-dispersive infrared absorption method, detecting sodium chloride content by potentiometric titration, detecting glycerin content by titration, detecting glycerin monomethyl ether content by gas spectrum quantification method, and detecting fresh water and concentrated water concentrated by membrane.
In conclusion, the method for recovering the glycerol monomethyl ether and the glycerol from the epichlorohydrin wastewater effectively realizes the full recovery of products and water resources in the wastewater, wherein the recovery rate of the glycerol monomethyl ether is more than or equal to 80 percent, preferably more than or equal to 90 percent, the mass concentration can reach more than 95 percent, the recovery rate of the glycerol is more than or equal to 80 percent, the mass concentration can reach more than 90 percent, the COD in the recovered water resources is less than or equal to 500ppm, and the recovered water resources can be directly discharged into a garden pipe network; and the energy consumption of public works is obviously reduced, the economic benefit is obviously improved, and the production cost of the epoxy chloropropane is greatly reduced.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A method for recovering glycerol monomethyl ether and glycerol from epichlorohydrin wastewater is characterized by comprising the following steps:
(1) desalting the epoxy chloropropane wastewater to obtain desalted fresh water;
(2) the desalted fresh water is subjected to membrane concentration to obtain membrane concentrated water;
(3) and the membrane concentrated water is subjected to secondary concentration and dehydration in sequence to obtain dehydrated materials, and the dehydrated materials are refined and separated to respectively obtain glycerol and glycerol monomethyl ether.
2. The method of claim 1, wherein the desalting of step (1) comprises electrodialysis desalting;
preferably, the electrodialysis membrane is any one of a homogeneous membrane, a heterogeneous membrane or an alloy membrane;
preferably, the operation temperature of the electrodialysis desalination is 5-35 ℃;
preferably, the electrodialysis desalted concentrated water is subjected to wet oxidation treatment.
3. The method according to claim 1 or 2, wherein the membrane for membrane concentration in step (2) is a permeable membrane;
preferably, the membrane-concentrated membrane comprises a membrane of the dupont XC series, the delameyer pro series, or the delameyer DTRO series.
4. The method according to any one of claims 1 to 3, wherein the membrane concentration in step (2) is performed at an operating pressure of 2 to 8 MPa;
preferably, the temperature of the membrane concentration is 5-45 ℃.
5. The method of any one of claims 1 to 4, wherein the secondary concentration of step (3) comprises multi-effect evaporative concentration.
6. The method of any one of claims 1 to 5, wherein the form of dehydration in step (3) comprises rectification dehydration;
preferably, COD in the effluent after dehydration is less than or equal to 500 ppm;
preferably, the water content of the dehydrated material is less than or equal to 0.2 wt%.
7. The method according to any one of claims 1 to 6, wherein the refining separation mode in the step (3) comprises rectification separation;
preferably, the absolute pressure of the rectification separation is 0.5-10 kPa;
preferably, the reflux ratio of the rectification separation is 1-10: 1.
8. The method according to any one of claims 1 to 7, characterized in that the epichlorohydrin wastewater contains glycerol and glycerol monomethyl ether;
preferably, the mass concentration of glycerol in the epoxy chloropropane wastewater is 0.1-5 wt%;
preferably, the mass concentration of the glycerol monomethyl ether in the epoxy chloropropane wastewater is 0.1-10 wt%.
9. The method according to any one of claims 1 to 8, characterized in that the epichlorohydrin wastewater further contains sodium chloride;
preferably, the mass concentration of sodium chloride in the epoxy chloropropane wastewater is 0.1-5.0 wt%.
10. A method according to any one of claims 1 to 9, characterized in that the method comprises the steps of:
(1) performing electrodialysis desalination on the epoxy chloropropane wastewater, wherein the operation temperature of the electrodialysis desalination is 5-35 ℃ to obtain desalted fresh water, and performing wet oxidation treatment on the concentrated water desalted by the electrodialysis;
(2) concentrating the desalted fresh water by using a membrane, wherein the operation pressure of the membrane concentration is 2-8 MPa, the temperature is 5-45 ℃, and membrane concentrated water is obtained, and the membrane concentrated by using the membrane comprises membranes of Dupont XC series, Dellam Merr pro series or Dellam Merr DTRO series;
(3) the membrane concentrated water is sequentially subjected to multi-effect evaporation concentration and rectification dehydration to obtain effluent with COD (chemical oxygen demand) less than or equal to 500ppm and a dehydrated material with water content less than or equal to 0.2 wt%, the dehydrated material is subjected to rectification separation, absolute pressure of the rectification separation is 0.5-10 kPa, reflux ratio is 1-10: 1, and glycerin and glycerol monomethyl ether are respectively obtained.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110929843.XA CN113461246A (en) | 2021-08-13 | 2021-08-13 | Method for recovering glycerol monomethyl ether and glycerol from epichlorohydrin wastewater |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110929843.XA CN113461246A (en) | 2021-08-13 | 2021-08-13 | Method for recovering glycerol monomethyl ether and glycerol from epichlorohydrin wastewater |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113461246A true CN113461246A (en) | 2021-10-01 |
Family
ID=77866483
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110929843.XA Pending CN113461246A (en) | 2021-08-13 | 2021-08-13 | Method for recovering glycerol monomethyl ether and glycerol from epichlorohydrin wastewater |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113461246A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115043539A (en) * | 2022-04-20 | 2022-09-13 | 江苏瑞祥化工有限公司 | Treatment method of wastewater in epoxy resin production |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102557164A (en) * | 2010-12-15 | 2012-07-11 | 益海天成(连云港)化工有限公司 | Recycling method of high-salt industrial wastewater containing glycerin |
| CN104230084A (en) * | 2014-08-21 | 2014-12-24 | 波鹰(厦门)科技有限公司 | Device for recovering sodium chloride and glycerinum from high-salinity and high-depth organic wastewater containing glycerinum |
| CN107973481A (en) * | 2016-10-21 | 2018-05-01 | 中国科学院青岛生物能源与过程研究所 | A kind of Treatment and recovery technique for the high salt high-COD waste water that preparing epoxy chloropropane by using glycerol method produces |
| WO2021120133A1 (en) * | 2019-12-19 | 2021-06-24 | 万华化学集团股份有限公司 | Method for treating production wastewater from preparation of propylene oxide with co-oxidation method |
-
2021
- 2021-08-13 CN CN202110929843.XA patent/CN113461246A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102557164A (en) * | 2010-12-15 | 2012-07-11 | 益海天成(连云港)化工有限公司 | Recycling method of high-salt industrial wastewater containing glycerin |
| CN104230084A (en) * | 2014-08-21 | 2014-12-24 | 波鹰(厦门)科技有限公司 | Device for recovering sodium chloride and glycerinum from high-salinity and high-depth organic wastewater containing glycerinum |
| CN107973481A (en) * | 2016-10-21 | 2018-05-01 | 中国科学院青岛生物能源与过程研究所 | A kind of Treatment and recovery technique for the high salt high-COD waste water that preparing epoxy chloropropane by using glycerol method produces |
| WO2021120133A1 (en) * | 2019-12-19 | 2021-06-24 | 万华化学集团股份有限公司 | Method for treating production wastewater from preparation of propylene oxide with co-oxidation method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115043539A (en) * | 2022-04-20 | 2022-09-13 | 江苏瑞祥化工有限公司 | Treatment method of wastewater in epoxy resin production |
| CN115043539B (en) * | 2022-04-20 | 2024-02-09 | 江苏瑞祥化工有限公司 | Treatment method of wastewater in epoxy resin production |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108997141B (en) | Preparation method of 1, 5-pentanediamine | |
| CN109097408B (en) | Preparation method of nylon 56 salt | |
| CN111484178B (en) | Comprehensive treatment method for seawater or strong brine | |
| CN107265734B (en) | Reverse osmosis concentrated seawater treatment system and method | |
| CN101993165B (en) | Method for treating nitrochlorobenzene high-salt organic wastewater | |
| CN102689936A (en) | Method for processing wastewater from production of epoxy chloropropane by using glycerol as material | |
| CN105198143A (en) | High-concentration wastewater zero-discharging method | |
| CN1180322A (en) | Nanofiltration of concentrated aqueous salt solutions | |
| CN105819588B (en) | The method for reducing pollutant emission in phenol-acetone production | |
| CN109575088B (en) | Refining method of xylose in hemicellulose hydrolysate | |
| CN110482756B (en) | Method for recycling epichlorohydrin wastewater | |
| CN105461157A (en) | High-salinity high-organic-matter contentwastewater zero discharge method | |
| CN109665661B (en) | Method for separating sulfuric acid, acetic acid and furfural from furfural wastewater | |
| CN112374676B (en) | Device and method for separating and purifying byproducts in epichlorohydrin wastewater | |
| CN111253007A (en) | Method for treating epichlorohydrin wastewater | |
| CN105692996A (en) | Novel process for treating industrial wastewater with benzyl alcohol | |
| CN113461246A (en) | Method for recovering glycerol monomethyl ether and glycerol from epichlorohydrin wastewater | |
| CN111348794A (en) | Separation method of salt in high-sulfur low-chlorine salt-containing wastewater | |
| CN112408432A (en) | Method for separating and purifying mixed salt in aromatic compound nitration wastewater | |
| CN106082519A (en) | A kind of polyvinyl alcohol produces the recovery and treatment method of waste liquid | |
| CN102311193B (en) | Method for treating filter cake filter-press filtrate in polyolefin catalyst production | |
| CN107311254A (en) | A kind of resource utilization method of thiram waste water | |
| CN110818160A (en) | Treatment process of high-salt high-COD wastewater | |
| CN104829030A (en) | Treatment and recovery method of wastewater containing sodium terephthalate and 1,4-butanediol | |
| CN213171875U (en) | High-salinity organic wastewater zero-discharge treatment system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20211001 |