CN106630083B - A kind of harmless treatment method of epoxidation wastewater - Google Patents
A kind of harmless treatment method of epoxidation wastewater Download PDFInfo
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- 239000002351 wastewater Substances 0.000 title claims abstract description 88
- 238000006735 epoxidation reaction Methods 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 32
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 56
- SSZWWUDQMAHNAQ-UHFFFAOYSA-N 3-chloropropane-1,2-diol Chemical compound OCC(O)CCl SSZWWUDQMAHNAQ-UHFFFAOYSA-N 0.000 claims abstract description 37
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000007864 aqueous solution Substances 0.000 claims abstract description 22
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 11
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 4
- 239000011541 reaction mixture Substances 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- JQQJROWLUNBRMP-UHFFFAOYSA-N 1-chloro-1-methoxypropan-1-ol Chemical compound CCC(O)(Cl)OC JQQJROWLUNBRMP-UHFFFAOYSA-N 0.000 claims description 29
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 5
- -1 alkali metal salt Chemical class 0.000 claims description 5
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 5
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical group [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 4
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 3
- 150000008041 alkali metal carbonates Chemical group 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 231100000331 toxic Toxicity 0.000 abstract description 5
- 230000002588 toxic effect Effects 0.000 abstract description 5
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 19
- 235000011187 glycerol Nutrition 0.000 description 17
- PSJBSUHYCGQTHZ-UHFFFAOYSA-N 3-Methoxy-1,2-propanediol Chemical compound COCC(O)CO PSJBSUHYCGQTHZ-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 11
- 239000012527 feed solution Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XVINJFQWMHZPNI-UHFFFAOYSA-N 1-chloro-1-methoxypropan-2-ol Chemical compound COC(Cl)C(C)O XVINJFQWMHZPNI-UHFFFAOYSA-N 0.000 description 1
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 241000721662 Juniperus Species 0.000 description 1
- 241000283984 Rodentia Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical group [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229960004063 propylene glycol Drugs 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000003716 rejuvenation Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 description 1
- 229910000026 rubidium carbonate Inorganic materials 0.000 description 1
- 239000003802 soil pollutant Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
-
- 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
- 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
- C02F2101/36—Organic compounds containing halogen
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Epoxy Compounds (AREA)
Abstract
一种环氧化废水的无害化处理方法，包括：a)将3‑氯丙烯与过氧化氢环氧化合成环氧氯丙烷的环氧化废水与碱性水溶液在废水处理反应器中接触混合，使其中的3‑氯‑1,2‑丙二醇转化为甘油；b)可选地，中和步骤a)所得到的反应混合物。采用本发明的方法，可以方便地将3‑氯丙烯与过氧化氢环氧化合成环氧氯丙烷过程中产生的有毒有害的环氧化废水转化为无毒无害的废水。A harmless treatment method for epoxidation wastewater, comprising: a) contacting epoxidation wastewater obtained by epoxidizing 3-propene chloride and hydrogen peroxide to synthesize epichlorohydrin and an alkaline aqueous solution in a wastewater treatment reactor Mixing so that 3-chloro-1,2-propanediol is converted into glycerol; b) optionally, neutralizing the reaction mixture obtained in step a). By adopting the method of the invention, the toxic and harmful epoxidation waste water produced in the process of epoxidizing 3-chloropropene and hydrogen peroxide to synthesize epichlorohydrin can be conveniently converted into non-toxic and harmless waste water.
Description
Technical Field
The invention relates to a harmless treatment method of epoxy wastewater, in particular to a harmless treatment method of wastewater generated in the epoxidation reaction of 3-chloropropene and hydrogen peroxide to synthesize epichlorohydrin.
Background
Hydrogen peroxide is a green oxidant, and as disclosed in USP4833260, epichlorohydrin can be synthesized efficiently and cleanly by the epoxidation reaction of 3-chloropropene with hydrogen peroxide in the presence of a titanium silicalite catalyst and methanol as a solvent. Epichlorohydrin is an important basic organic chemical raw material and intermediate, and is widely applied to synthesis of epoxy resin, chlorohydrin rubber, medicines, pesticides, surfactants, plasticizers and other industrial products.
CN101747296A and CN101747297A disclose methods for producing epichlorohydrin by epoxidation reaction of 3-chloropropene and hydrogen peroxide, which realizes continuous and stable synthesis of epichlorohydrin for a long time under the condition that the conversion rate of hydrogen peroxide is higher than 97% and the selectivity of epichlorohydrin is higher than 95%. CN101293882A further discloses a method for economically and efficiently separating epichlorohydrin from the epoxidation reaction product of 3-chloropropene and hydrogen peroxide, which can produce a certain amount of epoxidation wastewater while obtaining epichlorohydrin product and recovering 3-chloropropene and methanol.
The epoxidation wastewater contains 0.1 to 1 mass% of 3-chloro-1, 2-propanediol and 0.2 to 2 mass% of chlorinated organic compounds such as chloropropanediol monomethyl ether. It is known that chlorinated organic compounds are a class of surface water and soil pollutants (baulun, zhang jun, wuhong, lao warrior, rejuvenation, research progress on biodegradation of halogenated organic substances, journal of chinese health examination, 2002, 12 (3): 376 to 380), especially 3-chloro-1, 2-propanediol, as reported by kunshun et al (cynhun, sunset, galloanser, sun juniper, berubine. food pollutants 3-chloro-1, 2-propanediol toxicology progress, food industry science and technology, 2013-chloro-1, 2-propanediol is a chlorinated organic compound with obvious toxicity and carcinogenicity to rodents. Therefore, the toxic and harmful epoxidation wastewater needs to be subjected to harmless treatment to remove the 3-chloro-1, 2-propanediol and chloropropanediol monomethyl ether.
For the epoxidation wastewater of epoxy chloropropane synthesized by epoxidizing 3-chloropropene containing 3-chloro-1, 2-propanediol and chloropropanediol monomethyl ether with hydrogen peroxide, no published report for directly decomposing the 3-chloro-1, 2-propanediol and chloropropanediol monomethyl ether exists.
Disclosure of Invention
The invention aims to provide a harmless treatment method of toxic and harmful epoxidation wastewater generated in the process of synthesizing epoxy chloropropane by epoxidizing 3-chloropropene and hydrogen peroxide, so as to realize the harmless treatment of the epoxidation wastewater.
The invention provides a harmless treatment method of epoxidation wastewater, which comprises the following steps: a) contacting and mixing epoxidation wastewater obtained by epoxidizing 3-chloropropene and hydrogen peroxide to synthesize epichlorohydrin with an alkaline aqueous solution in a wastewater treatment reactor to convert 3-chloro-1, 2-propanediol therein into glycerol; b) optionally, neutralizing the reaction mixture obtained in step a); the alkaline aqueous solution is an aqueous solution of alkali metal hydroxide, alkaline earth metal hydroxide and alkali metal salt.
The harmless treatment method of the epoxidation wastewater provided by the invention has the beneficial effects that:
the harmless treatment method of the epoxidation wastewater provided by the invention can convert the toxic and harmful epoxidation wastewater generated in the process of synthesizing epoxy chloropropane by epoxidizing 3-chloropropene and hydrogen peroxide into non-toxic and harmless wastewater, thereby realizing the harmless treatment of the epoxidation wastewater. The method provided by the invention can eliminate toxic and harmful 3-chloro-1, 2-propanediol and chloropropanediol monomethyl ether in the epoxidation wastewater, realize harmless treatment of the epoxidation wastewater, and has the advantages of simple process and easy realization of industrialization.
Detailed Description
The harmless treatment method of the epoxidation wastewater provided by the invention is implemented as follows:
a harmless treatment method of epoxidized wastewater comprises the following steps: a) contacting and mixing epoxidation wastewater generated in the process of synthesizing epichlorohydrin by epoxidizing 3-chloropropene and hydrogen peroxide with an alkaline aqueous solution in a wastewater treatment reactor to convert 3-chloro-1, 2-propanediol in the wastewater into glycerol; b) optionally, neutralizing the reaction mixture obtained in step a); the alkaline aqueous solution is an aqueous solution of alkali metal hydroxide, alkaline earth metal hydroxide and alkali metal salt.
In the method for the harmless treatment of the epoxidized wastewater, the content of 3-chloro-1, 2-propanediol in the epoxidized wastewater is 0.1-1 mass%. Preferably, the harmless treatment method of the epoxidation wastewater provided by the invention is used for preferably treating wastewater containing 3-chloro-1, 2-propanediol and chloropropanediol monomethyl ether, wherein the content of the chloropropanediol monomethyl ether is 0.2-2 mass%.
In the method for treating epoxidation wastewater provided by the invention, the alkali metal hydroxide is lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide and cesium hydroxide, and preferably lithium hydroxide, sodium hydroxide and potassium hydroxide.
The alkaline earth metal hydroxide is calcium hydroxide, strontium hydroxide and barium hydroxide, preferably barium hydroxide.
The alkali metal salt is an alkali metal carbonate. The alkali metal carbonate is sodium carbonate, potassium carbonate, rubidium carbonate and cesium carbonate, and sodium carbonate and potassium carbonate are preferred.
More preferably, the alkaline aqueous solution is an aqueous sodium hydroxide solution.
In the method for treating epoxidation wastewater provided by the invention, the content of the alkaline compound in the alkaline aqueous solution is 1-60% by mass, preferably 10-50% by mass.
The invention provides an epoxidation wasteIn the water treatment method, preferably, the temperature for contact mixing of the epoxidation wastewater and the alkaline aqueous solution in the wastewater treatment reactor is 0-300 ℃, the pressure is 0.1-10.0 MPa, and the addition amount of the alkaline aqueous solution is 1-30 mass% of the amount of the wastewater; more preferably, the wastewater treatment reactor adopts a plug flow reactor, wherein the temperature of contact mixing is 0-300 ℃, the pressure is 0.1-10.0 MPa, and the hourly space velocity of the feeding liquid of the epoxidation wastewater is 0.1-20 h-1The volume space velocity of the alkaline aqueous solution is 0.01-0.5 h-1。
More preferably, the contact mixing temperature of the epoxidation wastewater and the alkaline aqueous solution in the wastewater treatment reactor is 50-250 ℃, the pressure is 0.1-5.0 MPa, and the hourly space velocity of the feeding liquid of the epoxidation wastewater is 0.3-15 h-1。
The following examples further illustrate the process of the present invention but are not intended to limit the invention thereto.
Example 1
In a 350mL stirred autoclave, 300.00g of the epoxidation wastewater having a 3-chloro-1, 2-propanediol content of 0.24 mass% and 8.43g of an aqueous sodium hydroxide solution having a sodium hydroxide content of 30 mass% were charged, respectively, and mixed at 100 ℃ and 0.1MPa with stirring for 1 hour, whereby 100.00% of the 3-chloro-1, 2-propanediol was converted into glycerol.
Example 2
The epoxidized wastewater was treated in the same manner as in example 1, except that the content of 3-chloro-1, 2-propanediol in the epoxidized wastewater was 0.49% by mass, the content of chloropropanediol monomethyl ether was 0.89% by mass, the amount of the aqueous sodium hydroxide solution was 12.18g, and the wastewater treatment temperature was 80 ℃. As a result of the treatment of the epoxidation wastewater, 100.00% of 3-chloro-1, 2-propanediol was converted into glycerol and 100.00% of chloropropanediol monomethyl ether was converted into glycerol monomethyl ether.
Example 3
Epoxidized wastewater was treated in the same manner as in example 1, except that the epoxidized wastewater had a 3-chloro-1, 2-propanediol content of 0.92 mass% and a chloropropanediol monomethyl ether content of 1.51 mass%, 10.28g of an alkaline aqueous solution having a potassium hydroxide content of 50 mass% was added, and the wastewater treatment temperature was 70 ℃. As a result of the treatment of the epoxidation wastewater, 100.00% of 3-chloro-1, 2-propanediol was converted into glycerol and 100.00% of chloropropanediol monomethyl ether was converted into glycerol monomethyl ether.
Example 4
Epoxidized wastewater was treated in the same manner as in example 3 except that 21.10g of an aqueous alkaline solution having a lithium hydroxide content of 20 mass% was added. As a result of the treatment of the epoxidation wastewater, 100.00% of 3-chloro-1, 2-propanediol was converted into glycerol and 100.00% of chloropropanediol monomethyl ether was converted into glycerol monomethyl ether.
Example 5
Epoxidized wastewater was treated in the same manner as in example 4 except that 81.58g of an aqueous alkaline solution having a barium hydroxide content of 10 mass% was added. As a result of the treatment of the epoxidation wastewater, 100.00% of 3-chloro-1, 2-propanediol was converted into glycerol and 100.00% of chloropropanediol monomethyl ether was converted into glycerol monomethyl ether.
Example 6
Epoxidized wastewater was treated in the same manner as in example 4 except that the epoxidized wastewater had a 3-chloro-1, 2-propanediol content of 0.57 mass% and a chloropropanediol monomethyl ether content of 0.81 mass%, and 16.97g of an alkaline aqueous solution having a sodium carbonate content of 30 mass% was added. As a result of the treatment of the epoxidation wastewater, the conversion of 3-chloro-1, 2-propanediol into glycerol was 93.19%, and the conversion of chloropropanediol monomethyl ether into glycerol monomethyl ether was 87.98%.
Example 7
Epoxidized wastewater was treated in the same manner as in example 4 except that 3-chloro-1, 2-propanediol content was 0.78 mass% and chloropropanediol monomethyl ether content was 0.96 mass%, and 22.10g of an alkaline aqueous solution containing 30 mass% of potassium carbonate was added. As a result of the treatment of the epoxidation wastewater, the conversion of 3-chloro-1, 2-propanediol into glycerin was 87.57%, and the conversion of chloropropanediol monomethyl ether into glycerol monomethyl ether was 86.21%.
Example 8
The epoxidation wastewater was treated in the same manner as in example 1 except that the treatment temperature of the epoxidation wastewater was 60 ℃ and the treatment result of the epoxidation wastewater was 81.05% in the conversion of 3-chloro-1, 2-propanediol into glycerol and 91.73% in the conversion of chloropropanediol monomethyl ether into glycerol monomethyl ether.
Example 9
Continuously treating the epoxidation wastewater in a jacketed pipe type reactor with the effective volume of 86mL, wherein the content of 3-chlorine-1, 2-propylene glycol in the epoxidation wastewater is 0.45 mass percent, the content of chloropropylene glycol monomethyl ether is 1.05 mass percent, and the feeding volume liquid hourly space velocity of the epoxidation wastewater is 13.95h-1The hourly space velocity of the feed solution of the 30 mass% aqueous sodium hydroxide solution was 0.22h-1The temperature of the jacket oil bath was kept constant at 240 ℃ and the pressure at the outlet of the reactor was kept constant at 4.3MPa, and after 1 hour of continuous feeding, a liquid sample at the outlet of the reactor was taken for analysis, and the pH of the liquid sample was 7, in which 3-chloro-1, 2-propanediol had been 100.00% converted to glycerol and chloropropanediol monomethyl ether had been 100.00% converted to glycerol monomethyl ether.
Example 10
Epoxidation waste water was continuously treated in the same manner as in example 9 except that the hourly space velocity of the feed solution of 30 mass% aqueous sodium hydroxide solution was 0.23h-1And as a result of the treatment of the epoxidation wastewater, the pH value of the epoxidation wastewater is 8-9, wherein the conversion rate of 3-chloro-1, 2-propanediol into glycerol is 100.00%, and the conversion rate of chloropropanediol monomethyl ether into glycerol monomethyl ether is 100.00%.
Example 11
Epoxidation waste water was continuously treated in the same manner as in example 9 except that the hourly space velocity of the feed solution of 30 mass% aqueous sodium hydroxide solution was 0.21 hr-1And as a result of the treatment of the epoxidation wastewater, the pH value of the epoxidation wastewater is 3-4, wherein the conversion rate of 3-chloro-1, 2-propanediol into glycerol is 100.00%, and the conversion rate of chloropropanediol monomethyl ether into glycerol monomethyl ether is 96.91%.
Example 12
By the use ofExample 9 the epoxidation wastewater was continuously treated in the same manner as in example 9 except that the hourly space velocity of the feed solution of the 30 mass% aqueous sodium hydroxide solution was 0.18h-1And as a result of the treatment of the epoxidation wastewater, the pH value of the epoxidation wastewater is 2-3, wherein the conversion rate of 3-chloro-1, 2-propanediol into glycerol is 100.00%, and the conversion rate of chloropropanediol monomethyl ether into glycerol monomethyl ether is 94.04%.
Example 13
The epoxidation wastewater was continuously treated in the same manner as in example 9 except that the content of 3-chloro-1, 2-propanediol in the epoxidation wastewater was 0.73% by mass, the content of chloropropanediol monomethyl ether was 1.61% by mass, and the feed volume liquid hourly space velocity of the epoxidation wastewater was 9.77h-1The hourly space velocity of the feed solution of 30% by mass aqueous sodium hydroxide solution was 0.28h-1And after 2 hours of continuous feeding, the pH value of the epoxidation wastewater is 13-14, wherein the conversion rate of 3-chloro-1, 2-propylene glycol into glycerol is 100.00%, and the conversion rate of chloropropanediol monomethyl ether into glycerol monomethyl ether is 100.00%.
Example 14
The epoxidation wastewater was continuously treated in the same manner as in example 9 except that the content of 3-chloro-1, 2-propanediol in the epoxidation wastewater was 0.53% by mass, the content of chloropropanediol monomethyl ether was 1.28% by mass, and the feed volume liquid hourly space velocity of the epoxidation wastewater was 4.88h-1The hourly space velocity of the feed solution of the 30 mass% aqueous sodium hydroxide solution was 0.14h-1The temperature of the jacket oil bath is constant at 150 ℃, the outlet pressure of the reactor is constant at 0.6MPa, and after 2 hours of continuous feeding, the pH value of the epoxidation wastewater is 13-14, wherein the conversion rate of 3-chloro-1, 2-propanediol into glycerol is 100.00%, and the conversion rate of chloropropanediol monomethyl ether into glycerol monomethyl ether is 100.00%.
Example 15
The epoxidized wastewater was continuously treated by the same method as in example 9, except that the content of 3-chloro-1, 2-propanediol in the epoxidized wastewater was 0.42 mass% and the content of chloropropanediol monomethyl ether was 1.02 mass%,the feed volume liquid hourly space velocity of the epoxidation wastewater is 0.489h-1The hourly space velocity of the feed solution of 30% by mass aqueous sodium hydroxide solution was 0.014h-1The temperature of the jacket oil bath is constant at 60 ℃, the outlet pressure of the reactor is constant at 0.1MPa, and after continuous feeding is carried out for 6 hours, the pH value of the epoxidation wastewater is 13-14, the conversion rate of 3-chloro-1, 2-propylene glycol into glycerol is 100.00%, and the conversion rate of chloropropanediol monomethyl ether into glycerol monomethyl ether is 94.83%.
The mode of the present invention has been described in detail above, but the present invention is not limited to the specific details of the above-described embodiments, and various simple modifications can be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
Claims (5)
1. A harmless treatment method for epoxidized wastewater is characterized by comprising the following steps:
a) contacting and mixing epoxidation wastewater obtained by epoxidizing 3-chloropropene and hydrogen peroxide to synthesize epichlorohydrin with an alkaline aqueous solution in a wastewater treatment reactor to convert 3-chloro-1, 2-propanediol therein into glycerol; the alkaline aqueous solution is an aqueous solution of an alkali metal hydroxide, an alkaline earth metal hydroxide and an alkali metal salt, the content of an alkaline compound in the alkaline aqueous solution is 10-50 mass%, the content of 3-chloro-1, 2-propanediol in the epoxidation wastewater is 0.1-1 mass%, and the content of chloropropanediol monomethyl ether is 0.2-2 mass%; the wastewater treatment reactor adopts a plug flow reactor, wherein the contact mixing temperature is 50-250 ℃, the pressure is 0.1-5.0 MPa, and the hourly space velocity of the feeding liquid of the epoxidation wastewater is 0.3-15 h-1The volume space velocity of the alkaline aqueous solution is 0.01-0.5 h-1。
2. The method for innocent treatment of epoxidized wastewater according to claim 1, further comprising: b) neutralizing the reaction mixture obtained in step a).
3. The innocent treatment method of epoxidized wastewater according to claim 1 or 2, wherein the wastewater treatment reactor is a packed bed reactor, a tower reactor, a tubular reactor or a microchannel reactor.
4. The innocent treatment method of the epoxidation wastewater as claimed in claim 1 or 2, wherein said alkali metal hydroxide is one or more of lithium hydroxide, sodium hydroxide and potassium hydroxide; the alkaline earth metal hydroxide is barium hydroxide; the alkali metal salt is an alkali metal carbonate.
5. The method according to claim 4, wherein the aqueous alkaline solution is an aqueous solution of sodium hydroxide, sodium carbonate or potassium carbonate.
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| WO2014042937A1 (en) * | 2012-09-14 | 2014-03-20 | Archer Daniels Midland Company | Processes for removing monochloropropanediols and/or glycidol from glycerol |
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| CN101006068A (en) * | 2005-05-20 | 2007-07-25 | 索尔维公司 | Method for making epoxide |
| CN101657400A (en) * | 2007-04-12 | 2010-02-24 | 陶氏环球技术公司 | Method and apparatus for the preparation of chlorohydrins |
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