CN105084494A - Method for removing ethinyl oestradiol and ethinylestradiol in wastewater of pharmaceutical factory - Google Patents
Method for removing ethinyl oestradiol and ethinylestradiol in wastewater of pharmaceutical factory Download PDFInfo
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- CN105084494A CN105084494A CN201510476051.6A CN201510476051A CN105084494A CN 105084494 A CN105084494 A CN 105084494A CN 201510476051 A CN201510476051 A CN 201510476051A CN 105084494 A CN105084494 A CN 105084494A
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Abstract
The invention relates to a method for removing ethinyl oestradiol and ethinylestradiol in wastewater of a pharmaceutical factory. The method includes the step that 4-isopropyltoluene, tetradecanoic acid-1-methylethyl ester, hydroxysuccinic acid, diethylenetriamine penta(methylene phosphonic acid) heptasaodium salt, argininyl-fructoyl-glucose, 4-acetoxy-3-methoxy-(2-allyl) benzene, 1H-tetrazole-1-acetic acid, acitene A, alpha-naphthol-8-sulfonic acid, amino trimethylene phosphonic acid, 3-[10,10-dimethyl-9(10H)-anthrylidene]-N,N-dimethylpropylamine hydrochloride, beta-caryophyllene, silicic acid hydrate, arginine and microcrystalline cellulose are sequentially added into the wastewater in three steps. According to the method, the complexing capacity with target substances is high, the complex sediment forming speed is high, and the removal rate can reach 99.9%; in addition, toxicity is low, the use amount is small, a water body is not damaged, the application range is wide, and the treatment cost is low.
Description
Technical field
The present invention relates to a kind of method removing ethinylestradiol and Ethinylestradiol in waste water in pharmaceutical plants, belong to environmental protection technical field.
Background technology
Ethinylestradiol and Ethinylestradiol are Estrogen class materials, clinically main forms compound as Short-term effective oral contraceptives with other hormonal substances, also change as long acting contraceptive by formulation, also can be used for treatment dysmenorrhoea, menoxenia.The factory effluent difficult for biological degradation of this kind of contraceptive bian, and there is potential source biomolecule harm.A research of Canadian Studies personnel finds, oral contraceptive composition in water drain has caused a series of chain reaction, under estrogenic effect, vitellin(Vt) can be produced in male Fish, then ovum is produced, cause a kind of fresh-water fishes blackhead small fish fish in a lake almost to become extinct, and then cause the predator lake trout quantity of this fish to decline, the quantity of the Major Foods of blackhead small fish fish---insect starts to increase.
The method of current domestic process contraceptive bian factory effluent mainly contains biological process and burning method two kinds:
1, biological process: such as SBR aerobic sludge method and AO membrane bioreactor, advantage is advantage of lower cost, but the reaction times is longer, and certain production load need be kept to maintain the stable water yield, is applicable to the enterprise that industrial scale is larger.
2, burning method: sewage sewage drying device is vaporized, sends the gas after vaporization into incinerator and burns.The salt slurry stayed during vaporization adds thermal bake-out in baking box, after organism is fully volatilized, then introduces in incinerator and burns.Advantage to ensure that organism fully resolves into inorganics and can not produce secondary pollution, and shortcoming is that incinerator need adopt the higher lumped coal of calorific value to reach regulation furnace temperature, and cost is higher.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of method removing ethinylestradiol and Ethinylestradiol in waste water in pharmaceutical plants is provided, it can with the ethinylestradiol in water and Ethinylestradiol effect, form complex compound sediment, remove by filtering, have low toxicity, non-environmental-pollution, clearance is high, applied widely, the advantage that cost is low.
Technology contents of the present invention is: a kind of method removing ethinylestradiol and Ethinylestradiol in waste water in pharmaceutical plants,
Step one: the material adding following massfraction in waste water:
4-isopropyl toluene 10-18 part,
TETRADECONIC ACID-1-methylethyl ester 15-30 part,
Hydroxy-butanedioic acid 0.7-1.1 part,
Diethylene triamine pentamethylene phosphonic seven sodium salt 15-19 part,
Final dedust 4-8 part,
Stir after 5-10 minute, leave standstill 10-20 minute, form suspension liquid;
Step 2: the material adding following massfraction in the suspension liquid that step one obtains:
4-acetoxy-3-methoxyl group-(2-propenyl) benzene 10-20 part,
1 hydrogen-tetrazolium-1-acetic acid 0.5-1.3 part,
6,6,10-trimethylammonium dicyclo-3,1,1-hept-2-ene" 6-10 part,
1-hydroxyl naphthalene-8-sulfonic acid 2-5 part,
Amino Trimethylene Phosphonic Acid 10-20 part,
Stir after 5-10 minute, leave standstill 10-20 minute, then filter to obtain supernatant liquor;
Step 3: the material adding following massfraction in the supernatant liquor that step 2 obtains:
3-[10,10-dimethyl-9 (10H)-anthracene subunit]-N, N-dimethyl propylene amine hydrochlorate 2-4 part,
β-caryophyllene 10-15 part,
Silicate hydrate 20-30 part,
1-isopropylamino-3-[p-(2-methoxyethyl) phenoxy group]-2-propyl alcohol (+)-tartrate 6-12 part,
2-amino-5-guanidinopentanoic acid 6-10 part,
Microcrystalline Cellulose is about 3-9 part,
Stir after 5-10 minute, leave standstill 10-20 minute, then filter to obtain the rear clear liquid of process;
Wherein, the quality summation of all substances of adding in step one to step 3 is 50mg/L with the ratio of the volume of processed waste water in pharmaceutical plants.
Preferably, each material also can add by following massfraction:
Step one: the material adding following massfraction in waste water:
4-isopropyl toluene 14 parts,
TETRADECONIC ACID-1-methylethyl ester 22 parts,
Hydroxy-butanedioic acid 0.9 part,
Diethylene triamine pentamethylene phosphonic seven sodium salt 17 parts,
Final dedust 6 parts,
Stir after 5-10 minute, leave standstill 10-20 minute, form suspension liquid;
Step 2: the material adding following massfraction in the suspension liquid that step one obtains:
4-acetoxy-3-methoxyl group-(2-propenyl) benzene 15 parts,
1 hydrogen-tetrazolium-1-acetic acid 0.9 part,
6,6,10-trimethylammonium dicyclo-3,1,1-hept-2-ene" 8 parts,
1-hydroxyl naphthalene-8-sulfonic acid 3 parts,
Amino Trimethylene Phosphonic Acid 15 parts,
Stir after 5-10 minute, leave standstill 10-20 minute, then filter to obtain supernatant liquor;
Step 3: the material adding following massfraction in the supernatant liquor that step 2 obtains:
3-[10,10-dimethyl-9 (10H)-anthracene subunit]-N, N-dimethyl propylene amine hydrochlorate 3 parts,
β-caryophyllene 12 parts,
Silicate hydrate 25 parts,
1-isopropylamino-3-[p-(2-methoxyethyl) phenoxy group]-2-propyl alcohol (+)-tartrate 9 parts,
2-amino-5-guanidinopentanoic acid 8 parts,
Microcrystalline Cellulose 6 parts,
Stir after 5-10 minute, leave standstill 10-20 minute, then filter to obtain the rear clear liquid of process.
The present invention has following beneficial effect:
(1) 4-isopropyl toluene, TETRADECONIC ACID-1-methylethyl ester, hydroxy-butanedioic acid, diethylene triamine pentamethylene phosphonic seven sodium salt, final dedust five kinds of materials produce synergy, can with ethinylestradiol effect, form complex compound sediment; 4-acetoxy-3-methoxyl group-(2-propenyl) benzene, 1 hydrogen-tetrazolium-1-acetic acid, 6,6,10-trimethylammonium dicyclos-3,1,1-hept-2-ene", 1-hydroxyl naphthalene-8-sulfonic acid, Amino Trimethylene Phosphonic Acid five kinds of materials produce synergy, can with ethinylestradiol effect, form complex compound sediment; 3-[10,10-dimethyl-9 (10H)-anthracene subunit]-N, N-dimethyl propylene amine hydrochlorate, β-caryophyllene, silicate hydrate, 2,3,23-trihydroxy-olea-12-alkene-28-acid, the amino-5-guanidinopentanoic acid of 2-, Microcrystalline Cellulose six kinds of materials produce synergy, can with Ethinylestradiol effect, formed complex compound sediment;
(2) strong with the complex ability of ethinylestradiol and Ethinylestradiol, form complex compound sediment speed fast, clearance can reach more than 99.9%;
(3) hypotoxicity, consumption is few, does not produce harm to water body;
(4) only need dosing and filtering separation device, low for equipment requirements, processing cost is low;
(5) use at any time and add at any time, by the restriction of producing load.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described, but the present invention's scope required for protection is not limited to the described scope of embodiment.
Embodiment 1
Remove a method for ethinylestradiol and Ethinylestradiol in waste water in pharmaceutical plants,
Step one: the material adding following massfraction in waste water:
4-isopropyl toluene 13 parts,
TETRADECONIC ACID-1-methylethyl ester 18 parts,
Hydroxy-butanedioic acid 0.8 part,
Diethylene triamine pentamethylene phosphonic seven sodium salt 15 parts,
Final dedust 5 parts,
Stir after 5-10 minute, leave standstill 10-20 minute, form suspension liquid;
Step 2: the material adding following massfraction in the suspension liquid that step one obtains:
4-acetoxy-3-methoxyl group-(2-propenyl) benzene 13 parts,
1 hydrogen-tetrazolium-1-acetic acid 0.7 part,
6,6,10-trimethylammonium dicyclo-3,1,1-hept-2-ene" 7 parts,
1-hydroxyl naphthalene-8-sulfonic acid 3 parts,
Amino Trimethylene Phosphonic Acid 13 parts,
Stir after 5-10 minute, leave standstill 10-20 minute, then filter to obtain supernatant liquor;
Step 3: the material adding following massfraction in the supernatant liquor that step 2 obtains:
3-[10,10-dimethyl-9 (10H)-anthracene subunit]-N, N-dimethyl propylene amine hydrochlorate 3 parts,
β-caryophyllene 11 parts,
Silicate hydrate 20 parts,
1-isopropylamino-3-[p-(2-methoxyethyl) phenoxy group]-2-propyl alcohol (+)-tartrate 8 parts,
2-amino-5-guanidinopentanoic acid 7 parts,
Microcrystalline Cellulose 5 parts,
Stir after 5-10 minute, leave standstill 10-20 minute, then filter to obtain the rear clear liquid of process.
Before process: containing ethinylestradiol 10mg, Ethinylestradiol 10mg in 1L water sample, add all substances 50mg altogether added in step one to step 3 successively;
After process: do not detect containing ethinylestradiol 0.01mg, Ethinylestradiol in 1L water sample.
Embodiment 2
Remove a method for ethinylestradiol and Ethinylestradiol in waste water in pharmaceutical plants,
Step one: the material adding following massfraction in waste water:
4-isopropyl toluene 15 parts,
TETRADECONIC ACID-1-methylethyl ester 25 parts,
Hydroxy-butanedioic acid 1.0 parts,
Diethylene triamine pentamethylene phosphonic seven sodium salt 18 parts,
Final dedust 7 parts,
Stir after 5-10 minute, leave standstill 10-20 minute, form suspension liquid;
Step 2: the material adding following massfraction in the suspension liquid that step one obtains:
4-acetoxy-3-methoxyl group-(2-propenyl) benzene 16 parts,
1 hydrogen-tetrazolium-1-acetic acid 1.0 parts,
6,6,10-trimethylammonium dicyclo-3,1,1-hept-2-ene" 9 parts,
1-hydroxyl naphthalene-8-sulfonic acid 4 parts,
Amino Trimethylene Phosphonic Acid 16 parts,
Stir after 5-10 minute, leave standstill 10-20 minute, then filter to obtain supernatant liquor;
Step 3: the material adding following massfraction in the supernatant liquor that step 2 obtains:
3-[10,10-dimethyl-9 (10H)-anthracene subunit]-N, N-dimethyl propylene amine hydrochlorate 4 parts,
β-caryophyllene 13 parts,
Silicate hydrate 25 parts,
1-isopropylamino-3-[p-(2-methoxyethyl) phenoxy group]-2-propyl alcohol (+)-tartrate 10 parts,
2-amino-5-guanidinopentanoic acid 9 parts,
Microcrystalline Cellulose 7 parts,
Stir after 5-10 minute, leave standstill 10-20 minute, then filter to obtain the rear clear liquid of process.
Before process: containing ethinylestradiol 8mg, Ethinylestradiol 12mg in 1L water sample, add all substances 50mg altogether added in step one to step 3 successively;
After process: in 1L water sample, ethinylestradiol and Ethinylestradiol all do not detect.
Embodiment 3
Remove a method for ethinylestradiol and Ethinylestradiol in waste water in pharmaceutical plants,
Step one: the material adding following massfraction in waste water:
4-isopropyl toluene 14 parts,
TETRADECONIC ACID-1-methylethyl ester 22 parts,
Hydroxy-butanedioic acid 0.9 part,
Diethylene triamine pentamethylene phosphonic seven sodium salt 17 parts,
Final dedust 6 parts,
Stir after 5-10 minute, leave standstill 10-20 minute, form suspension liquid;
Step 2: the material adding following massfraction in the suspension liquid that step one obtains:
4-acetoxy-3-methoxyl group-(2-propenyl) benzene 15 parts,
1 hydrogen-tetrazolium-1-acetic acid 0.9 part,
6,6,10-trimethylammonium dicyclo-3,1,1-hept-2-ene" 8 parts,
1-hydroxyl naphthalene-8-sulfonic acid 3 parts,
Amino Trimethylene Phosphonic Acid 15 parts,
Stir after 5-10 minute, leave standstill 10-20 minute, then filter to obtain supernatant liquor;
Step 3: the material adding following massfraction in the supernatant liquor that step 2 obtains:
3-[10,10-dimethyl-9 (10H)-anthracene subunit]-N, N-dimethyl propylene amine hydrochlorate 3 parts,
β-caryophyllene 12 parts,
Silicate hydrate 22 parts,
1-isopropylamino-3-[p-(2-methoxyethyl) phenoxy group]-2-propyl alcohol (+)-tartrate 9 parts,
2-amino-5-guanidinopentanoic acid 8 parts,
Microcrystalline Cellulose 6 parts,
Stir after 5-10 minute, leave standstill 10-20 minute, then filter to obtain the rear clear liquid of process.
Before process: containing ethinylestradiol 20mg, Ethinylestradiol 16mg in 1L water sample, add all substances 50mg altogether added in step one to step 3 successively;
After process: in 1L water sample, ethinylestradiol and Ethinylestradiol all do not detect.
The above; be only the specific embodiment of the present invention; but protection scope of the present invention is not limited thereto; any those of ordinary skill in the art are in the technical scope disclosed by the present invention; the change can expected without creative work or replacement, all should be encompassed within protection scope of the present invention.Therefore, the protection domain that protection scope of the present invention should limit with claims is as the criterion.
Claims (2)
1. remove a method for ethinylestradiol and Ethinylestradiol in waste water in pharmaceutical plants, it is characterized in that:
Step one: the material adding following massfraction in waste water:
4-isopropyl toluene 10-18 part,
TETRADECONIC ACID-1-methylethyl ester 15-30 part,
Hydroxy-butanedioic acid 0.7-1.1 part,
Diethylene triamine pentamethylene phosphonic seven sodium salt 15-19 part,
Final dedust 4-8 part,
Stir after 5-10 minute, leave standstill 10-20 minute, form suspension liquid;
Step 2: the material adding following massfraction in the suspension liquid that step one obtains:
4-acetoxy-3-methoxyl group-(2-propenyl) benzene 10-20 part,
1 hydrogen-tetrazolium-1-acetic acid 0.5-1.3 part,
6,6,10-trimethylammonium dicyclo-3,1,1-hept-2-ene" 6-10 part,
1-hydroxyl naphthalene-8-sulfonic acid 2-5 part,
Amino Trimethylene Phosphonic Acid 10-20 part,
Stir after 5-10 minute, leave standstill 10-20 minute, then filter to obtain supernatant liquor;
Step 3: the material adding following massfraction in the supernatant liquor that step 2 obtains:
3-[10,10-dimethyl-9 (10H)-anthracene subunit]-N, N-dimethyl propylene amine hydrochlorate 2-4 part,
β-caryophyllene 10-15 part,
Silicate hydrate 20-30 part,
1-isopropylamino-3-[p-(2-methoxyethyl) phenoxy group]-2-propyl alcohol (+)-tartrate 6-12 part,
2-amino-5-guanidinopentanoic acid 6-10 part,
Microcrystalline Cellulose is about 3-9 part,
Stir after 5-10 minute, leave standstill 10-20 minute, then filter to obtain the rear clear liquid of process;
Wherein, the quality summation of all substances of adding in step one to step 3 is 50mg/L with the ratio of the volume of processed waste water in pharmaceutical plants.
2. method according to claim 1, is characterized in that, step one: the material adding following massfraction in waste water:
4-isopropyl toluene 14 parts,
TETRADECONIC ACID-1-methylethyl ester 22 parts,
Hydroxy-butanedioic acid 0.9 part,
Diethylene triamine pentamethylene phosphonic seven sodium salt 17 parts,
Final dedust 6 parts,
Stir after 5-10 minute, leave standstill 10-20 minute, form suspension liquid;
Step 2: the material adding following massfraction in the suspension liquid that step one obtains:
4-acetoxy-3-methoxyl group-(2-propenyl) benzene 15 parts,
1 hydrogen-tetrazolium-1-acetic acid 0.9 part,
6,6,10-trimethylammonium dicyclo-3,1,1-hept-2-ene" 8 parts,
1-hydroxyl naphthalene-8-sulfonic acid 3 parts,
Amino Trimethylene Phosphonic Acid 15 parts,
Stir after 5-10 minute, leave standstill 10-20 minute, then filter to obtain supernatant liquor;
Step 3: the material adding following massfraction in the supernatant liquor that step 2 obtains:
3-[10,10-dimethyl-9 (10H)-anthracene subunit]-N, N-dimethyl propylene amine hydrochlorate 3 parts,
β-caryophyllene 12 parts,
Silicate hydrate 25 parts,
1-isopropylamino-3-[p-(2-methoxyethyl) phenoxy group]-2-propyl alcohol (+)-tartrate 9 parts,
2-amino-5-guanidinopentanoic acid 8 parts,
Microcrystalline Cellulose 6 parts,
Stir after 5-10 minute, leave standstill 10-20 minute, then filter to obtain the rear clear liquid of process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510476051.6A CN105084494A (en) | 2015-08-06 | 2015-08-06 | Method for removing ethinyl oestradiol and ethinylestradiol in wastewater of pharmaceutical factory |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510476051.6A CN105084494A (en) | 2015-08-06 | 2015-08-06 | Method for removing ethinyl oestradiol and ethinylestradiol in wastewater of pharmaceutical factory |
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| CN105084494A true CN105084494A (en) | 2015-11-25 |
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| CN201510476051.6A Pending CN105084494A (en) | 2015-08-06 | 2015-08-06 | Method for removing ethinyl oestradiol and ethinylestradiol in wastewater of pharmaceutical factory |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5582741A (en) * | 1994-03-08 | 1996-12-10 | Nec Environment Engineering Ltd. | Method for treating polluted water |
| CN2562834Y (en) * | 2002-08-13 | 2003-07-30 | 成刚 | Direct cooling type trimethylene recovering device |
| CN101787355A (en) * | 2010-03-08 | 2010-07-28 | 北京师范大学 | Oat acidovorax avenae strain capable of biodegrading natural estrogen and application thereof |
| CN101921717A (en) * | 2010-03-08 | 2010-12-22 | 北京师范大学 | Pseudomonas citronelloalis strain capable of degrading estrogen and application thereof |
| US20110180491A1 (en) * | 2008-07-28 | 2011-07-28 | Kurita Water Industries Ltd. | Method and apparatus for treating organic matter-containing water |
-
2015
- 2015-08-06 CN CN201510476051.6A patent/CN105084494A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5582741A (en) * | 1994-03-08 | 1996-12-10 | Nec Environment Engineering Ltd. | Method for treating polluted water |
| CN2562834Y (en) * | 2002-08-13 | 2003-07-30 | 成刚 | Direct cooling type trimethylene recovering device |
| US20110180491A1 (en) * | 2008-07-28 | 2011-07-28 | Kurita Water Industries Ltd. | Method and apparatus for treating organic matter-containing water |
| CN101787355A (en) * | 2010-03-08 | 2010-07-28 | 北京师范大学 | Oat acidovorax avenae strain capable of biodegrading natural estrogen and application thereof |
| CN101921717A (en) * | 2010-03-08 | 2010-12-22 | 北京师范大学 | Pseudomonas citronelloalis strain capable of degrading estrogen and application thereof |
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Application publication date: 20151125 |