A kind of integrated treatment process of Clindamycin Hydrochloride production waste water
Technical field
The invention belongs to technical field of waste water processing, and in particular to a kind of integrated processing of Clindamycin Hydrochloride production waste water
Technique.
Background technique
Clindamycin Hydrochloride (clindamycin) is also known as clindamycin, which mainly includes in its synthesis process
Mother liquor, equipment flushing water of formation etc. mainly contain part material and intermediate product in production process, such as glycerol, acetone, second
Alcohol, ammonium hydroxide, phosphorus oxychloride, dichloroethanes, pyridine, DMF, tetracycline, lincomycinum and residual fraction Clindamycin Hydrochloride, organic matter
Content is very high, and COD is up to 70000~80000mg/L, and salt content is up to 15%, belongs to the typical organic work of high concentration difficult to degrade
Industry waste water.
By research data both domestic and external it is found that the processing method of antibiotic waste water includes: physico-chemical process, biochemical method and a variety of
The group technology of method, various methods have the advantage and deficiency of its own.Physical chemistry method master for antibiotic waste water processing
Have: precipitating, burning, UF membrane, light degradation and electrolysis method etc., although materilization freatment method all has certain treatment effect,
But some need adds a large amount of chemical agents, so that processing cost improves, is complicated for operation;Some a large amount of by-products of generation, place
Manage it is improper easily cause secondary pollution, therefore all limit their application to a certain extent.Biological treatment mainly has aerobic
Biological treatment, anaerobic bio-treated and anaerobic-aerobic combined treatment process.Biological treatment removal rate is higher, and operating cost is low, surely
It is fixed, but since synthesis class antibiotic industrial waste water is with high salt, high concentrated organic wastewater, direct biological treatment need to former waste liquid into
The dilution that ten times or even hundred times of row, clear water, power consumption are very big, cause operating cost very high, can not meet increasingly stringent place
Reason requires.
Summary of the invention
Aiming at the problems existing in the prior art, the present invention provides a kind of integrated processing of Clindamycin Hydrochloride production waste water
Technique can be realized efficient process Clindamycin Hydrochloride waste water, while guaranteeing efficient removal rate, make waste water in treatment process
The utilization of waste as resource of middle generation, final discharged wastewater met the national standard.
In order to solve the above technical problems, the invention adopts the following technical scheme:
A kind of integrated treatment process of Clindamycin Hydrochloride production waste water, steps are as follows:
(1) Clindamycin Hydrochloride production waste water uses the concentrated mother liquor and foul condensate obtained after three-effect evaporation and condensation,
Middle concentrated mother liquor centrifuge separation, the crude salt that centrifuge separation is generated are sent into salt refining workshop, and the mother liquor for being centrifugated generation is collected
Get up for extracting phosphate;
(2) in salt refining workshop, crude salt is repeatedly dissolved, evaporates, be centrifugated, obtained high-purity villaumite, washed through methanol
Finished product villaumite (NaCl) is obtained after washing, the mother liquor of generation is collected for extracting phosphate, and cleaning solution rectifying recycling methanol follows
Ring uses;
(3) mother liquor that step (1) and step (2) generate is evaporated concentration, obtained after centrifuge separation crystalline mother solution with
Phosphate, phosphate obtain finished product phosphate (Na after methanol washs3PO4), cleaning solution rectifying is recycled methanol loop and is used, and evaporates
Slag is sent to hazardous waste processing center;
(4) crystalline mother solution that the foul condensate and step (3) centrifuge separation that step (1) triple effect evaporation generates generate closes
And anaerobic bio-treated, Aerobic biological process and advanced treating are successively carried out after homogeneous.
Crude salt in the step (2) needs to carry out 2~3 times and is redissolved, evaporation, is centrifugated, and obtains after methanol washs
Obtain finished product villaumite.
Crude salt is in subtractive process in the step (2), controls 0.18~0.22Mpa of steam pressure, and 70~80 DEG C of temperature,
When density reaches 1.38~1.40, it is centrifuged.
The mother liquor that step (1) and step (2) generate is evaporated concentration in the step (3), centrifugation obtains phosphate
The same step of method (2) in crude salt refining methd.
Clindamycin Hydrochloride waste water after step (4) desalination uses ABR Anaerobic Treatment, and the residence time is 16 ~ 24 small
When.
Waste water of the step (4) after Anaerobic Treatment carries out A/O biological treatment, and the residence time is 96 ~ 120 hours,
Wherein A pool volume is the 30% ~ 40% of O pool volume.
Advanced treating in the step (4) is Fenton oxidation, and the dosage of every liter of water is H2O20.6mL~1.2mL,
FeSO4·7H2O is 0.6g~1.5g.
The concrete principle of the integrated treatment process of Clindamycin Hydrochloride production waste water of the invention is as follows:
For Clindamycin Hydrochloride waste water, using triple effect evaporation processing method, since thermal energy has been used repeatedly, significantly
Ground reduces thermal energy consumption, and not needing to add reagent reduces expense cost.
After crude product salt is completely dissolved, 0.18~0.22Mpa of steam pressure is controlled, 70~80 DEG C of temperature in the kettle, is started dense
The later period is concentrated in contracting, every 30min detection density, when density p=1.38~1.40, starts to be centrifugated, obtains low-purity chlorine
Salt;After low-purity villaumite is completely dissolved, 0.18~0.22Mpa of steam pressure is controlled, 70~80 DEG C of temperature in the kettle, is started dense
The later period is concentrated in contracting, every 30min detection density, when density p=1.38~1.40, starts to be centrifugated, obtains high-purity chloro
Salt.Phosphate mother liquor is handled using same step, can get low-purity phosphate.
The solid salt of acquisition is evaporated, is centrifugated, need to wash to remove the organic matter adhered to thereon, be done through methanol
Net finished product salt uses methanol washing kettle when methanol washs, the primary 1000L methanol that extracts enters in washing kettle, opens stirring, side
1000kg solid salt is added in stirring side thereto, and after stirring 1 hour, centrifuge separation obtains finished product salt, this desalting refinement mistake after dry
Journey, the purity of sodium phosphate, which can reach 60% ~ 70%, NaCl, can reach 99.5%, finally achievable salt resource reutilization, rectifying washing
Liquid recycles methanol, controls 65~70 DEG C of temperature, starts that methanol is concentrated, the later period is concentrated, every 30min detectable concentration, when concentration≤
When 5%, steam off valve stops concentration, and still residue is transported to hazardous waste processing center after collecting.
The crystalline mother solution that the foul condensate and centrifuge separation that multiple-effect evaporation generates generate carries out aerobic-anaerobic after merging homogeneous
Biological treatment, which is ABR anaerobism, A/O is aerobic, advanced treating is finally carried out, using Fenton oxidation technology.
For above-mentioned bioremediation, the special structure of ABR reactor, is complete relative to the fluidised form in single lattice region
Mixed flow is plug-flow again for entire reactor, this special hydraulics, and system is enabled to have good impact resistance
Power makes it have stable treatment effect, due to upward flow relatively under to the sectional area of stream want small, thus in the speed of upward flow
It is fast, anaerobic sludge can be allowed effectively and rapidly to be contacted with sewage, pollutant can be accelerated to contact with bacterium, mentioned
The high capacity utilization of system, can accordingly greatly reduce reaction dead zone, and the dead zone of ABR system can control when operation
37% hereinafter, but commonly the dead zone of anaerobic filter is up to 50% ~ 93%;And this special fluidised form is more conducive to anaerobic grain sludge
Formation, by ABR sections, hydraulic detention time is 16~for 24 hours when, the removal rate of COD can reach 90%~92%.
After ABR anaerobic bio-treated, waste water carries out A/O Aerobic Process for Treatment again.A/O technique is good by leading portion anoxic section and back segment
Oxygen section is cascaded, and A sections of DO are not more than 0.2mg/L, O sections of DO=2~4mg/L.In anoxic section heterotroph by the shallow lake in sewage
The suspended contaminants such as powder, fiber, carbohydrate and dissolved organic matter are hydrolyzed to organic acid, are decomposed into larger molecular organics
Small organic molecule, insoluble organic matter are converted to dissolved organic matter, when these products through anaerobic hydrolysis enter it is aerobic
When pond carries out Aerobic Process for Treatment, the biodegradability of sewage and the utilization efficiency of oxygen can be improved;Heterotroph is organic by protein, fat etc.
Object carries out ammonification (amino in N or amino acid in organic chain) free ammonia (NH out3、NH4 +), under sufficient oxygen supply condition, from
The nitrification of bacteria is by NH3- N(NH4 +) it is oxidized to NO3 -, by flowing back, control is back to the pond A, under anoxic conditions, heterotrophic bacteria
Denitrification by NO3 -It is reduced to molecular nitrogen (N2) circulation of C, N, O in ecology is completed, realize the innoxious place of sewage
Reason.The technology have high-efficient, process is simple, anoxic denitrification process to pollutant degradation efficiency with higher and anoxic/
The features such as resistance to overload shock ability of aerobic process is strong.
A/O reactor residence time is 96 ~ 120 hours, and A pool volume is the 30% ~ 40% of O pool volume.Volumetric loading=1 COD
~1.25kgCOD/(m3.d), by A/O Aerobic Process for Treatment COD removal rate up to 94% ~ 96%.
Waste water after above-mentioned A/O Aerobic Process for Treatment is handled through Fenton oxidation again, and Fenton oxidation handling principle is H2O2?
Fe2+Catalytic action under decompose and generate OH, oxidizing potential reaches 2.8V, it is by approach such as electronics transfers by organic matter oxygen
Small molecule inorganic matter is resolved into change.Meanwhile Fe2+It is oxidized to Fe3+Coagulating sedimentation is generated, suspended organic matter is removed.Fenton examination
Agent has oxidation and two kinds of effects of coagulation in water process.
Beneficial effects of the present invention: this integrated treatment process uses triple effect evaporation to remove according to the characteristics of chemical synthesis pharmacy
A large amount of salt in waste water makes the salinity in waste water meet the needs of biological treatment.After the salt of removing is washed with methanol, recycling
Comprehensive utilization, reduces the amount of landfill of solid waste, uses anaerobic-aerobic processing technique, removal by above-mentioned pretreated waste water
Most of organic matter, the waste water after biological treatment finally carry out Fenton oxidation, and method provided by the invention is multiple-effect evaporation, first
A kind of integrated approach that alcohol rectifying and biological treatment combine, with resource rational utilization, at low cost, easy to operate, operation
The features such as stablizing, COD, TP, the removal of the pollutants such as TN meet scientific development concepts up to 96% or more.
Detailed description of the invention
Fig. 1 is the process flow chart of the specific embodiment of the invention.
Specific embodiment
Combined with specific embodiments below, the present invention will be further described.It should be understood that following embodiment is merely to illustrate this
The person skilled in the art of the range of invention and is not intended to limit the present invention, the field can make one according to the content of foregoing invention
A little nonessential modifications and adaptations.
A kind of integrated treatment process of Clindamycin Hydrochloride production waste water of the invention is applied into Mr. Yu's pharmacy corporation, is obtained
Ideal effect.
The Clindamycin Hydrochloride waste water is derived from Henan enterprise Clindamycin Hydrochloride workshop.Enterprise's hydrochloric acid crin is mould
The production technology of element is to sum it up with chloro agent using Lincomycin Hydrochloride as raw material, make chloro substituted hydroxy group, through alkalization, water
Solution is extracted, at obtained after salt, concentration, crystallization.Its technique waste water water-quality constituents is complicated, and organic concentration is high, difficult to degrade and have
Harmful toxic matter is more, and waste water is in goldenrod and has intense stimulus smell, belongs to the biggish high-concentration organic industrial waste water of processing difficulty.
Embodiment 1
It can reach everywhere for the water quality characteristics of Clindamycin Hydrochloride waste water using integrated processing method of the invention
Manage unit stable operation, standard water discharge discharge, economical and efficient processing target, specific process method step is as follows:
(1) the production waste water of Clindamycin Hydrochloride and other cleaning waste water mixed collections are directly pumped into sewage treatment system
Sewage is first carried out three-effect evaporation and condensation and is centrifugated out saliferous organic matter again by system, the sewage disposal system;
(2) in salt refining workshop, after crude product salt is completely dissolved, 0.18~0.22Mpa of steam pressure, temperature in the kettle are controlled
70~80 DEG C, start to be concentrated, the later period is concentrated, every 30min detection density, when density p=1.38~1.40, starts centrifugation point
From acquisition low-purity villaumite;After low-purity villaumite is completely dissolved, 0.18~0.22Mpa of steam pressure, temperature in the kettle 70 are controlled
~80 DEG C, start to be concentrated, the later period is concentrated, every 30min detection density, when density p=1.38~1.40, is centrifugated, obtains
High-purity villaumite;Since when temperature raising is evaporated, Na3PO4Solubility can significantly increase, therefore although solvent subtracts
It is few that crystallization can't still be precipitated immediately, and the solubility with temperature of NaCl increases variation and is not obvious, therefore solvent is reduced, meeting
NaCl can be purified, be separated from salt-mixture by this method by the preferential crystalline solid that NaCl is precipitated, and NaCl's is pure
Degree is up to 99.5%;
(3) phosphate mother liquor is handled using same step, can get low-purity phosphate, is evaporated, is centrifuged point
Solid salt from acquisition need to wash to remove the organic matter adhered to thereon through methanol, obtain clean finished product salt Na3PO4,
Na3PO4Purity up to 60%~70%;NaCl can be used for the preparation of lincomycin, Na again3PO4It can be used for lacking applying for phosphorus soil
Fertilizer;
(4) crystalline mother solution that the foul condensate and centrifuge separation that triple effect evaporation generates generate finally carries out after merging homogeneous
Oxygen anaerobic bio-treated, which is ABR anaerobism, A/O is aerobic and Fenton oxidation is handled;When ABR sections of stop
Between be 16h, the removal rate of COD can reach 90% removal to 5000mg/L;The residence time of A/O Aerobic Process for Treatment is 96h, wherein A
Pool volume is 30%, the COD removal rate of O pool volume up to 94%, be can remove to 300mg/L;Fenton oxidation COD removal rate is reachable
60%, wherein every liter of water need to add H2O2For 0.6mL, FeSO4·7H2O is 1.5g, and COD can remove to 120mg/L.
Embodiment 2
Specific process method step is as follows:
(1) the production waste water of Clindamycin Hydrochloride and other cleaning waste water mixed collections are directly pumped into sewage treatment system
Sewage is first carried out three-effect evaporation and condensation and is centrifugated out saliferous organic matter again by system, the sewage disposal system;
(2) in salt refining workshop, after crude product salt is completely dissolved, 0.18~0.22Mpa of steam pressure, temperature in the kettle are controlled
70~80 DEG C, start to be concentrated, the later period is concentrated, every 30min detection density, when density p=1.38~1.40, starts centrifugation point
From acquisition low-purity villaumite;After low-purity villaumite is completely dissolved, 0.18~0.22Mpa of steam pressure, temperature in the kettle 70 are controlled
~80 DEG C, start to be concentrated, the later period is concentrated, every 30min detection density, when density p=1.38~1.40, is centrifugated, obtains
High-purity villaumite;Since when temperature raising is evaporated, Na3PO4Solubility can significantly increase, therefore although solvent subtracts
It is few that crystallization can't still be precipitated immediately, and the solubility with temperature of NaCl increases variation and is not obvious, therefore solvent is reduced, meeting
NaCl can be purified, be separated from salt-mixture by this method by the preferential crystalline solid that NaCl is precipitated, and NaCl's is pure
Degree is up to 99.5%;
(3) phosphate mother liquor is handled using same step, can get low-purity phosphate, is evaporated, is centrifuged point
Solid salt from acquisition need to wash to remove the organic matter adhered to thereon through methanol, obtain clean finished product salt Na3PO4,
Na3PO4Purity up to 60%~70%;NaCl can be used for the preparation of lincomycin, Na again3PO4It can be used for lacking applying for phosphorus soil
Fertilizer;
(4) crystalline mother solution that the foul condensate and centrifuge separation that triple effect evaporation generates generate finally carries out after merging homogeneous
Oxygen anaerobic bio-treated, which is ABR anaerobism, A/O is aerobic and Fenton oxidation is handled;When ABR sections of stop
Between be 20h, the removal rate of COD can reach 91% removal to 4500mg/L;The residence time of A/O Aerobic Process for Treatment is 112h, wherein A
Pool volume is 35%, the COD removal rate of O pool volume up to 95%, be can remove to 225mg/L;Fenton oxidation COD removal rate is reachable
62%, wherein every liter of water need to add H2O2For 0.8mL, FeSO4·7H2O is 1.3g, and COD can remove to 85.5mg/L.
Embodiment 3
Specific process method step is as follows:
(1) the production waste water of Clindamycin Hydrochloride and other cleaning waste water mixed collections are directly pumped into sewage treatment system
Sewage is first carried out three-effect evaporation and condensation and is centrifugated out saliferous organic matter again by system, the sewage disposal system;
(2) in salt refining workshop, after crude product salt is completely dissolved, 0.18~0.22Mpa of steam pressure, temperature in the kettle are controlled
70~80 DEG C, start to be concentrated, the later period is concentrated, every 30min detection density, when density p=1.38~1.40, starts centrifugation point
From acquisition low-purity villaumite;After low-purity villaumite is completely dissolved, 0.18~0.22Mpa of steam pressure, temperature in the kettle 70 are controlled
~80 DEG C, start to be concentrated, the later period is concentrated, every 30min detection density, when density p=1.38~1.40, is centrifugated, obtains
High-purity villaumite;Since when temperature raising is evaporated, Na3PO4Solubility can significantly increase, therefore although solvent subtracts
It is few that crystallization can't still be precipitated immediately, and the solubility with temperature of NaCl increases variation and is not obvious, therefore solvent is reduced, meeting
NaCl can be purified, be separated from salt-mixture by this method by the preferential crystalline solid that NaCl is precipitated, and NaCl's is pure
Degree is up to 99.5%;
(3) phosphate mother liquor is handled using same step, can get low-purity phosphate, is evaporated, is centrifuged point
Solid salt from acquisition need to wash to remove the organic matter adhered to thereon through methanol, obtain clean finished product salt Na3PO4,
Na3PO4Purity up to 60%~70%;NaCl can be used for the preparation of lincomycin, Na again3PO4It can be used for lacking applying for phosphorus soil
Fertilizer;
(4) crystalline mother solution that the foul condensate and centrifuge separation that triple effect evaporation generates generate finally carries out after merging homogeneous
Oxygen anaerobic bio-treated, which is ABR anaerobism, A/O is aerobic and Fenton oxidation is handled;When ABR sections of stop
Between for for 24 hours, the removal rate of COD can reach 92% removal to 4000mg/L;The residence time of A/O Aerobic Process for Treatment is 120h, wherein A
Pool volume is 40%, the COD removal rate of O pool volume up to 96%, be can remove to 160mg/L;Fenton oxidation COD removal rate is reachable
65%, wherein every liter of water need to add H2O2For 1.2mL, FeSO4·7H2O is 0.6g, and COD can remove to 56mg/L.
It is the long-term detection data of enterprise below:
After pretreatment, into biochemical system index:
Final COD, BOD, TP, TN, SS removal rate of the wastewater treatment method can achieve 96% or more.
The above course of work and the result shows that, the set for each physical chemistry method that the present invention uses, can cross give full play to it is each
The advantages of a processing unit, reduces operating cost while guaranteeing efficient degradation rate to greatest extent, in processing hydrochloric acid gram
There is certain advantage in terms of woods mycin waste water.
It should be pointed out that specific embodiment described above can make those skilled in the art that this hair be more fully appreciated
Bright creation, but do not limit the invention in any way are created.Although above-mentioned elaborate the present invention, but not limited to this,
Those skilled in the art can be modified with principle according to the present invention, and therefore, all principles according to the invention carry out
Various modifications all should be understood as falling into protection scope of the present invention.