CN108264936A - A kind of harmlessness disposing of Wastewater in Biologic Pharmacy utilizes method - Google Patents
A kind of harmlessness disposing of Wastewater in Biologic Pharmacy utilizes method Download PDFInfo
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- CN108264936A CN108264936A CN201810283624.7A CN201810283624A CN108264936A CN 108264936 A CN108264936 A CN 108264936A CN 201810283624 A CN201810283624 A CN 201810283624A CN 108264936 A CN108264936 A CN 108264936A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/46—Gasification of granular or pulverulent flues in suspension
- C10J3/48—Apparatus; Plants
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/72—Other features
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/16—Integration of gasification processes with another plant or parts within the plant
- C10J2300/1603—Integration of gasification processes with another plant or parts within the plant with gas treatment
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/16—Integration of gasification processes with another plant or parts within the plant
- C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
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- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Industrial Gases (AREA)
Abstract
The present invention provides a kind of harmlessness disposing of Wastewater in Biologic Pharmacy using method, the described method comprises the following steps：Pretreatment fluid is made in pending Wastewater in Biologic Pharmacy；Pretreatment fluid, auxiliary agent and carbon source material are mixed, water-coal-slurry is made；By water-coal-slurry in oxygen-containing atmosphere, gasification reaction is carried out under 1000 DEG C~1700 DEG C and 0.5MPa~5MPa, obtains gaseous products and molten slag；By gaseous products and molten slag progress Quench and isolated mixed gas and glassy state slag.Organic component in Wastewater in Biologic Pharmacy is converted to CO, H by the present invention using coal water slurry gasification technology2And SO2Gases are waited, are obtained after purified and conversion process rich in H2And CO2Purification gas, can as production ammonium hydrogen carbonate raw material, and the poisonous and harmful substances such as heavy metal be fixed in property stabilization glassy state slag in, avoid the secondary pollution risk to environment, realize the higher value application of Wastewater in Biologic Pharmacy.
Description
Technical field
The invention belongs to wastewater treatment and recycling fields, are related to a kind of harmlessness disposing profit of Wastewater in Biologic Pharmacy
Method is utilized with method more particularly to a kind of harmlessness disposing of the Wastewater in Biologic Pharmacy containing organic solvent.
Background technology
Biological-pharmacy is the heavy polluter of pharmaceutical industry, and pollution sources come from fermentation waste water and extraction waste water.Its
In, the fermentation waste water mainly remaining nutrients of fermentation, such as carbohydrate, protein, fat and inorganic salts；It is main to extract waste water
It is using the Liquid Residue after useful component in organic solvent extraction ferment filtrate.Therefore, this two classes waste water forms bio-pharmaceuticals work
The primary pollution source of industry has the characteristics that complicated component, organic concentration are high.
For such waste water, the prior art is mainly handled using biological degradation method and high temperature sterilization.It is biodegradable
Method combination anaerobic and aerobic treatment technology handles waste water, right due to containing antibiotic agents in Wastewater in Biologic Pharmacy
Microbial environment used in biological degradation method influences seriously, thus reduces its activity and service life.High temperature sterilization is in temperature
Degree, which is higher than at 100 DEG C, handles waste water, as the Chinese invention patent of Publication No. 104016428A discloses a kind of biology
Pharmacy wastewater treatment method uses high temperature sterilization that waste water is continuously passed through to ultra-high temperature sterilization device, kills micro- life in waste water
Object.Although the method is extremely effective to killing the microorganism in waste water, the organic matter in waste water can not be effectively removed, to ecology
Environment still has secondary pollution risk.In addition, the Chinese invention patent of Publication No. 101020135A discloses one kind for locating
The catalyst and preparation method of Wastewater in Biologic Pharmacy are managed, it will be organic in Wastewater in Biologic Pharmacy containing noble metal catalyst by preparation
Object is degraded by catalytic to carboxylic acid.It is organic that carbohydrate, albumen and fat in Wastewater in Biologic Pharmacy etc. can not be effectively treated due to this method
Object, the harmlessness disposing problem of still unresolved Wastewater in Biologic Pharmacy.
It can be seen that it there is no the harmlessness disposing that can realize Wastewater in Biologic Pharmacy and higher value application in the prior art
Method, there is an urgent need for the exploitation harmlessness disposing of Wastewater in Biologic Pharmacy and higher value application new technologies, are given up with effective prevention and control bio-pharmaceuticals
Water is to the pollution risk of ecological environment and health.
Invention content
The complete harmlessness disposing of Wastewater in Biologic Pharmacy and recycling bottleneck, this hair are difficult to realize for the prior art
A kind of bright harmlessness disposing of Wastewater in Biologic Pharmacy of offer utilizes method.The present invention makes biological system using coal water slurry gasification technology
Medicine waste water carries out rapidly gasification reaction at high temperature, and organic component therein is converted into CO, H2And SO2Etc. mixed gas, then pass through
It is obtained after desulfurization and conversion process rich in H2And CO2Purification gas, can be used as producing the originals of the chemical products such as ammonium hydrogen carbonate
Material；And the grey substance for failing to gasify that grades then is converted into the glassy state slag of property stabilization, by poisonous and harmful substances such as heavy metals
It is fixed, it, can be as the auxiliary material of production construction material to environment non-secondary pollution risk.Therefore, method provided by the invention is both real
Show quick, the thorough harmlessness disposing of Wastewater in Biologic Pharmacy, and realize its higher value application.
For this purpose, the present invention uses following technical scheme：
The present invention provides a kind of harmlessness disposing of Wastewater in Biologic Pharmacy using method, the method includes following steps
Suddenly：
(1) pretreatment fluid is made in pending Wastewater in Biologic Pharmacy；
(2) step (1) described pretreatment fluid with auxiliary agent and carbon source material is mixed, water-coal-slurry is made；
(3) by step (2) described water-coal-slurry in oxygen-containing atmosphere, under 1000 DEG C~1700 DEG C and 0.5MPa~5MPa into
Row gasification reaction, obtains gaseous products and molten slag；
(4) gaseous products and molten slag the progress Quench obtained step (3) and isolated mixed gas and glass
State slag.
Wherein, step (3) the gasification reaction temperature can be 1000 DEG C, 1050 DEG C, 1100 DEG C, 1150 DEG C, 1200 DEG C,
1250 DEG C, 1300 DEG C, 1350 DEG C, 1400 DEG C, 1450 DEG C, 1500 DEG C, 1550 DEG C, 1600 DEG C, 1650 DEG C or 1700 DEG C etc., but simultaneously
Cited numerical value is not limited only to, other unrequited numerical value are equally applicable in the numberical range；The reaction pressure can be
0.5MPa, 1MPa, 1.5MPa, 2MPa, 2.5MPa, 3MPa, 3.5MPa, 4MPa, 4.5MPa or 5MPa etc., it is not limited to institute
The numerical value enumerated, other interior unrequited numerical value of the numberical range are equally applicable.
Water-coal-slurry is made after Wastewater in Biologic Pharmacy is uniformly mixed with auxiliary agent and carbon source material in the method for the invention, through upper
The organic component almost all after step process in Wastewater in Biologic Pharmacy is stated to be converted into containing CO, H2、CO2、SO3And CH4Deng mixing
Gas obtains H after purified and conversion process2And CO2Volume content is more than 95% purification gas, can be used as production carbon
The raw material of the chemical products such as sour hydrogen ammonium.In the present invention, the ash content and a small amount of unreacted C in water-coal-slurry are more than ash fusion point (stream
Dynamic temperature) at a high temperature of form the molten slag of molten state, can obtain after Quench is handled property it is stable, to environment without secondary dirt
The glassy state slag of risk is contaminated, the auxiliary material for producing construction material, and the cooling water and/or washing slag water generated in chilling process can be used as
It can be recycled after filtering.Therefore, the method for the invention can realize Wastewater in Biologic Pharmacy complete harmlessness disposing and
It can realize the higher value application of its organic component, and then be expected to realize the waste " near-zero release " of Wastewater in Biologic Pharmacy.
The method of the invention differs markedly from the prior art, and the present invention can be made biology using coal water slurry gasification technology
Poisonous and harmful substance in medicine waste water is thoroughly decomposed, and will not generate secondary pollution, and what is obtained contains CO, H2、CO2、SO3And CH4Deng
Mixed gas is purified and conversion process after be converted into H2And CO2Purification gas as main component can be used as production carbonic acid
The raw material of the chemical products such as hydrogen ammonium.Ash content and a small amount of unreacted C in water-coal-slurry is in the height more than ash fusion point (flowing temperature)
The molten slag of molten state is formed under temperature, property stabilization is can obtain after Quench is handled, to the glass of environment non-secondary pollution risk
Glass state slag, can be as the auxiliary material of production construction material, and cooling water and/or washing slag water can be recycled after filtering.Therefore, this hair
Bright the method can realize the complete harmlessness disposing and higher value application of Wastewater in Biologic Pharmacy.
The present invention needs to control temperature, pressure, time and the reaction atmosphere of gasification reaction, not in above-mentioned gasification reaction temperature
In degree, pressure, time and reaction atmosphere range, then target gaseous product and fluid slag that cannot be described.
In the present invention, the Quench mainly carries out being quickly cooled down processing to gaseous products and molten slag, to detach
To mixed gas and glassy state slag.The Quench carries out in shock chamber, molten slag after being contacted with chilled water quick Quench consolidate
Change, forming properties are stable and to the glassy state slag of environment non-secondary pollution risk after cooling.The glassy state slag can be used as production
The auxiliary material of construction material realizes the harmlessness disposing and higher value application of Wastewater in Biologic Pharmacy.
Below as currently preferred technical solution, but not as the limitation of technical solution provided by the invention, pass through
Following technical scheme can preferably reach and realize the technical purpose and advantageous effect of the present invention.
As currently preferred technical solution, step (1) the pending Wastewater in Biologic Pharmacy is biological pharmaceutical factory
Residual solution of fermenting and/or extraction waste water.Wherein, it is described extraction waste water refer to by organic solvent extract ferment filtrate in it is useful into
Liquid Residue after point.
Preferably, the pH value of pending Wastewater in Biologic Pharmacy is adjusted in step (1) to 4~6, obtains pretreatment fluid, wherein
PH value can be 4,4.3,4.5,4.7,5,5.3,5.5,5.7 or 6 etc., it is not limited to cited numerical value, the numberical range
Other interior unrequited numerical value are equally applicable.
Herein, by adjusting the pH value of pending Wastewater in Biologic Pharmacy, the viscosity for follow-up regulation and control water-coal-slurry lays the foundation,
To ensure subsequently to obtain the excellent water-coal-slurry of mobility, and destruction will not be generated to the auxiliary agent of other in water-coal-slurry.
Preferably, using the pH value of the pending Wastewater in Biologic Pharmacy of acidic materials adjusting to 4~6.
Preferably, the acidic materials are any one in inorganic acid, organic acid or salt of weak acid or at least two combination,
The combination is typical but non-limiting examples have：The combination of the combination of inorganic acid and organic acid, organic acid and salt of weak acid, it is inorganic
Combination of acid, organic acid and salt of weak acid etc..
Preferably, the acidic materials for any one in nitric acid, sulfuric acid, hydrochloric acid, sodium bicarbonate, citric acid or oxalic acid or
At least two combination, the combination is typical but non-limiting examples have：The combination of nitric acid and sulfuric acid, hydrochloric acid and sodium bicarbonate
Combination, the combination of citric acid and oxalic acid, the combination of nitric acid, sulfuric acid and hydrochloric acid, the combination of hydrochloric acid, sodium bicarbonate and citric acid, carbon
Combination of sour hydrogen sodium, citric acid and oxalic acid etc..
As currently preferred technical solution, auxiliary agent described in step (2) is amphiphilic surfactant.
In the present invention, " amphipathic " refers to lipophile and hydrophily.The present invention lives using with amphiphilic surface
Property agent, can effectively be adsorbed in coal surface, improve the hydrophily of coal, and electric double layer can be formed on coal surface and three-dimensional is hindered
Hinder, and then help to improve paste-forming properties, prevent separation of solid and liquid.
Preferably, step (1) described auxiliary agent is naphthalene sulfonate, lignosulfonates, sulfonated humic acid salt, polyene hydrocarbon sulfonate
Any one in salt, polyacrylate, carboxylate or phosphate or at least two combination, the combination are typical but nonrestrictive
Example has：The combination of naphthalene sulfonate and lignosulfonates, the combination of sulfonated humic acid salt and polyolefm sulfonates, polyacrylic acid
Ester, carboxylate are combined with phosphatic, preferably sodium naphthalene sulfonate, potassium lignosulfonate, sulfonated humic acid sodium, polyene hydrocarbon sulfonate
Any one in potassium or sodium phosphate or at least two combination.
As currently preferred technical solution, step (2) described carbon source material for charcoal, coal, coke powder, carbon black or with C,
Any one in H and O organic matters as main component or at least two combination, the combination typical case but non-limiting examples
Have：The combination of the combination of charcoal and coal, coke powder and organic matter, the combination of charcoal, coal and coke powder, the group of coal, carbon black and organic matter
Close etc., as long as the carbon source can obtain water-coal-slurry.
Preferably, the mass ratio of step (2) pretreatment fluid, auxiliary agent and carbon source material is 100:(0.2~2.0):(50
, such as 100~200):0.2:(50~200), 100:0.5:(50~200), 100:1:(50~200), 100:1.5:(50~
Or 100 200):2:(50~200) etc., for another example 100:(0.2~2.0):50、100:(0.2~2.0):70、100:(0.2~
2.0):100、100:(0.2~2.0):130、100:(0.2~2.0):150、100:(0.2~2.0):170 or 100:(0.2~
2.0):200 etc., can also be 100:0.2:50、100:0.5:70、100:1:100、100:1.3:130、100:1.5:150、100:
1.7:170 or 100:2:200 etc., it is not limited to cited numerical value, other interior unrequited numerical value of the numberical range are same
Sample is applicable in, and preferably 100:(0.5~1.0):(100~150).
In the present invention, by regulating and controlling pretreatment fluid, auxiliary agent and the proportioning of carbon source material, be conducive to follow-up water-coal-slurry and prepared
Uniform and stable, not stratified water-coal-slurry is formed in journey, and ensures it with excellent mobility, and then convenient for passing through nozzle by water
Coal slurry uniformly sprays into gasification furnace.What is more important, containing the necessary component that can form glassy state slag in the carbon source material,
By regulating and controlling the proportioning of pretreatment fluid and carbon source material, property stabilization is advantageously formed and to the glass of environment non-secondary pollution risk
Glass state slag, and then the trace heavy metal element in Wastewater in Biologic Pharmacy is fixed wherein.Furthermore it is ensured that Wastewater in Biologic Pharmacy
In organic matter fully reacted with the C in carbon source, and then be converted into target gaseous product.
As currently preferred technical solution, step (2) is described to be mixed into defibrination process, it is not limited at defibrination
Reason, is prepared water-coal-slurry, therefore details are not described herein again by this field conventional technical means.
Preferably, water-coal-slurry made from step (2) adjusts its viscosity as 300mPas~700mPas, such as
300mPa·s、350mPa·s、400mPa·s、450mPa·s、500mPa·s、550mPa·s、600mPa·s、
650mPas or 700mPas etc., it is not limited to cited numerical value, other interior unrequited numerical value of the numberical range
It is equally applicable；Solid masses content is 40%~70%, such as 40%, 45%, 50%, 55%, 60%, 65% or 70% etc.,
It is not limited to cited numerical value, other interior unrequited numerical value of the numberical range are equally applicable.
In the present invention, by regulate and control water-coal-slurry viscosity and solid masses content in a zone of reasonableness, convenient for making water
Coal slurry passes through nozzle and uniformly sprays into gasification furnace.Meanwhile the solid masses content for regulating and controlling water-coal-slurry can improve processing effect
Rate and effect, rational solid masses content can be such that the organic component in water-coal-slurry converts completely, and be conducive to obtain higher
H2With the mixed gas of CO volume contents.
As currently preferred technical solution, volume content >=99.5% of oxygen in step (3) described oxygen-containing atmosphere,
Such as 99.5%, 99.6%, 99.7%, 99.8% or 99.9% etc., it is not limited to cited numerical value, the numberical range
Other interior unrequited numerical value are equally applicable.
Preferably, step (3) the gasification reaction temperature is 1200 DEG C~1500 DEG C, pressure is 1MPa~3MPa, this is
Further preferred gasification reaction conditions, effect are more excellent compared with the reaction condition of 1000 DEG C~1700 DEG C and 0.5MPa~5MPa.
Preferably, step (3) the gasification reaction time be 2s~15s, such as 2s, 4s, 6s, 8s, 10s, 12s, 14s or
15s etc., it is not limited to cited numerical value, other interior unrequited numerical value of the numberical range are equally applicable, preferably 5s
~10s.
Preferably, step (3) described gasification reaction carries out in gasification furnace.
As currently preferred technical solution, step (4) described Quench is is quickly cooled to 100 in 0.5s~10s
DEG C~300 DEG C, cooling time can be 0.5s, 1s, 2s, 3s, 4s, 5s, 6s, 7s, 8s, 9s or 10s etc., it is not limited to institute
The numerical value enumerated, other interior unrequited numerical value of the numberical range are equally applicable；Its temperature reached after cooling down can be 100
DEG C, 130 DEG C, 150 DEG C, 170 DEG C, 200 DEG C, 230 DEG C, 250 DEG C, 270 DEG C or 300 DEG C etc., it is not limited to cited number
Value, other interior unrequited numerical value of the numberical range are equally applicable, and 100 DEG C~200 are preferably quickly cooled in 1s~4s
℃。
Preferably, the cooling water and/or washing slag water generated in step (4) described chilling process recycles after filtering,
Such as the use water of Quench processing is can be recycled for use as, it can also be used as other purposes as needed.
As currently preferred technical solution, the isolated mixed gas of step (4) is carried out at desulfurization and transformation
Reason is obtained rich in H2And CO2Purification gas.
Herein, the desulfurization and conversion process have routine techniques for this field, and so it will not be repeated, with institute of the present invention
Other step coordinateds of method are stated, form the harmlessness disposing and higher value application of Wastewater in Biologic Pharmacy of the present invention
Complete technical solution.
Preferably, H in the purification gas2And CO2Volume content >=95%, such as 95%, 96%, 97%, 98% or
99% etc., it is not limited to cited numerical value, other interior unrequited numerical value of the numberical range are equally applicable.
Preferably, it is described to be rich in H2And CO2Purification gas for producing ammonium hydrogen carbonate.
As currently preferred technical solution, the glassy state slag that step (4) obtains can be as the auxiliary of production construction material
Material.
As currently preferred technical solution, the described method comprises the following steps：
(1) pH value of pending Wastewater in Biologic Pharmacy is adjusted to 4~6, and pretreatment fluid is made；
(2) by step (1) pretreatment fluid, auxiliary agent and carbon source material in mass ratio 100:(0.2~2.0):(50~
200) it is uniformly mixed, the water-coal-slurry that viscosity is 300mPas~700mPas, solid masses content is 40%~70% is made；
(3) by step (2) described water-coal-slurry in the oxygen-containing atmosphere of oxygen volume content >=99.5%, in 1200 DEG C~
Gasification reaction 5s~10s is carried out under 1500 DEG C and 1MPa~3MPa, obtains gaseous products and molten slag；
(4) gaseous products and molten slag obtained step (3) are cooled to 100 DEG C~200 DEG C and are divided in 1s~4s
From mixed gas and glassy state slag is obtained, desulfurization and conversion process are carried out to obtained mixed gas, obtain H2And CO2Volume contains
The purification gas of amount >=95%, can be as the raw material of the chemical products such as production ammonium hydrogen carbonate；The cooling generated in chilling process
Water and/or washing slag water recycle after filtering；Obtained glassy state slag property is stablized, and to environment non-secondary pollution risk,
It can be used as producing the auxiliary material of construction material.
The effect that the present invention under these conditions carries out Wastewater in Biologic Pharmacy harmlessness disposing and higher value application is optimal.
Compared with prior art, the invention has the advantages that：
(1) the method for the invention can thoroughly decompose the poisonous and harmful substance in Wastewater in Biologic Pharmacy, will not generate
Secondary pollution had not only reached the target of Wastewater in Biologic Pharmacy harmlessness disposing, but also its organic component is converted into target gaseous mixture
Body, and then realize the higher value application of Wastewater in Biologic Pharmacy.
(2) main component that the method for the invention obtains mixed gas is H2And CO, it is purified to be obtained with after conversion process
To rich in H2And CO2Purification gas, can be used as produce ammonium hydrogen carbonate raw material；Obtained glassy state slag can be by bio-pharmaceuticals
The poisonous and harmful substances such as the heavy metal in waste water are fixed, and property is stable, to environment non-secondary pollution risk, can be used as production and builds
Build the auxiliary material of material.
(3) harmlessness disposing of Wastewater in Biologic Pharmacy provided by the invention can be utilized in Wastewater in Biologic Pharmacy using method
Moisture prepares water-coal-slurry, and the cooling water and/or washing slag water that Quench processing generates can be recycled after filtering so that entire processing
Process non-wastewater discharge had not only avoided the secondary pollution of ecological environment, but also can reduce the cost of disposal of Wastewater in Biologic Pharmacy.
Description of the drawings
Fig. 1 is that a kind of harmlessness disposing of Wastewater in Biologic Pharmacy of the present invention utilizes the flow diagram of method.
Specific embodiment
For the present invention is better described, technical scheme of the present invention is easy to understand, below to the present invention further specifically
It is bright.But following embodiments is only the simple example of the present invention, does not represent or limit the scope of the present invention, this
Invention protection domain is subject to claims.
Specific embodiment of the invention part provides a kind of harmlessness disposing of Wastewater in Biologic Pharmacy using method, such as schemes
Shown in 1, it the described method comprises the following steps：
(1) pretreatment fluid is made in pending Wastewater in Biologic Pharmacy；
(2) step (1) pretreatment fluid, auxiliary agent and carbon source material are uniformly mixed, water-coal-slurry is made；
(3) by step (2) described water-coal-slurry in oxygen-containing atmosphere, under 1000 DEG C~1700 DEG C and 0.5MPa~5MPa into
Row gasification reaction, obtains gaseous products and molten slag；
(4) gaseous products and molten slag the progress Quench obtained step (3) and isolated mixed gas and glass
State slag.
But non-limiting example typical for the present invention below：
Embodiment 1：
A kind of harmlessness disposing of Wastewater in Biologic Pharmacy is present embodiments provided using method, the method includes following steps
Suddenly：
(1) pH value for adjusting pending Wastewater in Biologic Pharmacy with sulfuric acid solution obtains pretreatment fluid to 4.0；
(2) by pretreatment fluid, sodium naphthalene sulfonate and coke in mass ratio 100:0.5:100 are uniformly mixed, and carry out ball-milling treatment,
The water-coal-slurry that solid masses content is 50%, viscosity is 416mPas is made；
(3) water-coal-slurry made from step (2) by nozzle is uniformly sprayed into the gasification furnace of oxygen-containing atmosphere and carries out gasified reverse
Should, reaction temperature is 1400 DEG C, the volume content of oxygen is 99.5% in pressure 1.5MPa, oxygen-containing atmosphere, the residence time is
4s obtains gaseous products and molten slag；
(4) gaseous products and molten slag obtained step (3) Quench in 2s to 150 DEG C, obtains mixed gas, property
Matter is stable and to glassy state slag, cooling water and the washing slag water of environment non-secondary pollution risk；The glassy state slag can be used as production
The auxiliary material of construction material；The cooling water and/or washing slag water can be recycled after filtering；
(5) mixed gas obtained to step (4) is purified and conversion process, obtains H2And CO2Volume content is 98%
Purification gas；
(6) purification gas for obtaining step (5) and the N obtained after air space division2For producing ammonium hydrogen carbonate.
Embodiment 2：
A kind of harmlessness disposing of Wastewater in Biologic Pharmacy is present embodiments provided using method, the method includes following steps
Suddenly：
(1) pH value for adjusting pending Wastewater in Biologic Pharmacy with salpeter solution obtains pretreatment fluid to 6.0；
(2) by pretreatment fluid, carboxylic acid sodium and coal dust in mass ratio 100:1.0:80 are uniformly mixed, and carry out ball-milling treatment, system
Into the water-coal-slurry that solid masses content is 60%, viscosity is 649mPas；
(3) water-coal-slurry made from step (2) by nozzle is uniformly sprayed into the gasification furnace of oxygen-containing atmosphere and carries out gasified reverse
Should, reaction temperature is 1500 DEG C, the volume content of oxygen is 99.8% in pressure 2.5MPa, oxygen-containing atmosphere, the residence time is
6s obtains gaseous products and molten slag；
(4) gaseous products and molten slag obtained step (3) Quench in 1s to 160 DEG C, obtains mixed gas, property
Matter is stable and to glassy state slag, cooling water and the washing slag water of environment non-secondary pollution risk；The glassy state slag can be used as production
The auxiliary material of construction material；The cooling water and/or washing slag water can be recycled after filtering；
(5) mixed gas obtained to step (4) is purified and conversion process, obtains H2And CO2Volume content is 96%
Purification gas；
(6) purification gas for obtaining step (5) and the N obtained after air space division2For producing ammonium hydrogen carbonate.
Embodiment 3：
A kind of harmlessness disposing of Wastewater in Biologic Pharmacy is present embodiments provided using method, the method includes following steps
Suddenly：
(1) pH value for adjusting pending Wastewater in Biologic Pharmacy with sodium bicarbonate solution obtains pretreatment fluid to 5.2；
(2) by pretreatment fluid, sulfonated humic acid sodium and charcoal in mass ratio 100:2.0:200 are uniformly mixed, and carry out ball milling
Processing, is made the water-coal-slurry that solid masses content is 70%, viscosity is 700mPas；
(3) water-coal-slurry made from step (2) by nozzle is uniformly sprayed into the gasification furnace of oxygen-containing atmosphere and carries out gasified reverse
Should, reaction temperature is 1600 DEG C, the volume content of oxygen is 99.5% in pressure 3.5MPa, oxygen-containing atmosphere, the residence time is
10s obtains gaseous products and molten slag；
(4) gaseous products and molten slag obtained step (3) in 10s Quench to 100 DEG C, obtain mixed gas,
Property is stable and to glassy state slag, cooling water and the washing slag water of environment non-secondary pollution risk；The glassy state slag can be used as life
Produce the auxiliary material of construction material；The cooling water and/or washing slag water can be recycled after filtering；
(5) mixed gas obtained to step (4) is purified and conversion process, obtains H2And CO2Volume content is 98%
Purification gas；
(6) purification gas for obtaining step (5) and the N obtained after air space division2It is used to prepare ammonium hydrogen carbonate.
Embodiment 4：
A kind of harmlessness disposing of Wastewater in Biologic Pharmacy is present embodiments provided using method, the method includes following steps
Suddenly：
(1) pH value for adjusting pending Wastewater in Biologic Pharmacy with citric acid solution obtains pretreatment fluid to 4.6；
(2) by pretreatment fluid, polyacrylate and coke in mass ratio 100:0.2:70 are uniformly mixed, and carry out at ball milling
Reason, is made the water-coal-slurry that solid masses content is 40%, viscosity is 300mPas；
(3) water-coal-slurry made from step (2) by nozzle is uniformly sprayed into the gasification furnace of oxygen-containing atmosphere and carries out gasified reverse
Should, reaction temperature is 1000 DEG C, the volume content of oxygen is 99.8% in pressure 5.0MPa, oxygen-containing atmosphere, the residence time is
3s obtains gaseous products and molten slag；
(4) gaseous products and molten slag obtained step (3) Quench in 3s to 120 DEG C, obtains mixed gas, property
Matter is stable and to glassy state slag, cooling water and the washing slag water of environment non-secondary pollution risk；The glassy state slag can be used as production
The auxiliary material of construction material；The cooling water and/or washing slag water can be recycled after filtering；
(5) mixed gas obtained to step (4) is purified and conversion process, obtains H2And CO2Volume content is
97.6% purification gas；
(6) purification gas for obtaining step (5) and the N obtained after air space division2It is used to prepare ammonium hydrogen carbonate.
Embodiment 5：
A kind of harmlessness disposing of Wastewater in Biologic Pharmacy is present embodiments provided using method, the method includes following steps
Suddenly：
(1) pH value for adjusting pending Wastewater in Biologic Pharmacy with oxalic acid solution obtains pretreatment fluid to 5.2；
(2) by pretreatment fluid, polyacrylate and biomass carbon source in mass ratio 100:0.8:100 are uniformly mixed, and carry out
The water-coal-slurry that solid masses content is 48%, viscosity is 431mPas is made in ball-milling treatment；
(3) water-coal-slurry made from step (2) by nozzle is uniformly sprayed into the gasification furnace of oxygen-containing atmosphere and carries out gasified reverse
Should, reaction temperature is 1700 DEG C, the volume content of oxygen is 99.7% in pressure 0.5MPa, oxygen-containing atmosphere, the residence time is
2s obtains gaseous products and molten slag；
(4) gaseous products and molten slag obtained step (3) in 0.5s Quench to 300 DEG C, obtain mixed gas,
Property is stable and to glassy state slag, cooling water and the washing slag water of environment non-secondary pollution risk；The glassy state slag can be used as life
Produce the auxiliary material of construction material；The cooling water and/or washing slag water can be recycled after filtering；
(5) mixed gas obtained to step (4) is purified and conversion process, obtains H2And CO2Volume content is
96.2% purification gas；
(6) purification gas for obtaining step (5) and the N obtained after air space division2It is used to prepare ammonium hydrogen carbonate.
Comparative example 1：
This comparative example provides a kind of harmlessness disposing of Wastewater in Biologic Pharmacy using method, and the method is with reference to embodiment
1 the method, difference lies in：Gasification reaction temperature is 800 DEG C (1000 DEG C of ＜, i.e. gasification reaction temperature is too low) in step (3).
This comparative example the method is since gasification reaction temperature is too low, Wastewater in Biologic Pharmacy nothing within the reaction time
Method is reacted completely, leads to CO and H in gaseous products2Volume content is very low, can not obtain target gaseous product and molten slag, into
And it can not realize the harmlessness disposing and higher value application of Wastewater in Biologic Pharmacy.
Comparative example 2：
This comparative example provides a kind of harmlessness disposing of Wastewater in Biologic Pharmacy using method, and the method is with reference to embodiment
1 the method, difference lies in：Gasification reaction temperature is 1800 DEG C of (1700 DEG C of ＞, i.e. gasification reaction temperature mistake in step (3)
It is high).
This comparative example the method can not be cooled to no Er Evil since gasification reaction temperature is excessively high in very short time
The temperature of English generation, leads to not obtain target gaseous product and molten slag, and then can not realize the nothing of Wastewater in Biologic Pharmacy
Evilization is disposed and higher value application.
Comparative example 3：
This comparative example provides a kind of harmlessness disposing of Wastewater in Biologic Pharmacy using method, and the method is with reference to embodiment
1 the method, difference lies in：Gasification reaction pressure is 0.3MPa (＜ 0.5MPa, i.e. gasification reaction pressure mistake in step (3)
It is low).
This comparative example the method is due to gasification reaction hypotony, Wastewater in Biologic Pharmacy nothing within the reaction time
Method is reacted completely, leads to CO and H in gaseous products2Volume content is very low.In addition, silicon, aluminium in added carbon source material and its
The oxide of his element is difficult to form glass state material in a short time.Although can make it by extending the time the reaction was complete,
But easily generate dioxin to environmental hazard higher poisonous and harmful substance.Therefore, gasification reaction hypotony, can not
Target gaseous product and molten slag are obtained, and then can not realize the harmlessness disposing and higher value application of Wastewater in Biologic Pharmacy.
Comparative example 4：
This comparative example provides a kind of harmlessness disposing of Wastewater in Biologic Pharmacy using method, and the method is with reference to embodiment
1 the method, difference lies in：Gasification reaction pressure is 6MPa (＞ 5MPa, i.e. gasification reaction hypertonia) in step (3).
This comparative example the method can not obtain target gaseous product due to gasification reaction hypertonia, gasification reaction product
And molten slag, and then can not realize the harmlessness disposing and higher value application of Wastewater in Biologic Pharmacy.
Comparative example 5：
This comparative example provides a kind of harmlessness disposing of Wastewater in Biologic Pharmacy using method, and the method is with reference to embodiment
1 the method, difference lies in：Gasification reaction in step (3) is relatively low (volume content ＜ 99.5%) in anaerobic or oxygen content
Atmosphere in carry out.
This comparative example the method is since gasification reaction is in the gas of anaerobic or oxygen content relatively low (volume content ＜ 99.5%)
It is carried out in atmosphere, gasification reaction product can not obtain target gaseous product and molten slag, and then can not realize Wastewater in Biologic Pharmacy
Harmlessness disposing and higher value application.
Summary embodiment and comparative example can be seen that the method for the invention can be by having in Wastewater in Biologic Pharmacy
Malicious harmful substance is thoroughly decomposed, and will not generate secondary pollution, has not only realized the harmlessness disposing of Wastewater in Biologic Pharmacy, but also by it most
Be converted into eventually can higher value application be rich in H2And CO2Purification gas.
Meanwhile the method for the invention obtain mixed gas main component be H2And CO, after purified and conversion process
It can obtain being rich in H2And CO2Purification gas, can be as the raw material of the production chemical products with high added-value such as ammonium hydrogen carbonate；It obtains
Glassy state slag property it is stable, to environment non-secondary pollution risk, the auxiliary material for producing construction material can be used as.
Also, a kind of harmlessness disposing of Wastewater in Biologic Pharmacy of the present invention can be given up using method using bio-pharmaceuticals
Moisture in water prepares water-coal-slurry, and the cooling water and/or washing slag water that Quench processing generates can be recycled after filtering so that whole
A technical process non-wastewater discharge, not only effective prevention and control were to the secondary pollution risk of ecological environment, but also reduced bio-pharmaceuticals and give up
The cost of disposal of water.
Applicant declares, and the present invention illustrates the detailed applications method of the present invention by above-described embodiment, but the present invention is simultaneously
Above-mentioned detailed applications method is not limited to, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implement.Affiliated skill
The technical staff in art field is it will be clearly understood that any improvement in the present invention, to the equivalence replacement and auxiliary of products material of the present invention
Selection of the addition of ingredient, concrete operations condition and mode etc., all falls within protection scope of the present invention and the open scope.
Claims (10)
1. a kind of harmlessness disposing of Wastewater in Biologic Pharmacy utilizes method, which is characterized in that the described method comprises the following steps：
(1) pretreatment fluid is made in pending Wastewater in Biologic Pharmacy；
(2) step (1) described pretreatment fluid with auxiliary agent and carbon source material is mixed, water-coal-slurry is made；
(3) by step (2) described water-coal-slurry in oxygen-containing atmosphere, into promoting the circulation of qi under 1000 DEG C~1700 DEG C and 0.5MPa~5MPa
Change reaction, obtain gaseous products and molten slag；
(4) gaseous products and molten slag the progress Quench obtained step (3) and isolated mixed gas and glassy state slag.
2. a kind of harmlessness disposing of Wastewater in Biologic Pharmacy according to claim 1 utilizes method, which is characterized in that step
(1) the pending Wastewater in Biologic Pharmacy is the fermentation residual solution of biological pharmaceutical factory and/or extraction waste water；
Preferably, the pH value of pending Wastewater in Biologic Pharmacy is adjusted in step (1) to 4~6, obtains pretreatment fluid；
Preferably, using the pH value of the pending Wastewater in Biologic Pharmacy of acidic materials adjusting to 4~6；
Preferably, the acidic materials are any one in inorganic acid, organic acid or salt of weak acid or at least two combination；
Preferably, the acidic materials are for any one in nitric acid, sulfuric acid, hydrochloric acid, sodium bicarbonate, citric acid or oxalic acid or extremely
Combination two kinds few.
3. a kind of harmlessness disposing of Wastewater in Biologic Pharmacy according to claim 1 or 2 utilizes method, which is characterized in that
Auxiliary agent described in step (2) is amphiphilic surfactant；
Preferably, step (1) described auxiliary agent for naphthalene sulfonate, lignosulfonates, sulfonated humic acid salt, polyolefm sulfonates,
Any one in polyacrylate, carboxylate or phosphate or at least two combination, preferably sodium naphthalene sulfonate, lignin sulfonic acid
Any one in potassium, sulfonated humic acid sodium, polyolefin potassium sulfonate or sodium phosphate or at least two combination.
4. method, feature are utilized according to a kind of harmlessness disposing of Wastewater in Biologic Pharmacy of claim 1-3 any one of them
Be, step (2) described carbon source material for charcoal, coal, coke powder, carbon black or in C, H and O organic matter as main component appoint
It anticipates a kind of or at least two combinations；
Preferably, the mass ratio of step (2) pretreatment fluid, auxiliary agent and carbon source material is 100:(0.2~2.0):(50~
200), preferably 100:(0.5~1.0):(100~150).
5. method, feature are utilized according to a kind of harmlessness disposing of Wastewater in Biologic Pharmacy of claim 1-4 any one of them
It is, step (2) is described to be mixed into defibrination process；
Preferably, water-coal-slurry made from step (2) adjusts its viscosity as 300mPas~700mPas, solid masses content
It is 40%~70%.
6. method, feature are utilized according to a kind of harmlessness disposing of Wastewater in Biologic Pharmacy of claim 1-5 any one of them
It is, volume content >=99.5% of oxygen in step (3) described oxygen-containing atmosphere；
Preferably, step (3) the gasification reaction temperature is 1200 DEG C~1500 DEG C, pressure is 1MPa~3MPa；
Preferably, step (3) the gasification reaction time is 2s~15s, preferably 5s~10s；
Preferably, step (3) described gasification reaction carries out in gasification furnace.
7. method, feature are utilized according to a kind of harmlessness disposing of Wastewater in Biologic Pharmacy of claim 1-6 any one of them
It is, step (4) described Quench is preferably cooled to be cooled to 100 DEG C~300 DEG C in 0.5s~10s in 1s~4s
100 DEG C~200 DEG C；
Preferably, the cooling water and/or washing slag water generated in step (4) described chilling process recycles after filtering.
8. method, feature are utilized according to a kind of harmlessness disposing of Wastewater in Biologic Pharmacy of claim 1-7 any one of them
It is, the mixed gas isolated to step (4) carries out desulfurization and conversion process, obtains rich in H2And CO2Purification gas；
Preferably, H in the purification gas2And CO2Total volume content >=95%；
Preferably, it is described to be rich in H2And CO2Purification gas for producing ammonium hydrogen carbonate.
9. method, feature are utilized according to a kind of harmlessness disposing of Wastewater in Biologic Pharmacy of claim 1-8 any one of them
It is, auxiliary material of the glassy state slag that step (4) obtains as production construction material.
10. method, feature are utilized according to a kind of harmlessness disposing of Wastewater in Biologic Pharmacy of claim 1-9 any one of them
It is, the described method comprises the following steps：
(1) pH value of pending Wastewater in Biologic Pharmacy is adjusted to 4~6, and pretreatment fluid is made；
(2) by step (1) pretreatment fluid and auxiliary agent and carbon source material in mass ratio 100:(0.2~2.0):(50~200)
It is uniformly mixed, the water-coal-slurry that viscosity is 300mPas~700mPas, solid masses content is 40%~70% is made；
(3) by step (2) described water-coal-slurry in the oxygen-containing atmosphere of oxygen volume content >=99.5%, in 1200 DEG C~1500 DEG C
With progress gasification reaction 5s~10s under 1MPa~3MPa, gaseous products and molten slag are obtained；
(4) gaseous products and molten slag obtained step (3) Quench in 1s~4s to 100 DEG C~200 DEG C and detaches
To mixed gas and glassy state slag, obtained mixed gas is subjected to desulfurization and conversion process, obtains H2And CO2Volume content >=
95% purification gas, the raw material as production ammonium hydrogen carbonate chemical products；Obtained glassy state slag is as production Building wood
The auxiliary material of material；The cooling water and/or washing slag water generated in chilling process recycles after filtering.
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