CN103816860B - A kind of composition and method of making the same and application processing Citric Acid Production waste liquid - Google Patents
A kind of composition and method of making the same and application processing Citric Acid Production waste liquid Download PDFInfo
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- CN103816860B CN103816860B CN201410065756.4A CN201410065756A CN103816860B CN 103816860 B CN103816860 B CN 103816860B CN 201410065756 A CN201410065756 A CN 201410065756A CN 103816860 B CN103816860 B CN 103816860B
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Abstract
The invention discloses a kind of composition and method of making the same and the application that process Citric Acid Production waste liquid, said composition represents by mass percentage: comprise the natural zeolite of 5 ~ 20%, the heat modification zeolite of 5 ~ 20%, the attapulgite clay of 5 ~ 20% and 50% ~ 75% heat modification attapulgite clay; Take the finished product namely obtaining composition after above-mentioned component mixes in proportion.When said composition uses, said composition is added in Citric Acid Production liquid waste treating apparatus according to the ratio of 30g/L ~ 100g/L, under 20 DEG C ~ 40 DEG C conditions, constant temperature stirs 60 ~ 80 minutes, make composition and Citric Acid Production waste liquid fully mix, adsorb, then namely separation of supernatant and precipitation complete the process of Citric Acid Production waste liquid.Composition of the present invention effectively can remove total acid, total nitrogen and total reducing sugar in Citric Acid Production waste liquid, improves the pH value of waste liquid, reduces content of organics in waste liquid, reduces costs and increase the benefit.
Description
Technical field
The present invention relates to field of waste water treatment, specifically a kind of cost low, pollute little and the composition and method of making the same of the process Citric Acid Production waste liquid that treatment effect is good and application.
Background technology
China is Citric Acid Production state maximum in the world, and citric acid annual production has reached 980,000 tons, accounts for more than 60% of Gross World Product.Citric Acid Production mainly adopts fermentation method, can produce a large amount of waste liquid during the fermentation, often produce 1 ton of citric acid have the waste liquid more than 7.5 tons to produce, have even up to more than 10 tons.Analysis shows, containing a large amount of organic matters such as sugar, protein, organic acid in citric acid waste liquid, must it be made to reach industrial wastewater discharge standard after the method process such as Aerobic biological process method, anaerobic biological process, processing cost be high.
Summary of the invention
The object of the invention is the defect existed for prior art, provide a kind of cost low, pollute little and the composition and method of making the same of the process Citric Acid Production waste liquid that treatment effect is good and application.
The object of the invention is to solve by the following technical programs:
Process a composition for Citric Acid Production waste liquid, it is characterized in that: described composition represents by mass percentage: comprise the natural zeolite of 5 ~ 20%, the heat modification zeolite of 5 ~ 20%, the attapulgite clay of 5 ~ 20% and 50% ~ 75% heat modification attapulgite clay.
The fineness of described natural zeolite is between 60 ~ 80 orders and ammonia absorption value is not less than 100mmol/100g; In described natural zeolite, the content of clinoptilolite is not less than 50%.
The fineness of described heat modification zeolite between 60 ~ 80 orders, and this heat modification zeolite by zeolite materials at 300 ~ 400 DEG C after high-temperature calcination 3-4h cooling obtain.
Described zeolite materials comprises the clinoptilolite that content is not less than 50%.
The fineness of described attapulgite clay and the fineness of heat modification attapulgite clay are neither lower than 100 orders.
Described heat modification attapulgite clay adopts attapulgite clay to cool after high-temperature calcination 3-4h at 200 ~ 300 DEG C and obtains.
A kind of preparation method processing the composition of Citric Acid Production waste liquid, it is characterized in that: the step of described preparation method is: take natural zeolite, heat modification zeolite, attapulgite clay and heat modification attapulgite clay Homogeneous phase mixing according to the above ratio, the composition of this process Citric Acid Production waste liquid can be obtained.
A kind of application processing the composition of Citric Acid Production waste liquid, it is characterized in that: described application process is: get the above-mentioned composition for preparing and add in Citric Acid Production liquid waste treating apparatus according to the ratio of 30g/L ~ 100g/L, under 20 DEG C ~ 40 DEG C conditions, constant temperature stirs 60 ~ 80 minutes, make composition and Citric Acid Production waste liquid fully mix, adsorb, then namely separation of supernatant and precipitation complete the process of Citric Acid Production waste liquid.
Supernatant and precipitation adopt natural subsidence mode to be separated, and supernatant overflows Citric Acid Production liquid waste treating apparatus, carry out drying process after the solid content employing plate and frame filter press press filtration of precipitation.
The present invention has the following advantages compared to existing technology:
The present invention is by being optimized composite assembling by zeolite and attapulgite clay, effectively can remove the materials such as total acid, carbohydrate, protein and the ammonia nitrogen in Citric Acid Production waste liquid, improve waste liquid pH value, reduce waste liquid organic matter and ammonia-nitrogen content, citric acid production wastewater after process is met and produces the requirement of citric acid water, realize waste liquid circulation recycling, effectively reduce the harm that Citric Acid Production waste liquid causes to environment.
The present invention selected there is the multiple good characteristic such as selective absorption, ion-exchange and cheap zeolite, attapulgite clay and both modified products carry out composite optimization assembling, while effectively disposing waste liquid, reduce Citric Acid Production environmental protection of enterprise expense, improve Business Economic Benefit, be suitable for promoting the use of.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further illustrated.
Process a composition for Citric Acid Production waste liquid, said composition represents by mass percentage: comprise the natural zeolite of 5 ~ 20%, the heat modification zeolite of 5 ~ 20%, the attapulgite clay of 5 ~ 20% and 50% ~ 75% heat modification attapulgite clay.The fineness of the natural zeolite wherein selected is between 60 ~ 80 orders and ammonia absorption value is not less than 100mmol/100g, and in this natural zeolite, the content of clinoptilolite is not less than 50%; The fineness of the heat modification zeolite selected is between 60 ~ 80 orders, and this heat modification zeolite is cooled after high-temperature calcination 3-4h by zeolite materials and obtains at 300 ~ 400 DEG C, comprises at zeolite materials the clinoptilolite that content is not less than 50%; The fineness of attapulgite clay and the fineness of heat modification attapulgite clay are neither lower than 100 orders, the raw material selection attapulgite clay content of attapulgite clay and heat modification attapulgite clay is not less than the natural raw ore of 50%, and heat modification attapulgite clay employing attapulgite clay cools after high-temperature calcination 3-4h and obtains at 200 ~ 300 DEG C in addition.
A kind of preparation method processing the composition of Citric Acid Production waste liquid, the step of this preparation method is: take natural zeolite, heat modification zeolite, attapulgite clay and heat modification attapulgite clay Homogeneous phase mixing according to the above ratio, can obtain the composition of this process Citric Acid Production waste liquid.
A kind of application processing the composition of Citric Acid Production waste liquid, this application process is: get the above-mentioned composition for preparing and add in Citric Acid Production liquid waste treating apparatus according to the ratio of 30g/L ~ 100g/L, under 20 DEG C ~ 40 DEG C conditions, constant temperature stirs 60 ~ 80 minutes, make composition and Citric Acid Production waste liquid fully mix, adsorb, then namely separation of supernatant and precipitation complete the process of Citric Acid Production waste liquid.In above process, supernatant and precipitation adopt natural subsidence mode to be separated, and supernatant overflows Citric Acid Production liquid waste treating apparatus, carry out drying process after the solid content employing plate and frame filter press press filtration of precipitation.
embodiment 1:
Process a composition for Citric Acid Production waste liquid, said composition represents by mass percentage: comprise the natural zeolite of 5%, the heat modification zeolite of 20%, the attapulgite clay of 10% and 65% heat modification attapulgite clay.
embodiment 2:
Process a composition for Citric Acid Production waste liquid, said composition represents by mass percentage: comprise the natural zeolite of 10%, the heat modification zeolite of 10%, the attapulgite clay of 5% and 75% heat modification attapulgite clay.
contrast test
In order to verify the effect of said composition process Citric Acid Production waste liquid, composition embodiment 1 prepared carries out the test of Citric Acid Production liquid waste processing.Precision measures Fresh Lemon acid fermentation raffinate 10 parts, every part of 100mL, be placed in tool plug conical flask respectively, and number consecutively, every bottle of composition adding 5g above-mentioned process Citric Acid Production waste liquid, tool plug conical flask stirs 70 min at 30 DEG C of temperature, then makes supernatant be separated with precipitation natural subsidence, gets supernatant to be measured.PHS-3C electronics pH meter is adopted to measure citric acid fermentation broth pH value before and after process; Measure citric acid fermentation broth total acid content before and after process with reference to GB/T15308-2006, calculate total acid clearance; Adopt the total nitrogen content of citric acid waste liquid before and after Kjeldahl nitrogen determination absorption; Method with reference to GB/T15308-2006 measures the total sugar content of citric acid waste liquid before and after process.Result is as shown in table 1, and after process, citric acid waste liquid pH value is 5.24, and total acid, total nitrogen and total reducing sugar clearance are respectively 73.21%(
p<0.05), 70.49%(
pand 40.74%(<0.05)
p<0.05).The composition that the embodiment of the present invention 1 is prepared in sum effectively can remove total acid, total reducing sugar and ammonia nitrogen in Citric Acid Production waste liquid, improves the pH value of waste liquid.
Table 1 adsorbs pH value, total acid, total nitrogen, total sugar content and clearance in the citric acid waste liquid of front and back
| Before absorption | After absorption | Clearance (%) | |
| PH value | 2.67±0.05 | 5.24±0.04 | |
| Total acid (g/L) | 1.90±0.01 a | 0.51±0.01 b | 73.21±0.12 |
| Total nitrogen (g/L) | 0.84±0.01 a | 0.25±0.01 b | 70.49±0.17 |
| Total reducing sugar (g/L) | 16.95±0.01 a | 10.05±0.01 b | 40.74±0.08 |
Note: colleague's shoulder marking-up mother (a, b) different expression significant difference (
p<0.05), lower same.
The attapulgite clay that composition prepared by the present invention is selected and zeolite are class nonmetallic mineral materials, all have the multiple good characteristic such as adsorption selection, ion-exchange, and cheap.Natural zeolite effectively can remove the ammonia nitrogen in waste liquid, attapulgite clay is better than zeolite to organic adsorption capacity, therefore, zeolite and attapulgite clay are optimized composite assembling, effectively can remove total acid, total nitrogen and the total reducing sugar in Citric Acid Production waste liquid, improve waste liquid pH value, reduce content of organics in waste liquid, the citric acid production wastewater after process is made to realize cycling and reutilization, the harm that effective minimizing Citric Acid Production waste liquid causes to environment, reduce Citric Acid Production environmental protection of enterprise expense, improve Business Economic Benefit.
Above embodiment is only and technological thought of the present invention is described, can not limit protection scope of the present invention with this, every technological thought proposed according to the present invention, and any change that technical scheme basis is done, all falls within scope; The technology that the present invention does not relate to all is realized by prior art.
Claims (4)
1. process a composition for Citric Acid Production waste liquid, it is characterized in that: described composition represents by mass percentage: comprise the natural zeolite of 5 ~ 20%, the heat modification zeolite of 5 ~ 20%, the attapulgite clay of 5 ~ 20% and 50% ~ 75% heat modification attapulgite clay; The fineness of described natural zeolite is between 60 ~ 80 orders and ammonia absorption value is not less than 100mmol/100g; In described natural zeolite, the content of clinoptilolite is not less than 50%; The fineness of described heat modification zeolite between 60 ~ 80 orders, and this heat modification zeolite by zeolite materials at 300 ~ 400 DEG C after high-temperature calcination 3-4h cooling obtain; Described zeolite materials comprises the clinoptilolite that content is not less than 50%; The fineness of described attapulgite clay and the fineness of heat modification attapulgite clay are neither lower than 100 orders; Described heat modification attapulgite clay adopts attapulgite clay to cool after high-temperature calcination 3-4h at 200 ~ 300 DEG C and obtains.
2. one kind processes the preparation method of the composition of Citric Acid Production waste liquid as claimed in claim 1, it is characterized in that: the step of described preparation method is: take natural zeolite, heat modification zeolite, attapulgite clay and heat modification attapulgite clay Homogeneous phase mixing according to the above ratio, the composition of this process Citric Acid Production waste liquid can be obtained.
3. one kind processes the application of the composition of Citric Acid Production waste liquid as claimed in claim 1, it is characterized in that: described application process is: get the above-mentioned composition for preparing and add in Citric Acid Production liquid waste treating apparatus according to the ratio of 30g/L ~ 100g/L, under 20 DEG C ~ 40 DEG C conditions, constant temperature stirs 60 ~ 80 minutes, make composition and Citric Acid Production waste liquid fully mix, adsorb, then namely separation of supernatant and precipitation complete the process of Citric Acid Production waste liquid.
4. the application of the composition of process Citric Acid Production waste liquid according to claim 3, it is characterized in that: supernatant and precipitation adopt natural subsidence mode to be separated, supernatant overflows Citric Acid Production liquid waste treating apparatus, carries out drying process after the solid content employing plate and frame filter press press filtration of precipitation.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5008227A (en) * | 1989-05-16 | 1991-04-16 | Engelhard Corporation | Process for making acid activated bleaching earth using high susceptibility source clay and novel bleaching earth product |
| CN101186351A (en) * | 2007-12-06 | 2008-05-28 | 合肥工业大学 | Method for processing industrial waste acid solution and preparing drying agent by using dolomite-containing attapulgite clay |
-
2014
- 2014-02-26 CN CN201410065756.4A patent/CN103816860B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5008227A (en) * | 1989-05-16 | 1991-04-16 | Engelhard Corporation | Process for making acid activated bleaching earth using high susceptibility source clay and novel bleaching earth product |
| CN101186351A (en) * | 2007-12-06 | 2008-05-28 | 合肥工业大学 | Method for processing industrial waste acid solution and preparing drying agent by using dolomite-containing attapulgite clay |
Non-Patent Citations (1)
| Title |
|---|
| 非金属矿物在废水处理中的应用研究;林鑫等;《环境科学与管理》;20130930;第38卷(第9期);第64-67页 * |
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Inventor after: Zhuang Su Inventor after: Yan Rui Inventor after: Zhou Yanmin Inventor after: Gao Feng Inventor after: Huang Jie Inventor after: Wen Chao Inventor after: Tang Zhigang Inventor before: Zhuang Su Inventor before: Yan Rui Inventor before: Zhou Yanmin Inventor before: Huang Jie Inventor before: Wen Chao Inventor before: Tang Zhigang |
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Address after: 211225 Lishui County, Nanjing City, white horse town national agricultural science and Technology Park, Nanjing Agricultural University, Co-patentee after: Jiangsu supernatural power biological Polytron Technologies Inc Patentee after: Nanjing Agricultural University Address before: 211225 Lishui County, Nanjing City, white horse town national agricultural science and Technology Park, Nanjing Agricultural University, Co-patentee before: JIANGSU SHENLITE BIOLOGICAL SCIENCE & TECHNOLOGY CO., LTD. Patentee before: Nanjing Agricultural University |