CN104609525B - The processing method of high concentration pectin wastewater - Google Patents
The processing method of high concentration pectin wastewater Download PDFInfo
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Abstract
The invention discloses the processing method of a kind of high concentration pectin wastewater, this processing method include will in mandarin orange can production process produce acidleach water draw, in acidleach water add composite flocculation agent, agitated after, carry out solid-liquid separation with centrifugation, complete processing procedure；Composite flocculation agent is made up of with organic polymer coargulator inorganic flocculating agent, and inorganic flocculating agent is aluminium polychlorid and/or Al2(SO4)3, organic polymer coargulator is one or more in PAMC, dimethyl diallyl ammonium chloride acrylamide copolymer and cation Dicyandiamine-formaldehyde condensation product.The disposal methods of the present invention is effective, and operating cost is low, and processes process stabilizing.
Description
Technical field
The present invention relates to the processing method of a kind of pectin wastewater, be specifically related to a kind of mandarin orange can processing middle and high concentration pectin
The processing method of waste water.
Background technology
Through how making thorough investigation and study, mandarin orange can processing enterprise is because of the feature of self production technology, in some production processes
The sewage of different quality can be given off, after the waste water that wherein concentration of pectin is higher mostlys come from acidleach water, alkali process water, alkali bubble
Second time rinse water, Xi Guoshui after washings, the rossing-mill ground flushing water that COD concentration is higher, boiling hot fruit water, alkali bubble for the first time
Etc. operation, concentration of pectin can reach 5000mg/L.Owing to the existence of pectin can cause waste water sticky, make chemical coagulation effect significantly
Reduce, process therefore to the subsequent biochemical of waste water and bring the biggest difficulty.Test and engineering operation experience have shown that: pectin density is relatively
Little, substantial amounts of pectin flco suspends or swims on the water surface, water outlet a large amount of band mud, makes the materials such as pectin enter subsequent biochemical system
System, the microbes in biological treatment system loses activity because of the package action of pectin；It addition, the existence of pectin can make waste water
Middle dissolved oxygen is not enough, affects the growth of aerobic microbiological in biochemistry pool, the most also can cause sludge filtration dehydration difficulty.Existing fruit
In glue wastewater processing technology, the separation for pectin typically uses air supporting method, the sedimentation method and filter press technique.There is power and disappear in air supporting method
Consumption is high, pectin moisture content is high, and inferior separating effect.And the sedimentation method not only sedimentation time length, poor processing effect, and because fruit
Glue density is relatively light, often floats on the water surface and crusts, has a strong impact on subsequent treatment effect.And during filter press technique process pectin wastewater,
Owing to the viscosity of pectin wastewater is high, cause filter pressing effect the most undesirable.Therefore, it is badly in need of seeking the place of a kind of high concentration pectin wastewater
Reason method, to solving the critical problem during mandarin orange can processing waste water processes.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, it is provided that a kind of high treating effect, run into
This is low, the processing method of the high concentration pectin wastewater of process process stabilizing.
For solve above-mentioned technical problem, the present invention by the following technical solutions:
The processing method of a kind of high concentration pectin wastewater, comprises the following steps: by produce in mandarin orange can production process
Acidleach water draw, in acidleach water add composite flocculation agent, agitated after, carry out solid-liquid separation with centrifugation, complete process
Process；Described composite flocculation agent is made up of with organic polymer coargulator inorganic flocculating agent, and described inorganic flocculating agent is polymerization
Aluminum chloride (i.e. PAC) and/or Al2(SO4)3, described organic polymer coargulator be PAMC (i.e. CPAM), two
One or many in methyl diallyl ammonium chloride-acrylamide copolymer (i.e. PDA) and cation Dicyandiamine-formaldehyde condensation product
Kind.
In above-mentioned processing method, it is preferred that described acidleach water: inorganic flocculating agent: organic polymer coargulator=10mL
～300mL: 5mg～160mg: 0.5mg～8mg.
In above-mentioned processing method, it is furthermore preferred that described acidleach water: inorganic flocculating agent: organic polymer coargulator=
30mL～150mL: 10mg～96mg: 0.5mg～4mg.
In above-mentioned processing method, it is preferred that described composite flocculation agent is by aluminium polychlorid and PAMC
Composition, aluminium polychlorid adds in acidleach water the most in form of an aqueous solutions with PAMC, and aluminium polychlorid is molten
The concentration of liquid is 2g/L, and the concentration of PAMC solution is 1g/L, acidleach water: polymeric aluminum chlorides solution: cation
Polyacrylamide solution=30mL～150mL: 5mL～48mL: 0.5mL～4mL.
In above-mentioned processing method, it is preferred that described composite flocculation agent is by Al2(SO4)3With PAMC group
Become, Al2(SO4)3Add the most in form of an aqueous solutions in acidleach water with PAMC, Al2(SO4)3Solution dense
Degree is 2g/L, and the concentration of PAMC solution is 1g/L, acidleach water: Al2(SO4)3Solution: cation polypropylene acyl
Amine aqueous solution=30mL～150mL: 5mL～48mL: 0.5mL～4mL.
In above-mentioned processing method, it is preferred that the pH value of described acidleach water is 0.4～4.
In above-mentioned processing method, it is preferred that described centrifugal speed is 2500rpm～6000rpm, described centrifugal time
Between be 8min～40min.
In above-mentioned processing method, it is preferred that the speed of described stirring is 20rpm～60rpm, the time of described stirring is
5min～15min.
In above-mentioned processing method, it is preferred that before described composite flocculation agent adds in acidleach water, first acidleach water is carried out
Filter.Coarse impurities in this step removable acidleach water.
In the present invention, composite flocculation agent is made up of with organic polymer coargulator inorganic flocculating agent, inorganic flocculating agent with
Organic polymer coargulator can be separately added in acidleach water, it is possible to adds in acidleach water after mixing.
In the present invention, acidleach water is primarily referred to as in the mandarin orange can course of processing, discharges when using acid soak mandarin orange operation
The highest acid waste water of pectin content.
Compared with prior art, it is an advantage of the current invention that:
1, the processing method of the present invention is the acidleach that the concentration of pectin with the acidleach operation discharge of mandarin orange can processing enterprise is high
Water is object of study, carries out being collected separately and individual processing by acidleach water, it is achieved dirty dirty shunting, and use by inorganic flocculating agent and
The technical study that acidleach water is processed by the composite flocculation agent of organic polymer coargulator composition.The processing method of the present invention can
It is effectively improved the treatment effect of acidleach water, reduces operating cost, it is achieved pectin reclaims and resource, also solve mandarin orange tank simultaneously
Head processing waste water process causes processing the difficult problem that technological effect is poor because of the existence of pectin, improves integrated artistic safety and stablize
Property, it is achieved discharged wastewater met the national standard, process process optimization offer technical support for realizing pectin wastewater.
2, the present invention uses centrifugation to carry out solid-liquid separation, has reached good water treatment effect.Due to existing skill
In art, high concentration pectin wastewater viscosity is relatively big, and pectin is suspension, and high concentration pectin wastewater solid-liquid separation is that mandarin orange can processes
During a great problem, common dewatering type be difficult to effectively realizes solid-liquid separation, commonly used in the most existing engineering
Filter press dehydrating effect is very poor, is substantially at stoppage in transit state.The present invention uses the water sample that composite flocculation agent processed, with filter
When paper filters, it is easy to forming one layer of adhesive film on filter paper, hinder and filter, therefore, the present invention uses composite flocculation agent
After processing acidleach water, then use centrifugal mode to carry out solid-liquid separation, extraordinary water treatment effect can be realized.
Accompanying drawing explanation
Fig. 1 is composite flocculation agent different ratio and elimination rate of pectic in acidleach water in the embodiment of the present invention 2 and embodiment 3
Graph of relation.
Detailed description of the invention
Below in conjunction with Figure of description and concrete preferred embodiment, the invention will be further described, but the most therefore and
Limit the scope of the invention.
In following embodiment and comparative example, the experimental facilities of employing, experimental pharmacy, mensuration project and assay method etc. as
Under:
Experimental facilities mainly includes six blenders, high speed centrifuge, pH meter, COD analyzer and spectrophotometer etc., all
For commercially available.
Mensuration project relates to pH, COD and concentration of pectin mensuration etc., according to the assay method of standard, needs use to arrive
Medicament mainly has: analytical pure chemical agent: Al2(SO4)3、FeCl3、Fe2(SO4)3、FeSO4、H2O2、CaO、CaCl2.Industry medication
Agent: CPAM (PAMC), PAC (aluminium polychlorid), kieselguhr.Above medicament is convenient for experiment, is all configured to
The aqueous solution of respective concentration, after concentration is listed in each title, each medicament is commercially available.
In mensuration project, pH measures and uses glass electrode method, and COD measures and uses dichromate titration, and pectin measures and uses ratio
Color method, corresponding analytical procedure is all analyzed method by national standard and is performed.
Object of study is the high concentration pectin wastewater (i.e. acidleach water) of mandarin orange can processing enterprise acidleach operation discharge, specifically
Water quality situation as shown in table 1 below.
Table 1 acidleach water water quality detection table
Embodiment 1
The processing method of a kind of high concentration pectin wastewater, comprises the following steps: by produce in mandarin orange can production process
Acidleach water is drawn, and is first filtered by acidleach hydromining multilamellar (usually 3～5 layers) gauze, i.e. water sample pretreatment, then in mistake
Acidleach water after filter adds composite flocculation agent, for comparing the impact on acidleach water treatment efficiency of the different composite flocculant, carries out
Four groups of experiments (due to only qualitative experiment, observe flocculating effect, therefore do not take the operation of centrifugation), respectively take after filtering
Water sample 30mL, in four groups of water samples, be separately added into following flocculant aqueous solution:
A group, 5mLPAC+0.5mLCPAM (composite flocculation agent of the present invention)
B group, 5mL Al2(SO4)3+ 0.5mLCPAM (composite flocculation agent of the present invention)
C group, 5mL FeCl3+ 0.5mLCPAM (matched group)
D group, 5mL Fe2(SO4)3+ 0.5mLCPAM (matched group)
Wherein, each experiment reagent and concentration thereof are: CPAM (1g/L), PAC (2g/L), Al2(SO4)3(2g/L)、FeCl3
(2g/L)、Fe2(SO4)3(2g/L)；
Being stirred during dropping, mix homogeneously postprecipitation stands about 1h simultaneously, obtains experiment knot as shown in table 2
Really.
Table 2 acidleach water flocculation precipitation qualitative experiment result
As shown in Table 2, respectively with PAC, Al in the present embodiment2(SO4)3、FeCl3And Fe2(SO4)3Composition is mixed with CPAM
Composite flocculation agent (is called A, B, C, D class composite flocculation agent), in this qualitative experiment is studied, and the consumption of fixing CPAM,
Under identical conditions of mixture ratios, iron salt class composite flocculation agent does not shows flocculating effect, but containing PAC or Al2(SO4)3Composite flocculation
Agent effect is fine.Visible, the composite flocculation agent of the present invention high concentration pectin wastewater tool to producing in mandarin orange can acidleach operation
There is good treatment effect.
Embodiment 2
The processing method of the high concentration pectin wastewater of a kind of present invention, comprises the following steps: by mandarin orange can production process
The acidleach water of middle generation is drawn, and is first filtered with three layers of gauze by acidleach hydromining, adds in acidleach water the most after filtration
Composite flocculation agent, stirs 10min under 30rpm rotating speed, then carries out solid-liquid separation with centrifugation, and centrifugal speed is 4000rpm,
Centrifugation time is 10min, completes processing procedure.
In the present embodiment, composite flocculation agent is specially CPAM (1g/L) and PAC (2g/L).
In the present embodiment, take 4 groups of each 150mL of acidleach water sample after filtering, press respectively following requirements add reagent:
A、6mLPAC+4mLCPAM
B、12mLPAC+4mLCPAM
C、24mLPAC+4mLCPAM
D、48mLPAC+4mLCPAM
It is stirred during dropping simultaneously, after mix homogeneously, carries out solid-liquid separation with centrifugation again, take supernatant and survey
Measuring its concentration of pectin, arrange blank group simultaneously, result is as shown in table 3.
Table 3 composite flocculation agent difference dosage experimental result unit: (mg/L)
As shown in Table 3, in the present embodiment, investigate the composite flocculation agent being made up of CPAM with PAC under different conditions of mixture ratios
On the impact of elimination rate of pectic in acidleach water, result as it is shown in figure 1, the clearance of pectin increases with the increase of PAC consumption,
Consumption is to respectively reach 69.51% and 78.70% when 24 and 48mL.
Embodiment 3
The processing method of the high concentration pectin wastewater of a kind of present invention, comprises the following steps: by mandarin orange can production process
The acidleach water of middle generation is drawn, and is first filtered with three layers of gauze by acidleach hydromining, adds in acidleach water the most after filtration
Composite flocculation agent, stirs 10min under 30rpm rotating speed, then carries out solid-liquid separation with centrifugation, and centrifugal speed is 4000rpm,
Centrifugation time is 10min, completes processing procedure.
In the present embodiment, composite flocculation agent is specially CPAM (1g/L) and Al2(SO4)3(2g/L)。
In the present embodiment, take 4 groups of each 150mL of water sample after filtering, press respectively following requirements add reagent:
A、6mL Al2(SO4)3+4mLCPAM
B、12mL Al2(SO4)3+4mLCPAM
C、24mL Al2(SO4)3+4mLCPAM
D、48mL Al2(SO4)3+4mLCPAM
It is stirred during dropping simultaneously, after mix homogeneously, carries out solid-liquid separation with centrifugation again, take supernatant and survey
Measuring its concentration of pectin, arrange blank group simultaneously, result is as shown in table 4.
Table 4 composite flocculation agent difference dosage experimental result unit: (mg/L)
As shown in Table 4, in the present embodiment, investigate by CPAM and Al2(SO4)3The composite flocculation agent of composition is at different ratio bar
On the impact of elimination rate of pectic in acidleach water under part, result is as it is shown in figure 1, the clearance of pectin is with Al2(SO4)3The increase of consumption
And increase, at Al2(SO4)3Consumption is to reach the highest during 48mL, is 71.77%.It addition, by embodiment 2 and the result of embodiment 3
Comparing discovery, from the point of view of economy, composite flocculation agent (PAC+CPAM) is more suitable for the process of pectin in wastewater pickling.
Embodiment 4
The processing method of the high concentration pectin wastewater of a kind of present invention, investigates the impact that pH value processes for acidleach water.
Experiment reagent: CPAM (1g/L), PAC (2g/L), NaOH (1mol/L) solution.
Laboratory operating procedures is substantially the same manner as Example 2, and difference is: take 9 groups of each 30mL of water sample after filtering, respectively
The pH value of 9 groups of water samples is regulated to 0.4,1,2,3,4,5,6,7,8 (containing matched groups).5mLPAC+ is dripped respectively in 9 groups of water samples
0.5mLCPAM carries out flocculating experiment.
Table 5 acidleach water flocculation precipitation qualitative experiment result
| PH value | Experimental phenomena |
| 0.4 | Flco is agglomerating, and effect is fine |
| 1 | Flco is agglomerating, effective |
| 2 | Flco is agglomerating, and effect is preferable |
| 3 | Flco is agglomerating, and effect is preferable |
| 4 | Flco is little, more disperses |
| 5 | Phenomenon without flocculation sediment |
| 6 | Phenomenon without flocculation sediment |
| 7 | Phenomenon without flocculation sediment |
| 8 | Phenomenon without flocculation sediment |
As shown in Table 5, composite flocculation agent when pH value is less than 4, all can produce flocculation reaction for high concentration pectin wastewater,
PH value is the lowest, and the effect of composite flocculation agent is the best.In the pectin wastewater that pH is 5～8, use the present invention composite flocculation agent without
Flocculation phenomenon, thus explanation acidleach high concentration pectin wastewater is under conditions of pH is higher, and flocculating effect is poor.
Embodiment 5
The processing method of the high concentration pectin wastewater of a kind of present invention, investigates what solid-liquid separation method processed for acidleach water
Impact.This processing method comprises the following steps: draw, the acidleach water produced in mandarin orange can production process first by acidleach hydromining
Filter with three layers of gauze, acidleach water the most after filtration adds composite flocculation agent, stirs under 30rpm rotating speed
10min, then complete processing procedure with different solid-liquid separation methods.
In the present embodiment, composite flocculation agent is 5mLPAC+0.5mLCPAM, wherein, and CPAM (1g/L), Al2(SO4)3(2g/
L)。
In the present embodiment, for comparing the impact on acidleach water treatment efficiency of the different solid separate mode, 4 groups are carried out in fact
Testing, the water sample 30mL after mix homogeneously of respectively learning from else's experience, 4 groups of water samples are respectively adopted following solid-liquid separation method:
A, centrifugation: centrifugal speed is 4000rpm, centrifugation time is 10min；
B, sucking filtration: negative pressure leaching is dehydrated；
C, air supporting: pressurized dissolved air flotation；
D, precipitation: sedimentation time 1h.
Table 6 different solid separate mode affects result to acidleach water flocculation
| Solid-liquid separation method | Experimental phenomena |
| A | Supernatant is clarified, and pectin is removed in a large number |
| B | Solution viscosity is big, blocks filter paper, sucking filtration effect extreme difference |
| C | The floating pectin in liquid level upper strata, a large amount of foams produce, solutions turbid |
| D | Bottom precipitum is little, one layer of pectin of surface flotation, solutions turbid |
As shown in Table 6, in conventional pectin wastewater solid-liquid separating method, even if sucking filtration, air supporting and the sedimentation method are in acidleach
In the case of there is floc sedimentation after adding composite flocculation agent in water, its solid-liquid separation effect is the most undesirable, and its main cause exists
The character big in the viscosity of pectin wastewater own, density is little, there is power consumption height, pectin moisture content height, and separates in air supporting method
Weak effect.And the sedimentation method not only sedimentation time length, poor processing effect, and because pectin density is relatively light, often float on the water surface
And crust, have a strong impact on subsequent treatment effect.And during filter press technique process pectin wastewater, owing to the viscosity of pectin wastewater is high, cause
Filter pressing effect is the most undesirable, and uses the centrifugal separation of the present invention to coordinate the use of composite flocculation agent to be avoided that said method
Defect, well realizes the solid-liquid separation of pectin wastewater.
Comparative example 1
The processing method of a kind of high concentration pectin wastewater, uses Fenton method that acidleach water (pH=0.83) is carried out Strong oxdiative
Process, investigate the strong oxidation treatment effect for acidleach water.
Experiment reagent: FeSO4(20g/L)、H2O2(mass fraction 30%), NaOH (1mol/L), CaO (5g/L), kieselguhr
(5g/L)。
Laboratory operating procedures is substantially the same manner as Example 2, and difference is: take 4 groups of each 150mL of water sample after filtering, point
Not Jia Ru:
Table 7 Fenton experimental result
As shown in Table 7, using Fenton method that acidleach water is carried out Strong oxdiative process, the alumen ustum generated is that suspension is stable
Dispersion is in the solution or along with flocculation aid kieselguhr, the addition of CaO, solution directly becomes pasty state or produces a large amount of foam, it is difficult to real
Existing solid-liquid separation.This phenomenon also illustrate that for acidleach hydromining Fenton method treatment effect very poor.
Embodiment 6
The processing method of the high concentration pectin wastewater of a kind of present invention, comprises the following steps:
The acidleach water produced in mandarin orange can production process is drawn, acidleach water adds composite flocculation agent, agitated
After, carry out solid-liquid separation with centrifugation, complete processing procedure；Composite flocculation agent is to be wadded a quilt with cotton with organic polymer by inorganic flocculating agent
Solidifying agent composition, inorganic flocculating agent is PAC and/or Al2(SO4)3, organic polymer coargulator is CPAM, PDA and the double cyanogen of cation
One or more in amine formaldehyde condensation polymer.
In the present embodiment, acidleach water: inorganic flocculating agent: organic polymer coargulator=10mL～300mL: 5mg～160mg
: 0.5mg～8mg.
Preferably, acidleach water: inorganic flocculating agent: organic polymer coargulator=30mL～150mL: 10mg～96mg:
0.5mg～4mg.
It is furthermore preferred that composite flocculation agent is made up of PAC with CPAM, PAC Yu CPAM adds acid the most in form of an aqueous solutions
In immersion, the concentration of PAC solution be the concentration of 2g/L, CPAM solution be 1g/L, acidleach water: PAC solution: CPAM solution=30mL
～150mL: 5mL～48mL: 0.5mL～4mL.
It is furthermore preferred that composite flocculation agent is by Al2(SO4)3Form with CPAM, Al2(SO4)3With CPAM respectively with aqueous solution
Form adds in acidleach water, Al2(SO4)3The concentration of solution be the concentration of 2g/L, CPAM solution be 1g/L, acidleach water: Al2
(SO4)3Solution: CPAM solution=30mL～150mL: 5mL～48mL: 0.5mL～4mL.
In the present embodiment, the pH value of acidleach water is 0.4～4.
In the present embodiment, centrifugal speed is 2500rpm～6000rpm, and the centrifugal time is 8min～40min.
In the present embodiment, the speed of stirring is 20rpm～60rpm, and the time of stirring is 5min～15min.
In the present embodiment, before composite flocculation agent adds in acidleach water, the most first acidleach water is filtered, removable acid
Coarse impurities in immersion.
The above is only the preferred embodiment of the present invention, and protection scope of the present invention is not limited merely to above-mentioned enforcement
Example.All technical schemes belonged under thinking of the present invention belong to protection scope of the present invention.It it is noted that for the art
Those of ordinary skill for, improvements and modifications under the premise without departing from the principles of the invention, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (6)
1. a processing method for high concentration pectin wastewater, comprises the following steps: the acid that will produce in mandarin orange can production process
Immersion draw, in acidleach water add composite flocculation agent, agitated after, carry out solid-liquid separation with centrifugation, complete to process
Journey；Described composite flocculation agent is made up of with organic polymer coargulator inorganic flocculating agent, and described inorganic flocculating agent is polymerization chlorine
Change aluminum and/or Al2(SO4)3, described organic polymer coargulator is PAMC, dimethyl diallyl chlorination
One or more in ammonium-acrylamide copolymer and cation Dicyandiamine-formaldehyde condensation product；
The pH value of described acidleach water is 0.4～4；
Described centrifugal speed is 2500rpm～6000rpm, and the described centrifugal time is 8min～40min；
Described acidleach water: inorganic flocculating agent: organic polymer coargulator=10mL～300mL: 5mg～160mg: 0.5mg～
8mg。
Processing method the most according to claim 1, it is characterised in that described acidleach water: inorganic flocculating agent: organic polymer
Flocculant=30mL～150mL: 10mg～96mg: 0.5mg～4mg.
Processing method the most according to claim 2, it is characterised in that described composite flocculation agent by aluminium polychlorid with sun from
Sub-polyacrylamide forms, and aluminium polychlorid adds in acidleach water the most in form of an aqueous solutions with PAMC,
The concentration of polymeric aluminum chlorides solution is 2g/L, and the concentration of PAMC solution is 1g/L, acidleach water: aluminium polychlorid
Solution: PAMC solution=30mL～150mL: 5mL～48mL: 0.5mL～4mL.
Processing method the most according to claim 2, it is characterised in that described composite flocculation agent is by Al2(SO4)3With cation
Polyacrylamide forms, Al2(SO4)3Add the most in form of an aqueous solutions in acidleach water with PAMC, Al2
(SO4)3The concentration of solution is 2g/L, and the concentration of PAMC solution is 1g/L, acidleach water: Al2(SO4)3Solution: sun
Cationic polyacrylamide solution=30mL～150mL: 5mL～48mL: 0.5mL～4mL.
5. according to the processing method according to any one of Claims 1 to 4, it is characterised in that the speed of described stirring is 20rpm
～60rpm, the time of described stirring is 5min～15min.
6. according to the processing method according to any one of Claims 1 to 4, it is characterised in that described composite flocculation agent adds acid
Before in immersion, first acidleach water is filtered.
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