CN110117120A - A kind of reverse osmosis membrane combines the method for concentration biogas slurry with solar energy heating negative pressure evaporation - Google Patents
A kind of reverse osmosis membrane combines the method for concentration biogas slurry with solar energy heating negative pressure evaporation Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/14—Treatment of water, waste water, or sewage by heating by distillation or evaporation using solar energy
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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Abstract
The present invention provides a kind of method that reverse osmosis membrane combines concentration biogas slurry with solar energy heating negative pressure evaporation, comprising: (1) biogas slurry stoste is by coagulation, filtering, biogas slurry after being pre-processed；(2) pH of biogas slurry after pretreatment is adjusted to 3~7, interior circulation concentration is carried out by reverse osmosis membrane, being concentrated is 1/6~1/2 of biogas slurry volume after pre-processing, obtains reverse osmosis membrane concentrate and reverse osmosis membrane permeate；(3) resulting reverse osmosis membrane concentrate solar energy heating negative pressure evaporation is concentrated, obtain solar energy evaporation concentrated solution and distillate, 50 DEG C of water temperature > in solar thermal collector, vacuum degree 0.005-0.015Mpa carry out the concentration more than or equal to 5 times of volume concentration multiples.Compared to traditional film concentration or negative pressure evaporation concentration, higher volume concentration multiple can be concentrated in this method, and biggish biogas slurry volume can be concentrated, nutrient retention rate >=90% of N P and K in last gained concentrate.
Description
Technical field
The present invention relates to Pollution from livestock and poultry control and liquid fertilizer technical field more particularly to a kind of reverse osmosis membrane and too
The method that sun can heat negative pressure evaporation joint concentration biogas slurry.
Background technique
Current China has been that biogas project applies largest country in the world, although biogas project is crossed over
The development of formula, but the comprehensive utilization of biogas slurry relatively lags behind.Although and there is a large amount of organic matter, humic acid etc. pair in biogas slurry
The beneficial substance of plant and different types of nutrient, if reuse farmland can be improved crop yield, but usually there is
The problems such as neighbouring farmland digestion capability is insufficient, remote transportation cost is excessively high, meanwhile, compare chemical fertilizer and organic commercial fertilizer, natural pond
Each nutritive element content in liquid is too low, and peasant is not high using the enthusiasm of biogas slurry, limits agricultural consumption to a certain extent
Feasibility.Thus, it separates the nutriment in concentration biogas slurry and makes biogas slurry minimizing, for promoting the industrial chain of biogas project deep
Degree development plays an important role.
Currently, the technology for biogas slurry concentration mainly has guanite sedimentation, membrane concentration method, Municipal Solid Waste Landfillies
Three kinds:
(1) guanite sedimentation: using the N in guanite precipitation method recycling biogas slurry, P element, in biogas slurry after processing
N, P drop to it is untreated before 10% or so, the guanite of recycling precipitating can be used as a kind of slow release fertilizer in crop-planting,
But the guanite precipitation method are there is also operating cost height simultaneously, the problems such as guanite purity of recycling is lower.
(2) membrane concentration method: film concentration especially reverse osmosis membrane concentration largely grind by domestic and foreign scholars in recent years
Study carefully and applies, it is reverse osmosis although reverse osmosis membrane has good concentrated effect to biogas slurry as the main way of biogas slurry concentration
Film volume concentration multiple it is higher or concentration later period salinity it is higher when, desalination rate rise, cause reverse osmosis membrane salt rejection rate and thoroughly
Water rate reduces, while also will increase the burden of reverse osmosis membrane processing, adds somewhat to the frequency of replacement reverse osmosis membrane, increases
Operating cost is added.Thus traditional film is concentrated due to fouling membrane, can not be concentrated higher volume concentration multiple and
Nutrient retention rate is lower.
(3) Municipal Solid Waste Landfillies: Municipal Solid Waste Landfillies concentration technique has been widely used in wastewater treatment at present, food adds
The fields such as work, medicine production, but in biogas slurry treatment field using less, there is high energy consumption, the higher problem of operating cost, limits
Make the further development and application of negative pressure evaporation concentration.China has a vast territory, and most territory range is in temperate zone and Ya Re
, there are a solar energy resources more abundant in band area, while solar energy is as a kind of cleaning, the reproducible energy, in seawater negative
Pressure desalination etc. fields have been extensively studied, using solar energy be used as the heat source of negative pressure evaporation, although solar energy negative pressure evaporation be concentrated by
The influence of volume concentration multiple is smaller, and energy consumption is lower, but the concentration yield of usually solar energy evaporation and concentration is lower, no
The energy biggish biogas slurry of concentration volume, it is more difficult to meet the huge biogas slurry treatment of volume.
Summary of the invention
It is an object of the invention to overcome the defect of the prior art, a kind of reverse osmosis membrane and solar energy heating negative pressure are provided
The method of evaporation joint concentration biogas slurry, can be concentrated higher volume concentration multiple, and biggish biogas slurry volume can be concentrated, most
N P and K total nutrient (N+P in the concentrate obtained afterwards2O5+K2O) >=4%, the nutrient of the N P and K in solar energy evaporation concentrated solution
Retention rate >=90%.
The present invention is implemented as follows:
It is an object of that present invention to provide a kind of reverse osmosis membranes to combine the method that biogas slurry is concentrated with solar energy heating negative pressure evaporation,
Described method includes following steps:
The pretreatment of step 1, biogas slurry: biogas slurry stoste is by coagulation, filtering, biogas slurry after being pre-processed；(concentration 1m3's
Biogas slurry stoste needs to consume polyaluminum ferric chloride (PAFC) 1.1kg, consumes cationic polyacrylamide (CPAM) 0.01kg, disappears
Consume concentrated sulfuric acid 3.3L, biogas slurry 20L after being pre-processed that mass concentration is 98%.)
Step 2, reverse osmosis membrane concentration: being adjusted to 3~7 (preferably 5) for the pH of biogas slurry after the resulting pretreatment of step 1,
And by reverse osmosis membrane carry out in circulation concentration, by biogas slurry volume concentration be after pre-processing biogas slurry volume 1/6~1/2 (preferably
1/4), to obtain reverse osmosis membrane concentrate and reverse osmosis membrane permeate；
Step 3, the concentration of solar energy heating negative pressure evaporation: the resulting reverse osmosis membrane concentrate of step 2 is used into solar energy collection
Hot water in hot device carries out circulating-heating as heat medium, carries out negative pressure to the reverse osmosis membrane concentrate in solar still
It is concentrated by evaporation, obtains solar energy evaporation concentrated solution and distillate, wherein (Wei≤80 You Xuan 50 DEG C of water temperature > in solar thermal collector
DEG C), adjusting the vacuum degree in solar still using vacuum pump is 0.005-0.015Mpa, is carried out to reverse osmosis concentrated liquid big
In the negative pressure evaporation concentration for being equal to 5 times of volumes (Wei≤10 times You Xuan volume).
The invention has the following advantages:
1, a kind of reverse osmosis membrane provided by the invention combines the method for concentration biogas slurry, step with solar energy heating negative pressure evaporation
The pH of biogas slurry after pretreatment is adjusted to 3~7 in 2, by biogas slurry volume concentration be pretreatment after biogas slurry volume 1/6~1/2；Step
The negative pressure evaporation for be more than or equal to 5 times of volumes to reverse osmosis concentrated liquid in rapid 3 is concentrated, water temperature > 50 in solar thermal collector
DEG C, adjusting the vacuum degree in solar still using vacuum pump is 0.005-0.015Mpa；To guarantee concentration speed it is fast (because
And higher volume concentration multiple can be concentrated, biggish biogas slurry volume can be concentrated) and the concentrate that finally obtains in nitrogen phosphorus
Potassium total nutrient (N+P2O5+K2O) >=4%, nutrient retention rate >=90% of the N P and K in solar energy evaporation concentrated solution, wherein real
Example 4 is applied as most preferred embodiment, TN, TP, TK nutrient retention rate are respectively 92.5%, 93.7%, 91.2%.
2, a kind of reverse osmosis membrane provided by the invention combines the method for concentration biogas slurry, step with solar energy heating negative pressure evaporation
Reverse osmosis membrane concentrate and reverse osmosis membrane permeate are obtained in 2, reverse osmosis membrane permeate rinses water circulation use as cultivation, instead
Permeable membrane concentrate continues through the concentration of solar energy heating negative pressure evaporation；Solar energy evaporation concentrated solution and distillation are obtained in step 3
Liquid, distillate rinse water circulation use as cultivation, and solar energy evaporation concentrated solution is used as high-valued liquid fertilizer, thus real
The recycling treatment of polluter in biogas slurry is showed, there is significant environmental effect and economic benefit.
3, a kind of reverse osmosis membrane provided by the invention combines the method for concentration biogas slurry with solar energy heating negative pressure evaporation, uses
The more energy efficient environmental protection of solar energy reduces operating cost, and the energy biggish biogas slurry of concentration volume, is convenient for large scale processing biogas slurry.
Detailed description of the invention
Fig. 1 is that a kind of reverse osmosis membrane provided in an embodiment of the present invention combines concentration biogas slurry with solar energy heating negative pressure evaporation
The flow chart of method；
Fig. 2 is biogas slurry concentration speed under different biogas slurry initial pH values；
Fig. 3 is biogas slurry concentration front and back Main Nutrients concentration and nutrient rejection under different biogas slurry initial pH values；Wherein (A) is
Biogas slurry concentration front and back Main Nutrients concentration；(B) front and back nutrient rejection is concentrated for biogas slurry；
Fig. 4 is the concentration speed under different biogas slurry volume concentration multiples；
Fig. 5 is Main Nutrients concentration and nutrient rejection under different biogas slurry volume concentration multiples；Wherein (A) is biogas slurry concentration
Front and back Main Nutrients concentration；(B) front and back nutrient rejection is concentrated for biogas slurry；
Fig. 6 is the condensation water quantity under different vacuum degrees in the concentration of biogas slurry negative pressure；85% vacuum degree is 0.015Mpa in Fig. 6；
90% vacuum degree is 0.01Mpa；95% vacuum degree is 0.005Mpa；And so on；
Fig. 7 is the condensation water quantity under different bath temperatures in the concentration of biogas slurry negative pressure.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts all other
Embodiment shall fall within the protection scope of the present invention.
Embodiment 1
The present invention provides a kind of method that reverse osmosis membrane combines concentration biogas slurry with solar energy heating negative pressure evaporation, including as follows
Step:
Step 1, be added in 2L biogas slurry stoste polyaluminum ferric chloride (PAFC) and cationic polyacrylamide (CPAM) into
Row coagulation keeps 60~90s's wherein adding cationic polyacrylamide (CPAM) after first adding polyaluminum ferric chloride (PAFC)
Time interval, the dosage of coagulant used are respectively 1100mg/L, 10mg/L.Clarification biogas slurry after taking coagulant precipitation passes through respectively
Two-stage pp cotton and ultrafiltration membrance filter；
Step 2, the biogas slurry that will transmit through ultrafiltration membrane carry out pH value adjusting, and the concentrated sulfuric acid for the use of mass concentration being 98% is by natural pond
Liquid pH is adjusted to 5, and the pressure for adjusting high-pressure plunger pump is 35bar, and biogas slurry is carried out interior circulation concentration by coiled reverse osmosis membrane,
The concentration that 4 times of volume concentration multiples are carried out to biogas slurry, obtains reverse osmosis membrane concentrate；
Step 3, progress solar energy heating negative pressure evaporation concentration use solar energy collection under the conditions of summer bright day gas
Electric heating control hot water initial temperature is 80 DEG C in hot device, and adjusting the vacuum degree in evaporator with vacuum pump is 0.005Mpa, right
Reverse osmosis membrane concentrate carries out the negative pressure evaporation concentration of 5 times of volume concentration multiples in evaporator, obtains solar energy evaporation concentrated solution.
Embodiment 2
The present invention provides a kind of method that reverse osmosis membrane combines concentration biogas slurry with solar energy heating negative pressure evaporation, including as follows
Step:
Step 1, be added in 2L biogas slurry stoste polyaluminum ferric chloride (PAFC) and cationic polyacrylamide (CPAM) into
Row coagulation keeps 60~90s's wherein adding cationic polyacrylamide (CPAM) after first adding polyaluminum ferric chloride (PAFC)
Time interval, the dosage of coagulant used are respectively 1100mg/L, 10mg/L.Clarification biogas slurry after taking coagulant precipitation passes through respectively
Two-stage pp cotton and ultrafiltration membrance filter；
Step 2, the biogas slurry that will transmit through ultrafiltration membrane carry out pH value adjusting, and the concentrated sulfuric acid for the use of mass concentration being 98% is by natural pond
Liquid pH is adjusted to 3, and the pressure for adjusting high-pressure plunger pump is 50bar, and biogas slurry is carried out interior circulation concentration by coiled reverse osmosis membrane,
The concentration that 6 times of volume concentration multiples are carried out to biogas slurry, obtains reverse osmosis membrane concentrate；
Step 3, progress solar energy heating negative pressure evaporation concentration use solar energy collection under the conditions of summer bright day gas
Electric heating control hot water initial temperature is 70 DEG C in hot device, and adjusting the vacuum degree in evaporator with vacuum pump is 0.015Mpa, right
Reverse osmosis membrane concentrate carries out the negative pressure evaporation concentration of 10 times of volume concentration multiples in evaporator, obtains solar energy evaporation and concentration
Liquid.
Embodiment 3
The present invention provides a kind of method that reverse osmosis membrane combines concentration biogas slurry with solar energy heating negative pressure evaporation, including as follows
Step:
Step 1, be added in 2L biogas slurry stoste polyaluminum ferric chloride (PAFC) and cationic polyacrylamide (CPAM) into
Row coagulation keeps 60~90s's wherein adding cationic polyacrylamide (CPAM) after first adding polyaluminum ferric chloride (PAFC)
Time interval, the dosage of coagulant used are respectively 1100mg/L, 10mg/L.Clarification biogas slurry after taking coagulant precipitation passes through respectively
Two-stage pp cotton and ultrafiltration membrance filter；
Step 2, the biogas slurry that will transmit through ultrafiltration membrane carry out pH value adjusting, and the concentrated sulfuric acid for the use of mass concentration being 98% is by natural pond
Liquid pH is adjusted to 7, and the pressure for adjusting high-pressure plunger pump is 30bar, and biogas slurry is carried out interior circulation concentration by coiled reverse osmosis membrane,
The concentration that 2 times of volume concentration multiples are carried out to biogas slurry, obtains reverse osmosis membrane concentrate；
Step 3, progress solar energy heating negative pressure evaporation concentration use solar energy collection under the conditions of summer bright day gas
Electric heating control hot water initial temperature is 90 DEG C in hot device, and adjusting the vacuum degree in evaporator with vacuum pump is 0.012Mpa, right
Reverse osmosis membrane concentrate carries out the negative pressure evaporation concentration of 15 times of volume concentration multiples in evaporator, obtains solar energy evaporation and concentration
Liquid.
Embodiment 4
The present invention provides a kind of method that reverse osmosis membrane combines concentration biogas slurry with solar energy heating negative pressure evaporation, including as follows
Step:
Step 1, be added in 2L biogas slurry stoste polyaluminum ferric chloride (PAFC) and cationic polyacrylamide (CPAM) into
Row coagulation keeps 60~90s's wherein adding cationic polyacrylamide (CPAM) after first adding polyaluminum ferric chloride (PAFC)
Time interval, the dosage of coagulant used are respectively 1100mg/L, 10mg/L.Clarification biogas slurry after taking coagulant precipitation passes through respectively
Two-stage pp cotton and ultrafiltration membrance filter；
Step 2, the biogas slurry that will transmit through ultrafiltration membrane carry out pH value adjusting, and the concentrated sulfuric acid for the use of mass concentration being 98% is by natural pond
Liquid pH is adjusted to 5, and the pressure for adjusting high-pressure plunger pump is 35bar, and biogas slurry is carried out interior circulation concentration by coiled reverse osmosis membrane,
The concentration that 4 times of volume concentration multiples are carried out to biogas slurry, obtains reverse osmosis membrane concentrate；
Step 3, progress solar energy heating negative pressure evaporation concentration use solar energy collection under the conditions of summer bright day gas
Electric heating control hot water initial temperature is 80 DEG C in hot device, and adjusting the vacuum degree in evaporator with vacuum pump is 0.01Mpa, to steaming
The negative pressure evaporation concentration that reverse osmosis membrane concentrate in device carries out 10 times of volume concentration multiples is sent out, solar energy evaporation concentrated solution is obtained.
Biogas slurry is concentrated in the individual reverse osmosis membrane of comparative example 1
The step of biogas slurry is concentrated in the comparative example are as follows:
Step 1, be added in 2L biogas slurry stoste polyaluminum ferric chloride (PAFC) and cationic polyacrylamide (CPAM) into
Row coagulation keeps 60~90s's wherein adding cationic polyacrylamide (CPAM) after first adding polyaluminum ferric chloride (PAFC)
Time interval, the dosage of coagulant used are respectively 1100mg/L, 10mg/L；
Step 2 takes the clarification biogas slurry after coagulant precipitation to pass through two-stage pp cotton and ultrafiltration membrance filter respectively, will transmit through ultrafiltration
The biogas slurry of film carries out pH value adjusting, and biogas slurry pH is adjusted to 5 using the concentrated sulfuric acid that mass concentration is 98%；
Step 3, the pressure for adjusting high-pressure plunger pump are 35bar, interior circulation concentration are carried out by coiled reverse osmosis membrane, to natural pond
Liquid carries out the concentration of 20 times of volume concentration multiples, obtains reverse osmosis membrane concentrate.
The individual solar energy of comparative example 2 is concentrated by evaporation biogas slurry
The step of biogas slurry is concentrated in the comparative example are as follows:
Step 1, be added in 2L biogas slurry stoste polyaluminum ferric chloride (PAFC) and cationic polyacrylamide (CPAM) into
Row coagulation keeps 60-90s's wherein adding cationic polyacrylamide (CPAM) after first adding polyaluminum ferric chloride (PAFC)
Time interval, the dosage of coagulant used are respectively 1100mg/L, 10mg/L；
Step 2 takes the clarification biogas slurry after coagulant precipitation to pass through two-stage pp cotton and ultrafiltration membrance filter respectively, will transmit through ultrafiltration
The biogas slurry of film carries out pH value adjusting, and biogas slurry pH is adjusted to 5 using the concentrated sulfuric acid that mass concentration is 98%；
Biogas slurry after adjusting pH value is carried out the concentration of solar energy heating negative pressure evaporation by step 3, in summer bright day gas
Under the conditions of, the use of electric heating control hot water initial temperature in solar thermal collector is 80 DEG C, is adjusted in evaporator with vacuum pump
Vacuum degree is 0.01Mpa, and the negative pressure evaporation for carrying out 20 times of volume concentration multiples to biogas slurry in evaporator is concentrated, and obtains solar energy steaming
Send out concentrate；
Reverse osmosis membrane joint concentration biogas slurry after the first solar energy evaporation of comparative example 3
The step of biogas slurry is concentrated in the comparative example are as follows:
Step 1, be added in 2L biogas slurry stoste polyaluminum ferric chloride (PAFC) and cationic polyacrylamide (CPAM) into
Row coagulation keeps 60-90s's wherein adding cationic polyacrylamide (CPAM) after first adding polyaluminum ferric chloride (PAFC)
Time interval, the dosage of coagulant used are respectively 1100mg/L, 10mg/L.Clarification biogas slurry after taking coagulant precipitation passes through respectively
Two-stage pp cotton and ultrafiltration membrance filter；
Step 2, the biogas slurry that will transmit through ultrafiltration membrane carry out pH value adjusting, and the concentrated sulfuric acid for the use of mass concentration being 98% is by natural pond
Liquid pH is adjusted to 5, carries out the concentration of solar energy heating negative pressure evaporation and uses solar energy heating under the conditions of summer bright day gas
Electric heating control hot water initial temperature is 80 DEG C in device, and adjusting the vacuum degree in evaporator with vacuum pump is 0.01Mpa, to evaporation
Biogas slurry carries out the negative pressure evaporation concentration of 4 times of volume concentration multiples in device, obtains solar energy evaporation concentrated solution；
Step 3, the pressure for adjusting high-pressure plunger pump are 35bar, and solar energy evaporation concentrated solution is passed through coiled reverse osmosis membrane
Circulation concentration in carrying out, the concentration of 5 times of volume concentration multiples is carried out to biogas slurry, obtains reverse osmosis membrane concentrate.
Experimental example 1
It records and the time used in biogas slurry is concentrated in Statistics Implementation example 1-3 and comparative example 1-3 gained, finally in gained concentrate
The concentration and retention rate of nutrient TN, TK, TP, the results are shown in Table 1.(permeate or distillate nutrient are dense for nutrient retention rate=1-
Degree × permeate or distillate volume)/(biogas slurry volume before biogas slurry nutrient density × concentration before being concentrated).In addition, biogas slurry is each
Initial nutrient density is not necessarily equal, but changes little.
Table 1
As shown in Table 1, the result of embodiment 1 and comparative example 1-3 is compared it is found that in identical biogas slurry volume
Under cycles of concentration (20 times), (the biogas slurry stoste of same volume is dense much higher than comparative example 2 and comparative example 3 for the concentration speed of embodiment 1
Being reduced to the time used in identical multiple greatly shortens)；Each nutrient concentrated effect and each nutrient retention rate of embodiment 1 be higher than pair
Ratio 1.
In addition, being compared by the result of embodiment 1 and comparative example 3 it is found that solar energy negative pressure evaporation after the concentration of first reverse osmosis membrane
Joint cocnentration factor elder generation solar energy negative pressure evaporation after reverse osmosis membrane joint concentration speed faster, simultaneously because individually it is reverse osmosis
Film is there are reverse osmosis membrane pollution when compared with high concentration multiple, and solar energy concentration is influenced smaller by cycles of concentration, is considered simultaneously
The yield being concentrated to solar energy is lower, therefore the joint concentration of solar energy negative pressure evaporation is better than the first sun after first reverse osmosis membrane concentration
The joint concentration of reverse osmosis membrane after energy negative pressure evaporation.
In conclusion a kind of reverse osmosis membrane provided by the invention combines the side of concentration biogas slurry with solar energy heating negative pressure evaporation
Higher volume concentration multiple can be concentrated in method, and biggish biogas slurry volume can be concentrated, nitrogen phosphorus in the concentrate finally obtained
Nutrient retention rate >=90% of potassium.
Experimental example 2
1, in step 2 pH value exploration
Different biogas slurry initial pH values is set, and under the conditions of measuring different biogas slurry initial pH values, the reverse osmosis membrane of biogas slurry is concentrated
Rate as shown in Fig. 2, and each nutrient density and nutrient rejection it is as shown in Figure 3.
Fig. 2 indicates the reverse osmosis membrane concentration speed of biogas slurry with the situation of change of pH value.As shown in Figure 2, as biogas slurry is initial
The reverse osmosis membrane concentration speed of the raising of pH value, biogas slurry is gradually reduced.When lower due to pH value, the carbonic acid in film surface can be prevented
The formation of calcium scale increases reverse osmosis membrane concentration speed to increase membrane flux.
Fig. 3 indicates each nutrient density and nutrient rejection under the conditions of different biogas slurry initial pH values.From the figure 3, it may be seen that with natural pond
The raising of liquid initial pH value, npk nutrient concentration and nutrient rejection gradually decrease, this is because with the raising of pH value,
Reverse osmosis membrane concentration speed gradually decreases, and the flow rate of permeate gradually becomes smaller, and the moisture that biogas slurry penetrates tails off, to lead
Each Main Nutrients concentration in concentrate is caused to gradually become smaller.And with the raising of pH, each nutrient retention takes the lead in slightly elevated dropping again
Low, when pH is 5, nutrient rejection reaches maximum, may make the electricity in film surface and feed liquid due to constantly regulate with pH
Lotus changes, and affects nutrient rejection.
To sum up, in conjunction with biogas slurry concentration speed, nutrient density and nutrient rejection, pH is adjusted to 3~7 preferably, and pH is 5 for most
Good technological parameter.
2, in step 2 cycles of concentration exploration
Measure the concentration speed (as shown in Figure 4) under different biogas slurry volume concentration multiples, and different biogas slurry volume concentrations
Each Main Nutrients concentration in concentration front and back and nutrient rejection situation (as shown in Figure 5) under multiple.
As shown in Figure 4, with the raising of biogas slurry volume concentration multiple, biogas slurry concentration speed is gradually reduced.This be mainly because
Higher for cycles of concentration, pollutant concentration is higher in concentrate, and pollutant is easy to parse to form fouling in film surface, makes film
Permeation flux reduce, be gradually reduced so as to cause biogas slurry concentration speed.
As shown in Figure 5, in terms of each nutrient density, in addition to TP, each nutrient is with the raising of biogas slurry volume concentration multiple
And be gradually increased, and TP is with the increase of cycles of concentration that its variation is little, it is seen that reverse osmosis membrane is general to the concentrated effect of TP；NH3-
N, TN changing rule is consistent, and nutrient density gradually slows down after first increasing, and nutrient growth trend slows down after 4 times of volume concentration, can
It can be since salt concentration raising increases osmotic pressure in water accordingly after 4 times of volume concentration, to make reverse osmosis motive force
Decline, salt rejection rate also decline therewith, and nutrient density in concentrate is caused to increases slowly；The nutrient density of TK is dense with biogas slurry volume
The raising of demagnification number and be gradually increased, it is seen that reverse osmosis membrane is preferable to the concentrated effect of TK.
In terms of nutrient rejection, each nutrient rejection with the raising of biogas slurry volume concentration multiple have it is different degrees of
It reduces, each nutrient rejection decline is obvious after especially 2 times of volume concentration.Comprehensively consider biogas slurry concentration speed, in concentrate
Nutrient density and nutrient rejection select 2~6 times of biogas slurry volume concentration multiple；Wherein 4 times of biogas slurry volume concentration multiple
The cycles of concentration most suitable as reverse osmosis concentration.
3, in step 3 vacuum degree exploration
By the volume of biogas slurry condensed water under each vacuum degree, reflect that the concentration speed of biogas slurry, the bigger explanation of volume are dense
Contracting rate is faster.Condensation water quantity is shown in Fig. 6 with the situation of change of vacuum degree.It will be appreciated from fig. 6 that in identical concentration time
The condensation water volume of (0.5h), Municipal Solid Waste Landfillies concentration biogas slurry increase with the raising of vacuum degree, illustrate that vacuum degree is bigger, phase
The concentration speed answered is also faster.And under actual conditions, the maximum vacuum of evaporator is generally 0.01Mpa (90%) left and right, because
This selects the vacuum degree of 0.01Mpa (90%) for most suitable vacuum degree.
4, in step 3 in solar thermal collector water temperature exploration
Fig. 7 indicates the condensation water quantity under different bath temperatures in the concentration of biogas slurry negative pressure.As shown in Figure 7, with bath temperature
Raising, the condensation water volume of generation is gradually increased, i.e., concentration speed is gradually accelerated.And in order to carry out evaporation can quickly,
Evaporating temperature should be made to be higher than boiling temperature (50 DEG C of the boiling temperature of 90% vacuum degree, thus the selection sun of 90% vacuum degree
50 DEG C of water temperature > in energy heat collector), while the temperature the high more helps to evaporate, it is contemplated that the thermal loss in diabatic process, because
This chooses 80 DEG C of water temperature of solar thermal collector as best starting thickening temperature.
4, the cycles of concentration in step 3
The applicant has found that cycles of concentration is 4 in step 2 by a large amount of experimental exploring, be respectively set 4 in step 3,
5, a series of 6,7,8,9,10,15 cycles of concentration, and other experiment conditions measure in last gained concentrate with embodiment 1
N P and K total nutrient (N+P2O5+K2O) content, as shown in table 2.
Table 2
It can be carried out the concentration more than or equal to 5 times by the sun, make N P and K total nutrient (N+P in biogas slurry2O5+K2O) content energy
Enough reach 2.23% or more.
Preferably, to make N P and K total nutrient (N+P in biogas slurry2O5+K2O) content can reach 4% or more, pass through the sun
It can be carried out the concentration more than or equal to 10 times.
By a large amount of experimental exploring discovery of applicant, last cycles of concentration (cycles of concentration × step 3 in step 2
In cycles of concentration) be more than or equal to 20 times (preferably 40 times), N P and K total nutrient (N+ in the concentrate finally obtained can be made
P2O5+K2O) >=4%, nutrient retention rate >=90% of N P and K.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of reverse osmosis membrane combines the method for concentration biogas slurry with solar energy heating negative pressure evaporation, which is characterized in that the method
Include the following steps:
The pretreatment of step 1, biogas slurry: biogas slurry stoste is by coagulation, filtering, biogas slurry after being pre-processed；
Step 2, reverse osmosis membrane concentration: the pH of biogas slurry after the resulting pretreatment of step 1 is adjusted to 3~7, and passes through reverse osmosis membrane
Carry out in circulation concentration, by biogas slurry volume concentration be pre-process after biogas slurry volume 1/6~1/2, obtain reverse osmosis membrane concentrate
With reverse osmosis membrane permeate；
Step 3, the concentration of solar energy heating negative pressure evaporation: the resulting reverse osmosis membrane concentrate of step 2 is used into solar thermal collector
In hot water as heat medium carry out circulating-heating, in solar still reverse osmosis membrane concentrate carry out negative pressure evaporation
Concentration, obtains solar energy evaporation concentrated solution and distillate, wherein 50 DEG C of water temperature > in solar thermal collector, in solar still
Vacuum degree be 0.005-0.015Mpa, the negative pressure evaporation for be more than or equal to 5 times of volumes to reverse osmosis concentrated liquid is concentrated.
2. the method as described in claim 1, which is characterized in that coagulant is added in the step 1 in coagulation process, it is described mixed
Solidifying agent is polyaluminum ferric chloride and cationic polyacrylamide, adds cation polypropylene acyl after first adding polyaluminum ferric chloride
Amine keeps the time interval of 60~90s, and the dosage of coagulant used is respectively 1100mg/L, 10mg/L.
3. the method as described in claim 1, which is characterized in that the specific steps filtered in the step 1 are as follows: take coagulant precipitation
Rear clarification biogas slurry carries out subsequent pretreatment, make biogas slurry pass through two-stage pp cotton respectively and ultrafiltration membrance filter complete it is pretreated
Journey.
4. the method as described in claim 1, which is characterized in that the pH of biogas slurry after pretreatment is adjusted to 5 in the step 2,
It is the concentrated sulfuric acid that mass concentration is 98% that the pH, which adjusts the reagent used,.
5. the method as described in claim 1, which is characterized in that interior circulation concentration is carried out by reverse osmosis membrane in the step 2,
By biogas slurry volume concentration be pretreatment after biogas slurry volume 1/4.
6. the method as described in claim 1, which is characterized in that the reverse osmosis membrane in the step 2 is high pressure rolling polyamide
Composite membrane.
7. the method as described in claim 1, which is characterized in that Wen≤80 DEG C Shui in solar thermal collector in the step 3.
8. the method as described in claim 1, which is characterized in that be more than or equal in the step 3 to reverse osmosis concentrated liquid
The negative pressure evaporation concentration of 10 times of volumes.
9. the method as described in claim 1, which is characterized in that adjust solar still using vacuum pump in the step 3
In vacuum degree be 0.01Mpa.
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