CN112979352A - Method for recovering phosphate in urine - Google Patents
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- CN112979352A CN112979352A CN202110251434.9A CN202110251434A CN112979352A CN 112979352 A CN112979352 A CN 112979352A CN 202110251434 A CN202110251434 A CN 202110251434A CN 112979352 A CN112979352 A CN 112979352A
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- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B7/00—Fertilisers based essentially on alkali or ammonium orthophosphates
Abstract
The invention provides a method for recovering phosphate in urine, which belongs to the technical field of resource recovery and comprises the following steps: collecting reverse osmosis strong salt wastewater generated by intercepting circulating cooling water of a thermal power plant through desalination treatment; adding the original release urine or the hydrolyzed urine into the reverse osmosis strong salt wastewater collected in the last step, and fully mixing; adding an acid-base pH regulating solution into the mixed solution obtained in the last step, regulating the pH to be more than 7, stirring and reacting at room temperature for 1s-1h, standing or centrifuging for 1s-1h, and separating out solid substances; washing the solid obtained in the last step with clear water for at least 1 time to obtain a usable solid substance. The method for recovering phosphate in urine provided by the invention provides that the reverse osmosis concentrated brine is used as a precipitator source for recovering nitrogen and phosphorus in urine, no commercial precipitator is required to be additionally added, the one-time investment cost is low, and the operation cost is low. The multi-time utilization efficiency of water resources is improved, and the problems of difficult treatment and high treatment cost of reverse osmosis strong salt wastewater are solved.
Description
Technical Field
The invention belongs to the technical field of resource recovery, and particularly relates to a method for recovering phosphate in urine.
Background
Phosphorus is an important element in human production and life. Currently, phosphate is a non-renewable resource. The loss of phosphate from the ore to land-produced wastewater to the ocean results in a severe loss of phosphate reserves. Meanwhile, serious pollution of fresh water resources and damage of coastal marine ecosystems are caused. It is estimated that by the end of this century, with economic development and refining, the global reserve of phosphorus resources will be depleted to the bare extent. The discharge of phosphorus from phosphorus-containing wastewater results in eutrophication of water bodies in rivers, lakes, and shorelines. The recovery and recycling of phosphorus in wastewater is considered as a strategic and crucial way for the recycling of phosphorus and the sustainable supply of non-renewable phosphorus resources.
The waste water comprises livestock and poultry breeding waste water, sludge waste water generated by sludge digestion and dehydration, waste water generated by industrial composting, urine waste water and the like. The recovery of phosphorus from various waste waters is an important way of phosphorus recovery. In the total amount of domestic wastewater, the phosphorus content only accounts for 1 percent, the phosphorus content accounts for lower total amount of the wastewater, the treatment is difficult, the treatment cost is high, and the treatment efficiency is low; however, urine wastewater contains about 50% of phosphorus, 85% of nitrogen and 55% of potassium, so that it is necessary to provide a method for directly recovering phosphorus from urine wastewater.
Disclosure of Invention
The invention aims to provide a method for recovering phosphate in urine, and aims to solve the technical problems of low phosphorus content in the total amount of wastewater, difficult treatment, high treatment cost and low treatment efficiency in the conventional process.
In order to achieve the purpose, the invention adopts the technical scheme that: a method for recovering phosphate in urine is provided, which comprises the following steps:
step 3, adding an acid-base pH regulating solution into the mixed solution obtained in the step 2, regulating the pH to be more than 7, stirring and reacting for 1s-1h at room temperature, standing or centrifuging for 1s-1h, and then separating out solid substances;
and 4, cleaning the solid substance obtained in the step 3 to obtain an available solid substance.
Preferably, the reverse osmosis concentrated salt wastewater contains calcium ions or/and magnesium ions.
Preferably, the original release urine or/and the hydrolyzed urine is/are urine containing phosphorus element.
Preferably, the water quality index parameters of the original released urine are as follows: pH 6.35 + -0.12, Total Phosphorus (TP) 400 + -119 mg/L, Phosphate (PO)4 3-323 plus or minus 60mg/L of P, 5680 plus or minus 1120mg/L of Total Nitrogen (TN), and ammonia Nitrogen (NH)4 +-N)＝425±35mg/L，Ca2+＝98±27mg/L，Mg2+＝42±8.9mg/L。
Preferably, the index parameters of the water quality of the hydrolyzed urine are as follows: pH 9.23 + -0.20, Total Phosphorus (TP) 289 + -42 mg/L, Phosphate (PO)4 3-246 plus or minus 21mg/L of P, 4580 plus or minus 967mg/L of Total Nitrogen (TN), and NH4 +-N)＝3850±870mg/L。
Preferably, the acid-base pH adjusting solution is at least one of sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium oxide, calcium oxide, hydrochloric acid, sulfuric acid, nitric acid, and acetic acid.
Preferably, the water quality index parameters of the reverse osmosis strong brine are as follows: pH 8.60 + -0.10, Total Phosphorus (TP) 2.44 + -0.13 mg/L, Phosphate (PO)4 3--P) ═ 0.36 ± 0.05mg/L, Total Nitrogen (TN) ═ 18.6 ± 1.3mg/L, ammonia Nitrogen (NH)4 +-N)＝1.7±0.2mg/L，Ca2+＝458±36mg/L，Mg2+＝187±25mg/L。
Preferably, the reverse osmosis concentrated salt wastewater is a product generated after the circulating cooling water of the thermal power plant is subjected to desalination treatment.
Preferably, the usable solid substance contains at least one of the elements calcium, magnesium, nitrogen and phosphorus.
Preferably, the usable solid substance requires water rinsing before use, the water including at least one of natural water, tap water, purified water, mineral water, distilled water, and ultrapure water.
The method for recovering phosphate in urine provided by the invention has the beneficial effects that: compared with the prior art, the method for recovering phosphate in urine provided by the invention has the advantages that the reverse osmosis strong brine is used as a potential precipitator for phosphorus recovery, the urine containing nitrogen and phosphorus is mixed with the reverse osmosis strong brine containing calcium and magnesium, no commercial precipitator is required to be additionally added, the one-time investment cost is low, the operation is simple, and the time consumption is short. And the problems of low phosphorus content in the total amount of the wastewater, difficult treatment, high treatment cost and low treatment efficiency can be solved simultaneously. The reuse of reverse osmosis strong brine waste water has promoted water resource utilization efficiency many times, has improved the problem that reverse osmosis strong brine waste water treatment is difficult, the treatment cost is high. The concentrated salt wastewater and the urine nitrogen and phosphorus resources are recycled, so that the resources are effectively developed and utilized, and the purposes of treating wastes with processes of wastes against one another and changing wastes into valuables are achieved.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed for the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 shows the reverse osmosis concentrated saline versus TP and PO in the original release urine and the hydrolyzed urine at different volume ratios in example 1 according to the present invention4 3--P and NH4 +-recovery of N;
FIG. 2 is a graph showing the reverse osmosis of concentrated saline versus TP and PO in the original urine solution under different pH reaction conditions in example 2 according to the present invention4 3--P and NH4 +Recovery of N.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Referring to fig. 1 and fig. 2, a method for recovering phosphate from urine according to the present invention will now be described. The method for recovering phosphate in urine comprises the following steps:
s1, collecting reverse osmosis strong salt wastewater generated after desalting treatment of circulating cooling water of a thermal power plant;
the reverse osmosis desalination treatment process is an important treatment unit in sewage and wastewater recycling engineering, but the treatment of reverse osmosis concentrated brine intercepted by a reverse osmosis membrane becomes a serious problem in the desalination treatment of municipal and industrial wastewater. The reverse osmosis strong brine has multivalent cations and various inorganic elements, causes environmental pollution by direct discharge, and has high technical requirements in conventional treatment. The invention therefore proposes to use it as a precipitant for phosphorus recovery.
The obtained reverse osmosis concentrated salt wastewater contains calcium ions or/and magnesium ions.
S2, adding the original release urine or the hydrolyzed urine into the reverse osmosis concentrated salt wastewater collected in the step S1, and fully mixing to obtain a mixed solution;
the original release urine and the hydrolyzed urine respectively contain nitrogen and phosphorus elements.
S3, adding the pH adjusting solution into the mixed solution obtained in the step S2, adjusting the pH to be more than 7, stirring and reacting for 1S-1h at room temperature, standing or centrifuging for 1S-1h, and separating out solid substances;
the pH regulating solution is at least one of sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium oxide, calcium oxide, hydrochloric acid, sulfuric acid, nitric acid and acetic acid.
S4, washing the solid substance obtained in the step S3 with clear water for at least 1 time to obtain an available solid substance which contains elements such as calcium, magnesium, nitrogen and phosphorus and has economic value.
The solid substance is washed with water before use, and the water includes all water such as natural water, tap water, purified water, mineral water, distilled water and ultrapure water, excluding sewage and wastewater.
The solid substance can be rich in calcium, magnesium and nitrogen and phosphorus elements.
According to the method for recovering phosphate in urine, provided by the invention, reverse osmosis concentrated salt wastewater is taken as a precipitator, and then urine containing nitrogen and phosphorus is mixed with reverse osmosis concentrated salt wastewater containing calcium and magnesium, so that the problems of nitrogen and phosphorus pollution in urine, difficulty in treatment of reverse osmosis concentrated salt water and high treatment cost can be solved, the purpose of resource recovery can be achieved, and the method has the characteristics of environmental friendliness and high treatment efficiency.
Example 1
A method for recovering phosphate in urine comprises the following operation steps:
1. the required reagents include:
the first reagent is either the original release urine or/and the hydrolyzed urine.
The basic water quality index parameters of the original released urine are as follows: pH 6.35 + -0.12, Total Phosphorus (TP) 400 + -119 mg/L, Phosphate (PO)4 3-323 plus or minus 60mg/L of P, 5680 plus or minus 1120mg/L of Total Nitrogen (TN), and ammonia Nitrogen (NH)4 +-N)＝425±35mg/L，Ca2+＝98±27mg/L，Mg2+＝42±8.9mg/L。
The storage temperature condition of the original release urine is 4 ℃, the urine collecting barrel and the storage container are treated by 1M HCl every day, possible precipitates are removed, and hydrolysis of urea nitrogen is inhibited;
the basic water quality index parameters of the hydrolyzed urine are as follows: pH 9.23 + -0.20, Total Phosphorus (TP) 289 + -42 mg/L, Phosphate (PO)4 3-246 plus or minus 21mg/L of P, 4580 plus or minus 967mg/L of Total Nitrogen (TN), and NH4 +-N)＝3850±870mg/L，Ca2+And Mg2+None was detected.
The hydrolyzed urine is collected in a closed container and stored for more than 2 months at room temperature to form completely hydrolyzed urine with stable ammonia nitrogen concentration.
The second reagent is reverse osmosis strong brine (recorded as reverse osmosis strong brine) of a certain Beijing thermal power plant, and the basic water quality index parameters are as follows: the basic water quality index parameters are as follows: pH 8.60 + -0.10, TP 2.44 + -0.13 mg/L, PO4 3--P＝0.36±0.05mg/L，TN＝18.6±1.3mg/L，NH4 +-N＝1.7±0.2mg/L，Ca2+＝458±36mg/L，Mg2+＝187±25mg/L。
The third reagent was a 1M NaOH solution.
The fourth reagent was 1M HCl solution.
2. The reaction steps are as follows:
taking 5 parts of each 500mL of original release urine and each 500mL of hydrolyzed urine, and filtering by using a filter membrane with the pore diameter of 0.45 mu m to remove suspended solids;
taking second reagents with the volumes of 1000, 750, 500, 375 and 250mL respectively, and adding the second reagents into the original release urine in portions; the second reagent was taken up in volumes of 1000, 750, 500, 375, 250mL, respectively, and added in portions to the hydrolyzed urine.
Stirring each mixed solution of the first reagent and the second reagent for 30s at room temperature (14-17 ℃) to completely mix the first reagent and the second reagent;
sequentially dropwise adding a third reagent and a fourth reagent, and adjusting the pH value of the mixed solution to 9.0; the mixed solution was put on a magnetic stirrer, stirred at 200rpm for 30min, and then allowed to stand.
3. And (3) solid recovery:
standing for 20min, removing supernatant, and retaining precipitate solid; washing the obtained precipitate with distilled water for 3 times; then using a vacuum drying oven to dry the solid for 72 hours at the temperature of 45 ℃ and then storing the solid;
the main components of the precipitated solid comprise calcium, magnesium, nitrogen and phosphorus elements and can be used as a phosphate fertilizer.
Example 2
A method for recovering phosphate in urine comprises the following operation steps:
1. the required reagents include:
the first reagent is primary release urine. The basic water quality index parameters of the first reagent are as follows: pH 6.35 + -0.12, Total Phosphorus (TP) 400 + -119 mg/L, Phosphate (PO)4 3-323 plus or minus 60mg/L of P, 5680 plus or minus 1120mg/L of Total Nitrogen (TN), and ammonia Nitrogen (NH)4 +-N)＝425±35mg/L，Ca2+＝98±27mg/L，Mg2+＝42±8.9mg/L。
The original release urine is stored at 4 deg.C, and the urine collecting barrel and the storage container are treated with 1M HCl every day to remove the precipitate and inhibit hydrolysis of urea nitrogen.
Second trialThe agent is reverse osmosis strong brine (recorded as reverse osmosis strong brine) of a certain heat power plant in Beijing, and the basic water quality index parameters are as follows: pH 8.60 + -0.10, TP 2.44 + -0.13 mg/L, PO4 3--P＝0.36±0.05mg/L，TN＝18.6±1.3mg/L，NH4 +-N＝1.7±0.2mg/L，Ca2+＝458±36mg/L，Mg2+＝187±25mg/L。
The third reagent was a 1M NaOH solution.
The fourth reagent was 1M HCl solution.
2. The reaction steps are as follows:
taking 6 parts of first reagent, wherein each part of the first reagent takes 500 ml; taking 6 parts of a second reagent, wherein each part of the second reagent is 500ml, and adding the second reagent into the first reagent in portions; the mixture of the first reagent and the second reagent is stirred and mixed completely. Then, a third reagent and a fourth reagent are sequentially dripped to ensure that the pH values of the mixed solution of the first reagent and the second reagent are respectively 7.0, 7.5, 8.0, 8.5, 9.0 and 9.5; the mixture was then placed on a magnetic stirrer, stirred at 200rpm for 30min, and then allowed to stand. Standing for 20min, removing supernatant to obtain precipitate solid, and washing the precipitate solid with distilled water for 3 times; then using a vacuum drying oven to dry the precipitated solid for 72 hours at the temperature of 45 ℃ and then storing;
the main elements of the precipitated solid comprise calcium, magnesium, nitrogen and phosphorus, and can be used as a phosphate fertilizer.
The invention provides a method for recovering phosphate in urine, in particular to a method for separating and recovering phosphate in raw urine and hydrolyzed urine by using reverse osmosis strong brine generated by a reverse osmosis treatment process of circulating cooling water of a thermal power plant as a precipitator. And the problems of low phosphorus content in the total amount of the wastewater, difficult treatment, high treatment cost and low treatment efficiency can be solved simultaneously. The reuse of reverse osmosis strong brine waste water has promoted water resource utilization efficiency many times, has improved the problem that reverse osmosis strong brine waste water treatment is difficult, the treatment cost is high. The concentrated salt wastewater and the urine nitrogen and phosphorus resources are recycled, so that the resources are effectively developed and utilized, and the purposes of treating wastes with processes of wastes against one another and changing wastes into valuables are achieved.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A method for recovering phosphate from urine, comprising the steps of:
step 1, collecting reverse osmosis strong salt wastewater;
step 2, adding the original release urine or the hydrolyzed urine into the reverse osmosis concentrated salt wastewater collected in the step 1, and fully mixing;
step 3, adding an acid-base pH regulating solution into the mixed solution obtained in the step 2, regulating the pH to be more than 7, stirring and reacting for 1s-1h at room temperature, standing or centrifuging for 1s-1h, and then separating out solid substances;
and 4, cleaning the solid substance obtained in the step 3 to obtain an available solid substance.
2. A method of recovering phosphate from urine as claimed in claim 1, wherein: the reverse osmosis concentrated salt wastewater contains calcium ions or/and magnesium ions.
3. A method of recovering phosphate from urine as claimed in claim 1, wherein: the original release urine or/and the hydrolyzed urine is/are urine containing phosphorus element.
4. The method for recovering phosphate in urine according to claim 3, wherein the water quality index parameters of the original released urine are as follows: pH 6.35 + -0.12, Total Phosphorus (TP) 400 + -119 mg/L, Phosphate (PO)4 3--P) ═ 323 ± 60mg/L, Total Nitrogen (TN) ═ 5680 ± 1120mg/L, ammonia Nitrogen (NH)4 +-N)＝425±35mg/L，Ca2+＝98±27mg/L，Mg2+＝42±8.9mg/L。
5. The method for recovering phosphate in urine according to claim 3, wherein the water quality index parameters of the hydrolyzed urine are as follows: pH 9.23 + -0.20, Total Phosphorus (TP) 289 + -42 mg/L, Phosphate (PO)4 3-246 plus or minus 21mg/L of P, 4580 plus or minus 967mg/L of Total Nitrogen (TN), and NH4 +-N)＝3850±870mg/L。
6. A method of recovering phosphate from urine as claimed in claim 1, wherein: the pH adjusting solution is at least one of sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium oxide, calcium oxide, hydrochloric acid, sulfuric acid, nitric acid and acetic acid.
7. A method of recovering phosphate from urine as claimed in claim 1, wherein: the water quality index parameters of the reverse osmosis strong brine are as follows: pH 8.60 + -0.10, Total Phosphorus (TP) 2.44 + -0.13 mg/L, Phosphate (PO)4 3--P) ═ 0.36 ± 0.05mg/L, Total Nitrogen (TN) ═ 18.6 ± 1.3mg/L, ammonia Nitrogen (NH)4 +-N)＝1.7±0.2mg/L，Ca2+＝458±36mg/L，Mg2+＝187±25mg/L。
8. A method of recovering phosphate from urine as claimed in claim 1, wherein: the reverse osmosis strong salt wastewater is a product intercepted by the circulating cooling water of the thermal power plant through desalination treatment.
9. A method of recovering phosphate from urine as claimed in claim 1, wherein: the usable solid substance contains at least one of calcium, magnesium, nitrogen and phosphorus elements.
10. A method of recovering phosphate from urine as claimed in claim 1, wherein: the usable solid substance requires water rinsing before use, the water including at least one of natural water, tap water, purified water, mineral water, distilled water, and ultrapure water.
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Application publication date: 20210618 |