CN111302505A - Method and system for recycling calcium carbonate by reverse osmosis concentrated water regeneration - Google Patents
Method and system for recycling calcium carbonate by reverse osmosis concentrated water regeneration Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 246
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 101
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 51
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000004064 recycling Methods 0.000 title claims abstract description 20
- 230000008929 regeneration Effects 0.000 title claims abstract description 14
- 238000011069 regeneration method Methods 0.000 title claims abstract description 14
- 239000011575 calcium Substances 0.000 claims abstract description 60
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 9
- 229910001425 magnesium ion Inorganic materials 0.000 claims abstract description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 62
- 239000002002 slurry Substances 0.000 claims description 55
- 239000004571 lime Substances 0.000 claims description 54
- 238000001556 precipitation Methods 0.000 claims description 54
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 52
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 52
- 238000006243 chemical reaction Methods 0.000 claims description 45
- 239000008267 milk Substances 0.000 claims description 45
- 210000004080 milk Anatomy 0.000 claims description 39
- 235000013336 milk Nutrition 0.000 claims description 39
- 239000000292 calcium oxide Substances 0.000 claims description 35
- 235000012255 calcium oxide Nutrition 0.000 claims description 35
- 239000000843 powder Substances 0.000 claims description 28
- 150000002500 ions Chemical class 0.000 claims description 27
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 claims description 24
- 239000012065 filter cake Substances 0.000 claims description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 21
- 239000000047 product Substances 0.000 claims description 18
- 230000029087 digestion Effects 0.000 claims description 14
- 230000001376 precipitating effect Effects 0.000 claims description 14
- 238000005086 pumping Methods 0.000 claims description 14
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 13
- 239000000920 calcium hydroxide Substances 0.000 claims description 13
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 13
- 239000012716 precipitator Substances 0.000 claims description 13
- 239000011777 magnesium Substances 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 12
- 238000003860 storage Methods 0.000 claims description 12
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 9
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000000706 filtrate Substances 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 8
- 230000001172 regenerating effect Effects 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- 210000000481 breast Anatomy 0.000 claims description 6
- 239000001095 magnesium carbonate Substances 0.000 claims description 6
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000004572 hydraulic lime Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 4
- 238000010298 pulverizing process Methods 0.000 claims description 4
- -1 iron ions Chemical class 0.000 claims description 3
- 239000011268 mixed slurry Substances 0.000 claims description 3
- 238000004537 pulping Methods 0.000 claims description 3
- 210000001503 joint Anatomy 0.000 claims description 2
- 239000013049 sediment Substances 0.000 claims 1
- 239000002910 solid waste Substances 0.000 abstract description 7
- 239000002351 wastewater Substances 0.000 abstract description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 6
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 230000018109 developmental process Effects 0.000 abstract description 3
- 229910021645 metal ion Inorganic materials 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 229910017053 inorganic salt Inorganic materials 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 description 7
- 238000011084 recovery Methods 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 238000009388 chemical precipitation Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 229910000020 calcium bicarbonate Inorganic materials 0.000 description 2
- 239000013505 freshwater Substances 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229940024545 aluminum hydroxide Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 description 1
- 229960003563 calcium carbonate Drugs 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910000022 magnesium bicarbonate Inorganic materials 0.000 description 1
- 229960001708 magnesium carbonate Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/02—Softening water by precipitation of the hardness
- C02F5/06—Softening water by precipitation of the hardness using calcium compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
- C01F11/181—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by control of the carbonation conditions
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2/00—Lime, magnesia or dolomite
- C04B2/02—Lime
- C04B2/04—Slaking
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
A method and a system for recycling calcium carbonate by reverse osmosis concentrated water regeneration belong to the technical field of water treatment. Using Ca (OH)2Calcium and magnesium ions and high-valence metal ions in the concentrated water are precipitated and separated to obtain a calcium carbonate product, and the concentrated water is regenerated and converted into raw water. The method realizes the linkage breakthrough of the field of wastewater regeneration and the inorganic salt industrial technology, the effect of wastewater regeneration and solid waste zero discharge shows obvious technical progress, the capability of utilizing concentrated water as a resource and recycling high-added-value calcium carbonate finished products to change waste into valuable represents the development direction in the future, and the advantages of low investment, convenient matching, simple operation, low operation cost and the like presented by the technical scheme determine the wide popularization prospect.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a method and a system for recycling calcium carbonate by reverse osmosis concentrated water regeneration.
Background
The use of reverse osmosis plants for producing pure water has been widely adopted by numerous industrial enterprises and households. However, this technique has a disadvantage that high-salt ion concentrated water of approximately 50% in amount has to be discarded while pure water is obtained. Although the eliminated concentrated water cannot cause harm to the environment, and the water can also be used for greening flower watering and road dust suppression, for industrial industries with large water consumption, such as power plants, steel plants, chemical enterprises and other enterprises, the eliminated water quantity is too large, so that the water cannot be digested and utilized at all, and only can be selected as industrial wastewater to be discharged, and huge waste of water resources is formed. Moreover, the high cost paid by the sewage discharge also increases the cost of the enterprise. In the long term, the policy requirement of zero discharge of wastewater is higher and higher, and the recovery and treatment and resource utilization of reverse osmosis concentrated water are urgent.
In the aspect of reverse osmosis concentrated water treatment, many enterprises adopt a method of carrying out secondary concentration treatment on concentrated water by using high-pressure reverse osmosis to obtain concentrated high-salt concentrated water for discharge so as to reduce the quantity of the concentrated water as much as possible, but the method can only recycle 50% of the concentrated water again at a higher cost and does not achieve a substantial effect; some enterprises adopt a concentration and crystallization means to crystallize out soluble salt in the concentrated water, so that the concentrated water is recovered to be close to the property of the original water for recovery, and the technology can solve the problem of concentrated water recycling, but also has the problem of solid waste of a small amount of soluble mixed salt, and especially the high treatment cost limits the technical development; there is also a technical trend of precipitating calcium and magnesium ions from concentrated water by a chemical precipitation method and converting the concentrated water into raw water after separating the precipitate, which is theoretically feasible, but there are also problems of weak theoretical research, lack of certification in practice, and disposal of the formed solid waste. For example, the chinese patent application No. 201410641681.X discloses a method and a system for recycling reverse osmosis concentrated water with high efficiency and high recovery rate, although it mentions a better idea of "softening or chemically precipitating reverse osmosis concentrated water with slaked lime and soda ash to remove calcium ions, magnesium ions and silicon causing scaling", 2 serious disadvantages of the solution itself determine that the technology is still imperfect and difficult to meet the environmental requirements: firstly, sodium carbonate and hydrochloric acid are used for treating the concentrated water in the scheme, so that the content of soluble sodium chloride salt in the concentrated water is increased, and the environmental protection hidden trouble of waste salt discharge is increased; secondly, the solid-waste mixture obtained by the scheme has no other purposes and is selected to be buried, so that no secondary pollution to the environment is caused. The method also objectively reflects the outstanding problems of low recovery rate, high recovery rate and high cost which are both increased rapidly and the high recovery rate and the environmental protection hidden trouble exist in the prior art.
Therefore, in the field of reverse osmosis concentrated water treatment, the problems of incomplete utilization of wastewater, high running cost, environmental protection hidden danger caused by using certain chemical agents and secondary pollution caused by solid waste are also commonly existed, even if a theoretical blank exists in the technical field of treating concentrated water by using chemical means, such as precipitation method, the prior art lacks theoretical basis and practical support, even has misunderstanding and spurious, and needs interactive infiltration and innovation of various industrial technologies.
Disclosure of Invention
The invention aims to provide a method and a system for recycling calcium carbonate by regenerating reverse osmosis concentrated water, which can regenerate the concentrated water into clear water with components close to raw water while performing resource precipitation separation on hardness ions such as calcium, magnesium, iron, aluminum, zinc and the like in the concentrated water, obtain calcium carbonate while realizing zero discharge of wastewater and solid waste, greatly reduce the cost and obtain higher economic benefit.
The invention is based on the technical theory that: based on northern groundwater quality, most of raw water quality presents calcium bicarbonate type temporary hardness, so that the concentrated water discharged by reverse osmosis mainly contains Ca (HCO)3)2And a small amount of Mg (HCO)3)2In the presence of small amounts of Fe2 +、AL3+、Zn2+A high valence metal ion salt and Na+、K+、NH4 +Isovalent ionic salt, some SO being also present4 2-、CI-、NO3 -Plasma, wherein: ca (HCO)3)2And Mg (HCO)3)2The two salts account for more than 95% of the salt content of the concentrated water, and the total content is 8-15 mmol/L. Calcium and magnesium ions and high-valence metal ions in the concentrated water are precipitated and separated by a chemical precipitation method to obtain a calcium carbonate product containing a small amount of magnesium and trace amounts of iron, aluminum and zinc, so that the concentrated water is regenerated and converted into raw water. Adding Ca (OH) to the concentrated water2Milk, can be made of Ca (HCO)3)2Reaction to form CaCO3Precipitating Mg (HCO)3)2React to form MgCO3Precipitating; due to Ca (OH)2Adding the slurry to raise the pH value of water, and separating iron, aluminum and zinc ions from concentrated water in hydroxide statePrecipitating out; after calcium and magnesium ions and iron, aluminum and zinc ions are efficiently separated, the total hardness of the concentrated water is reduced to be fresh water with the components close to those of the raw water, and the fresh water is the raw water and can be called as the regenerated raw water.
In order to achieve the aim, the invention provides a method for recycling calcium carbonate by regenerating reverse osmosis concentrated water, which comprises the following steps:
a. precipitating agent Ca (OH)2Preparing milk: the slaking method is characterized in that the slaking method is adopted to prepare the calcium oxide CaO blocks or powder and the slaked lime powder, based on the calcium oxide CaO powder, concentrated water and the calcium oxide are quantitatively added into the slaker in a stirring state, the mass ratio of the concentrated water to the calcium oxide CaO is 10: 5-3, and the slaking reaction is carried out to obtain Ca (OH)2Pulping, digesting, adding concentrated water to obtain Ca (OH)2Adjusting the slurry to slurry containing certain CaO solid content, and pumping the adjusted Ca (OH) with lime milk pump2Pumping the slurry into a lime slurry metering tank for later use; namely:
CaO+H2O→Ca(OH)2；
b. reacting a precipitator with concentrated water to precipitate hardness ions so as to regenerate raw water: the precipitation reactor is dosed with concentrated water and with a quantity of precipitant Ca (OH)2The slurry is subjected to precipitation reaction with hardness ions in the concentrated water to obtain calcium ions Ca with main content2+The precipitation reaction forms CaCO which is difficult to dissolve3Precipitating to obtain secondary content of Mg ions2+Precipitation reaction to form insoluble MgCO3Precipitating to remove iron ions Fe existing in trace amount2+Precipitation reaction to form Fe (OH)2Precipitate, aluminum ion AL3+Precipitation reaction to form AL (OH)3Precipitate, zinc ion Zn2+Precipitation reaction to form Zn (OH)2Precipitation, precipitant Ca (OH)2The total hardness, the total alkalinity and the phenolphthalein alkalinity of the regenerated raw water are changed by the adding amount of the slurry, when the total hardness of the regenerated raw water in the precipitation reactor is stabilized between 2-4mmoL/L and the total alkalinity is stabilized between 1-3mmoL/L, the index that the phenolphthalein alkalinity is not more than 0.1mmoL/L is taken as a standard for judging the reaction endpoint, which indicates that the concentrated water is regenerated into raw water or clear water after most hardness ions are removed, namely:
Ca(HCO3)2+Ca(OH)2→2CaCO3↓+2H2O
Mg(HCO3)2+Ca(OH)2→CaCO3↓+MgCO3↓+2H2O
Ca(OH)2→Ca2++2OH-
Fe2++2OH-→Fe(OH)2↓
AL3++3OH-→AL(OH)3↓
Zn2++2OH-→Zn(OH)2↓；
c. and (3) recovering calcium carbonate: pumping the regenerated raw water containing the precipitate obtained in the step b into a filter by using a slurry pump for solid-liquid separation, wherein the filtrate is clear water with the components close to those of the raw water, delivering the clear water to a clear water storage tank for storing the raw water, and delivering the regenerated raw water to a raw water system by using a clear water pump; the filter cake is the raw material of the calcium carbonate recovered by the invention, the filter cake is conveyed to a dryer for drying by a belt conveyor, the dried product is conveyed to a crusher for crushing, and the powder is packaged to obtain the magnesium-containing light calcium carbonate product.
Preferably, in the step a, concentrated water and quicklime are quantitatively added according to the mass ratio of 3: 1, after the digestion exothermic reaction is finished, the concentrated water is added to adjust the solid content of CaO to be Ca (OH) with about 10% w/w2And (4) milk.
Preferably, the quicklime added in the step a is lime powder, and the quality requirements are that CaO is more than or equal to 93%, the fineness of 200-mesh sieve residue is less than or equal to 1%, and Fe is less than or equal to 0.1%.
Preferably, the slaked lime powder Ca (OH) can be directly used in the step a2Preparation of the precipitant Ca (OH)2And c, directly adding the slurry into the step b to react with the concentrated water to precipitate hardness ions so as to regenerate raw water.
In order to achieve the purpose, the invention also provides a system for recycling calcium carbonate by regenerating reverse osmosis concentrated water, which is characterized in that: include digestion ware, lime breast pump, lime breast metering tank, precipitation reactor, slurry pump, clean water pump, filter, clear water tank that connect gradually through the pipeline and by material transport connection or accordant connection's belt feeder, desicator, rubbing crusher, wherein:
the slaker comprises a stirrer, a lime feed inlet and a reverse osmosis concentrated water inlet connected with a reverse osmosis concentrated water pipe, and is used for carrying out slaking reaction of concentrated water and quicklime blocks/lime powder or slaked lime powder to prepare Ca (OH)2Milk;
the lime milk pump is connected between the slaker and the lime milk metering tank through a pipeline and is used for preparing Ca (OH) from the slaker2Pumping the slurry into a lime slurry metering tank;
the feed inlet of the lime milk metering tank is connected with a lime milk pump, and the discharge outlet of the lime milk metering tank is connected with the feed inlet of the precipitation reactor;
the precipitation reactor comprises a stirrer, a feed inlet connected with a lime milk metering tank and a reverse osmosis concentrated water inlet connected with a reverse osmosis concentrated water pipe, and is used for finishing the reaction of precipitating hardness ions by using a precipitator and concentrated water to obtain or regenerate raw water;
the slurry pump is connected between the precipitation reactor and the filter through a pipeline and is used for pumping the raw water and the precipitation mixed slurry regenerated in the precipitation reactor into the filter for solid-liquid separation;
the clean water tank is connected with a clean water outlet of the filter and used for storing regenerated raw water separated from filtrate of the filter, and the clean water pump is connected between the clean water tank and the raw water system and used for sending the regenerated raw water back to the raw water system;
the belt conveyor is arranged at a filter cake outlet of the filter and is used for conveying a filter cake into the dryer;
the dryer is arranged between the belt conveyor and the crusher and used for drying filter cakes conveyed by the belt conveyor, an inlet of the dryer is connected with an outlet of the belt conveyor in a matched manner, and an outlet of the dryer is connected with an inlet of the crusher in a matched manner;
the pulverizer comprises a feed inlet and a powder calcium carbonate outlet, wherein the feed inlet is in butt joint with the dryer outlet, and the powder calcium carbonate outlet is used for pulverizing the dried materials into finished calcium carbonate products.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a method and a system for recycling calcium carbonate by regenerating reverse osmosis concentrated water, which adopt Ca (OH)2Calcium, magnesium, iron, aluminum and zinc impurity ions in the concentrated water are precipitated by the slurry to form insoluble calcium carbonate, magnesium carbonate, ferric hydroxide, aluminum hydroxide and zinc hydroxide precipitates respectively, the hardness of the concentrated water is efficiently and rapidly reduced, and the concentrated water is regenerated into raw water except for the recovered calcium carbonate product. Compared with the prior art: the invention perfects the theory and practice foundation of the chemical precipitation method for the regeneration of the concentrated water in the aspect of technical innovation, achieves the aim of regenerating the concentrated water into the raw water under the condition of no wastewater and solid waste through the linkage breakthrough of the wastewater regeneration field and the inorganic salt industrial technology, shows obvious technical progress, represents the development direction in the future by the capacity of utilizing the concentrated water as a resource and recycling high-added-value calcium carbonate finished products to change waste into valuable, and determines the wide popularization prospect by the advantages of small investment, convenient matching, simple operation, low operation cost and the like expressed by the technical scheme.
Drawings
The invention is further described below with reference to the accompanying drawings and embodiments, it is obvious that the drawings in the following description are only one embodiment of the invention, and that other drawings can be obtained by those skilled in the art without inventive effort.
FIG. 1 is a schematic diagram of a method for recycling calcium carbonate by reverse osmosis concentrated water regeneration and a system configuration thereof according to the present invention; in the figure: 1-slaker, 2-lime milk pump, 3-lime milk metering tank, 4-precipitation reactor, 5-slurry pump, 6-clear water pump, 7-filter, 8-belt conveyor, 9-clear water storage tank, 10-dryer and 11-pulverizer
Detailed Description
Example 1: as can be seen from FIG. 1, the invention provides a method for recycling calcium carbonate by reverse osmosis concentrated water regeneration, which comprises the following steps:
a. precipitating agent Ca (OH)2Preparing milk: prepared by a quicklime powder CaO digestion method, 100 is added into a digestion device 1 in a stirring state0Kg of concentrated water, and 300Kg of quicklime powder are added to carry out digestion reaction to generate Ca (OH)2After the slurry is digested and the exothermic reaction is finished, 1500Kg of concentrated water is added to the slurry, Ca (OH)2Adjusting the slurry to be convenient for conveying and the slurry with CaO solid content of 10 percent, and using a lime milk pump 2 to adjust the adjusted Ca (OH)2Pumping the slurry into a lime slurry metering tank 3 for later use;
b. reacting a precipitator with concentrated water to precipitate hardness ions so as to regenerate raw water: 100 tons of concentrated water are added into a precipitation reactor 4, and then 0.6 ton of precipitator Ca (OH) in a lime milk metering tank 3 is added2The slurry is subjected to precipitation reaction with hardness ions in the concentrated water to obtain calcium ions Ca with main content2+The precipitation reaction forms CaCO which is difficult to dissolve3Precipitating to obtain secondary content of Mg ions2+Precipitation reaction to form insoluble MgCO3Precipitating to remove iron ions Fe existing in trace amount2+Precipitation reaction to form Fe (OH)2Precipitate, aluminum ion AL3+Precipitation reaction to form AL (OH)3Precipitating; precipitating agent Ca (OH)2The total hardness, the total alkalinity and the phenolphthalein alkalinity of the regenerated water are changed by the adding amount of the slurry, when the total hardness of the regenerated raw water in the precipitation reactor 4 is stabilized between 2 and 4mmoL/L and the total alkalinity is stabilized between 1 and 3mmoL/L, the index that the phenolphthalein alkalinity is not more than 0.1mmoL/L is taken as a standard for judging the reaction end point, which indicates that the concentrated water is regenerated into the raw water after most hardness ions are removed;
c. and (3) recovering calcium carbonate: pressing the regenerated raw water containing the precipitate obtained in the step b into a filter 7 by using a slurry pump 5 for filtering and separating, wherein the filtrate is clear water with the components close to the raw water, sending the clear water to a clear water storage tank 9 for storage, and sending the regenerated raw water to a raw water system by using a clear water pump 6; the filter cake is the raw material of the recovered calcium carbonate, the filter cake is conveyed to a dryer 10 through a belt conveyer 8 for drying, the dried product is crushed through the outlet of the dryer 10 matching with the inlet of a crusher 11, and the powder is packaged to obtain the magnesium-containing light calcium carbonate product.
Example 2: as can be seen from FIG. 1, the invention provides a method for recycling calcium carbonate by reverse osmosis concentrated water regeneration, which comprises the following steps:
a. precipitating agent Ca (OH)2Preparing milk: using quicklime blocks CThe aO digestion method is characterized in that 1000Kg of concentrated water is added into a digestion device 1 in a stirring state, 320Kg of quicklime blocks are added for digestion reaction to obtain Ca (OH)2After the slurry is digested and the exothermic reaction is finished, 1500Kg of concentrated water is added to the slurry, Ca (OH)2Adjusting the slurry to be convenient for conveying and the CaO solid content is about 10 percent, and using a lime milk pump 2 to adjust the adjusted Ca (OH)2Pumping the slurry into a lime slurry metering tank 3 for later use;
b. reacting a precipitator with concentrated water to precipitate hardness ions so as to regenerate raw water: 100 tons of concentrated water are added into a precipitation reactor 4, and then 0.7 ton of precipitator Ca (OH) in a lime milk metering tank 3 is added2The slurry is subjected to precipitation reaction with hardness ions in the concentrated water; controlling a reaction end point by detecting the total hardness, the total alkalinity and the phenolphthalein alkalinity of the regenerated water, and when the total hardness of the regenerated raw water in the precipitation reactor 4 is stabilized between 2 and 4mmoL/L and the total alkalinity is stabilized between 1 and 3mmoL/L, taking an index that the phenolphthalein alkalinity is not more than 0.1mmoL/L as a standard for judging the reaction end point, and indicating that the concentrated water is regenerated into the raw water after most hardness ions are removed;
c. and (3) recovering calcium carbonate: pressing the regenerated raw water containing the precipitate obtained in the step b into a filter 7 by using a slurry pump 5 for filtering and separating, wherein the filtrate is clear water with the components close to the raw water, sending the clear water to a clear water storage tank 9 for storage, and sending the regenerated raw water to a raw water system by using a clear water pump 6; the filter cake is the raw material of the calcium carbonate recovered by the invention, the filter cake is conveyed to a dryer 10 by a belt conveyer 8 for drying, and the dried product is conveyed to a crusher 11 for crushing and packaging to obtain the magnesium-containing light calcium carbonate product.
Example 3: as can be seen from FIG. 1, the invention provides a method for recycling calcium carbonate by reverse osmosis concentrated water regeneration, which comprises the following steps:
a. precipitating agent Ca (OH)2Preparing milk: using slaked lime Ca (OH)2Direct pulping of powder to Ca (OH)2Adding 3000Kg of concentrated water into the slaker 1 while stirring, and adding slaked lime Ca (OH)2500Kg of powder was slurried to obtain Ca (OH)2Milk, then adjusted Ca (OH) by a lime milk pump 22Pumping the slurry into a lime slurry metering tank 3 for later use;
b. by usingThe precipitator reacts with the concentrated water to precipitate hardness ions to regenerate raw water: 100 tons of concentrated water are added into the precipitation reactor 4, and 0.6 ton of precipitator Ca (OH) from a lime milk metering tank 3 is added2The slurry is subjected to precipitation reaction with hardness ions in the concentrated water; controlling a reaction end point by detecting the total hardness, the total alkalinity and the phenolphthalein alkalinity of the regenerated raw water, and when the total hardness of the regenerated raw water in the precipitation reactor 4 is stabilized between 2 and 4mmoL/L and the total alkalinity is stabilized between 1 and 3mmoL/L, taking an index that the phenolphthalein alkalinity is not more than 0.1mmoL/L as a standard for judging the reaction end point, and indicating that concentrated water is regenerated into the raw water after most hardness ions are removed;
c. and (3) recovering calcium carbonate: pressing the regenerated raw water containing the precipitate obtained in the step b into a filter 7 by using a slurry pump 5 for filtering and separating, wherein the filtrate is clear water with the components close to the raw water, sending the clear water to a clear water storage tank 9 for storage, and sending the regenerated raw water to a raw water system by using a clear water pump 6; the filter cake is the raw material of the calcium carbonate recovered by the invention, the filter cake is conveyed to a dryer 10 by a belt conveyer 8 for drying, and the dried product is conveyed to a crusher 11 for crushing and packaging to obtain the magnesium-containing light calcium carbonate product.
Example 4: as shown in fig. 1, the invention also provides a system for recycling calcium carbonate by reverse osmosis concentrated water regeneration, which is characterized in that: include digestion device 1, lime breast pump 2, lime breast metering tank 3, precipitation reactor 4, slurry pump 5, clean water pump 6, filter 7, clear water tank 8 that connect gradually through the pipeline and by material transport connection or accordant connection's belt feeder 9, desicator 10, rubbing crusher 11, wherein:
the slaker 1 comprises a stirrer, a lime feeding port and a reverse osmosis concentrated water feeding port connected with a reverse osmosis concentrated water pipe, and is used for carrying out slaking reaction of concentrated water and quicklime blocks/lime powder or slaked lime powder to prepare Ca (OH)2Milk;
the lime milk pump 2 is connected between the slaker 1 and the lime milk metering tank 3 through a pipeline and is used for preparing Ca (OH) from the slaker 12Pumping the slurry into a lime slurry metering tank 3;
the feed inlet of the lime milk metering tank 3 is connected with the lime milk pump 2, and the discharge outlet of the lime milk metering tank 3 is connected with the feed inlet of the precipitation reactor 4;
the precipitation reactor 4 comprises a stirrer, a feed inlet connected with the lime milk metering tank 3 and a reverse osmosis concentrated water inlet connected with a reverse osmosis concentrated water pipe, and is used for finishing the reaction of precipitating hardness ions by using a precipitator and concentrated water to regenerate raw water;
the slurry pump 5 is connected between the precipitation reactor 4 and the filter 7 through a pipeline and is used for pumping the raw water and the precipitation mixed slurry regenerated in the precipitation reactor 4 into the filter 7 for solid-liquid separation;
the clean water tank 9 is connected with a clean water outlet of the filter 7 and used for storing regenerated raw water separated from filtrate of the filter 7, and the clean water pump 6 is connected between the clean water tank 9 and the raw water system and used for sending the regenerated raw water back to the raw water system;
the belt conveyor 8 is arranged at a filter cake outlet of the filter 7 and is used for conveying filter cakes to the dryer 10;
the dryer 10 is arranged between the belt conveyor 8 and the pulverizer 11 and is used for drying filter cakes conveyed by the belt conveyor 8, an inlet of the dryer 10 is connected with an outlet of the belt conveyor 8 in a matched manner, and an outlet of the dryer 10 is connected with an inlet of the pulverizer 11 in a matched manner;
the pulverizer 11 comprises a feed inlet butted with the outlet of the dryer 10 and a powder calcium carbonate outlet, and is used for pulverizing the dried material into a finished calcium carbonate product.
Claims (4)
1. A method for recycling calcium carbonate by regenerating reverse osmosis concentrated water comprises the following steps:
a. precipitating agent Ca (OH)2Preparing milk: the slaking method is characterized in that the slaking method is adopted to prepare the calcium oxide CaO blocks or powder and the slaked lime powder, based on the calcium oxide CaO powder, concentrated water and the calcium oxide are quantitatively added into a slaker (1) in a stirring state, the mass ratio of the concentrated water to the calcium oxide CaO is 10: 5-3, and the slaking reaction is carried out to obtain Ca (OH)2Pulping, digesting, adding concentrated water to obtain Ca (OH)2Adjusting the slurry to slurry containing certain CaO solid content, and using a lime milk pump (2) to adjust the adjusted Ca (OH)2Milk pumpThe lime milk metering tank (3) is used for standby;
b. reacting a precipitator with concentrated water to precipitate hardness ions so as to regenerate raw water: the precipitation reactor (4) is dosed with concentrated water and with a quantity of a precipitant Ca (OH)2The slurry is subjected to precipitation reaction with hardness ions in the concentrated water to obtain calcium ions Ca with main content2+The precipitation reaction forms CaCO which is difficult to dissolve3Precipitating to obtain secondary content of Mg ions2+Precipitation reaction to form insoluble MgCO3Precipitating to remove iron ions Fe existing in trace amount2+Precipitation reaction to form Fe (OH)2Precipitate, aluminum ion AL3+Precipitation reaction to form AL (OH)3Precipitate, zinc ion Zn2+Precipitation reaction to form Zn (OH)2Precipitating; precipitating agent Ca (OH)2The total hardness, the total alkalinity and the phenolphthalein alkalinity of the regenerated raw water are changed by the adding amount of the slurry, when the total hardness of the regenerated raw water in the precipitation reactor (4) is stabilized between 2 and 4mmoL/L and the total alkalinity is stabilized between 1 and 3mmoL/L, the index that the phenolphthalein alkalinity is not more than 0.1mmoL/L is taken as a standard for judging the reaction endpoint, which indicates that the concentrated water is regenerated into the raw water after most hardness ions are removed;
c. and (3) recovering calcium carbonate: pumping the regenerated raw water containing the precipitate obtained in the step b into a filter (7) by using a slurry pump (5) for solid-liquid separation, wherein the filtrate is clear water with the components close to the raw water, sending the clear water to a clear water storage tank (9) for storage as the raw water for use, and sending the regenerated raw water to a raw water system by using a clear water pump (6); the filter cake is the raw material of the recovered calcium carbonate, the filter cake is conveyed to a dryer (10) through a belt conveyor (8) for drying, the dried product is conveyed to a pulverizer (11) for pulverization, and the powder is packaged to obtain the magnesium-containing light calcium carbonate product.
2. The method for recycling calcium carbonate by regenerating reverse osmosis concentrated water according to claim 1, which is characterized in that: quantitatively adding concentrated water and quicklime in a mass ratio of 3: 1 in the step a, adjusting the concentrated water to Ca (OH) with CaO solid content of about 10% w/w after the digestion exothermic reaction is finished2And (4) milk.
3. The method for recycling calcium carbonate by regenerating reverse osmosis concentrated water according to claim 1, comprising the following steps:
a. precipitating agent Ca (OH)2Preparing milk: the lime powder is prepared by a CaO digestion method, 1000Kg of concentrated water is added into a digestion device (1) in a stirring state, and 300Kg of the lime powder is added for carrying out digestion reaction to generate Ca (OH)2After the slurry is digested and the exothermic reaction is finished, 1500Kg of concentrated water is added to the slurry, Ca (OH)2Adjusting the size to be convenient for conveying and the size with 10 percent of CaO solid content, and using a lime milk pump (2) to adjust the adjusted Ca (OH)2Pumping the slurry into a lime slurry metering tank (3) for later use;
b. reacting a precipitator with concentrated water to precipitate hardness ions so as to regenerate raw water: 100 tons of concentrated water are added into a precipitation reactor (4), and then 0.6 ton of precipitator Ca (OH) in a lime milk metering tank (3) is added2The slurry is subjected to precipitation reaction with hardness ions in the concentrated water; precipitating agent Ca (OH)2The total hardness, the total alkalinity and the phenolphthalein alkalinity of the regenerated water are changed by the adding amount of the slurry, when the total hardness of the regenerated raw water in the precipitation reactor (4) is stabilized between 2 and 4mmoL/L and the total alkalinity is stabilized between 1 and 3mmoL/L, the index that the phenolphthalein alkalinity is not more than 0.1mmoL/L is taken as a standard for judging the reaction endpoint, which indicates that the concentrated water is regenerated into the raw water after most hardness ions are removed;
c. and (3) recovering calcium carbonate: pressing the regenerated raw water containing the sediment obtained in the step b into a filter (7) by using a slurry pump (5) for filtering and separating, wherein the filtrate is clear water with the components close to the raw water, sending the clear water to a clear water storage tank (9) for storage, and sending the regenerated raw water to a raw water system by using a clear water pump (6); the filter cake is a raw material of the recovered calcium carbonate, the filter cake is conveyed to a dryer (10) through a belt conveyor (8) for drying, a dried product is crushed through an outlet of the dryer (10) matching with an inlet of a crusher (11), and powder is packaged to obtain a magnesium-containing light calcium carbonate product.
4. The utility model provides a system for reverse osmosis dense water regeneration retrieves calcium carbonate which characterized in that: include digestion ware (1), lime breast pump (2), lime breast metering tank (3), precipitation reactor (4), slurry pump (5), clean water pump (6), filter (7), clear water tank (9) that connect gradually through the pipeline and by material transport connection or accordant connection's belt feeder (8), desicator (10), rubbing crusher (11), wherein:
the slaker (1) comprises a stirrer, a lime feeding port and a reverse osmosis concentrated water feeding port connected with a reverse osmosis concentrated water pipe, and is used for carrying out slaking reaction of concentrated water and quicklime blocks/lime powder or slaked lime powder to prepare Ca (OH)2Milk;
the lime milk pump (2) is connected between the slaker (1) and the lime milk metering tank (3) through a pipeline and is used for preparing Ca (OH) from the slaker (1)2Pumping the slurry into a lime slurry metering tank (3);
the feed inlet of the lime milk metering tank (3) is connected with the lime milk pump (2), and the discharge outlet of the lime milk metering tank (3) is connected with the feed inlet of the precipitation reactor (4);
the precipitation reactor (4) comprises a stirrer, a feed inlet connected with the lime milk metering tank (3) and a reverse osmosis concentrated water inlet connected with a reverse osmosis concentrated water pipe, and is used for finishing the reaction of precipitating hardness ions by using a precipitator and the concentrated water to regenerate raw water;
the slurry pump (5) is connected between the precipitation reactor (4) and the filter (7) through a pipeline and is used for pumping the raw water and the precipitation mixed slurry regenerated in the precipitation reactor (4) into the filter (7) for solid-liquid separation;
the clean water tank (9) is connected with a clean water outlet of the filter (7) and used for storing regenerated raw water separated from filtrate of the filter (7), and the clean water pump (6) is connected between the clean water tank (9) and the raw water system and used for sending the regenerated raw water back to the raw water system;
the belt conveyor (8) is arranged at a filter cake outlet of the filter (7) and is used for conveying filter cakes into the dryer (10);
the dryer (10) is arranged between the belt conveyor (8) and the crusher (11) and used for drying filter cakes conveyed by the belt conveyor (8), an inlet of the dryer (10) is connected with an outlet of the belt conveyor (8) in a matched manner, and an outlet of the dryer (10) is connected with an inlet of the crusher (11) in a matched manner;
the pulverizer (11) comprises a feed inlet and a powder calcium carbonate outlet which are in butt joint with the outlet of the dryer (10), and is used for pulverizing the dried materials into calcium carbonate finished products.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1041340A (en) * | 1988-09-29 | 1990-04-18 | 水利电力部西北电力工程承包公司 | The lime treatment deslagging of water utilizes Processes and apparatus again |
| US20060196836A1 (en) * | 2002-11-05 | 2006-09-07 | Aharon Arakel | Process and apparatus for the treatment of saline water |
| CN102838235A (en) * | 2012-09-14 | 2012-12-26 | 北京市自来水集团有限责任公司 | Method for removing underground water hardness by combination of lime and ultrafiltration |
| CN212315717U (en) * | 2020-02-25 | 2021-01-08 | 邢台润天环保科技有限公司 | System for reverse osmosis concentrated water regeneration retrieves calcium carbonate |
-
2020
- 2020-02-25 CN CN202010137464.2A patent/CN111302505A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1041340A (en) * | 1988-09-29 | 1990-04-18 | 水利电力部西北电力工程承包公司 | The lime treatment deslagging of water utilizes Processes and apparatus again |
| US20060196836A1 (en) * | 2002-11-05 | 2006-09-07 | Aharon Arakel | Process and apparatus for the treatment of saline water |
| CN102838235A (en) * | 2012-09-14 | 2012-12-26 | 北京市自来水集团有限责任公司 | Method for removing underground water hardness by combination of lime and ultrafiltration |
| CN212315717U (en) * | 2020-02-25 | 2021-01-08 | 邢台润天环保科技有限公司 | System for reverse osmosis concentrated water regeneration retrieves calcium carbonate |
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