CN105692856A - Modified dolomites for hardening and tempering desalination water - Google Patents

Modified dolomites for hardening and tempering desalination water Download PDF

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CN105692856A
CN105692856A CN201610111730.8A CN201610111730A CN105692856A CN 105692856 A CN105692856 A CN 105692856A CN 201610111730 A CN201610111730 A CN 201610111730A CN 105692856 A CN105692856 A CN 105692856A
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dolomite
modified
water
desalination water
stage
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CN105692856B (en
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李鑫
甘树
陈红
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ZHEJIANG ZHIMEI ENVIRONMENT TECHNOLOGY Co Ltd
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ZHEJIANG ZHIMEI ENVIRONMENT TECHNOLOGY Co Ltd
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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
    • C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
    • C02F1/683—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water by addition of complex-forming compounds

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Non-Alcoholic Beverages (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
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Abstract

The invention provides modified dolomites for hardening and tempering desalination water and belongs to the technical field of seawater desalination. The modified dolomites are characterized by being prepared by modifying dolomite raw ores, the modification process includes a light roasting stage, a carbonation stage and a stabilization stage, the prepared modified dolomites are loose in crystal structure and large in porosity and are uniformly distributed, the porosity is not lower than 10%, more than 50 times of the porosity of the corresponding raw ores can be achieved, the dissolution rate of the dolomites is obviously improved when being used for hardening and tempering the desalination water, and the retention time is shortened by 10% compared with the retention time of the dolomite raw ores under the same conditions. Therefore, only the desalination water is needed to flow through a hardening and tempering tank containing the modified dolomites, additional reagents are not needed in the hardening and tempering process, the produced water subjected to the hardening and tempering is slightly alkaline, is moderate in hardness and alkalinity and contains small water molecule clusters, rich beneficial mineral elements including calcium, magnesium, iron, zinc and the like and rich bicarbonate.

Description

A kind of modification dolomite modified for desalination water
Technical field
The invention belongs to field of sea water desalting technology, be specifically related to a kind of modification dolomite modified for desalination water。
Background technology
Along with the development of membrane science technology, reverse osmosis has been increasingly becoming a kind of effective ways solving world's fresh water crisis。Reverse osmosis can remove most antibacterial, inorganic salt, Organic substance etc. in sea water, but to ion component each in sea water be not equal proportion remove, to Ca2+、Mg2+、SO4 2-High etc. bivalent ions rejection relatively monovalent ion so that the buffer capacity of desalination water is relatively weak。Additionally, due to reverse osmosis cannot retain the carbon dioxide in sea water, these carbon dioxide can return in water through membrane module arrival product water rear flank and be converted into HCO3 -, this has higher corrosivity by making desalination by reverse osmosis glassware for drinking water。This characteristic of desalination water so that in transport, calcium carbonate film is difficult on tube wall, bulkhead to precipitate in storage process so that metallic material corrosion and produce " red water " phenomenon, meanwhile, microorganism also can be grown on tube wall and aggravate piping corrosion。The acceptance of desalination water, disinfection efficiency and user's body health etc. all will be produced a series of impact by water supply cost, user by these。Therefore, consider from piping corrosion and human body drinking safety, it is necessary to desalination water water quality is adjusted。
The modified method of desalination water includes mixing source water blending method, adds medical method and dissolve Ore method。In blending method, desalination water is difficult to coordinate with the ratio mixing source water；When interpolation medicament is modified, the easy deliquescence of medicament, not Portable belt, and desalinization water water quality can be produced some side effect, for instance add Ca (OH)2Time may cause delivery turbidity increase, product, and water pH is too high, adds NaHCO3Time can make produce water astringent, impact drink mouthfeel；The raw ores such as dolomite, limestone, Maifanitum are directly used in desalination water modified time, though tcrude ore Mineral Concentrations enriches, and the effective adjustment to desalinization water pH, hardness, basicity, calcium-magnesium content etc. can be realized, but tcrude ore rate of dissolution is excessively slow, the desalination water time of staying in a device is long, and quenching and tempering device is excessive。If using H2SO4Or CO2Reduce inlet flow-patterm and accelerate Ore rate of dissolution, water outlet pH can be made in acidity, need dosing to carry out pH regulator and H2SO4With CO2Not portable, store inconvenience, greatly limit its application in boats and ships desalination water is modified。
" DesalinationandWaterTreatment " the 1st volume in 2009 the 58th page reports LiatBirnhack etc. and uses H2SO4Dissolving the dolomite being sequentially connected in series and carry out, with calcite reactor, the method that desalination water is modified, its effluent quality is: hardness=170mg/L(is with CaCO3Meter), basicity=75mg/L(is with CaCO3Meter), [Ca2+]=48mg/L, [Mg2+]=12.4mg/L, although H2SO4React, with dolomite, the carbon dioxide produced to can be used for dissolving calcite, thus saving H2SO4Dosage, but NaOH need to be added water outlet pH is adjusted, medicament storage problem limits its application。
Report that bodyguard perhaps is flourish etc. adopts limestone to carry out the test that low salinity water is modified " water supply and drainage " the 38th volume the 4th phase in 2012 the 31st page, the limestone of different sources has been screened by test, result shows, the limestone result of extraction that calcium content is high is imitated, when contacting 10min with limestone, go out the water hardness, basicity and about add 8mg/L (with CaCO3Meter)。This process of the test is without adding medicament, but the regulating effect of effluent quality is very micro-, to make out the water hardness, basicity etc. be significantly improved, need to extend hydraulic detention time, will certainly increase equipment volume, strengthens operation easier。
The preparation method that the Chinese invention patent of publication number CN102795737B discloses a kind of alkalescent drinking water, adjusting material used by its modified part is natural Muyu-Stone and medical stone granule:, although element abundant species contained by both adjusting materials, and heavy metal, nitrite, organic pollution etc. have certain absorbability, but natural crystal quality is hard, dissolution rate is slow, when the time of staying is shorter, water outlet pH can only be played certain adjustment effect, beneficial mineral constituent content effect in water is very micro-。
The Chinese utility model patent of publication number CN202785776U discloses a kind of medical stone mineralization equipment, and including mineralization device and the extraction element of plural serial stage, adjusting material used is natural medical stone。Although having certain effect for increasing water outlet mineral element with the medical stone mineralization device being sequentially connected in series, but equipment is many and floor space is big, and operation easier is big, and automaticity is low。
Adjusting material should meet be easy to carry, rate of dissolution is fast, the modified process feature without adding medicament, equipment is simple to operate, controllability is high, tradition adjusting material cannot meet above-mentioned requirements, therefore develops a kind of adjusting material that can meet above-mentioned requirements very necessary。
Summary of the invention
The modification dolomite technical scheme modified for desalination water made it is modified by dolomite raw ore, to overcome problems of the prior art it is desirable to provide a kind of。
Described a kind of modification dolomite modified for desalination water, it is characterized in that being modified by dolomite raw ore making, modifying process includes light-burned stage, carbonation stages, stabilisation stage, and the crystal structure of obtained modification dolomite loosens, and porosity is big and is evenly distributed。
Described a kind of modification dolomite modified for desalination water, it is characterised in that:
1) described dolomite raw ore be mainly composed of CaMg (CO3)2；
2) the light-burned stage described in carries out in carbon dioxide atmosphere, light-burned stage heating rate is 6 DEG C/min～15 DEG C/min, light roasting temperature is 650 DEG C～1000 DEG C, the light-burned time is 0.5h～3h, light-burned carbon dioxide in process is overflowed, dolomite inside and surface form uniform hole, and dolomite decomposition is calcium carbonate, calcium oxide and magnesium oxide, and dominant response formula is as follows:
,
；
3) carbonation stages described in adopts wet method carbonating, carbonation passes into steam and carbon dioxide, calcium oxide, magnesium oxide that steam and light-burned stage are formed react generation hydroxide, then generate carbonate, heavy carbonate with carbon dioxide reaction, and dominant response formula is as follows:
,
,
,
,
,
,
Described steam accounts for the 30%～50% of mixing gas volume, and carbonation temperature is 50 DEG C～150 DEG C, and carbonation time is 1.8h～3.2h；
4) the stabilisation stage described in carries out in carbon dioxide atmosphere, and stabilization temperature is 100 DEG C～150 DEG C, and the stabilisation time is 0.8h～2.2h。
Described a kind of modification dolomite modified for desalination water, it is characterised in that the porosity of described modification dolomite is not less than 10%。
Described a kind of modification dolomite modified for desalination water, it is characterised in that the particle diameter of the dolomite raw ore adopted is 3mm～5mm。
Above-mentioned a kind of modification dolomite modified for desalination water, crystal structure loosens, porosity is big and even aperture distribution, porosity is not less than 10%, more than 50 times of corresponding raw ore porosity can be reached, for desalination water modified time, the contact area of adjusting material and desalination water significantly increases, dissolution rate is substantially accelerated, the time of staying only needs 1～5min just can reach the effective adjustment to desalinization water water quality, lower than under equal conditions the 10% of the dolomite raw ore time of staying, therefore application this patent only need to make desalination water flow through the modified tank equipped with described modification dolomite, modified process is without adding medicament, modified water outlet is alkalescence, hardness, basicity is moderate, water molecule cluster is little, rich in calcium, magnesium, ferrum, the beneficial mineral elements such as zinc, heavy carbonate rich content。
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope analysis figure of modification dolomite of the present invention；
Fig. 2 is the scanning electron microscope analysis figure of dolomite raw ore of the present invention。
Detailed description of the invention
In conjunction with Figure of description and embodiment, describe the specific embodiment of the present invention in detail:
A kind of modification dolomite modified for desalination water, is modified by dolomite raw ore and makes, and modifying process includes light-burned stage, carbonation stages, stabilisation stage, wherein:
1) the dolomite raw ore described in be mainly composed of CaMg (CO3)2, particle diameter selects 3mm～5mm, and dolomite source of crude is big, and preparation method is simple；
2) the light-burned stage described in carries out in carbon dioxide atmosphere, this light-burned stage heating rate is 6 DEG C/min～15 DEG C/min, light roasting temperature is 650 DEG C～1000 DEG C, the light-burned time is 0.5h～3h, light-burned carbon dioxide in process is overflowed, dolomite inside and surface form uniform hole, and dolomite decomposition is calcium carbonate, calcium oxide and magnesium oxide, and dominant response formula is as follows:
,
；
3) carbonation stages described in adopts wet method carbonating, carbonation passes into steam and carbon dioxide, calcium oxide, magnesium oxide that steam and light-burned stage are formed react generation hydroxide, then carbonate, heavy carbonate are generated with carbon dioxide reaction, the carbonate, the heavy carbonate that generate are recrystallized product, short texture, hole is many, specific surface area is big, and this process dominant response formula is as follows:
,
,
,
,
,
,
The activation energy that calcium oxide, magnesium oxide and water react is far below the activation energy with carbon dioxide reaction, the introducing of water vapour makes carbonation time substantially shorten, efficiency significantly improves, in this process, steam accounts for the 30%～50% of mixing gas volume, carbonation temperature is 50 DEG C～150 DEG C, and carbonation time is 1.8h～3.2h；
4) the stabilisation stage described in carries out in carbon dioxide atmosphere, the heating rate in stabilisation stage is for for 0.6 DEG C/min～1.5 DEG C/min, stabilization temperature is 100 DEG C～150 DEG C, the stabilisation time is 0.8h～2.2h, the stabilisation stage carries out in carbon dioxide atmosphere, the carbonate, the heavy carbonate that are generated by recrystallization solidify, it is prevented that in transport, storage process, crystal comes off。
In above-mentioned embodiment, the carbon dioxide atmosphere in light-burned stage ensure that the reaction uniformity of carbonation；If the light-burned stage carries out in air, the steam that carbonation stages passes into partial condensation can form water seal in dolomite hole, generation hydroxide is reacted with CaO, MgO, prevent the generation of carbonate, heavy carbonate, and light-burned stage when carrying out in carbon dioxide atmosphere, carbon dioxide is filled in dolomite hole, after steam and CaO, MgO react generation hydroxide, then generates carbonate, heavy carbonate with carbon dioxide reaction。
Loosen through the modification dolomite crystal structure obtained by said process, hole is many and is evenly distributed, average pore size is 10nm ~ 25nm, porosity is not less than 10% and may be up to more than 25%, more than 50 times of corresponding raw ore porosity can be reached, for desalination water modified time, the contact area of adjusting material and desalination water significantly increases, and dissolution rate is substantially accelerated；The loose crystals structure of modification dolomite makes dissolution rate fast, for desalination water modified time the time of staying only need 1～5min, lower than under equal conditions the 10% of the dolomite raw ore time of staying, desalination water only need to being made to flow through the modified tank equipped with described modification dolomite during application this patent, and modified process is without adding medicament, modified water outlet is alkalescence, hardness, basicity are moderate, water molecule cluster is little, rich in the beneficial mineral elements such as calcium, magnesium, ferrum, zinc, heavy carbonate rich content。
Embodiment is below adopted to be specifically described embodiments of the present invention and remarkable result further:
1) bulk dolomite dust is broken into the granule that particle diameter is 3 ~ 5mm；
2) dolomite after pulverizing in carbon dioxide atmosphere at 850 DEG C light-burned 1 hour, when carbon dioxide atmosphere is cooled to 120 DEG C, pass into steam, control steam and account for the 50% of mixing gas volume, stop steam after 2 hours to pass into, be warming up to 150 DEG C of stabilisation 1 hours in carbon dioxide atmosphere；
3) modification dolomite is scanned electronic microscope photos, relatively its configuration of surface: the scanning electron microscope (SEM) photograph of obtained modification dolomite and dolomite raw ore is respectively as shown in Fig. 2 and Fig. 1, as seen from the figure, dolomite surface recrystallization becomes loose crystal after modified, form has had very big change, the cluster-shaped structure being cross-linked with each other on the one hand is conducive to the raising of adjusting material intensity, not broken in transport, storage process, is conducive to dissolution on the other hand。
4) obtained modification dolomite and dolomite raw ore being carried out pore-size distribution analysis, the result after before modified is in Table 1:
Table 1: modification dolomite and dolomite raw ore carry out pore-size distribution analytical table
Parameter Total pore volume Specific surface Average pore size (4V/A) Porosity
Unit mL/g m2/g nm %
Dolomite raw ore 0.0005 0.13 16.84 0.36
Modification dolomite 0.0184 4.60 7.56 19.36
As can be seen from Table 1, dolomite raw ore quality is hard, surface is substantially free of micropore, porosity is very low, for desalination water modified time dissolution rate slow, the hole area of modification dolomite unit mass of the present invention and pore volume significantly increase, define small nano-size pores, porosity increases, the present embodiment is analyzed the result of mensuration, the porosity of dolomite raw ore and modification dolomite respectively 0.36% and 19.36%, namely the porosity of modification dolomite of the present invention is about 54 times of corresponding dolomite raw ore。
5) adopting obtained modification dolomite to carry out desalination water modifier treatment: controlling hydraulic detention time is 1 minute, with the ratio of volume ratio 4:5 obtained modification dolomite and desalination water carried out stream modified, its modified effluent quality is in Table 2:
Table 2 desalination water and modification dolomite temper water water analysis
As can be seen from Table 2, modification dolomite modified go out the water hardness, basicity relatively desalination water be greatly improved, and bicarbonate content enrich, rich in beneficial mineral elements such as calcium and magnesium, long-term drink is good for one's health。
6) obtained modification dolomite and dolomite raw ore is adopted to carry out desalination water modifier treatment: controlling modification dolomite, dolomite raw ore is 4:5 with desalination water volume ratio, adopted streamed modified, making desalination water flow through the modified tank equipped with modification dolomite Yu dolomite raw ore, modified effluent quality is in Table 3:
Table 3 modification dolomite and dolomite raw ore temper water water analysis
As can be seen from Table 3, adopt modification dolomite to desalination water modified time, hydraulic detention time when being 1 minute modified go out the water hardness, basicity, calcium ions and magnesium ions content just can reach higher level；Adopt dolomite raw ore to desalination water modified time, hydraulic detention time when being 20 minutes modified effluent quality relatively modification dolomite also have certain gap。Adopt that modification dolomite is modified can be greatly shortened hydraulic detention time, reduce modified tank volume, reduce floor space。

Claims (4)

1. one kind is used for the modification dolomite that desalination water is modified, it is characterized in that being modified by dolomite raw ore making, modifying process includes light-burned stage, carbonation stages, stabilisation stage, and the crystal structure of obtained modification dolomite loosens, and porosity is big and is evenly distributed。
2. a kind of modification dolomite modified for desalination water as claimed in claim 1, it is characterised in that:
1) described dolomite raw ore be mainly composed of CaMg (CO3)2；
2) the light-burned stage described in carries out in carbon dioxide atmosphere, light-burned stage heating rate is 6 DEG C/min～15 DEG C/min, light roasting temperature is 650 DEG C～1000 DEG C, the light-burned time is 0.5h～3h, light-burned carbon dioxide in process is overflowed, dolomite inside and surface form uniform hole, and dolomite decomposition is calcium carbonate, calcium oxide and magnesium oxide, and dominant response formula is as follows:
,
；
3) carbonation stages described in adopts wet method carbonating, carbonation passes into steam and carbon dioxide, calcium oxide, magnesium oxide that steam and light-burned stage are formed react generation hydroxide, then generate carbonate, heavy carbonate with carbon dioxide reaction, and dominant response formula is as follows:
,
,
,
,
,
,
Described steam accounts for the 30%～50% of mixing gas volume, and carbonation temperature is 50 DEG C～150 DEG C, and carbonation time is 1.8h～3.2h；
4) the stabilisation stage described in carries out in carbon dioxide atmosphere, and stabilization temperature is 100 DEG C～150 DEG C, and the stabilisation time is 0.8h～2.2h。
3. a kind of modification dolomite modified for desalination water as claimed in claim 1, it is characterised in that the porosity of described modification dolomite is not less than 10%。
4. a kind of modification dolomite modified for desalination water as claimed in claim 1 or 2, it is characterised in that the particle diameter of the dolomite raw ore adopted is 3mm～5mm。
CN201610111730.8A 2016-02-29 2016-02-29 A kind of modification dolomite quenched for desalination water Active CN105692856B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106243814A (en) * 2016-08-29 2016-12-21 宁波江东甬风工业设计有限公司 A kind of preparation method conducting electricity uniform mineral material
CN110156129A (en) * 2019-06-10 2019-08-23 北京大学 A kind of method of quick change water pH
CN113769478A (en) * 2021-09-30 2021-12-10 武汉中地水石环保科技有限公司 Calcium-magnesium mineralized filter material and preparation method thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104692514A (en) * 2014-12-31 2015-06-10 浙江至美环境科技有限公司 Granular mineralizer for conditioning desalted water as well as preparation method and application of granular mineralizer

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104692514A (en) * 2014-12-31 2015-06-10 浙江至美环境科技有限公司 Granular mineralizer for conditioning desalted water as well as preparation method and application of granular mineralizer

Non-Patent Citations (1)

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Title
胡庆福等: "白云石碳化法生产轻质碳酸镁新工艺", 《非金属矿》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106243814A (en) * 2016-08-29 2016-12-21 宁波江东甬风工业设计有限公司 A kind of preparation method conducting electricity uniform mineral material
CN110156129A (en) * 2019-06-10 2019-08-23 北京大学 A kind of method of quick change water pH
CN110156129B (en) * 2019-06-10 2020-07-28 北京大学 Method for rapidly changing pH value of water
CN113769478A (en) * 2021-09-30 2021-12-10 武汉中地水石环保科技有限公司 Calcium-magnesium mineralized filter material and preparation method thereof
CN113769478B (en) * 2021-09-30 2023-02-10 武汉中地水石环保科技有限公司 Calcium-magnesium mineralized filter material and preparation method thereof

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