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WO2018035883A1 - 一种反渗透浓水的处理方法 - Google Patents

一种反渗透浓水的处理方法 Download PDF

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Publication number
WO2018035883A1
WO2018035883A1 PCT/CN2016/097631 CN2016097631W WO2018035883A1 WO 2018035883 A1 WO2018035883 A1 WO 2018035883A1 CN 2016097631 W CN2016097631 W CN 2016097631W WO 2018035883 A1 WO2018035883 A1 WO 2018035883A1
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Prior art keywords
reverse osmosis
water
concentrated water
osmosis concentrated
treatment
Prior art date
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PCT/CN2016/097631
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English (en)
French (fr)
Inventor
张宏科
范珍龙
王俊俊
刘小高
段美荣
周波
王瑞
衡华
华卫琦
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Wanhua Chemical Group Co Ltd
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Wanhua Chemical Group Co Ltd
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Priority to HU1900093A priority Critical patent/HU231153B1/hu
Priority to US16/327,641 priority patent/US10696574B2/en
Publication of WO2018035883A1 publication Critical patent/WO2018035883A1/zh
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
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    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • B01J37/0207—Pretreatment of the support
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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    • B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions

Definitions

  • the invention belongs to the technical field of wastewater treatment of environmental engineering, and more specifically to a method for treating reverse osmosis concentrated water.
  • reverse osmosis concentrated water (relative to the medium water before reverse osmosis) concentrated 3-5 times is produced, and the reverse osmosis concentrated water produced has the following defects: dissolution High content of organic matter, high chroma of solution, high salt content and poor biodegradability.
  • the conventional treatment method for high COD reverse osmosis concentrated water is to use ozone, hydrogen peroxide or the like as an oxidant, oxidize under the action of catalyst, ultrasonic, etc., and degrade organic matter to meet emission standards.
  • CN 102040294 A discloses a method for treating reverse osmosis concentrated water by using ozone and hydrogen peroxide as an oxidant and in combination with activated carbon adsorption, and the oxidant is added in a large amount and the running cost is relatively high.
  • a method for catalytically oxidizing ozone to treat reverse osmosis concentrated water is disclosed in CN 102153171 A. Since the aeration causes secondary pollution during the process, the exhaust gas needs to be treated.
  • CN 102633410 A discloses a method for treating reverse osmosis concentrated water by photocatalytic oxidation and biochemical combination. Since the process contains biochemical, it is only suitable for reverse osmosis concentrated water with low salt content, and photocatalytic oxidation and biochemical COD reduction. Poor effect, not suitable for reverse osmosis concentrated water with high COD.
  • CN 103449635 A discloses a method for treating reverse osmosis concentrated water by Fenton oxidation method. The disadvantage of this method is that the Fenton oxidation method needs to be carried out under acidic conditions, the process needs to adjust the pH, the process produces a large amount of precipitation, and the treatment cost is high.
  • CN 102849879 A discloses a method of recovering part of water by electrodialysis after pre-treatment of reverse osmosis concentrated water, but no specific solution is given for how to treat concentrated water produced by electrodialysis. It is disclosed in CN 103723799 A and CN 104445788 A that the reverse osmosis concentrated water is further processed by a combination of ultrafiltration and reverse osmosis, and part of the water is recovered. The amount of concentrated water produced is deeply concentrated by electrodialysis, and the fresh water produced by the concentration process is reused, and concentrated water is used for evaporation crystallization.
  • a reverse osmosis device disclosed in CN 104609610 A recovers a part of the water, the concentrated water is further concentrated by forward osmosis, the positive osmosis water is reused, and the remaining trace concentrated water is processed into the evaporation device to finally achieve zero discharge.
  • the advantage of the above scheme is that the reverse osmosis concentrated water is further recycled after being treated, so that the overall utilization rate of water is improved, but whether reverse osmosis, electrodialysis, or forward osmosis is used, concentrated water having a very high salt concentration (salt content) is generated. 15-18 wt%), which needs further treatment by evaporation crystallization.
  • the crystallizer is basically made of titanium, which has high investment and operating costs.
  • Multi-effect evaporation and mechanical vapor recompression (MVR) are two common methods of evaporation crystallization. With 10t/h high-salt wastewater, multi-effect evaporation technology requires 3 to 5 million yuan, and operating cost is 60-70 yuan. / ton; MVR technology investment needs 8 to 12 million yuan, operating costs 35-45 yuan / ton.
  • the bottleneck of the promotion and application of the reverse osmosis concentrated water near-zero emission process lies in the treatment of high salt difficult to treat concentrated water obtained after desalination treatment. Therefore, it is necessary to develop an efficient and economical process for near-zero discharge of reverse osmosis concentrated water.
  • the object of the present invention is to provide a method for treating reverse osmosis concentrated water, which is simple and easy to operate, has low investment operation cost, can effectively recycle waste water, realizes near zero discharge of waste water, and is environmentally friendly.
  • a method for treating reverse osmosis concentrated water comprising the following steps:
  • the obtaining optionally further comprises adsorbing the catalytically oxidized liquid;
  • the obtaining of the effluent optionally further comprises performing the oxidized liquid Adsorption treatment.
  • the reverse osmosis concentrated water preferably satisfies the following conditions: COD ⁇ 300 ppm, preferably 50-300 ppm, more preferably 50-250 ppm; and the reverse osmosis concentrated water has a Ca 2+ content of 0-1000 ppm, preferably 50 -500 ppm; Mg 2+ content is 0-500 ppm, preferably 50-200 ppm; SiO 2 content is 0-200 ppm, preferably 10-150 ppm.
  • the reverse osmosis concentrated water further preferably satisfies the following conditions: COD is 50-300 ppm, preferably 50-250 ppm; pH is 6-9, preferably 7-8; TDS is 1000-20000 ppm, preferably 2000- 10000 ppm; the cation includes one or more of Na + , K + , Ca 2+ , Mg 2+ , and the anion includes one or more of Cl - , SO 4 2- , NO 3 -, etc.; wherein Ca 2 + content is 0-1000 ppm, preferably 50-500 ppm, Mg 2+ content is 0-500 ppm, preferably 50-200 ppm; SiO 2 content is 0-200 ppm, preferably 10-150 ppm, NH 4 + content is 0-50 ppm Preferably, it is 0-10 ppm, the heavy metal element content is 0-5 ppm, preferably 0-0.5 ppm, and the suspended matter content is 0-1000 ppm,
  • the pH of the reverse osmosis concentrated water is adjusted to 6-12, preferably 9-11, and then a precipitant and an oxidizing agent are added thereto for treatment.
  • the pH adjusting agent used for adjusting the pH is an alkaline pH adjusting agent selected from the group consisting of NaOH, KOH, Ca(OH) 2 , Mg.
  • the obtaining of the primary treatment water optionally further includes the adsorption treatment of the liquid after the catalytic oxidation means that the catalytic oxidation may be optionally performed depending on the situation before the primary treatment water is obtained.
  • the liquid after that is subjected to adsorption treatment If the COD in the liquid after catalytic oxidation is ⁇ 50ppm, the first-stage treated water is directly obtained without adsorption treatment; if the COD in the liquid after catalytic oxidation is >50ppm, it needs to be adsorbed, and then the first-stage treated water is obtained. .
  • the obtaining of the effluent optionally further includes the adsorption treatment of the oxidized liquid means that the oxidized liquid may be optionally subjected to adsorption treatment before the effluent is obtained. . If the COD of the liquid after the oxidation treatment is ⁇ 50 ppm, the water is directly obtained without performing the adsorption treatment; if the COD in the liquid after the oxidation treatment is > 50 ppm, it is necessary to carry out adsorption treatment, and then the water is obtained.
  • the pH of the supernatant is adjusted to 6-9, preferably 7-8, before the catalyst is added to the supernatant.
  • the pH of the supernatant should be adjusted to 6-9, Preferably, it is 7-8, and then the supernatant after pH adjustment is filtered by a filtering device, and a catalyst is added to the obtained filtrate for catalytic oxidation.
  • the precipitating agent is selected from one or more of NaOH, KOH, Na 2 CO 3 and NaHCO 3 , preferably Na 2 CO 3 and/or NaHCO 3 .
  • Precipitant reacts with hardness ions such as Ca 2+ and Mg 2+ in reverse osmosis concentrated water to form a precipitate to reduce the hardness of reverse osmosis concentrated water.
  • SiO 2 magnesium ion
  • it reacts with metasilicate or silicate to form magnesium silicate, while magnesium silicate has low solubility, mostly precipitated, so as to achieve the purpose of simultaneous removal of SiO 2 .
  • the amount of precipitant is determined based on the initial amounts of Ca 2+ , Mg 2+ and SiO 2 in the reverse osmosis concentrated water.
  • the initial amounts of Ca 2+ , Mg 2+ and SiO 2 in the reverse osmosis concentrated water were obtained by performing water sample analysis on reverse osmosis concentrated water.
  • the oxidizing agent is selected from one or more of a compound containing an effective chlorine and a compound containing H 2 O 2 including NaClO, NaClO 3 , Cl 2 and ClO 2 ; the oxidizing agent is preferably NaClO and/or H 2 O 2 .
  • the oxidant decomposes some of the easily oxidizable organic matter in the reverse osmosis concentrated water into CO 2 and water through a redox reaction to reduce the COD of the reverse osmosis concentrated water.
  • the amount of the oxidizing agent is determined according to the initial amount of COD in the reverse osmosis concentrated water, and the molar ratio of the oxidizing agent to the reverse osmosis concentrated water COD (in terms of O 2 ) is from 0.5 to 2.5:1, preferably from 0.5 to 1.2:1, more preferably from 0.5 to 1. :1.
  • the initial amount of COD in the reverse osmosis concentrated water is also obtained by analyzing the water sample of the reverse osmosis concentrated water.
  • the molar ratio of the oxidant addition amount to the reverse osmosis concentrated water COD (in terms of O 2 ) is 1-3:1, which can be reduced to 0.5-1:1 in the present invention, which reduces economic input and improves economic benefits. .
  • the COD can be lowered to 40-200 ppm, and only partial degradation of the easily oxidizable organic substance can be achieved.
  • the precipitating agent and the oxidizing agent may be either commercially available industrial products or recycled products of by-products of chemical processes.
  • the oxidizing agent is NaClO
  • the precipitating agent is Na 2 CO 3 and NaOH
  • the precipitating agent and the oxidizing agent are derived from chlor-alkali industrial wastewater; and the chlor-alkali industrial wastewater, available chlorine
  • the content is 2-4 wt%
  • the Na 2 CO 3 content is 5-10 wt%
  • the NaOH content is 0.1-2 wt%.
  • the chlor-alkali industrial wastewater contains NaClO, Na 2 CO 3 and NaOH
  • the chlor-alkali industrial wastewater can be used as the precipitating agent and the oxidizing agent in the step (1) of the present invention.
  • the chlor-alkali industrial wastewater mainly contains NaOH, Na 2 CO 3 and low concentration of NaClO (NaHCO 3 is also present under weak alkali conditions). Due to the low effective chlorine content, the chlor-alkali industrial wastewater is difficult to be sold as a product. If the chlor-alkali industrial wastewater is directly discharged, it not only causes a large amount of waste of water resources, but also causes great harm to the environment and human life.
  • the treatment is mostly carried out by catalytic decomposition, and the sodium hypochlorite is eliminated by rapid catalytic decomposition of sodium hypochlorite by the catalyst, thereby completing the treatment of the chlor-alkali industrial wastewater containing sodium hypochlorite.
  • the treatment route is generally: reducing NaClO in the wastewater by using Na 2 SO 3 or H 2 O 2 , and adjusting the pH of the wastewater to 6-9 after HCl to discharge the sea.
  • Current treatments require a large amount of reagents to be consumed.
  • the present application utilizes NaClO, Na 2 CO 3 , NaHCO 3 and NaOH in the chlor-alkali industrial wastewater to treat the reverse osmosis concentrated water as an oxidizing agent and a precipitating agent, and utilizes NaClO in the chlor-alkali industrial wastewater for oxidation reaction.
  • the COD of the reverse osmosis concentrated water is lowered, and the solidification ions such as Ca 2+ and Mg 2+ in the reverse osmosis concentrated water are removed by using the precipitation reaction of Na 2 CO 3 , NaHCO 3 and NaOH in the chlor-alkali industrial wastewater.
  • the treatment of reverse osmosis concentrated water by using chlor-alkali industrial wastewater not only saves the cost of the oxidant and precipitant used in the reverse osmosis concentrated water treatment, but also saves the cost of the reducing agent used in the chlor-alkali industrial wastewater treatment, and effectively utilizes
  • the effective substances in the chlor-alkali industrial wastewater can achieve the purpose of waste treatment and waste, avoid economic waste, relieve environmental pressure, and significantly improve economic benefits.
  • the chlor-alkali industrial wastewater is used in an amount of 2-50 kg/t of reverse osmosis concentrated water, preferably 2-40 kg/t of reverse osmosis concentrated water, to meet the needs of treating reverse osmosis concentrated water.
  • the amount of oxidizing agent and precipitant is not limited to 2-50 kg/t of reverse osmosis concentrated water, preferably 2-40 kg/t of reverse osmosis concentrated water, to meet the needs of treating reverse osmosis concentrated water.
  • the amount of oxidizing agent and precipitant is used in an amount of 2-50 kg/t of reverse osmosis concentrated water, preferably 2-40 kg/t of reverse osmosis concentrated water.
  • step (1) when an oxidizing agent and a precipitating agent (or a chloralkali industrial wastewater containing an oxidizing agent and a precipitating agent) are added to the reverse osmosis concentrated water, polyaluminum chloride (PAC) and/or polypropylene may be added thereto.
  • the amount of amide (PAM), polyaluminum chloride (PAC) and polyacrylamide (PAM) is added to produce a large flake.
  • the precipitation may be removed by any suitable method in the art, such as filtration, and the filtration device used may use any filtration device known in the art, preferably a sedimentation tank, a sand filter, or more.
  • the filter produced by the medium filter or the like is subjected to pressure filtration treatment by a plate and frame filter press; due to the catalytic oxidation reaction, the decomposition of ClO - in the alkaline environment is slow, the degradation ability of the organic substance is poor, and in the acidic environment, the catalyst is easily lost. (The heavy metal active component in the catalyst is lost as the catalyst is lost), and at the same time, the effluent is difficult to meet the discharge requirement.
  • the supernatant after removal of the precipitate is adjusted to a pH of 6-9, preferably 7-8, through the clarification tank, and the catalyst can be prevented.
  • ClO - decomposes faster, improves the degradation ability of organic matter, and makes the effluent meet the discharge standard.
  • the supernatant after removal of the precipitate may also contain impurities such as suspended particles, colloids, fine precipitates, etc., such impurities easily block the micropores of the catalyst and the adsorbent, causing failure of the catalyst and the adsorbent or reducing the life. Therefore, preferably, Before the supernatant is subjected to catalytic oxidation treatment, the supernatant is subjected to secondary filtration using a filtering device to remove such impurities, mainly to remove particulate matter having a particle diameter of more than 4 ⁇ m in the supernatant.
  • the filtration device used for the secondary filtration includes one or more of a sand filter device, an activated carbon filter, a multi-media filter, a wire mesh filter, a microfiltration device, or a security filter, preferably a multi-media filter.
  • the reaction time of the catalytic oxidation is 0.5-2 h, preferably 0.5-1.5 h, and the suitable reaction time can decompose as much as possible to remove the organic matter in the reverse osmosis concentrated water, and reduce the anti- Permeate the COD value of concentrated water while decomposing most of the oxidant introduced.
  • the COD can be reduced to 20-80 ppm after catalytic oxidation at the above reaction time. At this time, there is still a part of organic matter in the catalytic oxidation water.
  • the COD When the COD is more than 50 ppm, it can be adsorbed into the micropores of the adsorbent by adsorption treatment, thereby lowering the COD value to below 50 ppm, and the adsorbent can be adsorbed in any field in the field.
  • Agents such as activated carbon.
  • COD For reverse osmosis concentrated water with COD of 50-200ppm, after catalytic oxidation treatment, COD can be directly treated to below 50ppm without adsorption treatment.
  • the adsorption treatment can be carried out in any adsorption apparatus known in the art, such as an adsorption column, an overflow enthalpy, etc., which can be loaded with an adsorbent, preferably an adsorption column.
  • the adsorption tower may be provided with one or more, and may be connected in parallel or in series, preferably a fixed bed type activated carbon adsorption tower.
  • the catalytic oxidation produced water according to the invention preferably has a residence time in the adsorption column of from 0.5 to 4 h, preferably from 1 to 2 h.
  • the adsorbent of the adsorption device used in the adsorption treatment is an adsorbent material having a specific surface area of 500-2000 m 2 /g and a mechanical strength of 50-100 N/cm, such as one or more of activated carbon, molecular sieve or macroporous adsorption resin, preferably activated carbon. Further preferred is a coal-like cylindrical activated carbon having a particle diameter of from 1 to 5 mm and an iodine value of from 1,000 to 1,200.
  • the catalyst comprises aluminum oxide and nickel, iron, manganese and lanthanum supported on the alumina in the form of an oxide;
  • the content of the following components in the catalyst is:
  • Iron 0.5-5.5wt%, preferably 1.5-5.0wt%;
  • Nickel is the main active component, and iron, manganese and bismuth are used as modifiers (ie, catalyst additives) for modifying the performance of the catalyst and improving the catalytic effect of the catalyst.
  • the modifier can also be used in other fields. Modifier.
  • the catalyst comprises a cerium modified alumina support and nickel, iron, manganese and cerium supported on the cerium modified alumina support in the form of an oxide;
  • the cerium modified alumina support comprises alumina and a ruthenium supported on the alumina in the form of an oxide, the ruthenium modified alumina carrier having a ruthenium content of 1.0 to 2.0 wt%, preferably 1.2 to 1.5 wt%, based on the weight of the alumina .
  • the cerium-modified alumina support is obtained by supporting cerium (the cerium is present in the form of an oxide) on the alumina
  • the cerium-modified alumina carrier comprises alumina and is supported in the form of an oxide. ⁇ on aluminum.
  • the catalyst Since the catalyst is obtained by further supporting nickel, iron, manganese and cerium (nickel, iron, manganese and cerium in the form of oxides) on the cerium-modified alumina support, the catalyst includes tampering An alumina support and nickel, iron, manganese and ruthenium supported on the ruthenium modified alumina support in the form of an oxide.
  • the amount of ruthenium supported on the yttrium-modified alumina support in the catalyst is from 0.5 to 2.0% by weight, preferably from 0.6 to 1.5% by weight, based on the weight of the alumina.
  • the content of ruthenium supported on the yttrium-modified alumina carrier in the catalyst refers to the content of ruthenium supported on the yttrium-modified alumina carrier when further loaded with nickel, iron, manganese and cerium.
  • the content of some ruthenium corresponds to the total content of ruthenium in the catalyst minus the ruthenium content of the ruthenium modified alumina support.
  • the support is a rhodium-modified alumina support
  • rhodium is present in two parts in the catalyst, and a part is present in the rhodium-modified alumina support.
  • the cerium in the cerium modified alumina carrier is highly dispersed on the alumina, and the inner surface of the alumina is physically divided, and the cerium can form a strong interaction with the alumina to anchor the role;
  • the ruthenium in the ruthenium-modified alumina carrier also serves as a guiding action to uniformly disperse the main active component and prevent aggregation.
  • the other part of the ruthenium is present in the support of the ruthenium-modified alumina support (ie, the main active component and the modulating agent), and the active group in the catalyst due to the anchoring and guiding action of ruthenium in the ruthenium-modified alumina support.
  • NiO x is an oxide of a main active component on the catalyst, and x represents 2 or 3, due to Ni 2+ , Ni in NiO x 3+ are present, the main active component oxide, the number of O atoms x is represented by strong interaction between) the active ingredient in - between the aluminum oxide (NiO x -Al 2 O 3)
  • the interaction force can effectively reduce the aggregation and loss of active components, especially suitable for long-term treatment of wastewater that is difficult to biochemically treat, has better activity and treatment effect, and has low operating treatment cost.
  • hydrazine has a good oxygen storage function.
  • the oxidant generating reactive oxygen radicals on the main active component of the catalyst is the key to degradation of organic matter.
  • the catalyst carrier is a cerium-modified alumina carrier
  • an oxidizing agent such as sodium hypochlorite
  • the active oxygen radical generated by the oxidizing agent on the main active component of the catalyst can migrate to the cerium-modified alumina carrier in time. Storage on the sputum increases the site of reactive oxygen species, increases the reaction site, and increases the rate of degradation and degradation of organic matter.
  • the oxidizing agent is sodium hypochlorite, ClO - generation of reactive oxygen species on NiO x, NiO x -CeO 2 -Al 2 O 3 structure capable of promptly generating NiO x
  • the reactive oxygen radicals migrate to CeO 2 to increase the number of reaction sites, effectively degrade organic matter, and increase COD removal rate.
  • the catalytic oxidation mechanism is as follows:
  • [O] represents a reactive oxygen radical
  • CAT represents a catalyst
  • ORG represents an organic substance
  • CAT-O represents an active site on a catalyst
  • [O] is present at the active site
  • ORG-O represents a combination with [O] Organic matter.
  • Formula 1 is a process in which sodium hypochlorite is catalyzed by a catalyst to produce [O] on a catalyst
  • Formula 2 is a process in which a catalyst having an [O] active site is contacted with an organic substance to transfer [O] to an organic substance
  • Formula 3 is an [O] The process by which the combined organic matter degrades into small molecules or carbon dioxide and water under the action of a catalyst.
  • the catalyst has a particle size of alumina of from 1.0 to 2.0 mm, preferably from 1.5 to 2.0 mm; a bulk density of from 0.30 to 0.50 g/ml, preferably from 0.40 to 0.48 g/ml; and a water absorption of from 50 to 70 vol%. , preferably 55-60 vol%; specific surface area 150-250 m 2 /g, preferably 180-220 m 2 /g; pore volume 1.2-1.8 ml/g, preferably 1.5-1.7 ml/g; average pore diameter 100-150 nm Preferably, it is 130-145 nm.
  • Some refractory organics in wastewater are usually macromolecules.
  • the use of large pore volume and large pore size alumina can provide proper pores, which is beneficial to the diffusion of macromolecular organic matter into the active sites inside the catalyst, which helps to improve catalytic oxidation.
  • the treatment effect is effective in degrading macromolecular organic matter.
  • the nickel, iron, manganese, and cerium are each derived from one or more of a nitrate, acetate or carbonate containing a corresponding metal element, preferably a nitrate.
  • the preparation method of the above catalyst comprises the following steps:
  • the drying temperature is 100-130 ° C, the drying time is 2-5 h, the baking temperature is 450-550 ° C, and the baking time is 3-6 h; further preferably, vacuum pretreatment is performed before alumina impregnation, and the vacuum pretreatment time is 10-30min, the degree of vacuum is 96.0-98.0KPa;
  • the catalyst is prepared; preferably impregnated by an equal volume impregnation process; preferably, the drying temperature is 100-130 ° C, the drying time is 2-5 h, the calcination temperature is 450-550 ° C, and the calcination time is 3-6 h.
  • the solvent of the immersion liquid in the steps (1) and (2) is selected from one or more of water, methanol and ethanol, preferably water and/or ethanol, more An aqueous ethanol solution having an ethanol concentration of 10 to 40% by weight is preferred.
  • the content of cerium in the impregnation liquid of the step (1) is 1.0-2.0 wt%, preferably 1.2-1.5 wt%, based on the weight of the alumina in the carrier;
  • the content of cerium in the impregnation liquid of the step (2) is from 0.5 to 2.0% by weight, preferably from 0.6 to 1.5% by weight;
  • the content of nickel is from 5.0 to 20% by weight, preferably from 5.5 to 12.0% by weight; and the content of iron is from 0.5 to 5.5.
  • the wt% preferably 1.5-5.0 wt%; the manganese content is 0.5-3.5 wt%, preferably 1.0-3.0 wt%; the total content of rhodium in the impregnation liquid of the step (1) and the step (2) is 1.5 -3.0 wt%, preferably 2.0-2.8 wt%.
  • the cerium salt in the step (1) and the nickel salt, the iron salt, the manganese salt and the cerium salt in the step (2) are nitrates and acetic acid containing the corresponding metal elements.
  • One or more of a salt or a carbonate is preferably a nitrate (Ce(NO 3 ) 3 , Ni(NO 3 ) 2 , Fe(NO 3 ) 3 , Mn(NO 3 ) 2 ).
  • the alumina in the carrier may be any shape of alumina such as spherical, cylindrical, clover, clover, gear spherical or the like, preferably spherical alumina.
  • the oxidant such as NaClO has a low reaction rate at normal temperature and in the absence of a catalyst, and NaClO mainly decomposes to form Cl - and O 2 , resulting in a low concentration of active oxygen radical [O].
  • [O] has strong oxidation ability, it can degrade macromolecular organic matter into small molecular organic matter, and at the same time completely degrade small organic organic matter into carbon dioxide and water, which can degrade various compounds such as amines, aldehydes, phenols, esters, aromatic hydrocarbons and halogenated hydrocarbons.
  • the purpose of decolorization and deodorization can also be achieved.
  • the above catalyst facilitates the formation of Cl - and [O] by ClO-, reduces the formation of O 2 and avoids the waste of oxidant.
  • the molar ratio of the conventional oxidizing agent to the reverse osmosis concentrated water COD is 1-3:1.
  • the COD removal rate in the wastewater can be increased from the conventional 20-40% to 60-80%, and at the same time
  • the molar ratio of the oxidant addition amount to the reverse osmosis concentrated water COD can be reduced to 0.5-1:1, which reduces economic input and improves economic efficiency.
  • the primary treated water obtained by the reverse osmosis concentrated water after the step (1) treatment has a decrease in hardness and COD value, and can satisfy the water inflow index of the reverse osmosis device as shown in Table 1, and is used as the reverse osmosis water in the step (2). Perform reverse osmosis treatment.
  • the membrane module of the reverse osmosis apparatus used in the reverse osmosis treatment is a flat plate type, a tubular type, a roll type or a hollow fiber type, preferably a roll type.
  • the material of the film in the membrane module is a cellulose acetate film or an aromatic polyamide film, preferably an aromatic polyamide film.
  • the membrane can withstand an absolute pressure of 1-2 MPa and the reverse osmosis membrane water recovery of 75-85 wt%.
  • step (2) in order to prevent contamination and scratching of the membrane in the reverse osmosis device by abnormal water quality, it is preferred to install a security filter before the reverse osmosis device, so as to filter the impurities in the primary treatment water before proceeding.
  • Reverse osmosis treatment improves the reverse osmosis treatment and prolongs the service life of the reverse osmosis unit.
  • the obtained second-stage reverse osmosis water can be directly reused, and the indexes of the second-stage reverse osmosis water production are shown in Table 2. If the indicators as shown in Table 2 are not reached, the treatment is continued until the The indicator is then reused; the obtained secondary reverse osmosis concentration index is shown in Table 3. If the indicator as shown in Table 3 is not reached, it will continue to be processed until it reaches the target, and then it will reach the indicator as shown in Table 3.
  • the reverse osmosis concentrated water is oxidized by step (3) to reduce its COD value, and some of the organic matter is degraded into CO 2 and water, and the macromolecular organic matter is decomposed into small molecular organic substances;
  • the oxidizing agent used is NaClO, H 2 O 2 , One or more of NaClO 3 , Cl 2 , and ClO 2 , and the molar ratio of the oxidant to the COD (in terms of O 2 ) in the secondary reverse osmosis concentrated water is 0.5-1.0:1.
  • the filtration device includes a sand filter device, an activated carbon filter, a multi-media filter, a wire mesh filter, a microfiltration device or a security filter.
  • a sand filter device an activated carbon filter
  • a multi-media filter a wire mesh filter
  • a microfiltration device or a security filter One or more, preferably a multi-media filter.
  • the reducing agent is selected from one or more of Na 2 SO 3 , Na 2 S 2 O 3 , H 2 O 2 , Na 2 S, FeSO 4 and H 2 , and the molar ratio of the reducing agent added amount to the excess oxidizing agent It is from 0.9 to 1.5:1, preferably from 0.9 to 1.1:1.
  • the filtering device may be selected from the group consisting of a sand filter device, an activated carbon filter, a multi-media filter, a wire mesh filter, One or more of a microfiltration device or a security filter, preferably a multi-media filter.
  • the standard of Table 2 in GB 31571-2015 can be met as the effluent discharge; if the COD in the reaction solution after the above treatment is >50ppm, it needs to be added thereto.
  • the adsorbent is subjected to adsorption treatment to have a COD of ⁇ 50 ppm, which satisfies the standard of Table 2 of GB 31571-2015, and is discharged as effluent.
  • the adsorption treatment can be carried out in any adsorption apparatus known in the art, such as an adsorption column, an overflow enthalpy, etc., which can be loaded with an adsorbent, preferably an adsorption column.
  • the adsorbent used in the adsorption treatment is an adsorbent material having a specific surface area of 500 to 2000 m 2 /g and a mechanical strength of 50 to 100 N/cm, such as one or more of activated carbon, molecular sieve or macroporous adsorption resin, preferably activated carbon.
  • the adsorption treatment time is 1-4 h.
  • the effluent water is the water of the reverse osmosis concentrated water treated by the method of the invention and reaches the standard of Table 2 of GB 31571-2015, and can be directly discharged.
  • the method comprises the steps of:
  • the catalyst used in the present invention can promote the generation of oxidant [O], improve the oxidizing ability of the oxidizing agent, and can process the difficult-oxidized reverse osmosis concentrated water to a COD ⁇ 50 ppm in accordance with the high-efficiency adsorption process, reaching the national standard GB 31571-2015.
  • the standard of Table 2 at the same time, due to the increase in the utilization rate of oxidant, the amount of oxidant added is greatly saved, and the economic benefit is remarkable.
  • Oxidation reaction tower, multi-media filter, activated carbon adsorption tower, security filter, sand filter device, microfiltration device and roll reverse osmosis membrane module are all purchased from Maiwang Environmental Engineering Technology Co., Ltd.;
  • Reverse osmosis membrane model SWC series seawater desalination membrane, purchased from Hyde Energy Company of the United States; activated carbon, purchased from Yantai General Activated Carbon Co., Ltd.;
  • the muffle furnace model VULCAN 3-1750, was purchased from Neytech, USA.
  • Hydrochloric acid 37wt%, purchased from Sinopharm Chemical Reagent Co., Ltd.;
  • an impregnation liquid having a total volume of 25 ml was prepared.
  • the above impregnation liquid is added to a vacuum impregnation bottle containing the above spherical alumina carrier, and the spherical alumina carrier is uniformly impregnated, immersed for 30 minutes, taken out and placed in an oven at 110 ° C for 3 hours, and then in the horse.
  • the furnace was calcined at 500 ° C for 6 h to obtain a ## catalyst.
  • the content of the following components was based on the weight of alumina: 12.0 wt% of nickel, 1.5 wt% of iron, 2.0 wt% of manganese, and 2.0 wt% of ruthenium.
  • the vacuum pretreatment time is 30min
  • the vacuum degree is 98.0KPa
  • the nickel content is 0.15.
  • the above impregnation liquid is added to a vacuum impregnation bottle containing the above spherical alumina carrier, and uniformly mixed, and the spherical alumina carrier is impregnated in equal volume, after immersing for 60 minutes, taken out and placed in an oven at 130 ° C for 2 hours, and then in the horse.
  • the furnace was calcined at 480 ° C for 6 h to obtain a ## catalyst.
  • the content of the following components is based on the weight of the alumina therein.
  • the amounts are as follows: nickel 16.0 wt%, iron 0.6 wt%, manganese 1.0 wt%, and rhodium 2.5 wt%.
  • cerium-modified alumina carrier After immersing for 30 min, it was taken out and dried in an oven at 120 ° C for 3 h, and then calcined at 500 ° C for 4 h in a muffle furnace to obtain a cerium-modified alumina carrier.
  • the content of cerium was 2.0% by weight based on the weight of the alumina.
  • the above impregnation liquid is added to a vacuum impregnation bottle containing the above-mentioned cerium-modified alumina carrier, and the above-mentioned cerium-modified alumina carrier is uniformly immersed, immersed for 60 minutes, taken out, and placed in an oven at 130 ° C for 2 hours. Then, it was baked at 480 ° C for 6 h in a muffle furnace to obtain a ## catalyst.
  • the physicochemical properties of the above spherical alumina carrier are: a particle size of 1.5 to 2.0 mm, a bulk density of 0.50 g/ml, a water absorption of 70 vol%, a specific surface area of 250 m 2 /g, a pore volume of 1.20 ml/g, and an average pore diameter of 130 nm.
  • the contents of the following components were as follows based on the weight of alumina: nickel 16.0 wt%, iron 0.6 wt%, manganese 1.0 wt%, and rhodium 2.5 wt%.
  • cerium-modified alumina carrier After immersion, immersed for 60 min, taken out and placed in an oven at 120 ° C for 2 h, After calcination at 450 ° C for 5 h in a muffle furnace, a cerium-modified alumina carrier was obtained.
  • the content of cerium was 1.0% by weight based on the weight of the alumina.
  • the above impregnation liquid is added to a vacuum impregnation bottle containing the above-mentioned cerium-modified alumina carrier, and the above-mentioned cerium-modified alumina carrier is uniformly impregnated, immersed for 60 minutes, taken out and placed in an oven at 110 ° C for 3 hours. Then, it was baked at 500 ° C for 6 h in a muffle furnace to obtain a ## catalyst.
  • the physicochemical properties of the above spherical alumina carrier are: a particle size of 1.0 to 1.5 mm, a bulk density of 0.30 g/ml, a water absorption of 50 vol%, a specific surface area of 150 m 2 /g, a pore volume of 1.80 ml/g, and an average pore diameter of 150 nm.
  • the content of the following components was as follows based on the weight of alumina: 12.0 wt% of nickel, 1.5 wt% of iron, 2.0 wt% of manganese, and 2.0 wt% of ruthenium.
  • Example 5 Treatment of reverse osmosis concentrated water (1# catalyst + chlor-alkali industrial wastewater)
  • Step (1) Take the reverse osmosis concentrated water shown in Table 4, adjust the pH to 11 with NaOH in the adjustment tank, and then input into the reaction tank, and add the chlor-alkali industrial wastewater as shown in Table 5 to the reaction tank. It is 28kg/t reverse osmosis concentrated water), and PAC and PAM solution are added until a large amount of floc appears, and the reaction is mixed for 1 hour. After the reaction is finished, the precipitation is filtered by a plate and frame filter press.
  • the solid waste is mainly CaCO 3 and Mg(OH). 2 , can be used as a raw material of building materials factory, filter the obtained clear liquid into the clarification tank, adjust the pH to 8 with HCl, and stay in the clarification tank for 1 h.
  • the COD of the reverse osmosis concentrated water is reduced to 240 ppm, and then enters the multi-media filter for filtration, and the obtained filtrate enters the oxidation reaction tower filled with the 1# catalyst, and stays for 90 minutes.
  • the COD was reduced to 80 ppm, the COD removal rate was 73.3%, and then entered into the activated carbon adsorption tower for adsorption treatment.
  • the effluent COD was 38 ppm, the pH was 8, and the SiO 2 was 10 ppm.
  • the CaCO 3 meter was 290 ppm.
  • Step (2) the effluent from the activated carbon adsorption tower is subjected to secondary filtration through a security filter, and the filtrate is subjected to reverse osmosis treatment in a roll-type reverse osmosis membrane module, and the water recovery rate is 75 wt%, and the second-stage reverse osmosis water production and the second-stage reaction are obtained. Penetrate concentrated water.
  • Step (3) The obtained secondary reverse osmosis water (COD is 5 ppm, ammonia nitrogen is 0.4 ppm, TDS is 100 ppm, conductivity is 190 ⁇ s/cm) as recycled water, and the obtained secondary reverse osmosis concentrated water (COD is 152 ppm).
  • the pH is 8.5
  • the SiO 2 is 49 ppm
  • the hardness (calculated as CaCO 3 is 1188 ppm) is further processed into the oxidation unit, specifically, 10% by weight of NaClO solution is added to the obtained secondary reverse osmosis concentrated water (addition amount is 3.5 kg/t).
  • Example 6 Treatment of reverse osmosis concentrated water (2# catalyst + chlor-alkali industrial wastewater)
  • Step (1) Take the reverse osmosis concentrated water shown in Table 4, adjust the pH to 11 with NaOH in the adjustment tank, and then input into the reaction tank, and add the chlor-alkali industrial wastewater as shown in Table 5 to the reaction tank. It is 2.9kg/t reverse osmosis concentrated water), and PAC and PAM solution are added until a large amount of floc appears, and the reaction is mixed for 1 hour. After the reaction is finished, the precipitation is filtered by a plate and frame filter press.
  • the solid waste is mainly CaCO 3 and Mg (OH). 2 , can be used as raw materials for building materials, filter the resulting clear liquid into the clarification tank, adjust the pH to 7.5 with HCl, and stay in the clarification tank for 1h.
  • the COD of the reverse osmosis concentrated water is reduced to 38 ppm, and then filtered through a sand filter device, and then enters the oxidation reaction column filled with the 2# catalyst, and stays for 30 min, after the above catalytic oxidation reaction. Thereafter, the COD was lowered to 20 ppm, the COD removal rate was 60%, the pH was 7.8, the SiO 2 was 10 ppm, and the hardness (calculated as CaCO 3 ) was 62 ppm.
  • Step (2) the effluent of the oxidation reaction tower is subjected to secondary filtration through a security filter, and the obtained filtrate enters the roll-type reverse osmosis membrane module for reverse osmosis treatment, and the water recovery rate is 85 wt%, and the second-stage reverse osmosis water production and the second-stage reaction are obtained. Penetrate concentrated water.
  • Step (3) The obtained secondary reverse osmosis water (COD is 3 ppm, ammonia nitrogen is 0.1 ppm, TDS is 40 ppm, conductivity is 70 ⁇ s/cm) as recycled water, and the obtained secondary reverse osmosis concentrated water (COD is 125 ppm)
  • the pH is 8.2
  • the SiO 2 is 50 ppm
  • the hardness (calculated as CaCO 3 is 389 ppm) is further processed into the oxidation unit, specifically, 10% by weight of NaClO solution is added to the obtained secondary reverse osmosis concentrated water (addition amount is 2.9 kg/t).
  • Example 7 Treatment of reverse osmosis concentrated water (3# catalyst + chlor-alkali industrial wastewater)
  • Step (1) Take the reverse osmosis concentrated water shown in Table 4, adjust the pH to 11 with NaOH in the adjustment tank, and then input into the reaction tank, and add the chlor-alkali industrial wastewater as shown in Table 5 to the reaction tank. It is 24kg/t reverse osmosis concentrated water), and PAC and PAM solution are added until a large amount of floc appears, and the mixed reaction is carried out for 0.5h. After the reaction, the precipitation is pressure-filtered by a plate and frame filter press.
  • the solid waste is mainly CaCO 3 and Mg. (OH) 2 , can be used as raw material of building materials factory, the supernatant liquid enters the clarification tank, the pH is adjusted to 8.5 with HCl, and stays in the clarification tank for 1 h.
  • the COD of the reverse osmosis concentrated water is reduced to 159 ppm, and then filtered through a multi-media filter, and then enters the oxidation reaction tower filled with the 3# catalyst, and stays for 60 min, after the above catalytic oxidation.
  • the COD was lowered to 38 ppm, the COD removal rate was 81.9%, the pH was 8.5, the SiO 2 was 7 ppm, and the hardness (calculated as CaCO 3 ) was 150 ppm.
  • Step (2) the effluent of the oxidation reaction tower is subjected to secondary filtration through a security filter, and the filtrate is subjected to reverse osmosis treatment in a roll-type reverse osmosis membrane module, and the water recovery rate is 80 wt%, and the second-stage reverse osmosis water production and the second-stage reaction are obtained. Penetrate concentrated water.
  • Step (3) The obtained secondary reverse osmosis water (COD is 3 ppm, ammonia nitrogen is 0.2 ppm, TDS is 80 ppm, conductivity is 170 ⁇ s/cm) as recycled water, and the obtained secondary reverse osmosis concentrated water (COD is 190 ppm)
  • the pH is 8.8, the SiO 2 is 29 ppm, and the hardness (calculated as CaCO 3 ) is 760 ppm.
  • the oxidation unit is further processed, specifically, 10% by weight of NaClO solution is added to the obtained secondary reverse osmosis concentrated water (addition amount is 4.4 kg/t).
  • Example 8 Treatment of reverse osmosis concentrated water (4# catalyst + chlor-alkali industrial wastewater)
  • Step (1) Take the reverse osmosis concentrated water shown in Table 4, adjust the pH to 11 with NaOH in the adjustment tank, and then input into the reaction tank, and add the chlor-alkali industrial wastewater as shown in Table 5 to the reaction tank. It is 18kg/t reverse osmosis concentrated water), and PAC and PAM solution are added until a large amount of floc appears, and the mixture reaction is carried out for 2 hours. After the reaction is finished, the precipitation is pressure-filtered by a plate and frame filter press, and the solid waste is mainly CaCO 3 and Mg ( OH) 2 can be used as a raw material for building materials. The supernatant enters the clarification tank, adjusts the pH to 6 with HCl, and stays in the clarifier for 1 h.
  • the COD of the reverse osmosis concentrated water is reduced to 123 ppm, and then filtered through a multi-media filter, and then enters the oxidation reaction column filled with the 4# catalyst, and stays for 30 minutes, after the above catalytic oxidation.
  • the COD was lowered to 34 ppm, the COD removal rate was 78.5%, the pH was 6.5, the SiO 2 was 5 ppm, and the hardness (calculated as CaCO 3 ) was 260 ppm.
  • Step (2) the effluent of the oxidation reaction tower is subjected to secondary filtration through a security filter, and the filtrate is subjected to reverse osmosis treatment in a roll-type reverse osmosis membrane module, and the water recovery rate is 80 wt%, and the second-stage reverse osmosis water production and the second-stage reaction are obtained. Penetrate concentrated water.
  • Step (3) The obtained secondary reverse osmosis water (COD is 2 ppm, ammonia nitrogen is 0.3 ppm, TDS is 80 ppm, conductivity is 172 ⁇ s/cm) as recycled water, and the obtained secondary reverse osmosis concentrated water (COD is 147 ppm).
  • the filtrate was subjected to adsorption treatment on an activated carbon adsorption tower for 2 h to obtain effluent.
  • the COD of the effluent was 23 ppm, and the COD removal rate was 84.4%, which reached the national standard GB 31571. - Table 2 standard in 2015.
  • Step (1) Take the reverse osmosis concentrated water shown in Table 4, adjust the pH to 11 with NaOH in the adjustment tank, and then input into the reaction tank, and add 10 wt% NaClO solution to the reaction tank (addition amount is 0.6 kg/ t reverse osmosis concentrated water), 30 wt% Na 2 CO 3 solution (addition amount is 0.87 kg / t reverse osmosis concentrated water) and 48 wt% NaOH solution (addition amount is 0.06 kg / t reverse osmosis concentrated water), and added PAC and PAM solution to large flakes, mixed reaction for 1h, after the reaction is completed, the precipitation is pressure-filtered by plate and frame filter press.
  • the solid waste is mainly CaCO 3 and Mg(OH) 2 , which can be used as raw materials for building materials and supernatant.
  • the liquid entered the clarifier and was adjusted to pH 7.5 with HCl and left in the clarifier for 1 h. After the above sodium hypochlorite oxidation and the hard silicon reduction process, and then filtered through a multi-media filter, the oxidation reaction column filled with the 2# catalyst is placed and left for 30 minutes. After the above catalytic oxidation reaction, the COD is reduced to 20 ppm, COD. removal rate was 60%, pH of 7.8, SiO 2 to 10ppm, hardness (as CaCO 3) to 62ppm.
  • Step (2) the effluent of the oxidation reaction tower is subjected to secondary filtration through a security filter, and the obtained filtrate enters the roll-type reverse osmosis membrane module for reverse osmosis treatment, and the water recovery rate is 85 wt%, and the second-stage reverse osmosis water production and the second-stage reaction are obtained. Penetrate concentrated water.
  • Step (3) The obtained secondary reverse osmosis water (COD is 3 ppm, ammonia nitrogen is 0.1 ppm, TDS is 41 ppm, conductivity is 74 ⁇ s/cm) as recycled water, and the obtained secondary reverse osmosis concentrated water (COD is 125 ppm)
  • the pH is 8.2
  • the SiO 2 is 50 ppm
  • the hardness (calculated as CaCO 3 is 389 ppm) is further processed into the oxidation unit, specifically, 10% by weight of NaClO solution is added to the obtained secondary reverse osmosis concentrated water (addition amount is 2.9 kg/t).
  • Example 10 Treatment of reverse osmosis concentrated water (4# catalyst + NaClO, Na 2 CO 3 and NaOH)
  • Step (1) Take the reverse osmosis concentrated water shown in Table 4, adjust the pH to 11 with NaOH in the adjustment tank, and then input into the reaction tank, and add 10 wt% NaClO solution to the reaction tank (addition amount is 3.6 kg/ t reverse osmosis concentrated water), 30 wt% Na 2 CO 3 solution (addition amount is 5.4 kg / t reverse osmosis concentrated water) and 48 wt% NaOH solution (addition amount is 0.375 kg / t reverse osmosis concentrated water), and added PAC and PAM solution to a large amount of floc, mixing reaction for 2h, after the reaction is completed, the precipitation is pressure-filtered by plate and frame filter press.
  • the solid waste is mainly CaCO 3 and Mg(OH) 2 , which can be used as raw materials for building materials and supernatant.
  • the liquid entered the clarifier and was adjusted to pH 6 with HCl and left in the clarifier for 1 h. After the above sodium hypochlorite oxidation and the hard silicon reduction process, the COD of the reverse osmosis concentrated water is reduced to 123 ppm, and then filtered through a multi-media filter, and then enters the oxidation reaction column filled with the 4# catalyst, and stays for 30 minutes, after the above catalytic oxidation.
  • the COD was lowered to 34 ppm, the COD removal rate was 78.5%, the pH was 6.5, the SiO 2 was 5 ppm, and the hardness (calculated as CaCO 3 ) was 260 ppm.
  • Step (2) the effluent of the oxidation reaction tower is subjected to secondary filtration through a security filter, and the filtrate is subjected to reverse osmosis treatment in a roll-type reverse osmosis membrane module, and the water recovery rate is 80 wt%, and the second-stage reverse osmosis water production and the second-stage reaction are obtained. Penetrate concentrated water.
  • Step (3) The obtained secondary reverse osmosis water (COD is 2 ppm, ammonia nitrogen is 0.3 ppm, TDS is 81 ppm, conductivity is 174 ⁇ s/cm) as recycled water, and the obtained secondary reverse osmosis concentrated water (COD is 147 ppm).
  • the filtrate was subjected to adsorption treatment on an activated carbon adsorption tower for 2 h to obtain effluent.
  • the COD of the effluent was 23 ppm, and the COD removal rate was 84.4%, which reached the national standard GB 31571. - Table 2 standard in 2015.
  • Example 11 Treatment of reverse osmosis concentrated water (CN 104549316A catalyst + chlor-alkali industrial wastewater)
  • Step (1) Take the reverse osmosis concentrated water shown in Table 4, adjust the pH to 11 with NaOH in the adjustment tank, and then input into the reaction tank, and add the chlor-alkali industrial wastewater as shown in Table 5 to the reaction tank. It is 28kg/t reverse osmosis concentrated water), and PAC and PAM solution are added until a large amount of floc appears, and the reaction is mixed for 1 hour. After the reaction is finished, the precipitation is filtered by a plate and frame filter press.
  • the solid waste is mainly CaCO 3 and Mg(OH). 2 , can be used as a raw material of building materials factory, filter the obtained clear liquid into the clarification tank, adjust the pH to 8 with HCl, and stay in the clarification tank for 1 h.
  • the COD of the reverse osmosis concentrated water is reduced to 240 ppm, and then filtered through a multi-media filter, and the obtained filtrate enters a catalytic oxidation tower of the catalyst of Example 1 in CN 104549316 A, and After staying for 90 min, after the above catalytic oxidation reaction, the COD decreased to 112 ppm, the COD removal rate was 62.7%, and then entered the activated carbon adsorption tower for adsorption treatment. After 2 h adsorption treatment, the effluent COD was 48 ppm, the pH was 8, and SiO 2 was 10 ppm, hardness (calculated as CaCO 3 ) was 290 ppm.
  • Step (2) the effluent from the activated carbon adsorption tower is subjected to secondary filtration through a security filter, and the filtrate is subjected to reverse osmosis treatment in a roll-type reverse osmosis membrane module, and the water recovery rate is 75 wt%, and the second-stage reverse osmosis water production and the second-stage reaction are obtained. Penetrate concentrated water.
  • Step (3) The obtained secondary reverse osmosis water (COD is 5 ppm, ammonia nitrogen is 0.4 ppm, TDS is 100 ppm, conductivity is 190 ⁇ s/cm) as recycled water, and the obtained secondary reverse osmosis concentrated water (COD is 205 ppm)
  • the pH is 8.5, the SiO 2 is 49 ppm, and the hardness (calculated as CaCO 3 is 1188 ppm).
  • the oxidation unit is further processed, specifically, 10% by weight of NaClO solution is added to the obtained secondary reverse osmosis concentrated water (addition amount is 4.8 kg/t).
  • the COD of the obtained effluent is 49 ppm, and the COD removal rate is 76.1%, which meets the standard of Table 2 in the national standard GB 31571-2015.
  • Comparative Example 1 Treatment of reverse osmosis concentrated water (Fenton oxidation method)
  • the effluent COD is 148 ppm and the COD removal rate is 50.7%. It is difficult to reach the reverse osmosis water input index, and it is difficult to reach the national standard GB 31571-2015. Table 2 is standard, so subsequent reverse osmosis and other treatments cannot be performed.
  • Step (1) Take the reverse osmosis concentrated water shown in Table 4, adjust the pH to 11 with NaOH in the adjustment tank, and then input into the reaction tank, and add 10 wt% NaClO solution to the reaction tank (addition amount is 0.58 kg/ t reverse osmosis concentrated water), 30 wt% Na 2 CO 3 solution (addition amount is 0.87 kg / t reverse osmosis concentrated water) and 48 wt% NaOH solution (addition amount is 0.06 kg / t reverse osmosis concentrated water), and added PAC and PAM solution to large flakes, mixed reaction for 1h, after the reaction is completed, the precipitation is pressure-filtered by plate and frame filter press.
  • the solid waste is mainly CaCO 3 and Mg(OH) 2 , which can be used as raw materials for building materials and supernatant.
  • the liquid entered the clarifier and was adjusted to pH 7.5 with HCl and left in the clarifier for 1 h.
  • the oxidation reaction column of the catalyst of Example 1 in CN101844828B is filled and left for 30 minutes, after which the COD is lowered after the above catalytic oxidation reaction.
  • the COD removal rate was 42%
  • the pH was 7.8
  • the SiO 2 was 10 ppm
  • the hardness (calculated as CaCO 3 ) was 62 ppm.
  • Step (2) the effluent of the oxidation reaction tower is subjected to secondary filtration through a security filter, and the obtained filtrate enters the roll-type reverse osmosis membrane module for reverse osmosis treatment, and the water recovery rate is 85 wt%, and the second-stage reverse osmosis water production and the second-stage reaction are obtained. Penetrate concentrated water.
  • Step (3) the obtained secondary reverse osmosis water (COD is 3 ppm) is used as recycled water, and the obtained secondary reverse osmosis concentrated water (COD is 188 ppm) is treated by Fenton oxidation method, specifically to the obtained secondary anti- 10% by weight of H 2 O 2 solution (4.0 kg/t secondary reverse osmosis concentrated water) and FeSO 4 (additional amount of 0.36 kg/t secondary reverse osmosis concentrated water) were added to the concentrated water, and the reaction was adjusted after 1 h. pH to 9, and added with PAC and PAM for flocculation and precipitation.
  • H 2 O 2 solution 4.0 kg/t secondary reverse osmosis concentrated water
  • FeSO 4 additional amount of 0.36 kg/t secondary reverse osmosis concentrated water
  • the COD of the effluent was 128 ppm
  • the COD removal rate was 32.0%
  • the reaction temperature was increased to 50 ° C
  • the reaction time was extended to 4 h.
  • the COD is 101 ppm and the COD removal rate is 46.3%, which is difficult to meet the Table 2 standard in the national standard GB31571-2015.
  • Comparative Example 3 Treatment of reverse osmosis concentrated water (catalyst + chlor-alkali industrial wastewater in CN 104549316 A)
  • Step (1) Take the reverse osmosis concentrated water shown in Table 4, adjust the pH to 11 with NaOH in the adjustment tank, and then input into the reaction tank, and add the chlor-alkali industrial wastewater as shown in Table 5 to the reaction tank. It is 18kg/t reverse osmosis concentrated water), and PAC and PAM solution are added until a large amount of floc appears, and the mixture reaction is carried out for 2 hours. After the reaction is finished, the precipitation is pressure-filtered by a plate and frame filter press, and the solid waste is mainly CaCO 3 and Mg ( OH) 2 can be used as a raw material for building materials. The supernatant enters the clarification tank, adjusts the pH to 6 with HCl, and stays in the clarifier for 1 h.
  • the COD of the reverse osmosis concentrated water is reduced to 123 ppm, and then filtered through a multi-media filter, and then enters the oxidation reaction tower of the catalyst of Example 1 in CN 104549316 A, and stays After 30 min, after the above catalytic oxidation reaction, the COD was lowered to 49 ppm, the COD removal rate was 68.9%, the pH was 6.5, the SiO 2 was 5 ppm, and the hardness (calculated as CaCO 3 ) was 260 ppm.
  • Step (2) the effluent of the oxidation reaction tower is subjected to secondary filtration through a security filter, and the filtrate is subjected to reverse osmosis treatment in a roll-type reverse osmosis membrane module, and the water recovery rate is 80 wt%, and the second-stage reverse osmosis water production and the second-stage reaction are obtained. Penetrate concentrated water.
  • Step (3) The obtained secondary reverse osmosis water (COD is 3 ppm, ammonia nitrogen is 0.2 ppm, TDS is 80 ppm, conductivity is 170 ⁇ s/cm) as recycled water, and the obtained secondary reverse osmosis concentrated water (COD is 247 ppm).
  • the Fenton oxidation method is used to specifically add 10 wt% of H 2 O 2 solution (addition amount of 5.2 kg/t of secondary reverse osmosis concentrated water) and FeSO 4 to the obtained secondary reverse osmosis concentrated water (addition amount is 0.47kg/t secondary reverse osmosis concentrated water), adjust the pH to 9 after 1h reaction, and add PAC and PAM for flocculation precipitation.
  • the COD of the effluent is 153ppm, and the COD removal rate is 38.0%.
  • the effluent COD was 127 ppm, the COD removal rate was 48.6%, and it was difficult to meet the Table 2 standard in the national standard GB 31571-2015.
  • the method for treating reverse osmosis concentrated water according to the present invention wherein the reverse osmosis concentrated water is treated as in steps (1), (2), and (3), and the organic matter and hardness in the reverse osmosis concentrated water are removed by using a precipitating agent and an oxidizing agent.
  • the ions, combined with the subsequent reverse osmosis treatment can recover 75-85 wt% of water (secondary reverse osmosis water), which improves the overall utilization of water; meanwhile, the subsequent oxidation step will also leave a small portion of water (secondary Reverse osmosis concentrated water) continues to be treated to meet the requirements of Table 2 in GB31571-2015 as external drainage discharge.
  • the environmental pressure is small, the economic input is small, and the method is simple and easy to operate;
  • the treatment results are indistinguishable, which means that the application can fully utilize the oxidation of a small amount of sodium hypochlorite contained in the chlor-alkali industrial wastewater, realize the treatment of the refractory organic pollutants in the reverse osmosis concentrated water, and fully utilize the NaOH contained in the chlor-alkali industrial wastewater.
  • chlor-alkali containing oxidant and precipitant can be used.
  • Industrial wastewater to treat reverse osmosis concentrated water saving the cost of chemicals compared to direct use of oxidants and precipitants, while also saving the cost and cost of processing chlor-alkali industrial wastewater;
  • the catalyst of the invention has high catalytic oxidation performance, thereby effectively degrading refractory organic pollutants in reverse osmosis concentrated water, and has good treatment effect on reverse osmosis concentrated water, COD removal rate. high;
  • the catalyst having the same content of each component and each component is a simple spherical alumina carrier with respect to the carrier, and when the carrier is a cerium-modified alumina carrier, the treatment effect on the reverse osmosis concentrated water is good, and the COD removal rate is high.
  • Example 5 a comparison of Example 5, Example 11 and Comparative Example 1 shows that:
  • the method of the present invention has a good treatment effect on reverse osmosis concentrated water and a high COD removal rate;
  • the catalyst of the invention and the catalytic oxidation of the oxidant by the catalyst of the prior art can all achieve the object of the invention, and the reverse osmosis, the concentrated water treatment effect is good, and the COD removal rate is high;
  • the reverse osmosis concentrated water is oxidized and precipitated by using chloralkali industrial wastewater containing NaClO, NaOH and Na 2 CO 3 , and the reverse osmosis concentrated water is directly treated with NaClO, NaOH and Na 2 CO 3 . Oxidation and precipitation treatment, the treatment results are indistinguishable.
  • Organic wastewater such as reverse osmosis concentrated water can be treated with chlor-alkali industrial wastewater containing NaClO, NaOH and Na 2 CO 3 to achieve the purpose of waste treatment;
  • the method of the present invention is treated with an oxidizing agent such as NaClO, a reducing agent such as Na 2 SO 3 , and activated carbon adsorption in the comparative example 2 , and the treatment effect of the second-stage reverse osmosis concentrated water is treated.
  • an oxidizing agent such as NaClO
  • a reducing agent such as Na 2 SO 3
  • activated carbon adsorption in the comparative example 2
  • the COD removal rate is high.
  • the reverse osmosis concentrated water is oxidized and precipitated by using chloralkali industrial wastewater containing NaClO, NaOH and Na 2 CO 3 , and the reverse osmosis concentrated water is directly treated with NaClO, NaOH and Na 2 CO 3 . Oxidation and precipitation treatment, the treatment results are indistinguishable.
  • Organic wastewater such as reverse osmosis concentrated water can be treated with chlor-alkali industrial wastewater containing NaClO, NaOH and Na 2 CO 3 to achieve the purpose of waste treatment.
  • the method of the present invention is treated with an oxidizing agent such as NaClO, a reducing agent such as Na 2 SO 3 , and activated carbon adsorption in the treatment of Comparative Example 3 with a Fenton oxidation method to treat the secondary reverse osmosis concentrated water.
  • an oxidizing agent such as NaClO
  • a reducing agent such as Na 2 SO 3
  • activated carbon adsorption in the treatment of Comparative Example 3 with a Fenton oxidation method to treat the secondary reverse osmosis concentrated water.
  • the effect is good and the COD removal rate is high.

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Abstract

一种反渗透浓水的处理方法，包括：(1)向反渗透浓水中加入沉淀剂和氧化剂进行处理，过滤得清液，向清液中加入用于水处理的催化剂进行催化氧化，得到一级处理水；所述一级处理水的获得任选地还包括对催化氧化后的液体进行吸附处理；(2)将一级处理水进行反渗透处理，得到二级反渗透产水和二级反渗透浓水；(3)向二级反渗透浓水中加入氧化剂进行氧化处理，得到出水，所述出水用于直接排放；所述出水的获得任选地还包括对氧化处理后的液体进行吸附处理。反渗透浓水的处理方法，不仅可回收75-85wt％的水，提高水的整体利用率，同时也将剩余一小部分水处理至外排标准，环境压力小，经济投入少，方法简单易操作。

Description

一种反渗透浓水的处理方法 技术领域
本发明属于环境工程的废水处理技术领域，更具体地说，是一种反渗透浓水的处理方法。
背景技术
近年来，随着石油化工行业的迅速发展，水资源短缺已成为制约我国经济和社会发展的重要因素，因此水的资源化利用受到越来越多的重视。反渗透不但能有效去除水中的无机盐类离子，还可除去水中的胶体、细菌、病毒、细菌内毒素和大部分有机物等杂质，且系统稳定性高、运行成本低，因此成为中水回用的主要技术手段。但反渗透处理后，除了可得到回用的水，还会产生浓缩了3-5倍的反渗透浓水(相对于反渗透前的中水)，产生的反渗透浓水存在以下缺陷：溶解性有机物含量较高、溶液色度大、含盐量高、可生化性差。
高COD反渗透浓水的常规处理方法为采用臭氧、双氧水等作为氧化剂，在催化剂、超声等作用下进行氧化，降解有机物，以达到排放标准。CN 102040294 A中公开了以臭氧和双氧水作为氧化剂并配合活性炭吸附处理反渗透浓水的方法，氧化剂投加量大，运行成本相对较高。CN 102153171 A中公开了臭氧催化氧化处理反渗透浓水的方法，由于过程中曝气会产生二次污染，需对尾气进行处理。CN 102633410 A中公开了以光催化氧化与生化联用处理反渗透浓水的方法，由于工艺包含生化，因此仅适用于盐含量较低的反渗透浓水，且光催化氧化和生化降COD的效果不佳，不适合COD较高的反渗透浓水。CN 103449635 A中公开了以芬顿氧化法处理反渗透浓水的方法，该方法缺点在于芬顿氧化法需在酸性条件下进行，处理过程需要调pH，过程产生大量沉淀，处理成本较高。
CN 102849879 A中公开了将反渗透浓水经过预处理后采用电渗析回收部分水的方法，但是对于电渗析过程产生的浓水如何处理，没有给出具体解决方案。CN 103723799 A和CN 104445788 A中公开了将反渗透浓水进一步采用超滤和反渗透组合的工艺处理，回收部分水 量，产生的浓水采用电渗析进行深度浓缩，浓缩过程产生的淡水回用、浓水进行蒸发结晶。CN 104609610 A中公开的利用反渗透装置回收部分水量，浓水采用正渗透进一步浓缩，正渗透产水回用，剩余微量浓水进蒸发装置处理，最终达到零排放的目的。以上方案优点在于将反渗透浓水经过处理后进一步回收利用，使水的整体利用率提高，但是无论采用反渗透、电渗析、还是正渗透等，都会产生盐浓度极高的浓水(盐含量15-18wt％)，需采用蒸发结晶对其进一步处理。由于盐含量高，结晶器基本采用钛材质，投资及运行成本较高。多效蒸发和机械式蒸汽再压缩(MVR)是常用的两种蒸发结晶技术手段，以10t/h的高盐废水计，多效蒸发技术投资需300-500万元，运行成本60-70元/吨；MVR技术投资需800-1200万元，运行成本35-45元/吨。综上，反渗透浓水近零排放工艺推广应用的瓶颈在于脱盐处理后得到的高盐难处理浓水的处理问题，因此需要开发一种高效、经济的反渗透浓水近零排放的工艺。
发明内容
本发明的目的在于提供一种反渗透浓水的处理方法，该处理方法简单易行，投资运行成本低，能对废水进行有效回收，实现了废水近零排放，绿色环保。
本发明的技术方案如下：
一种反渗透浓水的处理方法，包括以下步骤：
(1)向反渗透浓水中加入沉淀剂和氧化剂进行处理，过滤得清液，向所述清液中加入用于水处理的催化剂进行催化氧化，得到一级处理水；所述一级处理水的获得任选地还包括对催化氧化后的液体进行吸附处理；
(2)将步骤(1)得到的一级处理水进行反渗透处理，得到二级反渗透产水和二级反渗透浓水，所述二级反渗透产水用于回收使用；
(3)向步骤(2)得到的二级反渗透浓水中加入氧化剂进行氧化处理，得到出水，所述出水用于直接排放；所述出水的获得任选地还包括对氧化处理后的液体进行吸附处理。
步骤(1)中，所述反渗透浓水优选满足以下条件：COD≤300ppm， 优选50-300ppm，更优选50-250ppm；所述反渗透浓水中Ca2+含量为0-1000ppm，优选为50-500ppm；Mg2+含量为0-500ppm，优选为50-200ppm；SiO2含量为0-200ppm，优选为10-150ppm。
步骤(1)中，所述反渗透浓水进一步优选满足以下条件：COD为50-300ppm，优选50-250ppm；pH为6-9，优选7-8；TDS为1000-20000ppm，优选为2000-10000ppm；阳离子包括Na+、K+、Ca2+、Mg2+中的一种或多种，阴离子包括Cl-、SO4 2-、NO3 -等中的一种或多种；其中Ca2+含量为0-1000ppm，优选为50-500ppm，Mg2+含量为0-500ppm，优选为50-200ppm；SiO2含量为0-200ppm，优选为10-150ppm，NH4 +含量为0-50ppm，优选0-10ppm，重金属元素含量在0-5ppm，优选为0-0.5ppm，悬浮物含量在0-1000ppm，优选为0-200ppm。优选地，步骤(1)中，应先调节所述反渗透浓水的pH为6-12，优选9-11，然后再向其中加入沉淀剂和氧化剂进行处理。由于反渗透浓水的原始pH为6-9，因此此处调节pH所用的pH调节剂为碱性pH调节剂，所述碱性pH调节剂选自NaOH、KOH、Ca(OH)2、Mg(OH)2和氨水等中的一种或多种，优选NaOH和/或KOH。
“任选地”是指包括或不包括。
步骤(1)中，“所述一级处理水的获得任选地还包括对催化氧化后的液体进行吸附处理”是指，在获得一级处理水之前，可根据情况任选地对催化氧化后的液体进行吸附处理。若催化氧化后的液体中COD≤50ppm，则不用进行吸附处理，直接得到一级处理水；若催化氧化后的液体中COD＞50ppm，则需要对其进行吸附处理，然后才得到一级处理水。
步骤(3)中，“所述出水的获得任选地还包括对氧化处理后的液体进行吸附处理”是指，在获得出水之前，可根据情况任选地对氧化处理后的液体进行吸附处理。若氧化处理后的液体中COD≤50ppm，则不用进行吸附处理，直接得到出水；若氧化处理后的液体中COD＞50ppm，则需要对其进行吸附处理，然后才得到出水。
优选地，所述步骤(1)中，在向所述清液中加入催化剂之前，先调节所述清液的pH至6-9，优选7-8。
进一步优选地，步骤(1)中，应先调节所述清液的pH至6-9， 优选7-8，然后用过滤装置对调节pH后的清液进行过滤，再向所得滤液中加入催化剂进行催化氧化。
优选地，所述步骤(1)中，所述沉淀剂选自NaOH、KOH、Na2CO3和NaHCO3中的一种或多种，优选Na2CO3和/或NaHCO3。沉淀剂与反渗透浓水中的Ca2+、Mg2+等硬度离子反应生成沉淀以降低反渗透浓水的硬度，同时，Mg2+沉淀过程中会降低反渗透浓水中的SiO2(镁离子与偏硅酸根或硅酸根发生反应生成硅酸镁，而硅酸镁溶解度低，大部分为沉淀)，从而达到同步去除SiO2的目的。沉淀剂的用量根据反渗透浓水中Ca2+、Mg2+和SiO2的初始量确定。反渗透浓水中Ca2+、Mg2+和SiO2的初始量是通过对反渗透浓水进行水样分析得到的。
优选地，所述步骤(1)中，所述氧化剂选自含有有效氯的化合物和H2O2中的一种或多种，所述含有有效氯的化合物包括NaClO、NaClO3、Cl2和ClO2；所述氧化剂优选NaClO和/或H2O2。氧化剂通过氧化还原反应将反渗透浓水中的部分易氧化有机物降解为CO2和水，以降低反渗透浓水的COD。氧化剂的用量根据反渗透浓水中COD的初始量确定，氧化剂与反渗透浓水COD(以O2计)的摩尔比为0.5-2.5:1，优选为0.5-1.2:1，更优选0.5-1:1。反渗透浓水中COD的初始量也是通过对反渗透浓水进行水样分析得到的。
传统氧化法中氧化剂加入量与反渗透浓水COD(以O2计)的摩尔比为1-3:1，本发明中可降低为0.5-1:1，减少了经济投入，提高了经济效益。
对于COD在50-250ppm的反渗透浓水，在所述步骤(1)中经过沉淀剂和氧化剂处理后，COD可以降低至40-200ppm，只能实现对易氧化有机物的部分降解。
所述沉淀剂和氧化剂既可以是市售的工业产品，也可以是化工过程副产的回收品。
优选地，所述步骤(1)中，所述氧化剂为NaClO，所述沉淀剂为Na2CO3和NaOH，所述沉淀剂和氧化剂来源于氯碱工业废水；所述氯碱工业废水中，有效氯含量为2-4wt％，Na2CO3含量为5-10wt％，NaOH含量为0.1-2wt％。
由于氯碱工业废水中，含有NaClO、Na2CO3和NaOH，因此，氯 碱工业废水可以用做本发明步骤(1)中的沉淀剂和氧化剂。
氯碱工业废水中主要含有NaOH、Na2CO3以及低浓度的NaClO(在弱碱条件下时，也会存在NaHCO3)，由于其中有效氯含量较低，该氯碱工业废水难以作为产品外卖。而该氯碱工业废水如果直接排放，不仅造成水资源的大量浪费，也对环境和人类生活造成很大的危害。目前，对于含次氯酸钠的氯碱工业废水处理方案中，多以催化分解的方式处理，通过催化剂对次氯酸钠进行快速的催化分解而消除次氯酸钠，进而完成对含次氯酸钠的氯碱工业废水的处理问题。其处理路线一般为：采用Na2SO3或者H2O2还原废水中的NaClO，并用HCl调节废水的pH至6-9之后排海。目前的处理方式需要消耗大量的试剂。而本申请利用该氯碱工业废水中的NaClO、Na2CO3、NaHCO3和NaOH，将其用作氧化剂和沉淀剂对反渗透浓水进行处理，利用该氯碱工业废水中的NaClO进行氧化反应而降低反渗透浓水的COD，利用该氯碱工业废水中的Na2CO3、NaHCO3和NaOH进行沉淀反应去除反渗透浓水中的硬度离子，如Ca2+、Mg2+等。利用氯碱工业废水对反渗透浓水进行处理，不仅节省了反渗透浓水处理中使用的氧化剂和沉淀剂的药剂费用，同时也节省了氯碱工业废水处理中使用的还原剂的药剂费用，有效利用氯碱工业废水中的有效物质，达到以废治废的目的，可避免经济浪费、缓解环境压力、显著提高经济效益。
优选地，所述步骤(1)中，所述氯碱工业废水的用量为2-50kg/t反渗透浓水，优选为2-40kg/t反渗透浓水，以满足处理反渗透浓水所需要的氧化剂和沉淀剂的用量。
为方便过滤，步骤(1)中在向反渗透浓水中加入氧化剂和沉淀剂(或者含有氧化剂和沉淀剂的氯碱工业废水)时，可向其中加入聚合氯化铝(PAC)和/或聚丙烯酰胺(PAM)，聚合氯化铝(PAC)和聚丙烯酰胺(PAM)的加入量以产生大片絮状物为准。
步骤(1)中，发生氧化反应和沉淀反应后，可以通过本领域任何合适的方法除去沉淀，比如过滤，所用的过滤装置可以使用本领域公知的任意过滤装置，优选沉淀池、砂滤、多介质过滤器等，产生的沉淀采用板框压滤机进行压滤处理；由于催化氧化反应中，碱性环境下ClO-的分解缓慢，有机物降解能力差，而酸性环境下，容易造成催 化剂的流失(催化剂中的重金属活性组分随催化剂的流失而流失)，同时出水难以达到排放要求，因此，除去沉淀后的清液通过澄清池调节pH至6-9，优选7-8，能够在防止催化剂流失的前提下，使ClO-较快地分解，提高有机物的降解能力，使出水达到排放标准。
除去沉淀后的清液中可能还含有悬浮颗粒、胶体、细小沉淀物等杂质，这类杂质易堵塞催化剂、吸附剂的微孔，造成催化剂和吸附剂失效或减少寿命，因此，优选的，在清液进行催化氧化处理之前，使用过滤装置对清液进行二次过滤，以除去此类杂质，主要是除去清液中粒径大于4μm的颗粒物。二次过滤所用的过滤装置包括砂滤装置、活性炭过滤器、多介质过滤器、金属丝网过滤器、微滤装置或保安过滤器中的一种或多种，优选多介质过滤器。
优选地，所述步骤(1)中，所述催化氧化的反应时间为0.5-2h，优选为0.5-1.5h，合适的反应时间可以尽可能多地分解去除反渗透浓水中的有机物，降低反渗透浓水的COD值，同时将引入的大部分氧化剂分解。比如，对于COD在50-300ppm的反渗透浓水，在上述反应时间下催化氧化后，其COD可以降低至20-80ppm。这时催化氧化产水中还有一部分有机物，当COD大于50ppm时，可通过吸附处理将其吸附到吸附剂的微孔中，进而降低其COD值至50ppm以下，吸附剂可以为本领域任意的吸附剂，比如活性炭。对于COD在50-200ppm的反渗透浓水，经过催化氧化处理后可直接将COD处理至50ppm以下，不需经过吸附处理。
吸附处理可以在本领域公知的任意吸附设备中进行，比如吸附塔、溢流堰等可装填吸附剂的装置，优选吸附塔。所述吸附塔可设置一个或多个，可并联或串联，优选固定床式活性炭吸附塔。本发明所述的催化氧化产水优选在吸附塔内停留时间为0.5-4h，优选1-2h。
吸附处理中所用吸附装置的吸附剂为比表面积500-2000m2/g、机械强度50-100N/cm的吸附材料，比如活性炭、分子筛或大孔吸附树脂中的一种或多种，优选活性炭，进一步优选煤质圆柱形活性炭，所述煤质圆柱形活性炭的粒径为1-5mm，碘值为1000-1200。
优选地，所述步骤(1)中，所述催化剂包括氧化铝和以氧化物形态负载于所述氧化铝上的镍、铁、锰和铈；以所述氧化铝的重量为 基准计，所述催化剂中以下成分的含量为：
镍5.0-20wt％，优选5.5-12.0wt％；
铁0.5-5.5wt％，优选1.5-5.0wt％；
锰0.5-3.5wt％，优选1.0-3.0wt％；
铈1.5-3.0wt％，优选2.0-2.8wt％。
镍为主活性组分，铁、锰、铈作为调变剂(即，催化剂助剂)，用于对催化剂的性能进行修饰，提高催化剂的催化效果，调变剂也可以为其他本领域常用的调变剂。
优选地，所述催化剂包括铈改性氧化铝载体和以氧化物形态负载于所述铈改性氧化铝载体上的镍、铁、锰和铈；所述铈改性氧化铝载体包括氧化铝和以氧化物形态负载于所述氧化铝上的铈，以所述氧化铝的重量为基准计，所述铈改性氧化铝载体中铈的含量为1.0-2.0wt％，优选1.2-1.5wt％。
由于所述铈改性氧化铝载体是通过在氧化铝上负载铈(铈以氧化物形态存在)得到的，所以所述铈改性氧化铝载体包括氧化铝和以氧化物形态负载于所述氧化铝上的铈。
由于所述催化剂是通过在所述铈改性氧化铝载体上进一步负载镍、铁、锰和铈(镍、铁、锰和铈均以氧化物形态存在)得到的，所以所述催化剂包括铈改性氧化铝载体和以氧化物形态负载于所述铈改性氧化铝载体上的镍、铁、锰和铈。
优选地，以所述氧化铝的重量为基准计，所述催化剂中负载于所述铈改性氧化铝载体上的铈的含量为0.5-2.0wt％，优选0.6-1.5wt％。
所述催化剂中负载于所述铈改性氧化铝载体上的铈的含量，是指在所述铈改性氧化铝载体上进一步负载镍、铁、锰和铈时负载上的铈的含量，这部分铈的含量相当于催化剂中铈的总含量减去铈改性氧化铝载体中铈的含量。
载体为铈改性氧化铝载体时，铈在催化剂中是分两部分存在的，一部分存在于铈改性氧化铝载体中。铈改性氧化铝载体中的铈高度分散在氧化铝上，将氧化铝内表面进行物理割分，且铈能与氧化铝形成较强的相互作用，起到锚定作用；而在引入主活性组分及调变剂时，铈改性氧化铝载体中的铈还起到导向作用，使主活性组分分散均匀， 防止聚集。而另一部分铈存在于铈改性氧化铝载体的负载物(即，主活性组分及调变剂)中，由于铈改性氧化铝载体中铈的锚定作用和导向作用，催化剂中活性组分-氧化铈-氧化铝(即NiOx-CeO2-Al2O3，其中，NiOx是催化剂上主活性组分的氧化物，x代表2或3，由于NiOx中Ni2+、Ni3+均存在，所以主活性组分的氧化物中，O的原子数用x来表示)之间的相互作用力强于活性组分-氧化铝(NiOx-Al2O3)之间的相互作用力，因此可有效降低活性组分的聚集和流失，尤其适用于长周期处理难生化处理的废水，具有较好的活性和处理效果，运行处理成本低。
另外，铈具有较好的储氧功能。而氧化剂在催化剂的主活性组分上产生活性氧自由基是降解有机物的关键。当催化剂的载体为铈改性氧化铝载体时，催化剂对氧化剂(如次氯酸钠)进行催化氧化时，氧化剂在催化剂的主活性组分上产生的活性氧自由基可以及时迁移至铈改性氧化铝载体的铈上进行储存，使得活性氧自由基的位点增多，增加了反应位点，提高对有机物的降解速率和降解量。
比如，当催化剂的载体为铈改性氧化铝载体，氧化剂为次氯酸钠时，ClO-在NiOx上产生活性氧自由基，NiOx-CeO2-Al2O3的结构能够及时将NiOx上产生的活性氧自由基迁移至CeO2上，进而提高反应位点个数，有效降解有机物，提升COD去除率。其催化氧化机理如下：
ClO-→Cl-+[O]，即CAT+NaClO→CAT-O+NaCl  ①；
ORG+CAT-O→ORG-O+CAT                   ②；
ORG-O+CAT-O→H2O+CAT+CO3 2-              ③。
其中，[O]代表活性氧自由基，CAT代表催化剂，ORG代表有机物，CAT-O代表催化剂上的活性位点，活性位点上具有[O]，ORG-O代表与[O]相结合的有机物。式①是次氯酸钠经催化剂催化而在催化剂上产生[O]的过程；式②是具有[O]活性位点的催化剂与有机物接触将[O]转移到有机物上的过程；式③是与[O]相结合的有机物在催化剂作用下降解为小分子或二氧化碳和水的过程。
优选地，所述催化剂的载体中氧化铝的粒度为1.0-2.0mm，优选1.5-2.0mm；堆密度为0.30-0.50g/ml，优选0.40-0.48g/ml；吸水率为50-70vol％，优选55-60vol％；比表面积为150-250m2/g，优选180-220 m2/g；孔容为1.2-1.8ml/g，优选1.5-1.7ml/g；平均孔径为100-150nm，优选130-145nm。
废水中一些难降解的有机物通常是大分子的，选用大孔容、大孔径的氧化铝，能够提供恰当的孔道，有利于大分子有机物扩散进入催化剂内部的活性位点，有助于提高催化氧化处理效果，有效降解大分子有机物。
优选地，所述镍、铁、锰、铈分别来源于含有相应金属元素的硝酸盐、醋酸盐或碳酸盐中的一种或多种，优选硝酸盐。
上述催化剂的制备方法包括以下步骤：
(1)将铈盐的浸渍液加入到氧化铝中，对氧化铝浸渍30-120min，然后将所得固体干燥、焙烧，制得铈改性氧化铝载体；优选采用等体积浸渍工艺进行浸渍；优选干燥温度为100-130℃，干燥时间为2-5h，焙烧温度为450-550℃，焙烧时间为3-6h；进一步优选氧化铝浸渍前进行了真空预处理，所述的真空预处理的时间为10-30min，真空度为96.0-98.0KPa；
(2)将含有镍盐、铁盐、锰盐和铈盐的浸渍液加入到步骤(1)制得的铈改性氧化铝载体中，对其浸渍30-120min，然后将所得固体干燥，焙烧，制得所述催化剂；优选采用等体积浸渍工艺进行浸渍；优选干燥温度为100-130℃，干燥时间为2-5h，焙烧温度为450-550℃，焙烧时间为3-6h。
优选地，上述催化剂的制备方法中，所述步骤(1)和(2)中的浸渍液的溶剂均选自水、甲醇和乙醇中的一种或多种，优选水和/或乙醇，更优选乙醇浓度为10-40wt％的乙醇水溶液。
优选地，上述催化剂的制备方法中，以所述载体中氧化铝的重量为基准计，所述步骤(1)的浸渍液中铈的含量为1.0-2.0wt％，优选1.2-1.5wt％；所述步骤(2)的浸渍液中铈的含量为0.5-2.0wt％，优选0.6-1.5wt％；镍的含量为5.0-20wt％，优选5.5-12.0wt％；铁的含量为0.5-5.5wt％，优选1.5-5.0wt％；锰的含量为0.5-3.5wt％，优选1.0-3.0wt％；所述步骤(1)和所述步骤(2)的浸渍液中铈的总含量为1.5-3.0wt％，优选2.0-2.8wt％。
优选地，上述催化剂的制备方法中，所述步骤(1)中的铈盐与 步骤(2)中的镍盐、铁盐、锰盐和铈盐均为含有相应金属元素的硝酸盐、醋酸盐或碳酸盐中的一种或多种，优选硝酸盐(Ce(NO3)3、Ni(NO3)2、Fe(NO3)3、Mn(NO3)2)。
所述载体中的氧化铝可以采用任意形状的氧化铝，如球形、圆柱形、三叶草形、四叶草形、齿轮球形等，优选球形氧化铝。
氧化剂如NaClO在常温和无催化剂存在下反应速率低，NaClO主要分解生成Cl-和O2，导致产生的活性氧自由基[O]浓度低。而[O]氧化能力强，可降解大分子有机物为小分子有机物，同时将小分子有机物彻底降解为二氧化碳和水，可降解多种化合物，如胺、醛、酚、酯、芳烃、卤代烃等，同时也可以达到脱色除臭的目的。上述的催化剂有利于ClO-形成Cl-和[O]，减少O2的生成，避免了氧化剂的浪费。
传统氧化法氧化剂加入量与反渗透浓水COD的摩尔比为1-3:1，使用上述催化剂后，废水中的COD去除率可由传统的20-40％提高至60-80％，同时由于充分利用氧化剂，氧化剂加入量与反渗透浓水COD的摩尔比可降低为0.5-1:1，减少了经济投入，提高了经济效益。
反渗透浓水经步骤(1)处理后得到的一级处理水，硬度和COD值均下降，可以满足如表1所示的反渗透装置入水指标，用于作为步骤(2)的反渗透入水进行反渗透处理。
表1 反渗透入水指标
项目 数值 单位
COD <50 ppm
pH 6-9 /
SiO2 <40 ppm
硬度(以CaCO3计) <800 ppm
所述步骤(2)中，反渗透处理所使用的反渗透装置的膜组件为平板式、管式、卷式或中空纤维式，优选为卷式。所述膜组件中膜的材质为醋酸纤维素膜或芳香聚酰胺膜，优选为芳香聚酰胺膜。膜的可耐受绝对压力为1-2Mpa，反渗透膜水回收率为75-85wt％。
所述步骤(2)中，为了防止异常水质对反渗透装置中膜的污染和划伤，应优先在反渗透装置之前安装保安过滤器，以便于将一级处理水中的杂质滤除之后再进行反渗透处理，提高反渗透处理效果，延长反渗透装置的使用寿命。
所述步骤(2)中，得到的二级反渗透产水可以直接回用，二级反渗透产水的指标如表2所示，如未达到如表2的指标，则继续处理至达到该指标，然后回用；得到的二级反渗透浓水指标如表3所示，如未达到如表3的指标，则对其继续处理，直至达到该指标，然后将达到如表3的指标的反渗透浓水经步骤(3)进行氧化处理以降低其COD值，并将其中的部分有机物降解为CO2和水、大分子有机物分解为小分子有机物；所用氧化剂为NaClO、H2O2、NaClO3、Cl2、ClO2的一种或多种，氧化剂加入量与二级反渗透浓水中COD(以O2计)摩尔比为0.5-1.0:1。
表2 二级反渗透产水指标
项目 数值 单位
COD ≤5 ppm
氨氮 ≤0.5 ppm
TDS ≤200 ppm
电导率 ≤300 us/cm
表3 二级反渗透浓水指标
项目 数值 单位
COD 100-250 ppm
pH 6-9 /
SiO2 10-40 ppm
硬度(以CaCO3计) 100-2000 ppm
由于所述步骤(3)中，氧化处理后得到的氧化反应液中，过滤装置包括砂滤装置、活性炭过滤器、多介质过滤器、金属丝网过滤器、微滤装置或保安过滤器中的一种或多种，优选多介质过滤器。可能还有未完全反应的氧化剂，如直接进行吸附处理，可能会致使吸附剂被氧化而降低吸附剂寿命，甚至影响最终得到的出水水质，因此，所述步骤(3)中，优选先将所述氧化反应液的pH调节至6-9，然后向其中加入还原剂以除去过量的氧化剂。所述还原剂选自Na2SO3、Na2S2O3、H2O2、Na2S、FeSO4和H2中的一种或多种，还原剂添加量与过量氧化剂的摩尔比为0.9-1.5:1，优选为0.9-1.1:1。考虑到经上述处理后的反应液中可能还含有颗粒物或沉淀，可考虑对其采用过滤预处理，过滤装置可选自砂滤装置、活性炭过滤器、多介质过滤器、 金属丝网过滤器、微滤装置或保安过滤器中的一种或多种，优选多介质过滤器。如果经过上述一系列处理后的反应液中COD≤50ppm，则可满足GB 31571-2015中的表2标准，作为出水排放；如果经上述处理后的反应液中COD>50ppm，则需向其中加入吸附剂进行吸附处理，以使其COD≤50ppm，满足GB 31571-2015中的表2标准，作为出水排放。同样，吸附处理可以在本领域公知的任意吸附设备中进行，比如吸附塔、溢流堰等可装填吸附剂的装置，优选吸附塔。吸附处理所用的吸附剂为比表面积500-2000m2/g、机械强度50-100N/cm的吸附材料，比如活性炭、分子筛或大孔吸附树脂中的一种或多种，优选活性炭。吸附处理的时间为1-4h。
所述步骤(3)中，出水是所述反渗透浓水经本发明方法处理后达到GB 31571-2015中表2标准的水，可以直接外排。
优选地，所述方法包括以下步骤：
(1)先调节所述反渗透浓水的pH为9.5-11.5，然后向其中加入沉淀剂和氧化剂进行处理，过滤得清液，调节所述清液的pH至7-8，然后用多介质过滤器过滤，向所得滤液中加入上述催化剂进行催化氧化，得到反应液，然后将所述反应液输入吸附装置进行吸附处理，得到一级处理水；
(2)将步骤(1)得到的一级处理水进行反渗透处理，得到二级反渗透产水和二级反渗透浓水，所述二级反渗透产水用于回收使用；
(3)向步骤(2)得到的二级反渗透浓水中加入次氯酸钠进行氧化处理，得到氧化反应液，对所述氧化反应液调节pH至6-9，然后向其中加入还原剂如Na2SO3以除去过量的次氯酸钠，再将所得液体输入吸附装置进行吸附处理，得到出水，所述出水用于直接排放。
本发明的有益效果在于：
(1)本发明的反渗透浓水的处理方法，通过对反渗透浓水进行如步骤(1)、(2)、(3)的处理，用沉淀剂和氧化剂去除反渗透浓水中的有机物和硬度离子，不仅可回收75-85wt％的水，提高了水的整体利用率，同时也将剩余一小部分水处理至满足GB 31571-2015中的表2标准后作为外排水排放，环境压力小，经济投入少，方法简单易操作；
(2)有效处理氯碱工业废水，并能充分利用氯碱工业废水中含有的少量次氯酸钠的氧化性，实现对反渗透浓水中的难降解有机污染物的处理，充分利用氯碱工业废水中含有的NaOH、Na2CO3、NaHCO3发生沉淀反应，实现对反渗透浓水中Ca2+、Mg2+、SiO2等的去除，不仅节省了反渗透浓水处理中使用的氧化剂和沉淀剂的药剂费用，同时也节省了氯碱工业废水处理中使用的还原剂的药剂费用，有效利用氯碱工业废水中的有效物质，达到以废治废的目的，可避免经济浪费、缓解环境压力、显著提高经济效益；
(3)本发明所用的催化剂，能促使氧化剂产生[O]，提高氧化剂的氧化能力，配合高效吸附过程可将难氧化的反渗透浓水处理至COD≤50ppm，达到国家标准GB 31571-2015中的表2标准，同时由于氧化剂利用率提高，大大节约了氧化剂的加入量，经济效益显著。
具体实施方式
以下通过具体实施例对本发明技术方案及其效果做进一步说明。以下实施例仅用于说明本发明的内容，并不用于限制本发明的保护范围。应用本发明的构思对本发明进行的简单改变都在本发明要求保护的范围内。
在本发明的实施例1-11、对比例1-3中，所用的装置如下：
板框压滤机，型号XMKG70/1000-U，购自无锡通用机械厂有限公司；
氧化反应塔，多介质过滤器，活性炭吸附塔，保安过滤器、砂滤装置、微滤装置以及卷式反渗透膜组件，均购自麦王环保工程技术有限公司；
反渗透膜，型号SWC系列海水淡化膜，购自美国海德能公司；活性炭，购自烟台通用活性炭有限公司；
马弗炉，型号VULCAN 3-1750，购自美国Neytech公司。
在本发明的实施例1-11、对比例1-3中，所用的药品原料如下：
NaClO、Na2CO3、NaOH，分析纯，购自西陇化工股份有限公司；
PAC，分析纯，购自天津市科密欧化学试剂有限公司；
PAM，型号AN923SH，购自法国爱森公司；
Na2SO3，分析纯，购自国药集团化学试剂有限公司；
盐酸，37wt％，购自国药集团化学试剂有限公司；
FeSO4·7H2O，分析纯，购自西陇化工股份有限公司；
H2O2溶液，30wt％，购自国药集团化学试剂有限公司；
硝酸镍、硝酸铁、硝酸铈和硝酸锰，分析纯，购自西陇化工股份有限公司；
乙醇，分析纯，购自国药集团化学试剂有限公司。
实施例1：1#催化剂的制备
取来源于山东淄博物丰铝镁有限公司的球形氧化铝载体15g(约50ml)置于真空浸渍瓶中，进行真空预处理，真空预处理时间为30min，真空度为96.0KPa；同时取含镍0.15g/ml的硝酸镍水溶液12ml，含铁0.10g/ml的硝酸铁水溶液2.3ml，含锰0.10g/ml的硝酸锰水溶液3.0ml，含铈0.15g/ml的硝酸铈水溶液2.0ml，加入到乙醇浓度为10wt％的乙醇水溶液中，配制成总体积为25ml的浸渍液。将上述浸渍液加入到装有上述球形氧化铝载体的真空浸渍瓶中混合均匀后对上述球形氧化铝载体进行等体积浸渍，浸渍30min后，取出并置于烘箱内110℃干燥3h，然后在马弗炉内500℃焙烧6h，得到1#催化剂。
所得1#催化剂中，以其中氧化铝的重量为基准计，以下成分的含量如下：镍12.0wt％，铁1.5wt％，锰2.0wt％，铈2.0wt％。
实施例2：2#催化剂的制备
取来源于山东烟台百川汇通科技有限公司的球形氧化铝载体15g(约30ml)置于真空浸渍瓶中，进行真空预处理，真空预处理时间为30min，真空度为98.0KPa；同时取含镍0.15g/ml的硝酸镍水溶液16ml，含铁0.10g/ml的硝酸铁水溶液0.9ml，含锰0.10g/ml的硝酸锰水溶液1.5ml，含铈0.15g/ml的硝酸铈水溶液2.5ml，加入到去离子水中，配制成总体积为21ml的浸渍液。将上述浸渍液加入到装有上述球形氧化铝载体的真空浸渍瓶中混合均匀后对上述球形氧化铝载体进行等体积浸渍，浸渍60min后，取出并置于烘箱内130℃干燥2h，然后在马弗炉内480℃焙烧6h，得到2#催化剂。
所得2#催化剂中，以其中氧化铝的重量为基准计，以下成分的含 量如下：镍16.0wt％，铁0.6wt％，锰1.0wt％，铈2.5wt％。
实施例3：3#催化剂的制备
取来源于山东烟台百川汇通科技有限公司的球形氧化铝载体15g(约30ml)置于真空浸渍瓶中，进行真空预处理，真空预处理时间为20min，真空度为97.5KPa；取含铈0.05g/ml的硝酸铈水溶液6.0ml加入到乙醇浓度为30wt％的乙醇水溶液中，配制成体积为21ml的浸渍液，将浸渍液加入到真空浸渍瓶中混合均匀后对球形氧化铝载体进行等体积浸渍，浸渍30min后，取出并置于烘箱中120℃干燥3h，然后在马弗炉内500℃焙烧4h，制得铈改性氧化铝载体。所制得的铈改性氧化铝载体中，以氧化铝的重量为基准计，铈的含量为2.0wt％。
取上述铈改性氧化铝载体15g(约30ml)置于真空浸渍瓶中，进行真空预处理，真空预处理时间为30min，真空度为98.0KPa；同时取含镍0.15g/ml的硝酸镍水溶液16ml，含铁0.10g/ml的硝酸铁水溶液0.9ml，含锰0.10g/ml的硝酸锰水溶液1.5ml，含铈0.05g/ml的硝酸铈水溶液1.5ml，加入到去离子水中，配制成总体积为21ml的浸渍液。将上述浸渍液加入到装有上述铈改性氧化铝载体的真空浸渍瓶中混合均匀后对上述铈改性氧化铝载体进行等体积浸渍，浸渍60min后，取出并置于烘箱内130℃干燥2h，然后在马弗炉内480℃焙烧6h，得到3#催化剂。
上述球形氧化铝载体的物化性质为：粒度1.5-2.0mm，堆密度0.50g/ml，吸水率为70vol％，比表面积250m2/g，孔容1.20ml/g，平均孔径130nm。
所得3#催化剂中，以其中氧化铝的重量为基准计，以下成分的含量如下：镍16.0wt％，铁0.6wt％，锰1.0wt％，铈2.5wt％。
实施例4：4#催化剂的制备
取来源于山东淄博物丰铝镁有限公司的球形氧化铝载体15g(约50ml)置于真空浸渍瓶中，进行真空预处理，真空预处理时间为30min，真空度为98.0KPa；取含铈0.05g/ml的硝酸铈水溶液3.0ml加入到乙醇浓度为20wt％的乙醇水溶液中，配制成体积为25ml的浸渍液，将浸渍液加入到真空浸渍瓶中混合均匀后对球形氧化铝载体进行等体积浸渍，浸渍60min后，取出并置于烘箱中120℃干燥2h，然 后在马弗炉内450℃焙烧5h，制得铈改性氧化铝载体。所制得的铈改性氧化铝载体中，以氧化铝的重量为基准计，铈的含量为1.0wt％。
取上述铈改性氧化铝载体15g(约50ml)置于真空浸渍瓶中，进行真空预处理，真空预处理时间为30min，真空度为96.0KPa；同时取含镍0.15g/ml的硝酸镍水溶液12ml，含铁0.10g/ml的硝酸铁水溶液2.3ml，含锰0.10g/ml的硝酸锰水溶液3.0ml，含铈0.05g/ml的硝酸铈水溶液3.0ml，加入到乙醇浓度为10wt％的乙醇水溶液中，配制成总体积为25ml的浸渍液。将上述浸渍液加入到装有上述铈改性氧化铝载体的真空浸渍瓶中混合均匀后对上述铈改性氧化铝载体进行等体积浸渍，浸渍60min后，取出并置于烘箱内110℃干燥3h，然后在马弗炉内500℃焙烧6h，得到4#催化剂。
上述球形氧化铝载体的物化性质为：粒度1.0-1.5mm，堆密度0.30g/ml，吸水率为50vol％，比表面积150m2/g，孔容1.80ml/g，平均孔径150nm。
所得4#催化剂中，以其中氧化铝的重量为基准计，以下成分的含量如下：镍12.0wt％，铁1.5wt％，锰2.0wt％，铈2.0wt％。
在以下的实施例中，所用的原料中，反渗透浓水的取样分析结果见表4，氯碱工业废水的主要组成见表5。
表4 反渗透浓水的取样分析结果
Figure PCTCN2016097631-appb-000001
表5 氯碱工业废水的主要组成
氯碱工业废水 NaClO/wt％ Na2CO3/wt％ NaOH/wt％/
实施例5-8、11及对比例3 2 9 1
实施例5：反渗透浓水的处理(1#催化剂+氯碱工业废水)
步骤(1):取表4所示的反渗透浓水，于调节池内用NaOH调节其pH至11，然后输入反应池中，并向反应池内加入如表5所示的氯碱工业废水(加入量为28kg/t反渗透浓水)，并加入PAC和PAM溶液至出现大片絮状物，混合反应1h，反应结束后沉淀采用板框压滤机过滤，固体废物主要为CaCO3和Mg(OH)2，可以作为建材厂原料，过滤所得清液进入澄清池，用HCl调节pH为8，并在澄清池内停留1h。经过上述次氯酸钠氧化和除硬降硅过程后，反渗透浓水的COD降低至240ppm，然后进入多介质过滤器进行过滤，所得滤液进入填装1#催化剂的氧化反应塔，并停留90min，经过上述催化氧化反应后，其COD降低至80ppm，COD去除率为73.3％，然后进入活性炭吸附塔进行吸附处理，经过1h吸附处理后，出水COD为38ppm，pH为8，SiO2为10ppm，硬度(以CaCO3计)为290ppm。
步骤(2):活性炭吸附塔出水经过保安过滤器进行二次过滤，所得滤液进入卷式反渗透膜组件进行反渗透处理，水回收率为75wt％，得到二级反渗透产水和二级反渗透浓水。
步骤(3):所得二级反渗透产水(COD为5ppm，氨氮为0.4ppm，TDS为100ppm，电导率为190μs/cm)作为循环水回用，所得二级反渗透浓水(COD为152ppm，pH为8.5，SiO2为49ppm，硬度(以CaCO3计)为1188ppm)进入氧化单元继续处理，具体是向所得二级反渗透浓水中加入10wt％的NaClO溶液(加入量为3.5kg/t二级反渗透浓水)，混合液在氧化装置中反应1h，然后输入调节池内用HCl调节pH为7.5，并加入10wt％的H2O2(加入量为1.12kg/t二级反渗透浓水)还原过量的NaClO，进入多介质过滤器，然后进入活性炭吸附塔吸附处理2h，得到出水，所述出水的COD为25ppm，COD去除率为83.6％，达到国家标准GB 31571-2015中的表2标准。
实施例6：反渗透浓水的处理(2#催化剂+氯碱工业废水)
步骤(1):取表4所示的反渗透浓水，于调节池内用NaOH调节其pH至11，然后输入反应池中，并向反应池内加入如表5所示的氯碱工业废水(加入量为2.9kg/t反渗透浓水)，并加入PAC和PAM溶液至出现大片絮状物，混合反应1h，反应结束后沉淀采用板框压滤 机过滤，固体废物主要为CaCO3和Mg(OH)2，可以作为建材厂原料，过滤所得清液进入澄清池，用HCl调节pH为7.5，并在澄清池内停留1h。经过上述次氯酸钠氧化和除硬降硅过程后，反渗透浓水的COD降低至38ppm，然后经过砂滤装置过滤后，进入填装2#催化剂的氧化反应塔，并停留30min，经过上述催化氧化反应后，其COD降低至20ppm，COD去除率为60％，pH为7.8，SiO2为10ppm，硬度(以CaCO3计)为62ppm。
步骤(2):氧化反应塔出水经过保安过滤器进行二次过滤，所得滤液进入卷式反渗透膜组件进行反渗透处理，水回收率为85wt％，得到二级反渗透产水和二级反渗透浓水。
步骤(3):所得二级反渗透产水(COD为3ppm，氨氮为0.1ppm，TDS为40ppm，电导率为70μs/cm)作为循环水回用，所得二级反渗透浓水(COD为125ppm，pH为8.2，SiO2为50ppm，硬度(以CaCO3计)为389ppm)进入氧化单元继续处理，具体是向所得二级反渗透浓水中加入10wt％的NaClO溶液(加入量为2.9kg/t二级反渗透浓水)，混合液在氧化装置中反应1h，然后输入调节池内用HCl调节pH为8，并加入Na2SO3(加入量为0.34kg/t二级反渗透浓水)还原过量的NaClO，然后进入多介质过滤器，滤液进入活性炭吸附塔吸附处理2h，得到出水，所述出水的COD为15ppm，COD去除率为88.0％，达到国家标准GB 31571-2015中的表2标准。
实施例7：反渗透浓水的处理(3#催化剂+氯碱工业废水)
步骤(1):取表4所示的反渗透浓水，于调节池内用NaOH调节其pH至11，然后输入反应池中，并向反应池内加入如表5所示的氯碱工业废水(加入量为24kg/t反渗透浓水)，并加入PAC和PAM溶液至出现大片絮状物，混合反应0.5h，反应结束后沉淀采用板框压滤机进行压滤，固体废物主要为CaCO3和Mg(OH)2，可以作为建材厂原料，上清液进入澄清池，用HCl调节pH为8.5，并在澄清池内停留1h。经过上述次氯酸钠氧化和除硬降硅过程后，反渗透浓水的COD降低至159ppm，然后经过多介质过滤器过滤后，进入填装3#催化剂的氧化反应塔，并停留60min，经过上述催化氧化反应后，其COD降低至38ppm，COD去除率为81.9％，pH为8.5，SiO2为7ppm，硬度 (以CaCO3计)为150ppm。
步骤(2):氧化反应塔出水经过保安过滤器进行二次过滤，所得滤液进入卷式反渗透膜组件进行反渗透处理，水回收率为80wt％，得到二级反渗透产水和二级反渗透浓水。
步骤(3):所得二级反渗透产水(COD为3ppm，氨氮为0.2ppm，TDS为80ppm，电导率为170μs/cm)作为循环水回用，所得二级反渗透浓水(COD为190ppm，pH为8.8，SiO2为29ppm，硬度(以CaCO3计)为760ppm)进入氧化单元继续处理，具体是向所得二级反渗透浓水中加入10wt％的NaClO溶液(加入量为4.4kg/t二级反渗透浓水)，混合液在氧化装置中反应1h，然后输入调节池内用HCl调节pH为6-9，并加入Na2SO3(加入量为0.52kg/t二级反渗透浓水)还原过量的NaClO，然后进入微滤装置，滤液进入活性炭吸附塔吸附处理3h，得到出水，所述出水的COD为41ppm，COD去除率为78.4％，达到国家标准GB 31571-2015中的表2标准。
实施例8：反渗透浓水的处理(4#催化剂+氯碱工业废水)
步骤(1):取表4所示的反渗透浓水，于调节池内用NaOH调节其pH至11，然后输入反应池中，并向反应池内加入如表5所示的氯碱工业废水(加入量为18kg/t反渗透浓水)，并加入PAC和PAM溶液至出现大片絮状物，混合反应2h，反应结束后沉淀采用板框压滤机进行压滤，固体废物主要为CaCO3和Mg(OH)2，可以作为建材厂原料，上清液进入澄清池，用HCl调节pH为6，并在澄清池内停留1h。经过上述次氯酸钠氧化和除硬降硅过程后，反渗透浓水的COD降低至123ppm，然后经过多介质过滤器过滤后，进入填装4#催化剂的氧化反应塔，并停留30min，经过上述催化氧化反应后，其COD降低至34ppm，COD去除率为78.5％，pH为6.5，SiO2为5ppm，硬度(以CaCO3计)为260ppm。
步骤(2):氧化反应塔出水经过保安过滤器进行二次过滤，所得滤液进入卷式反渗透膜组件进行反渗透处理，水回收率为80wt％，得到二级反渗透产水和二级反渗透浓水。
步骤(3):所得二级反渗透产水(COD为2ppm，氨氮为0.3ppm，TDS为80ppm，电导率为172μs/cm)作为循环水回用，所得二级反 渗透浓水(COD为147ppm，pH为7，SiO2为25ppm，硬度(以CaCO3计)为1640ppm)进入氧化单元继续处理，具体是向所得二级反渗透浓水中加入10wt％的NaClO溶液(加入量为3.4kg/t二级反渗透浓水)，混合液在氧化装置中反应1h，然后输入调节池内用HCl调节pH为6-9，并加入Na2SO3(加入量为0.40kg/t二级反渗透浓水)还原过量的NaClO，停留1h，然后进入多介质过滤器过滤后，滤液进入活性炭吸附塔吸附处理2h，得到出水，所述出水的COD为23ppm，COD去除率为84.4％，达到国家标准GB 31571-2015中的表2标准。
实施例9：反渗透浓水的处理(2#催化剂+NaClO、Na2CO3和NaOH)
步骤(1):取表4所示的反渗透浓水，于调节池内用NaOH调节其pH至11，然后输入反应池中，并向反应池内加入10wt％的NaClO溶液(加入量为0.6kg/t反渗透浓水)、30wt％的Na2CO3溶液(加入量为0.87kg/t反渗透浓水)和48wt％的NaOH溶液(加入量为0.06kg/t反渗透浓水)，并加入PAC和PAM溶液至出现大片絮状物，混合反应1h，反应结束后沉淀采用板框压滤机进行压滤，固体废物主要为CaCO3和Mg(OH)2，可以作为建材厂原料，上清液进入澄清池，用HCl调节pH为7.5，并在澄清池内停留1h。经过上述次氯酸钠氧化和除硬降硅过程后，然后经过多介质过滤器过滤后，进入填装2#催化剂的氧化反应塔，并停留30min，经过上述催化氧化反应后，其COD降低至20ppm，COD去除率为60％，pH为7.8，SiO2为10ppm，硬度(以CaCO3计)为62ppm。
步骤(2):氧化反应塔出水经过保安过滤器进行二次过滤，所得滤液进入卷式反渗透膜组件进行反渗透处理，水回收率为85wt％，得到二级反渗透产水和二级反渗透浓水。
步骤(3):所得二级反渗透产水(COD为3ppm，氨氮为0.1ppm，TDS为41ppm，电导率为74μs/cm)作为循环水回用，所得二级反渗透浓水(COD为125ppm，pH为8.2，SiO2为50ppm，硬度(以CaCO3计)为389ppm)进入氧化单元继续处理，具体是向所得二级反渗透浓水中加入10wt％的NaClO溶液(加入量为2.9kg/t二级反渗透浓水)，混合液在氧化装置中反应1h，然后输入调节池内用HCl调节pH 为8，并加入Na2SO3(加入量为0.34kg/t二级反渗透浓水)还原过量的NaClO，然后进入多介质过滤器过滤，滤液进入活性炭吸附塔吸附处理2h，得到出水，所述出水的COD为15ppm，COD去除率为88.0％，达到国家标准GB 31571-2015中的表2标准。
实施例10：反渗透浓水的处理(4#催化剂+NaClO、Na2CO3和NaOH)
步骤(1):取表4所示的反渗透浓水，于调节池内用NaOH调节其pH至11，然后输入反应池中，并向反应池内加入10wt％的NaClO溶液(加入量为3.6kg/t反渗透浓水)、30wt％的Na2CO3溶液(加入量为5.4kg/t反渗透浓水)和48wt％的NaOH溶液(加入量为0.375kg/t反渗透浓水)，并加入PAC和PAM溶液至出现大片絮状物，混合反应2h，反应结束后沉淀采用板框压滤机进行压滤，固体废物主要为CaCO3和Mg(OH)2，可以作为建材厂原料，上清液进入澄清池，用HCl调节pH为6，并在澄清池内停留1h。经过上述次氯酸钠氧化和除硬降硅过程后，反渗透浓水的COD降低至123ppm，然后经过多介质过滤器过滤后，进入填装4#催化剂的氧化反应塔，并停留30min，经过上述催化氧化反应后，其COD降低至34ppm，COD去除率为78.5％，pH为6.5，SiO2为5ppm，硬度(以CaCO3计)为260ppm。
步骤(2):氧化反应塔出水经过保安过滤器进行二次过滤，所得滤液进入卷式反渗透膜组件进行反渗透处理，水回收率为80wt％，得到二级反渗透产水和二级反渗透浓水。
步骤(3):所得二级反渗透产水(COD为2ppm，氨氮为0.3ppm，TDS为81ppm，电导率为174μs/cm)作为循环水回用，所得二级反渗透浓水(COD为147ppm，pH为7，SiO2为25ppm，硬度(以CaCO3计)为1640ppm)进入氧化单元继续处理，具体是向所得二级反渗透浓水中加入10wt％的NaClO溶液(加入量为3.4kg/t二级反渗透浓水)，混合液在氧化装置中反应1h，然后输入调节池内用HCl调节pH为6-9，并加入Na2SO3(加入量为0.40kg/t二级反渗透浓水)还原过量的NaClO，停留1h，然后进入多介质过滤器过滤后，滤液进入活性炭吸附塔吸附处理2h，得到出水，所述出水的COD为23ppm，COD去除率为84.4％，达到国家标准GB 31571-2015中的表2标准。
实施例11：反渗透浓水的处理(CN 104549316A催化剂+氯碱工业废水)
步骤(1):取表4所示的反渗透浓水，于调节池内用NaOH调节其pH至11，然后输入反应池中，并向反应池内加入如表5所示的氯碱工业废水(加入量为28kg/t反渗透浓水)，并加入PAC和PAM溶液至出现大片絮状物，混合反应1h，反应结束后沉淀采用板框压滤机过滤，固体废物主要为CaCO3和Mg(OH)2，可以作为建材厂原料，过滤所得清液进入澄清池，用HCl调节pH为8，并在澄清池内停留1h。经过上述次氯酸钠氧化和除硬降硅过程后，反渗透浓水的COD降低至240ppm，然后进入多介质过滤器过滤，所得滤液进入填装CN 104549316 A中实施例1的催化剂的催化氧化塔，并停留90min，经过上述催化氧化反应后，其COD降低至112ppm，COD去除率为62.7％，然后进入活性炭吸附塔进行吸附处理，经过2h吸附处理后，出水COD为48ppm，pH为8，SiO2为10ppm，硬度(以CaCO3计)为290ppm。
步骤(2):活性炭吸附塔出水经过保安过滤器进行二次过滤，所得滤液进入卷式反渗透膜组件进行反渗透处理，水回收率为75wt％，得到二级反渗透产水和二级反渗透浓水。
步骤(3):所得二级反渗透产水(COD为5ppm，氨氮为0.4ppm，TDS为100ppm，电导率为190μs/cm)作为循环水回用，所得二级反渗透浓水(COD为205ppm，pH为8.5，SiO2为49ppm，硬度(以CaCO3计)为1188ppm)进入氧化单元继续处理，具体是向所得二级反渗透浓水中加入10wt％的NaClO溶液(加入量为4.8kg/t二级反渗透浓水)，混合液在氧化装置中反应1h，然后输入调节池内用HCl调节pH为7.5，并加入Na2SO3(加入量为0.57kg/t二级反渗透浓水)还原过量的NaClO，进入多介质过滤器，然后进入活性炭吸附塔吸附处理2h，得到出水，所述出水的COD为55ppm，COD去除率为73.2％，未达到国家标准GB 31571-2015中的表2标准；而当延长活性炭吸附塔吸附处理时间至3h时，得到的出水的COD为49ppm，COD去除率为76.1％，达到国家标准GB 31571-2015中的表2标准。
对比例1：反渗透浓水的处理(芬顿氧化法)
取表4所示的反渗透浓水，采用芬顿氧化法进行处理，先调节反应pH至3，向其中加入10wt％的H2O2溶液(加入量为6.4kg/t反渗透浓水)以及FeSO4(加入量为0.57kg/t反渗透浓水)，反应1h后调节pH至9，并加入一定量的PAC和PAM进行絮凝沉淀，采用多介质过滤器过滤，出水COD为172ppm，COD去除率为42.7％，提高反应的温度至50℃，并延长反应时间至4h，出水COD为148ppm，COD去除率为50.7％，难以达到反渗透入水指标，也难以达到国家标准GB 31571-2015中的表2标准，因此不能进行后续的反渗透等处理。
对比例2：反渗透浓水的处理(CN 101844828 B中催化剂+NaClO、Na2CO3和NaOH)
步骤(1):取表4所示的反渗透浓水，于调节池内用NaOH调节其pH至11，然后输入反应池中，并向反应池内加入10wt％的NaClO溶液(加入量为0.58kg/t反渗透浓水)、30wt％的Na2CO3溶液(加入量为0.87kg/t反渗透浓水)和48wt％的NaOH溶液(加入量为0.06kg/t反渗透浓水)，并加入PAC和PAM溶液至出现大片絮状物，混合反应1h，反应结束后沉淀采用板框压滤机进行压滤，固体废物主要为CaCO3和Mg(OH)2，可以作为建材厂原料，上清液进入澄清池，用HCl调节pH为7.5，并在澄清池内停留1h。经过上述次氯酸钠氧化和除硬降硅过程后，然后经过多介质过滤器过滤后，进入填装CN101844828B中实施例1的催化剂的氧化反应塔，并停留30min，经过上述催化氧化反应后，其COD降低至29ppm，COD去除率为42％，pH为7.8，SiO2为10ppm，硬度(以CaCO3计)为62ppm。
步骤(2):氧化反应塔出水经过保安过滤器进行二次过滤，所得滤液进入卷式反渗透膜组件进行反渗透处理，水回收率为85wt％，得到二级反渗透产水和二级反渗透浓水。
步骤(3):所得二级反渗透产水(COD为3ppm)作为循环水回用，所得二级反渗透浓水(COD为188ppm)采用芬顿氧化法进行处理，具体是向所得二级反渗透浓水中加入10wt％的H2O2溶液(加入量为4.0kg/t二级反渗透浓水)以及FeSO4(加入量为0.36kg/t二级反渗透浓水)，反应1h后调节pH至9，并加入PAC和PAM进行絮凝沉淀，经多介质过滤器过滤后，出水的COD为128ppm，COD去除 率为32.0％，提高反应的温度至50℃，并延长反应时间至4h，出水COD为101ppm，COD去除率为46.3％，难以达到国家标准GB31571-2015中的表2标准。
对比例3：反渗透浓水的处理(CN 104549316 A中催化剂+氯碱工业废水)
步骤(1):取表4所示的反渗透浓水，于调节池内用NaOH调节其pH至11，然后输入反应池中，并向反应池内加入如表5所示的氯碱工业废水(加入量为18kg/t反渗透浓水)，并加入PAC和PAM溶液至出现大片絮状物，混合反应2h，反应结束后沉淀采用板框压滤机进行压滤，固体废物主要为CaCO3和Mg(OH)2，可以作为建材厂原料，上清液进入澄清池，用HCl调节pH为6，并在澄清池内停留1h。经过上述次氯酸钠氧化和除硬降硅过程后，反渗透浓水的COD降低至123ppm，然后经过多介质过滤器过滤后，进入填装CN 104549316 A中实施例1的催化剂的氧化反应塔，并停留30min，经过上述催化氧化反应后，其COD降低至49ppm，COD去除率为68.9％，pH为6.5，SiO2为5ppm，硬度(以CaCO3计)为260ppm。
步骤(2):氧化反应塔出水经过保安过滤器进行二次过滤，所得滤液进入卷式反渗透膜组件进行反渗透处理，水回收率为80wt％，得到二级反渗透产水和二级反渗透浓水。
步骤(3):所得二级反渗透产水(COD为3ppm，氨氮为0.2ppm，TDS为80ppm，电导率为170μs/cm)作为循环水回用，所得二级反渗透浓水(COD为247ppm)采用芬顿氧化法进行处理，具体是向所得二级反渗透浓水中加入10wt％的H2O2溶液(加入量为5.2kg/t二级反渗透浓水)以及FeSO4(加入量为0.47kg/t二级反渗透浓水)，反应1h后调节pH至9，并加入PAC和PAM进行絮凝沉淀，经多介质过滤器过滤后，出水的COD为153ppm，COD去除率为38.0％，提高反应的温度至50℃，并延长反应时间至4h，出水COD为127ppm，COD去除率为48.6％，难以达到国家标准GB 31571-2015中的表2标准。
由实施例5-11与对比例1-3的比较可知：
1、本发明的反渗透浓水的处理方法，通过对反渗透浓水进行如步骤(1)、(2)、(3)的处理，用沉淀剂和氧化剂去除反渗透浓水中的有机物和硬度离子，结合后续的反渗透处理，可回收75-85wt％的水(二级反渗透产水)，提高了水的整体利用率；同时，后续的氧化步骤也将剩余一小部分水(二级反渗透浓水)继续处理至满足GB31571-2015中的表2标准后作为外排水排放，相对于对比例的处理方法，环境压力小，经济投入少，方法简单易操作；
2、用含有NaClO、NaOH和Na2CO3的氯碱工业废水来对反渗透浓水进行氧化和沉淀处理，与直接用NaClO、NaOH和Na2CO3来对反渗透浓水进行氧化和沉淀处理，其处理结果无区别，这说明本申请能充分利用氯碱工业废水中含有的少量次氯酸钠的氧化性，实现对反渗透浓水中的难降解有机污染物的处理，充分利用氯碱工业废水中含有的NaOH和Na2CO3发生沉淀反应，实现对反渗透浓水中Ca2+、Mg2+、SiO2等的去除，达到以废治废的目的，实际工业过程中，可用含有氧化剂和沉淀剂的氯碱工业废水来处理反渗透浓水，相对于直接用氧化剂和沉淀剂，节省了药剂费用，同时也节省了对氯碱工业废水进行处理的药剂费用和成本；
3、相对于现有技术的催化剂，本发明的催化剂，具有较高的催化氧化性能，进而有效降解反渗透浓水中的难降解有机污染物，对反渗透浓水的处理效果好，COD去除率高；
各成分及各成分含量相同的催化剂中，相对于载体为单纯的球形氧化铝载体，载体为铈改性氧化铝载体时，对反渗透浓水的处理效果好，COD去除率高。
具体地，由实施例5、实施例11与对比例1的比较可知：
相对于对比例1的现有技术，本发明的方法，对反渗透浓水的处理效果好，COD去除率高；
用本发明的催化剂与用现有技术的催化剂对氧化剂进行催化氧化均能达到本发明的目的，对反渗透，浓水的处理效果好，COD去除率高；
但是，相对于使用现有技术的催化剂，使用本发明的催化剂能提 高对反渗透浓水的处理效果，提高COD去除率。
由实施例5、实施例9与对比例2的比较可知：
步骤(1)中，用含有NaClO、NaOH和Na2CO3的氯碱工业废水来对反渗透浓水进行氧化和沉淀处理，与直接用NaClO、NaOH和Na2CO3来对反渗透浓水进行氧化和沉淀处理，其处理结果无区别，可用含有NaClO、NaOH和Na2CO3的氯碱工业废水对反渗透浓水等有机废水进行处理，达到以废治废的目的；
步骤(3)中，相对于对比例2中用芬顿氧化处理，本发明方法用氧化剂如NaClO，还原剂如Na2SO3、以及活性炭吸附等处理，对二级反渗透浓水的处理效果好，COD去除率高。
由实施例8与实施例10的比较同样可知：
步骤(1)中，用含有NaClO、NaOH和Na2CO3的氯碱工业废水来对反渗透浓水进行氧化和沉淀处理，与直接用NaClO、NaOH和Na2CO3来对反渗透浓水进行氧化和沉淀处理，其处理结果无区别，可用含有NaClO、NaOH和Na2CO3的氯碱工业废水对反渗透浓水等有机废水进行处理，达到以废治废的目的。
由实施例8与对比例3的比较同样可知：
步骤(3)中，相对于对比例3中用芬顿氧化法处理，本发明方法用氧化剂如NaClO，还原剂如Na2SO3、以及活性炭吸附等处理，对二级反渗透浓水的处理效果好，COD去除率高。

Claims (14)

  1. 一种反渗透浓水的处理方法，其特征在于，包括以下步骤：
    (1)向反渗透浓水中加入沉淀剂和氧化剂进行处理，过滤得清液，向所述清液中加入用于水处理的催化剂进行催化氧化，得到一级处理水；所述一级处理水的获得任选地还包括对催化氧化后的液体进行吸附处理；
    (2)将步骤(1)得到的一级处理水进行反渗透处理，得到二级反渗透产水和二级反渗透浓水，所述二级反渗透产水用于回收使用；
    (3)向步骤(2)得到的二级反渗透浓水中加入氧化剂进行氧化处理，得到出水，所述出水用于直接排放；所述出水的获得任选地还包括对氧化处理后的液体进行吸附处理。
  2. 根据权利要求1所述的处理方法，其特征在于，所述反渗透浓水的COD≤300ppm，优选50-300ppm，更优选50-250ppm；所述反渗透浓水中Ca2+含量为0-1000ppm，优选为50-500ppm；Mg2+含量为0-500ppm，优选为50-200ppm；SiO2含量为0-200ppm，优选为10-150ppm。
  3. 根据权利要求1或2所述的处理方法，其特征在于，所述步骤(1)中，所述沉淀剂选自NaOH、KOH、Na2CO3和NaHCO3中的一种或多种，优选Na2CO3和/或NaHCO3。
  4. 根据权利要求1-3任一项所述的处理方法，其特征在于，所述步骤(1)中，所述氧化剂选自含有有效氯的化合物和H2O2中的一种或多种，所述含有有效氯的化合物选自NaClO、NaClO3、Cl2和ClO2；所述氧化剂优选NaClO和/或H2O2。
  5. 根据权利要求1-4任一项所述的处理方法，其特征在于，所述步骤(1)中，所述氧化剂为NaClO，所述沉淀剂为Na2CO3和NaOH，所述沉淀剂和氧化剂来源于氯碱工业废水；所述氯碱工业废水中，有效氯含量为2-4wt％，Na2CO3含量为5-10wt％，NaOH含量为0.1-2wt％。
  6. 根据权利要求5所述的处理方法，其特征在于，所述步骤(1) 中，所述氯碱工业废水的用量为2-50kg/t反渗透浓水，优选为2-40kg/t反渗透浓水。
  7. 根据权利要求1-6任一项所述的处理方法，其特征在于，所述步骤(1)中，所述催化氧化的反应时间为0.5-2h，优选为0.5-1.5h。
  8. 根据权利要求1-7任一项所述的处理方法，其特征在于，所述步骤(1)中，所述催化剂包括氧化铝和以氧化物形态负载于所述氧化铝上的镍、铁、锰和铈；以所述氧化铝的重量为基准计，所述催化剂中以下成分的含量为：
    镍5.0-20wt％，优选5.5-12.0wt％；
    铁0.5-5.5wt％，优选1.5-5.0wt％；
    锰0.5-3.5wt％，优选1.0-3.0wt％；
    铈1.5-3.0wt％，优选2.0-2.8wt％。
  9. 根据权利要求8所述的处理方法，其特征在于，所述催化剂包括铈改性氧化铝载体和以氧化物形态负载于所述铈改性氧化铝载体上的镍、铁、锰和铈；所述铈改性氧化铝载体包括氧化铝和以氧化物形态负载于所述氧化铝上的铈；以所述氧化铝的重量为基准计，所述铈改性氧化铝载体中铈的含量为1.0-2.0wt％，优选1.2-1.5wt％。
  10. 根据权利要求9所述的处理方法，其特征在于，以所述氧化铝的重量为基准计，所述催化剂中负载于所述铈改性氧化铝载体上的铈的含量为0.5-2.0wt％，优选0.6-1.5wt％。
  11. 根据权利要求1-10中任一项所述的处理方法，其特征在于，所述步骤(1)中，在向所述反渗透浓水中加入沉淀剂和氧化剂之前，先调节所述反渗透浓水的pH为6-12，优选9-11。
  12. 根据权利要求11所述的处理方法，其特征在于，所述步骤(1)中，用pH调节剂调节所述反渗透浓水的pH，所述pH调节剂为碱性pH调节剂，所述碱性pH调节剂选自NaOH、KOH、Ca(OH)2、Mg(OH)2和氨水中的一种或多种，优选NaOH和/或KOH。
  13. 根据权利要求11或12所述的处理方法，其特征在于，所述步骤(1)中，在向所述清液中加入催化剂之前，先调节所述清液的 pH至6-9，优选7-8。
  14. 根据权利要求13所述的处理方法，其特征在于，所述方法包括以下步骤：
    (1)先调节所述反渗透浓水的pH为9.5-11.5，然后向其中加入沉淀剂和氧化剂进行处理，过滤得清液，调节所述清液的pH至7-8，然后用多介质过滤器过滤，向所得滤液中加入如权利要求9的催化剂进行催化氧化，得到反应液，然后将所述反应液输入吸附装置进行吸附处理，得到一级处理水；
    (2)将步骤(1)得到的一级处理水进行反渗透处理，得到二级反渗透产水和二级反渗透浓水，所述二级反渗透产水用于回收使用；
    (3)向步骤(2)得到的二级反渗透浓水中加入次氯酸钠进行氧化处理，得到氧化反应液，对所述氧化反应液调节pH至6-9，然后向其中加入还原剂以除去过量的次氯酸钠，然后将所得到的液体输入吸附装置进行吸附处理，得到出水，所述出水用于直接排放。
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