CN112390437A - Application of industrial wastewater treatment system in industrial wastewater treatment field - Google Patents

Application of industrial wastewater treatment system in industrial wastewater treatment field Download PDF

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Publication number
CN112390437A
CN112390437A CN201910744182.6A CN201910744182A CN112390437A CN 112390437 A CN112390437 A CN 112390437A CN 201910744182 A CN201910744182 A CN 201910744182A CN 112390437 A CN112390437 A CN 112390437A
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reverse osmosis
pressure
water
ultrafiltration
nanofiltration
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张新妙
魏玉梅
栾金义
彭海珠
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
    • C01D5/16—Purification
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • C02F1/048—Purification of waste water by evaporation
    • 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
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
    • 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
    • C02F1/447—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by membrane distillation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/101—Sulfur compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/18—Nature of the water, waste water, sewage or sludge to be treated from the purification of gaseous effluents

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The invention provides an application of an industrial wastewater treatment system in the field of industrial wastewater treatment, in particular to the field of catalytic cracking flue gas desulfurization wastewater treatment, and the industrial wastewater treatment system comprises: an ultrafiltration device; the high-pressure reverse osmosis device is connected with the ultrafiltration device; the roll type reverse osmosis device and the high-pressure nanofiltration device are respectively connected with the high-pressure reverse osmosis device; and the evaporative crystallization device is connected with the high-pressure nanofiltration device. Through the cooperation use of ultrafiltration device, high pressure reverse osmosis unit, formula of book reverse osmosis unit, high pressure nanofiltration device and evaporation crystallization device, fully combined the respective advantage of each device, on the basis of effective processing catalytic cracking flue gas desulfurization waste water, realized the recovery of the water resource in the waste water.

Description

Application of industrial wastewater treatment system in industrial wastewater treatment field
Technical Field
The invention relates to the field of industrial wastewater treatment, in particular to application of an industrial wastewater treatment system in the field of industrial wastewater treatment, especially in the field of catalytic cracking flue gas desulfurization wastewater treatment.
Background
SO as the consumption of fossil fuels continues to increase in modern societyXAnd NOXAnd the amount of the air pollutants such as dust and the like is increased, and the large amount of the substances discharged into the atmosphere can cause serious air pollution. National and local government to SOXAnd NOXAnd the particulate matter emission standard is increasingly strict and the pollution discharge cost is gradually increased, and meanwhile, the emission standard of pollutants in the petrochemical industry (GB31571-2015) requires SO2Less than 100mg/m3，NOXLess than 150mg/m3The particle content is less than 20mg/m3. Under the circumstances, in order to meet strict environmental protection requirements and self development requirements of enterprises, currently, a flue gas desulfurization system is established in catalytic cracking units of almost all petrochemical enterprises.
Domestic petrochemical enterprises widely adopt an EDV wet washing technology developed by Belco corporation, the method can effectively remove oxysulfide in flue gas and simultaneously elute dust in the flue gas, but a large amount of desulfurization wastewater is generated along with the method, and the desulfurization wastewater mainly contains catalyst dust, sulfurous acid, sodium sulfate and other substances. The existing treatment methods mainly comprise three methods: mixing biochemical treatment, diluting, discharging, evaporating and crystallizing. Wherein, the culture difficulty of high-salt biochemical flora is higher, the biochemical treatment effect is influenced, and the quality of effluent fluctuates; for example, in some large petrochemical enterprises, desulfurization wastewater is usually mixed with other wastewater and then treated as general wastewater, so that although the problem of environmental protection is temporarily solved, the salt content of the reuse water of sewage reuse enterprises is gradually increased, and the salt balance is difficult to realize; the evaporation crystallization desalination treatment is adopted, the operation cost is high, the existing pretreatment process is insufficient, catalyst dust, organic matters and the like in the desulfurization wastewater are not completely removed, the recovered salts are difficult to reach the national industrial salt standard, and the recovered salts can only be used as solid waste or dangerous waste for disposal.
The method is an effective method by utilizing a membrane combination process matched with an evaporation technology, and patent 201510275955.2 discloses a desulfurization wastewater zero-discharge process, wherein two-stage softening is adopted, then the desulfurization wastewater is treated by a membrane method combination process of ultrafiltration, nanofiltration and reverse osmosis, and then ion exchange, freeze crystallization and evaporation processes are used for realizing the separation and recovery of salts, but the process has the problems of high operation pressure, high pretreatment requirement, large softening dosage, high energy consumption and complex system and equipment.
Patent CN201710640319.4 and patent CN201010232059.5 all use bipolar membrane electrodialysis method to handle soda flue gas desulfurization waste water, realize the zero release of desulfurization waste water, but this system has the problem that investment is high, the energy consumption is big.
Disclosure of Invention
In view of the problems in the prior art, the present invention provides an industrial wastewater treatment system and an application of the system in the field of industrial wastewater treatment, which fully combines the advantages of an ultrafiltration device, a high-pressure reverse osmosis device, a roll-type reverse osmosis device, a high-pressure nanofiltration device and an evaporative crystallization device, and realizes the recovery of water resources in wastewater on the basis of effectively treating catalytic cracking flue gas desulfurization wastewater.
In one aspect, the present invention provides an industrial wastewater treatment system, comprising: an ultrafiltration device;
the high-pressure reverse osmosis device is connected with the ultrafiltration device;
the roll type reverse osmosis device and the high-pressure nanofiltration device are respectively connected with the high-pressure reverse osmosis device; and
and the evaporative crystallization device is connected with the high-pressure nanofiltration device.
In some preferred embodiments of the present invention, the ultrafiltration apparatus employs an external pressure type hollow fiber membrane module.
In some preferred embodiments of the present invention, the high pressure reverse osmosis device employs a disc tube reverse osmosis membrane module.
In some preferred embodiments of the present invention, the rolled reverse osmosis device employs a rolled reverse osmosis membrane module.
In some preferred embodiments of the present invention, the high-pressure nanofiltration device employs a high-pressure roll-type nanofiltration membrane module.
In some preferred embodiments of the present invention, the evaporative crystallization apparatus is a four-effect evaporative crystallization apparatus.
According to the invention, the disc-tube type reverse osmosis membrane component is in the form that a plurality of disc-type membrane sheets are connected in series on a central tube to form a disc-type membrane column.
According to the invention, the four-effect evaporative crystallization device can adopt waste heat such as factory waste heat and the like as a low-temperature heat source.
In another aspect, the present invention provides an application of the above-mentioned industrial wastewater treatment system in the field of industrial wastewater treatment, especially in the field of catalytic cracking flue gas desulfurization wastewater treatment, the industrial wastewater treatment system includes: an ultrafiltration device;
the high-pressure reverse osmosis device is connected with the ultrafiltration device;
the roll type reverse osmosis device and the high-pressure nanofiltration device are respectively connected with the high-pressure reverse osmosis device; and
and the evaporative crystallization device is connected with the high-pressure nanofiltration device.
In some preferred embodiments of the present invention, the ultrafiltration apparatus employs an external pressure type hollow fiber membrane module.
In some preferred embodiments of the present invention, the high pressure reverse osmosis device employs a disc tube reverse osmosis membrane module.
In some preferred embodiments of the present invention, the rolled reverse osmosis device employs a rolled reverse osmosis membrane module.
In some preferred embodiments of the present invention, the high-pressure nanofiltration device employs a high-pressure roll-type nanofiltration membrane module.
In some preferred embodiments of the present invention, the evaporative crystallization apparatus is a four-effect evaporative crystallization apparatus.
According to the invention, the disc-tube type reverse osmosis membrane component is in the form that a plurality of disc-type membrane sheets are connected in series on a central tube to form a disc-type membrane column.
According to the invention, the four-effect evaporative crystallization device can adopt waste heat such as factory waste heat and the like as a low-temperature heat source.
The inventor of the application finds in research that the industrial wastewater treatment system is particularly suitable for treating catalytic cracking flue gas desulfurization wastewater.
In another aspect, the present invention provides a method for treating catalytic cracking flue gas desulfurization wastewater, comprising:
enabling the catalytic cracking flue gas desulfurization wastewater to enter an ultrafiltration device, thereby carrying out ultrafiltration treatment on the catalytic cracking flue gas desulfurization wastewater to form ultrafiltration product water and an ultrafiltration concentrated phase;
enabling the ultrafiltration produced water to enter a high-pressure reverse osmosis device so as to perform high-pressure reverse osmosis treatment on the ultrafiltration produced water to form high-pressure reverse osmosis produced water and high-pressure reverse osmosis concentrated water;
enabling the high-pressure reverse osmosis produced water to enter a roll type reverse osmosis device, and performing roll type reverse osmosis treatment on the high-pressure reverse osmosis produced water to form roll type reverse osmosis produced water and roll type reverse osmosis concentrated water;
enabling the high-pressure reverse osmosis concentrated water to enter a high-pressure nanofiltration device, and thus carrying out high-pressure nanofiltration treatment on the high-pressure reverse osmosis concentrated water to form high-pressure nanofiltration produced water and high-pressure nanofiltration concentrated water; and
enabling the high-pressure nanofiltration concentrated water to enter an evaporative crystallization device, thereby carrying out evaporative crystallization treatment on the membrane distillation concentrated water to form sodium sulfate solid and evaporative crystallization water;
preferably, the high pressure nanofiltration produced water is recycled to a high pressure reverse osmosis device.
According to the invention, the ultrafiltration concentrated phase is treated by centralized transportation after sludge dehydration and solidification.
According to the invention, the roll-type reverse osmosis concentrated water is merged into a sewage treatment plant for mixing treatment.
In some preferred embodiments of the present invention, the ultrafiltration apparatus employs an external pressure type hollow fiber membrane module.
In some preferred embodiments of the present invention, the high pressure reverse osmosis device employs a disc tube reverse osmosis membrane module.
In some preferred embodiments of the present invention, the rolled reverse osmosis device employs a rolled reverse osmosis membrane module.
In some preferred embodiments of the present invention, the high-pressure nanofiltration device employs a high-pressure roll-type nanofiltration membrane module.
In some preferred embodiments of the present invention, the evaporative crystallization apparatus is a four-effect evaporative crystallization apparatus.
According to the invention, the disc-tube type reverse osmosis membrane component is in the form that a plurality of disc-type membrane sheets are connected in series on a central tube to form a disc-type membrane column.
According to the invention, the four-effect evaporative crystallization device can adopt waste heat such as factory waste heat and the like as a low-temperature heat source.
In some preferred embodiments of the invention, the pH of the catalytic cracking flue gas desulfurization wastewater is 7.5-8.5, the conductivity is 10000 us/cm-15000 mu S/cm, the suspended matter concentration is 100 mg/L-200 mg/L, the COD concentration is 20 mg/L-500 mg/L, the oil content is 0 mg/L-2 mg/L, and Cl is added-The concentration is 30 mg/L-150 mg/L, SO4 2-The concentration is 6000 Mg/L-7000 Mg/L, Mg2+Ca at a concentration of 1mg/L to 5mg/L2+The concentration is 4 mg/L-10 mg/L, Na+The concentration is 3000 mg/L-4000 mg/L, the concentration of the soluble silicon-containing compound is 3 mg/L-8 mg/L, and the total nitrogen concentration is 20 mg/L-50 mg/L.
In some preferred embodiments of the invention, the rolled reverse osmosis produced water and the evaporative crystallization produced water both meet the requirements of conductivity < 1200. mu.S/cm, COD < 60mg/L, Cl-concentration < 200mg/L, and oil content < 0.5 mg/L.
According to the invention, the conductivity is less than 1200 mu S/cm, COD is less than 60mg/L, Cl-concentration is less than 200mg/L, and the oil content is less than 0.5mg/L, which is the requirement of recycling the recycled circulating water. The rolled reverse osmosis produced water and the evaporative crystallization produced water meet the recycling requirement and can be recycled for supplementing circulating water.
In some preferred embodiments of the present invention, the pressure of the ultrafiltration treatment is 0.08MPa to 0.12 MPa.
According to the present invention, on the one hand, when the pressure of ultrafiltration treatment is less than 0.08MPa, the membrane flux is small, the number of required components is increased, and the cost is increased; on the other hand, when the pressure of the ultrafiltration treatment is more than 0.12MPa, membrane damage may be caused. Therefore, in order to obtain higher membrane flux and separation efficiency, the pressure of ultrafiltration treatment is limited to 0.08MPa to 0.12 MPa.
In some preferred embodiments of the present invention, the feed water of the high pressure reverse osmosis device has a pH of 7.5 to 8.5; the operating conditions of the high pressure reverse osmosis device include: the operation pressure is 7.0MPa to 9.0MPa, and the membrane flux is 7L/m2·h～10L/m2H; preferably, the high-pressure reverse osmosis concentrated water TDS is 75000-110000 mg/L.
According to an aspect of the invention, salt separation efficiency is low when the operating pressure is less than 7.0 MPa; on the other hand, when the operating pressure is more than 9.0MPa, membrane damage is easily caused, and the effluent quality is influenced. Therefore, in order to obtain better membrane flux and effluent quality, the invention limits the operating pressure to 7.0MPa to 9.0 MPa.
In some preferred embodiments of the invention, the pH of the inlet water of the roll-type reverse osmosis device is 7.5-8.5; the operation conditions of the roll type reverse osmosis device comprise: the operation pressure is 2.0MPa to 3.0MPa, and the membrane flux is 15L/m2·h～25L/m2·h。
According to the present invention, on the one hand, when the operating pressure is less than 2.0MPa, the membrane flux is low and the running time is long; on the other hand, when the operating pressure is more than 3.0MPa, damage may be caused to the reverse osmosis membrane module, and the operation cost is increased. Therefore, in order to obtain higher membrane flux, prevent the damage to the components and ensure the recovery rate of the system, the invention limits the operating pressure to 2.0 MPa-3.0 MPa.
In the inventionIn some preferred embodiments, the pH of the inlet water of the high-pressure nanofiltration device is 7.5-8.5; the operating conditions of the high-pressure nanofiltration device comprise: the operation pressure is 3.0MPa to 4.0MPa, and the membrane flux is 12L/m2·h～18L/m2·h。
According to the present invention, on the one hand, when the operating pressure is less than 3.0MPa, the separation efficiency is low; on the other hand, when the operating pressure is more than 4.0MPa, the membrane is easy to damage, and the effluent quality is influenced. Therefore, in order to obtain better membrane flux and effluent quality, the invention limits the operating pressure to 2.0MPa to 3.0 MPa.
According to the present invention, the conditions of the evaporative crystallization treatment include: the pressure is 0.4 Mpa-1 Mpa, the feeding temperature is 40 ℃ to 60 ℃, and the evaporation temperature is 50 ℃ to 70 ℃.
According to the invention, the term "COD" refers to the Chemical Oxygen Demand (Chemical Oxygen Demand) and the term "TDS" refers to the Total Dissolved Solids (Total Dissolved Solids).
The industrial wastewater treatment system provided by the invention is used for treating the catalytic cracking flue gas desulfurization wastewater, on the basis of effectively treating the catalytic cracking flue gas desulfurization wastewater, the water resource recovery in the wastewater is realized, the problems of high suspended matter content and high energy consumption of the catalytic cracking flue gas desulfurization wastewater in the treatment process are solved, the quality-divided crystallization treatment of the catalytic cracking flue gas desulfurization wastewater is realized, the system produced water formed after the treatment by the method can be directly recycled for the water supplement of circulating water, the advanced treatment and recycling of the wastewater are realized, and simultaneously, the high-purity sodium sulfate is obtained after the treatment by the method, so that the first-class standard of industrial anhydrous sodium sulfate (GB/T6009-2014) is met, and the industrial anhydrous sodium sulfate can also be recycled as a renewable resource. The water produced by the system refers to water produced by evaporative crystallization and water produced by roll type reverse osmosis.
The inventor of the application discovers through research that the ultrafiltration device can effectively remove catalyst dust and other suspended matters in industrial wastewater, and the ultrafiltration device also has the characteristics of simple equipment, high automation degree, easy operation and maintenance, strong environment adaptability, small occupied area and the like. And the combination of the high-pressure reverse osmosis device and the high-pressure nanofiltration device can fully combine the advantages of the high-pressure reverse osmosis device and the high-pressure nanofiltration device, reduce the operation cost and realize the salt-type mass-separation crystallization in the wastewater. The evaporative crystallization device can effectively utilize a low-temperature heat source, and the operation cost is reduced. The ultrafiltration device, the high-pressure reverse osmosis device, the roll type reverse osmosis device, the high-pressure nanofiltration device and the evaporative crystallization device are matched for use, so that the problem of difficulty in treating catalytic cracking flue gas desulfurization wastewater of petrochemical enterprises is solved, and resource utilization of water resources and salts is effectively realized.
Drawings
FIG. 1 is a process flow diagram of the method for treating catalytic cracking flue gas desulfurization wastewater of the present invention.
Detailed Description
The present invention will be described in detail below with reference to examples, but the scope of the present invention is not limited to the following description.
In the following examples and comparative examples,
the model of the external pressure type hollow fiber membrane component used in the ultrafiltration device is SFP-2880;
the model of a disc-tube type reverse osmosis membrane component used in the high-pressure reverse osmosis device is DTG W02187-1;
the model of the roll type reverse osmosis membrane module used in the roll type reverse osmosis device is BW30 FR;
the model of a high-pressure roll type nanofiltration membrane component used in the high-pressure nanofiltration device is PRN 10-50;
the model of the four-effect evaporation crystallization device is a forced circulation four-effect evaporator.
The reverse osmosis unit used in comparative example 1 was a roll-to-roll reverse osmosis unit, model BW30 FR.
Example 1
In this embodiment, the main water quality characteristics of the treated catalytic cracking flue gas desulfurization wastewater are as follows: pH is 7.8, conductivity of inlet water is 13000 mu S/cm, suspended matter is 120mg/L, COD is 50mg/L, oil content is 0.9mg/L, Cl-Concentration 50mg/L, SO4 2-Concentration 6200Mg/L, Mg2+Concentration 1.8mg/L, Ca2+Concentration 6mg/L, Na+The concentration is 3400mg/L, the concentration of dissolved silicon is 5.5mg/L, and the total nitrogen is 30 mg/L.
In this embodiment, the processing system used is:
an ultrafiltration device adopting an external pressure type hollow fiber membrane component;
the high-pressure reverse osmosis device is connected with the ultrafiltration device and adopts a disc tube type reverse osmosis membrane component;
a roll type reverse osmosis device adopting a roll type reverse osmosis membrane component and a pressure nanofiltration device adopting a high-pressure roll type nanofiltration membrane component which are respectively connected with the high-pressure reverse osmosis; and
and the four-effect evaporation crystallization device is connected with the high-pressure nanofiltration device.
The treatment system is used for treating the catalytic cracking flue gas desulfurization wastewater, and the treatment steps are as follows:
the method comprises the following steps of enabling catalytic cracking flue gas desulfurization wastewater to enter an ultrafiltration device, and carrying out ultrafiltration treatment on the catalytic cracking flue gas desulfurization wastewater under the pressure of 0.09MPa, so as to remove solid suspended matters and macromolecular substances in the wastewater, and finally forming ultrafiltration product water and an ultrafiltration concentrated phase, wherein the turbidity of the ultrafiltration product water is less than 0.1NTU, and the ultrafiltration concentrated phase is subjected to centralized transportation treatment after sludge dehydration and solidification;
the ultrafiltration water (pH 7.5) is fed into a high-pressure reverse osmosis device at 7.5MPa and 7.0L/m2·h～8.0L/m2H, performing high-pressure reverse osmosis treatment on the ultrafiltration produced water under the membrane flux to form high-pressure reverse osmosis produced water and high-pressure reverse osmosis concentrated water, wherein the TDS of the high-pressure reverse osmosis concentrated water is 75000 mg/L;
making high-pressure reverse osmosis produced water (pH 7.5) enter into roll type reverse osmosis device, under the pressure of 2.0MPa and 15.0L/m2·h～20.0L/m2Performing roll type reverse osmosis treatment on the high-pressure reverse osmosis produced water under the membrane flux of h to form roll type reverse osmosis produced water and roll type reverse osmosis concentrated water, wherein the roll type reverse osmosis produced water meets the water replenishing and recycling requirements of recycled circulating water, and in addition, the roll type reverse osmosis concentrated water is merged into a sewage treatment plant for mixing treatment;
making high pressure reverse osmosis concentrated water (pH 7.5) enter into high pressure nanofiltration device at 3.0MPa and 12.0L/m2H, performing high-pressure nanofiltration treatment on the high-pressure reverse osmosis concentrated water under the membrane flux to form high-pressure nanofiltration produced water and high-pressure nanofiltration concentrated water, wherein the conductivity of the high-pressure nanofiltration produced water is 500-800 muS/cm,the conductivity of the high-pressure nanofiltration concentrated water is 25 mS/cm-30 mS/cm, and the high-pressure nanofiltration produced water is circulated to the water inlet of the roll type reverse osmosis device; and
enabling high-pressure nanofiltration concentrated water to enter a four-effect evaporation and crystallization device, and carrying out evaporation and crystallization treatment on the membrane distillation concentrated water to form sodium sulfate solid and evaporation and crystallization produced water, wherein the sodium sulfate meets first-class standards of industrial anhydrous sodium sulfate (GB/T6009-2014), and the evaporation and crystallization produced water meets the recycling requirement of recycled circulating water replenishing water;
and (4) using the rolled reverse osmosis produced water and the evaporative crystallization produced water for supplementing circulating water.
Example 2
In this embodiment, the main water quality characteristics of the treated catalytic cracking flue gas desulfurization wastewater are as follows: pH of 8.0, inlet water conductivity of 14000 mu S/cm, suspended matter of 170mg/L, oil content of 1.2mg/L and Cl-Concentration 80mg/L, SO4 2-The concentration is 6700Mg/L, Mg2+Concentration 4mg/L, Ca2+The concentration is 7.5mg/L, Na+The concentration is 3600mg/L, the concentration of dissolved silicon is 6mg/L, and the total nitrogen is 30 mg/L.
In this embodiment, the same processing system as that of embodiment 1 is used.
The treatment system is used for treating the catalytic cracking flue gas desulfurization wastewater, and the treatment steps are as follows:
the method comprises the following steps of enabling catalytic cracking flue gas desulfurization wastewater to enter an ultrafiltration device, and carrying out ultrafiltration treatment on the catalytic cracking flue gas desulfurization wastewater under the pressure of 0.1MPa, so as to remove solid suspended matters and macromolecular substances in the wastewater, and finally forming ultrafiltration product water and an ultrafiltration concentrated phase, wherein the turbidity of the ultrafiltration product water is less than 0.1NTU, and the ultrafiltration concentrated phase is subjected to centralized transportation treatment after sludge dehydration and solidification;
the ultrafiltration water (pH 8.0) is fed into a high-pressure reverse osmosis device at 8.0MPa and 8.0L/m2·h～10.0L/m2H, performing high-pressure reverse osmosis treatment on the ultrafiltration produced water under the membrane flux to form high-pressure reverse osmosis produced water and high-pressure reverse osmosis concentrated water, wherein the TDS of the high-pressure reverse osmosis concentrated water is 90000 mg/L;
the high-pressure reverse osmosis produced water (pH is 8.0) enters a roll type reverse osmosis device and is subjected to 2.5MPa pressure、18.0L/m2·h～22.0L/m2Performing roll type reverse osmosis treatment on the high-pressure reverse osmosis produced water under the membrane flux of h to form roll type reverse osmosis produced water and roll type reverse osmosis concentrated water, wherein the roll type reverse osmosis produced water meets the water replenishing and recycling requirements of recycled circulating water, and in addition, the roll type reverse osmosis concentrated water is merged into a sewage treatment plant for mixing treatment;
making high pressure reverse osmosis concentrated water (pH 8.0) enter into high pressure nanofiltration device under 3.5MPa and 15.0L/m2H, performing high-pressure nanofiltration treatment on the high-pressure reverse osmosis concentrated water under the membrane flux to form high-pressure nanofiltration produced water and high-pressure nanofiltration concentrated water, wherein the conductivity of the high-pressure nanofiltration produced water is 700-1000 mu S/cm, the conductivity of the high-pressure nanofiltration concentrated water is 25-30 mS/cm, and the high-pressure nanofiltration produced water is circulated to a water inlet of the roll type reverse osmosis device; and
enabling high-pressure nanofiltration concentrated water to enter a four-effect evaporation and crystallization device, and carrying out evaporation and crystallization treatment on the membrane distillation concentrated water to form sodium sulfate solid and evaporation and crystallization produced water, wherein the sodium sulfate meets first-class standards of industrial anhydrous sodium sulfate (GB/T6009-2014), and the evaporation and crystallization produced water meets the recycling requirement of recycled circulating water replenishing water;
and (4) using the rolled reverse osmosis produced water and the evaporative crystallization produced water for supplementing circulating water.
Example 3
In this embodiment, the main water quality characteristics of the treated catalytic cracking flue gas desulfurization wastewater are as follows: pH of 8.5, inlet water conductivity of 14500 μ S/cm, suspended matter of 190mg/L, COD of 50mg/L, oil content of 2.0mg/L, and Cl-Concentration 80mg/L, SO4 2-At a concentration of 7000Mg/L, Mg2+Concentration 5mg/L, Ca2+Concentration 10mg/L, Na+The concentration is 4000mg/L, the concentration of dissolved silicon is 8mg/L, and the total nitrogen is 30 mg/L.
In this embodiment, the same processing system as that of embodiment 1 is used.
The treatment system is used for treating the catalytic cracking flue gas desulfurization wastewater, and the treatment steps are as follows:
the catalytic cracking flue gas desulfurization wastewater enters an ultrafiltration device, and is subjected to ultrafiltration treatment under the pressure of 0.12MPa, so that solid suspended matters and macromolecular substances in the wastewater are removed, and ultrafiltration product water and an ultrafiltration concentrated phase are finally formed, wherein the turbidity of the ultrafiltration product water is less than 0.1NTU, and the ultrafiltration concentrated phase is subjected to centralized transportation treatment after sludge dehydration and solidification;
the ultrafiltration water (pH 8.5) is fed into a high-pressure reverse osmosis device at 9.0MPa and 9.0L/m2·h～10.0L/m2H, performing high-pressure reverse osmosis treatment on the ultrafiltration produced water under the membrane flux to form high-pressure reverse osmosis produced water and high-pressure reverse osmosis concentrated water, wherein the TDS of the high-pressure reverse osmosis concentrated water is 110000 mg/L;
making high-pressure reverse osmosis water (pH 8.5) enter into roll type reverse osmosis device, and making the water flow into the roll type reverse osmosis device at a pressure of 3.0MPa and a flow rate of 20.0L/m2·h～25.0L/m2Performing roll type reverse osmosis treatment on the high-pressure reverse osmosis produced water under the membrane flux of h to form roll type reverse osmosis produced water and roll type reverse osmosis concentrated water, wherein the roll type reverse osmosis produced water meets the water replenishing and recycling requirements of recycled circulating water, and in addition, the roll type reverse osmosis concentrated water is merged into a sewage treatment plant for mixing treatment;
making high pressure reverse osmosis concentrated water (pH 8.5) enter into high pressure nanofiltration device under 4.0MPa and 16.0L/m2·h～18L/m2H, performing high-pressure nanofiltration treatment on the high-pressure reverse osmosis concentrated water under the membrane flux to form high-pressure nanofiltration produced water and high-pressure nanofiltration concentrated water, wherein the conductivity of the high-pressure nanofiltration produced water is 900-1200 mu S/cm, the conductivity of the high-pressure nanofiltration concentrated water is 25-30 mS/cm, and the high-pressure nanofiltration produced water is circulated to a water inlet of the roll type reverse osmosis device; and
enabling high-pressure nanofiltration concentrated water to enter a four-effect evaporation and crystallization device, and carrying out evaporation and crystallization treatment on the membrane distillation concentrated water to form sodium sulfate solid and evaporation and crystallization produced water, wherein the sodium sulfate meets first-class standards of industrial anhydrous sodium sulfate (GB/T6009-2014), and the evaporation and crystallization produced water meets the recycling requirement of recycled circulating water replenishing water;
and (4) using the rolled reverse osmosis produced water and the evaporative crystallization produced water for supplementing circulating water.
Comparative example 1
The water quality characteristics of the catalytic cracking flue gas desulfurization wastewater treated in the comparative example are the same as those of the example 1, and the comparative example 1 is different from the example 1 in that the treatment technology of ultrafiltration, reverse osmosis and MVR evaporative crystallization is adopted, wherein the ultrafiltration operation conditions are the same as those of the example 1;
the water produced by ultrafiltration enters a reverse osmosis device, the reverse osmosis operating pressure is 3MPa, and the membrane flux is 15L/m2·h～22L/m2H, forming reverse osmosis produced water and reverse osmosis concentrated water, wherein the reverse osmosis produced water meets the water replenishing and recycling requirements of recycled circulating water;
and (3) feeding the reverse osmosis concentrated water into an MVR evaporation crystallizer, preheating the feeding at 60 ℃, and evaporating at 70 ℃ in a forced circulation crystallizer at a flow rate of 3m/s to form sodium chloride and second evaporation crystallization produced water which can be used for supplementing water by circulating water.
The mixed salt of sodium chloride and sodium sulfate is obtained in the process flow, so that the salt can not be recycled.
Comparative example 2
The catalytic cracking flue gas desulfurization wastewater treated in the comparative example and the treatment system adopted in the comparative example are the same as those in example 1, except that the ultrafiltration treatment of the catalytic cracking flue gas desulfurization wastewater at a pressure of 0.06MPa is adopted instead of the ultrafiltration treatment of the catalytic cracking flue gas desulfurization wastewater at a pressure of 0.08MPa in example 1, and as a result, the membrane flux is reduced, the separation time is increased, and the effluent quality is reduced.
Comparative example 3
The catalytic cracking flue gas desulfurization wastewater treated in the comparative example and the treatment system adopted in the comparative example are the same as those in example 1, but the difference is that the catalytic cracking flue gas desulfurization wastewater is ultrafiltered under the pressure of 0.15MPa instead of the catalytic cracking flue gas desulfurization wastewater is ultrafiltered under the pressure of 0.08MPa in example 1, and as a result, the membrane is easily damaged, the requirement on equipment is increased, and the operation cost is increased.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.

Claims (10)

1. The application of an industrial wastewater treatment system in the field of industrial wastewater treatment, in particular in the field of catalytic cracking flue gas desulfurization wastewater treatment, comprises the following steps:
an ultrafiltration device;
the high-pressure reverse osmosis device is connected with the ultrafiltration device;
the roll type reverse osmosis device and the high-pressure nanofiltration device are respectively connected with the high-pressure reverse osmosis device; and
the evaporative crystallization device is connected with the high-pressure nanofiltration device;
preferably, the ultrafiltration device adopts an external pressure type hollow fiber membrane component; and/or the high-pressure reverse osmosis device adopts a disc tube type reverse osmosis membrane component; and/or the roll-type reverse osmosis device adopts a roll-type reverse osmosis membrane component; and/or the high-pressure nanofiltration device adopts a high-pressure roll-type nanofiltration membrane component; and/or the evaporative crystallization device is a four-effect evaporative crystallization device.
2. An industrial wastewater treatment system comprising:
an ultrafiltration device;
the high-pressure reverse osmosis device is connected with the ultrafiltration device;
the roll type reverse osmosis device and the high-pressure nanofiltration device are respectively connected with the high-pressure reverse osmosis device; and
and the evaporative crystallization device is connected with the high-pressure nanofiltration device.
3. The industrial wastewater treatment system according to claim 2, wherein the ultrafiltration device employs an external pressure type hollow fiber membrane module; and/or the high-pressure reverse osmosis device adopts a disc tube type reverse osmosis membrane component; and/or the roll-type reverse osmosis device adopts a roll-type reverse osmosis membrane component; and/or the high-pressure nanofiltration device adopts a high-pressure roll-type nanofiltration membrane component; and/or the evaporative crystallization device is a four-effect evaporative crystallization device.
4. A method for treating catalytic cracking flue gas desulfurization wastewater comprises the following steps:
enabling the catalytic cracking flue gas desulfurization wastewater to enter an ultrafiltration device, thereby carrying out ultrafiltration treatment on the catalytic cracking flue gas desulfurization wastewater to form ultrafiltration product water and an ultrafiltration concentrated phase;
enabling the ultrafiltration produced water to enter a high-pressure reverse osmosis device so as to perform high-pressure reverse osmosis treatment on the ultrafiltration produced water to form high-pressure reverse osmosis produced water and high-pressure reverse osmosis concentrated water;
enabling the high-pressure reverse osmosis produced water to enter a roll type reverse osmosis device, and performing roll type reverse osmosis treatment on the high-pressure reverse osmosis produced water to form roll type reverse osmosis produced water and roll type reverse osmosis concentrated water;
enabling the high-pressure reverse osmosis concentrated water to enter a high-pressure nanofiltration device, and thus carrying out high-pressure nanofiltration treatment on the high-pressure reverse osmosis concentrated water to form high-pressure nanofiltration produced water and high-pressure nanofiltration concentrated water; and
enabling the high-pressure nanofiltration concentrated water to enter an evaporative crystallization device, thereby carrying out evaporative crystallization treatment on the membrane distillation concentrated water to form sodium sulfate solid and evaporative crystallization water;
preferably, the high pressure nanofiltration produced water is recycled to a high pressure reverse osmosis device;
further preferably, the ultrafiltration device adopts an external pressure type hollow fiber membrane component; and/or the high-pressure reverse osmosis device adopts a disc tube type reverse osmosis membrane component; and/or the roll-type reverse osmosis device adopts a roll-type reverse osmosis membrane component; and/or the high-pressure nanofiltration device adopts a high-pressure roll-type nanofiltration membrane component; and/or the evaporative crystallization device is a four-effect evaporative crystallization device.
5. The process of claim 4, characterized in thatThe pH value of the catalytic cracking flue gas desulfurization wastewater is 7.5-8.5, the conductivity is 10000 muS/cm-15000 muS/cm, the concentration of suspended matters is 100 mg/L-200 mg/L, the concentration of COD is 20 mg/L-500 mg/L, the content of oil is 0 mg/L-2 mg/L, and Cl is added-The concentration is 30 mg/L-150 mg/L, SO4 2-The concentration is 6000 Mg/L-7000 Mg/L, Mg2+Ca at a concentration of 1mg/L to 5mg/L2+The concentration is 4 mg/L-10 mg/L, Na+The concentration is 3000 mg/L-4000 mg/L, the concentration of the soluble silicon-containing compound is 3 mg/L-8 mg/L, and the total nitrogen concentration is 20 mg/L-50 mg/L.
6. The treatment method according to claim 4 or 5, wherein the rolled reverse osmosis produced water and the evaporative crystallization produced water both meet the requirements of conductivity < 1200 μ S/cm, COD < 60mg/L, Cl-The concentration is less than 200mg/L, and the oil content is less than 0.5 mg/L.
7. The treatment process according to any one of claims 4 to 6, wherein the pressure of the ultrafiltration treatment is between 0.08MPa and 0.12 MPa.
8. The treatment method according to any one of claims 4 to 7, wherein the pH of the feed water of the high-pressure reverse osmosis device is 7.5 to 8.5; the operating conditions of the high pressure reverse osmosis device include: the operation pressure is 7.0MPa to 9.0MPa, and the membrane flux is 7L/m2·h～10L/m2H; preferably, the high-pressure reverse osmosis concentrated water TDS is 75000-110000 mg/L.
9. The treatment method according to any one of claims 4 to 8, wherein the pH of the inlet water of the roll-up reverse osmosis device is 7.5-8.5; the operation conditions of the roll type reverse osmosis device comprise: the operation pressure is 2.0MPa to 3.0MPa, and the membrane flux is 15L/m2·h～25L/m2·h。
10. The treatment method according to any one of claims 4 to 9, wherein the pH of the feed water of the high-pressure nanofiltration device is 7.5 to 8.5; the high-pressure nanofiltration deviceThe operating conditions include: the operation pressure is 3.0MPa to 4.0MPa, and the membrane flux is 12L/m2·h～18L/m2·h。
CN201910744182.6A 2019-08-13 2019-08-13 Application of industrial wastewater treatment system in industrial wastewater treatment field Pending CN112390437A (en)

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