CN104402161A - Energy-saving petrochemical engineering wastewater deep treatment system and treatment method thereof - Google Patents
Energy-saving petrochemical engineering wastewater deep treatment system and treatment method thereof Download PDFInfo
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- CN104402161A CN104402161A CN201410713999.4A CN201410713999A CN104402161A CN 104402161 A CN104402161 A CN 104402161A CN 201410713999 A CN201410713999 A CN 201410713999A CN 104402161 A CN104402161 A CN 104402161A
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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
- C02F9/00—Multistage treatment of water, waste water or sewage
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/04—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste liquors, e.g. sulfite liquors
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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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
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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
- C02F1/445—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by forward osmosis
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
- C02F2103/365—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds from petrochemical industry (e.g. refineries)
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- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses an energy-saving petrochemical engineering wastewater deep treatment system and a treatment method thereof. The system comprises a forward osmosis (FO) membrane concentration device and a multi-effect evaporator, wherein the FO membrane concentration device comprises one or more stages of airtight FO membrane exchange boxes, a sucked solution recycling device and a clear water recovering device; the sucked solution recycling device is connected with the stages of airtight FO membrane exchange boxes through electrical valves respectively; the clear water recovering device is connected with the sucked solution recycling device; the stages of airtight FO membrane exchange boxes are connected through liquid discharge electrical valves in sequence and connected with a mother liquid incineration furnace through overrunning electrical valves. The method is characterized in that for high osmotic pressure characteristic of petrochemical engineering wastewater, water resources are recycled while the petrochemical engineering wastewater is efficiently concentrated to generate electrical energy by preparing a sucked solution with relatively good colligative properties and utilizing osmotic pressure difference caused by colligative property difference of the solution; the automatic interlocking control is realized in a running process and the running mode can be adjusted according to different water feeding conditions.
Description
Technical field
The present invention relates to a kind of advanced treatment system for petrochemical wastewater and method thereof, belong to waste water advanced Treatment process field.
Background technology
Petrochemical industry is called for short petrochemical complex, refers to take oil and natural gas as raw material, produces the processing industry of petroleum products and petrochemicals.Petrochemical industry is infrastructural industries, and it is for industrial or agricultural such as agricultural, the energy, traffic, machinery, electronics, weaving, light industry, building, building materials and people's daily life provides supporting and service, occupies very important status in national economy.
Petroleum products, also known as oil product, mainly comprises various oil fuel (gasoline, kerosene, diesel oil etc.) and lubricating oil and liquefied petroleum gas (LPG), oil coke, paraffin, pitch etc.The course of processing of producing these products is often called as refining of petroleum, is called for short oil refining.The further chemical process of stock oil that petrochemicals provide with oil refining process obtains.Producing the first step of petrochemicals is carry out cracking to stock oil gentle (as propane, gasoline, diesel oil etc.), the basic chemical raw materials that to generate with ethene, propylene, divinyl, benzene,toluene,xylene be representative.Second step produces multiple Organic Chemicals (about 200 kinds) and synthetic materials (plastics, synthon, synthetic rubber) with basic chemical raw materials.The production of this two steps product belongs to the scope of petrochemical complex.Organic Chemicals continues the Chemicals that processing can obtain more multi items, does not belong to the scope of petrochemical complex traditionally.In some data, with Sweet natural gas, petroleum naphtha, heavy oil for Material synthesis ammonia, urea, even produce nitric acid and also list petrochemical complex in.
To be the by-product gas and the light oil such as petroleum naphtha produced with oil refining or heavy oil be petrochemical wastewater that raw material carries out thermo-cracking produces the industrial chemicals such as ethene, propylene, butylene, the various organic chemistry product of further Reactive Synthesis, forms the waste water that petrochemical complex is discharged.
Petrochemical industry is China's essential industry, and its turnout is large, and production technique is comparatively complicated, and the waste water therefore produced in production process is many, and because of the different waste water change of production scopes of production technique also very extensive, in the cracking of oil, refining, the waste water discharged in the refinery such as fractionation and synthesis process contains multiple poisonous organic pollutant, as benzopyrene, benzanthrene and other multiring aromatic hydrocarbon substance, have carcinogenic, teratogenesis or mutagenesis, simultaneously also containing benzene, phenol, sulphur compounds, gasoline, the pollutents such as crude oil, such discharge of wastewater is in environment, can to surface water, underground water and soil causes serious pollution, and because the contaminant component in petrochemical wastewater is complicated, the difficult degradation that these organic pollutants have or can not be biodegradable, so its intractability is large.
The efficient process of petrochemical wastewater has been become to the focus of water treatment field research, conventional treatment technology mainly comprises Physical, chemical method and biological process.
The feature such as complicated for pollutant kind in petrochemical wastewater, concentration is high and biodegradability is poor, the general physico-chemical process that adopts carries out pre-treatment, then adopts biochemical process to degrade further.Adopt absorption method, membrane separation process and advanced oxidation processes etc. can carry out the deep purifying of water outlet, realize the reuse of waste water.But treatment effect is undesirable, standard water discharge rate is not high, and main manifestations is water outlet COD, NH
4 +exceeding standard of the index such as-N and colourity.
Chinese patent literature CN102452766A disclosed " petrochemical wastewater treatment process ", CN1079946 disclosed " treatment process of petrochemical wastewater and equipment therefor thereof ", CN1669941 disclosed " a kind of method processing petrochemical wastewater " and CN103641269A disclosed " petrochemical wastewater treatment process ", be all the improvement to ordinary method, treatment effect has much room for improvement.
For this reason, be necessary the characteristic reanalysing petrochemical wastewater, on the basis of biochemical treatment, develop energy-conservation, efficient petrochemical wastewater further treatment technique.
Osmosis be the solution of two kinds of different concns every with semi-permeable membranes (allow solvent molecule pass through, do not allow the film that solute molecule passes through), water molecules or other solvent molecule to enter the phenomenon highly concentrated solution by semi-permeable membranes from the solution of lower concentration.Its condition occurred has two: one to be have semi-permeable membranes, and two is that semi-permeable membranes both sides have substance withdrawl syndrome poor.
Osmosis can be divided into again just permeates (FO), reverse osmosis (RO) and pressure damping infiltration (PRO).
(FO) process of just permeating is for motivating force with the permeable pressure head of semi-permeable membranes both sides, water molecules in solution is transmitted to low water chemistry gesture district (high ion concentration solution) from high water chemistry gesture district (low ion concns solution) by semi-permeable membranes, and solute molecule or ion are by a kind of process of osmosis stopped.
Reverse osmosis (RO) process is a kind of is impellent with pressure difference, isolates the membrane sepn operation of solvent from solution.Because it is contrary with the direction just permeated, therefore claims reverse osmosis.The osmotic pressure difference of different material can be utilized, use the reverse osmosis pressure being greater than osmotic pressure, reach separation, extraction, purifying and concentrated object.
Pressure damping infiltration (PRO) is between just permeating the pilot process with reverse osmosis process, refer to and apply pressure in the opposite direction of permeable pressure head, similar to reverse osmosis process, but water molecules remains and is diffused into high ion concentration side, similar to positive process of osmosis.
The colligative property of dilute solution (comprising petrochemical wastewater) refers to the numerical value of the vapor pressure lowering of solvent in dilute solution, depression of the freezing point, the elevation of boiling point and osmotic pressure, only relevant with the amount of solute in solution, have nothing to do with the person's character of solute, colligative property of solution draws liquid for exploitation special type and provides theoretical foundation, as long as namely configuration is necessarily colligative draw liquid, make its osmotic pressure higher than pending petrochemical wastewater, utilize osmosis, just petrochemical wastewater can be concentrated further.
For this reason, need badly on the basis of biochemical treatment, develop energy-conservation petrochemical wastewater advanced treatment system, osmosis is utilized especially just to permeate the permeable pressure head that (FO) acts on and colligative property of solution difference is brought, realize that petrochemical wastewater is effectively disposed, while recycle water resources, make full use of the pressure reduction acquisition electric energy just permeating (FO) and produce, save energy.
Summary of the invention
The present invention is directed to the deficiency that existing petrochemical wastewater treatment technology exists, according to the characteristic of petrochemical wastewater after biochemical treatment, utilize colligative property of solution, the petrochemical wastewater advanced treatment system that a kind for the treatment of effect is good, energy-conservation is provided.There is provided this system a kind of to the deep treatment method of petrochemical wastewater simultaneously.
Energy-saving petroleum wastewater from chemical industry advanced treatment system of the present invention, by the following technical solutions:
This system, comprise forward osmosis membrane concentrating unit and mother liquor incinerator, forward osmosis membrane concentrating unit comprises the airtight commuting case of FO film, draws liquid recycle device and clean water recovery device, the airtight commuting case of FO film at least arranges one-level, draw liquid recycle device to be connected respectively by electrically operated valve with the airtight commuting case of FO films at different levels, clean water recovery device with draw liquid recycle device and be connected, the airtight commuting case of FO films at different levels is connected by discharge opeing electrically operated valve successively, and is all connected with mother liquor incinerator by surmounting electrically operated valve.Mother liquor incinerator is supporting combustion-supporting fuel (Sweet natural gas, diesel oil or coke-oven gas etc.) burner and exhaust gas cleaner.
The inside of the airtight commuting case of FO film arranges membrane element, and airtight for FO film commuting case inside is divided into mother liquor district and draws liquid zone by membrane element, and the top in mother liquor district is provided with water inlet pipe, this water inlet pipe is provided with into water electrically operated valve; In the airtight commuting case of upper level FO film, the bottom in mother liquor district is connected with the top in mother liquor district in the airtight commuting case of next stage FO film by discharge opeing electrically operated valve, and in every airtight commuting case of one-level FO film, the bottom in mother liquor district is all connected with mother liquor incinerator by surmounting electrically operated valve simultaneously; The top of drawing liquid zone in the airtight commuting case of every one-level FO film is connected with the liquid commuting case that draws drawn in liquid recycle device respectively by drawing liquid transfer lime, respective draw liquid transfer lime is provided with draw liquid outlet electric valve door; The bottom of drawing liquid zone in the airtight commuting case of every one-level FO film is provided with draws liquid compensation electrically operated valve, and with draw drawing between liquid compensation box in liquid recycle device and be connected by drawing liquid offsetting pipe, draw liquid offsetting pipe is connected with and draw liquid compensated pump.
The outer setting drawing liquid zone have connect draw upper and lower, liquid zone draw liquid circulation tube, draw liquid circulation tube is provided with and draw liquid recycle pump.By draw liquid recycle pump will draw liquid drawing upper and lower, liquid zone formed circulation.
Mother liquor district is provided with agitator and temperature control equipment with drawing in liquid zone.
Mother liquor district is provided with COD on-line computing model, draws liquid zone and is provided with ionometer.
Draw liquid recycle device comprise draw liquid commuting case, draw liquid intermediate box, draw liquid multiple-effect evaporator, draw liquid dissolve case, draw liquid compensation box and molten medicine-chest, draw liquid commuting case top and be provided with commuting case electrically operated valve and commuting case electric-powered air release valve, and by commuting case electrically operated valve with draw liquid intermediate box and be connected; The bottom of drawing liquid commuting case is surmounted pipe electrically operated valve by commuting case and is drawn liquid intermediate box and be connected; Draw liquid intermediate box top and be provided with intermediate box electric-powered air release valve, draw liquid intermediate box and draw liquid multiple-effect evaporator and be connected; Draw liquid to dissolve case and draw liquid multiple-effect evaporator and be connected; The bottom of drawing liquid compensation box is connected with the bottom of drawing liquid and dissolve case by compensation box import electrically operated valve; The bottom of molten medicine-chest is connected with the bottom of drawing liquid compensation box by molten medicine outlet electric valve door.
Draw in liquid dissolving case and molten medicine-chest and be provided with agitator and ionometer.
Draw in liquid compensation box and be provided with ionometer.
Clean water device comprises filtered water tank, fresh water pump and clear water pipe, filtered water tank with draw liquid multiple-effect evaporator and be connected, clear water pipe is connected with filtered water tank, and fresh water pump is connected on clear water pipe, and clear water pipe is connected with molten medicine-chest.
Said system, also comprise infiltration energy utilization device, this device comprises airtight rotor casing and turbine generation unit, turbine wheel is provided with in rotor casing, turbine wheel is connected with turbine generation unit, the bottom of rotor casing is provided with rotor casing electric-powered air release valve, rotor casing by rotor casing water inlet electrically operated valve with draw liquid commuting case and be connected, while rotor casing also with draw liquid intermediate box and be connected.
The treatment process of said system, is:
First amount concentration (the ionic state amount of substance in solution and the molecular state amount of substance sum) S of the permeate substance of analytical calculation petrochemical wastewater
1according to required seepage water pressure (△ π, by whether waiting actual demand decision for generating electricity), (in operational process with COD on-line computing model display data approximate conversion), show that the airtight commuting case of required first step FO film draws the ionic concn J of liquid
1, J
1be greater than S
1, and draw the progression n of the airtight commuting case of FO film of needs and the number i of every grade of airtight commuting case of FO film; Then by drawing liquid recycle device preparation ionic concn J
1draw liquid, make to draw liquid and be full of the airtight commuting case of first step FO film; Open petrochemical wastewater water inlet electrically operated valve, petrochemical wastewater flows in the airtight commuting case of first step FO film, with draw liquid and exchange, water molecules in petrochemical wastewater is freely reached and draws liquid, what after dilution, volume increased draw liquid realizes drawing being separated of liquid solute (being generally gas) and water (solvent) by drawing multiple-effect evaporator in liquid recycle device, realize the recovery and reuse of drawing liquid solute, unnecessary water enters clean water device, realizes the recycling of water resources; Petrochemical wastewater is concentrated by the airtight commuting case of FO film step by step, finally cannot reconcentration or enter mother liquor incinerator without the need to the mother liquor of concentrated when more than 600000mg/L (general COD) further as required and carry out burning disposal.
The present invention is directed to the high osmotic pressure characteristic of petrochemical wastewater, by preparation colligative property higher draw liquid, the permeable pressure head utilizing colligative property of solution difference to bring, while making petrochemical wastewater obtain efficient concentration, recycle and reuse water resources, produces electric energy; Meanwhile, operational process realizes automatic interlock and controls, and can, according to different flow condition adjust operation mode, be convenient to implement.There is following characteristics:
1. make full use of colligative property of solution, by preparation colligative property higher draw liquid (as NH
4hCO
3deng), utilize the Thief zone pressure reduction of itself and petrochemical wastewater, while realizing petrochemical wastewater efficient concentration, recyclable great lot of water resources;
2. it is large that the FO film adopted has membrane flux, and the characteristic that concentration polarization phenomenon is few, can ensure the smooth realization of infiltration function;
3. the mother liquor incinerator adopted is general-purpose equipment, and special disposal high concentrated organic waste liquid, utilizes high temperature (850-1100 DEG C) pyrolysis, can organism fully in decomposing wasting liquid and chloride, benzene, phenols hazardous compound, and has following characteristics:
(1) tiny structure design, combustion safety is high, is provided with in stove the function do not got rid of flammable explosive gas before igniting and just can not light a fire, with gas explosion-proof in sequence of control;
(2) level of automation is high, comprehensive online detection and control, flameholding.
(3) adopt atomizing lance, spray imperceptible particle, ensure to gasify in the air in stove, oxygenolysis, can not drip.
(4) tangent line combustion atomization device internal mix formula twin fluid atomization device is adopted, its degree of mixing, atomizing effect combustionvelocity
High, surplus air is low, can save a large amount of fuel.
(5) venturi effect is good, and the burning residence time reaches more than 2 seconds, and burning is without dead angle.
(6) low-NO_x combustion technology, smokeless and odorless, without obnoxious flavour, can burn organic exhaust gas and a small amount of solid simultaneously.
(7) comprehensive rational vent gas treatment refining plant, ensures that environment protection emission is up to standard.
4. the osmotic energy that system produces can be converted into electric energy by the infiltration energy utilization device adopted, thus reduces cost for wastewater treatment;
5. make operational process realize automatic interlock by automation instrument to control, be convenient to according to different flow condition adjust operation mode;
6. modular design, can according to petrochemical wastewater actual concentrations and other implementation conditions, and independent assortment, has stronger handiness.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of the energy-efficient petrochemical wastewater treatment system of the present invention.
In figure: 1, water inlet electrically operated valve, 2, the airtight commuting case of FO film, 3, petrochemical wastewater agitator, 4, draw liquid agitator, 5, film frame, 6, membrane element, 7, petrochemical wastewater COD on-line computing model, 8, draw liquid ionometer, 9, temperature control equipment, 10, draw liquid delivery gauge, 11, draw liquid outlet electric valve door, 12, draw liquid recycle pump, 13, draw liquid commuting case, 14, commuting case tensimeter, 15, commuting case electrically operated valve, 16, airtight rotor casing, 17, turbine wheel, 18, turbine generation unit, 19, draw liquid intermediate box, 20, intermediate box electric-powered air release valve, 21, draw liquid multiple-effect evaporator, 22, intermediate box upflow tube, 23, draw liquid and dissolve case, 24, dissolve box mixer, 25, dissolve case ionometer, 26, compensation box import electrically operated valve, 27, draw liquid compensation box, 28, compensation box ionometer, 29, molten medicine outlet electric valve door, 30, molten medicine-chest, 31, molten medicine agitator, 32, draw liquid ionometer, 33, air-washer, 34, filtered water tank, 35, fresh water pump, 36, the first step surmounts pipe electrically operated valve, and 37, discharge opeing electrically operated valve, 38, the second stage surmounts pipe electrically operated valve, and 39, mother liquor incinerator import electrically operated valve, 40, mother liquor incinerator, 41, draw liquid compensated pump, 42, draw liquid and compensate electrically operated valve, 43, commuting case surmounts pipe electrically operated valve, and 44, water supply pipe, 45, commuting case electric-powered air release valve, 46, rotor casing electric-powered air release valve, 47, rotor casing water inlet electrically operated valve, 48, baffle, 49, combustion-supporting fuel burner, 50, exhaust gas cleaner.
Embodiment
Energy-efficient petrochemical wastewater treatment system of the present invention mainly comprises forward osmosis membrane concentrating unit, mother liquor incinerator 40 and infiltration energy utilization device, and each device is connected successively by pipeline.The concrete structure of each device as shown in Figure 1.
Forward osmosis membrane concentrating unit, comprises the airtight commuting case 2 (being provided with 3 grades in Fig. 1) of at least one-level FO film, draws liquid recycle device and clean water recovery device.
The bosom of the airtight commuting case 2 of single-stage FO film is provided with film frame 5, is provided with membrane element 6 in film frame 5.Airtight for FO film commuting case 2 is divided into mother liquor district, left side (petrochemical wastewater district) and right side to draw liquid zone two portions by film frame 5, and twoth district are complete isolated area, only carry out mass transfer by membrane element 6.The top in mother liquor district is provided with petrochemical wastewater water inlet pipe, this water inlet pipe is provided with into water electrically operated valve 1, petrochemical wastewater agitator 3, petrochemical wastewater COD on-line computing model 7 and temperature control equipment 9 (being arranged on bottom mother liquor district) is provided with in mother liquor district, temperature control equipment 9 can be electric drive, also can be interchanger.Draw in liquid zone to be provided with and draw liquid agitator 4, draw liquid ionometer 8 and well heater (be arranged on and draw bottom liquid zone), the outer setting drawing liquid zone have connect its upper and lower draw liquid circulation tube, draw liquid circulation tube is provided with and draw liquid recycle pump 12, liquid being drawn drawing the formation circulation of upper and lower, liquid zone by drawing liquid recycle pump 12, accelerating mass transfer.
In the airtight commuting case of upper level FO film 2, the bottom in mother liquor district is connected with the top in mother liquor district in the airtight commuting case of next stage FO film by liquid discharge pipe, liquid discharge pipe is provided with discharge opeing electrically operated valve 37, in every airtight commuting case of one-level FO film, the bottom of concentrated liquid zone is all connected with mother liquor incinerator 40 by surmounting pipe simultaneously, surmount and pipe arranges electrically operated valve (surmount pipe electrically operated valve 36 as the first step in Fig. 1 and the second stage surmounts pipe electrically operated valve 38), surmount pipe and be connected with mother liquor incinerator 40 by mother liquor incinerator import electrically operated valve 39.Supporting on mother liquor incinerator 40 have combustion-supporting fuel (Sweet natural gas, diesel oil or coke-oven gas etc.) burner 49 and exhaust gas cleaner 50.The top of drawing liquid zone in the airtight commuting case of every one-level FO film is connected with the airtight liquid commuting case 13 that draws respectively by drawing liquid transfer lime, respective draw liquid transfer lime is provided with draw liquid delivery gauge 10 and draw liquid outlet electric valve door 11.The bottom of drawing liquid zone in the airtight commuting case of every one-level FO film is provided with draws liquid compensation electrically operated valve 42, and be connected by drawing liquid offsetting pipe with drawing between liquid compensation box 27, draw liquid offsetting pipe is connected with and draw liquid compensated pump 41, draw on liquid compensation box 27 and be provided with compensation box ionometer 28.
Draw liquid recycle device to comprise and draw liquid commuting case 13, draw liquid intermediate box 19, draw liquid multiple-effect evaporator 21, draw liquid and dissolve case 23, draw liquid compensation box 27 and molten medicine-chest 30, draw liquid commuting case 13, draw liquid intermediate box 19, draw liquid multiple-effect evaporator 21, draw liquid and dissolve case 23 and to draw liquid compensation box 27 be all airtight.It is airtight for drawing liquid commuting case 13, and its top is provided with commuting case tensimeter 14, commuting case electrically operated valve 15 and commuting case electric-powered air release valve 45, and is connected with the top of drawing liquid intermediate box 19 by commuting case electrically operated valve 15; The bottom of drawing liquid commuting case 13 surmounts pipe electrically operated valve 43 by commuting case and is connected with the bottom of drawing liquid intermediate box 19.Draw liquid intermediate box 19 inside and be provided with baffle 48, its top is provided with intermediate box electric-powered air release valve 20.Draw liquid intermediate box 19 and draw liquid multiple-effect evaporator 21 bottom and be connected, and top is connected with intermediate box upflow tube 22.Draw liquid to dissolve case 23 and draw liquid multiple-effect evaporator 21 and be connected, draw liquid and dissolve in case 23 to be provided with and dissolve box mixer 24 and dissolve case ionometer 25, draw bottom liquid dissolving case 23 and be connected with air-washer 33 (scrubber tower).The bottom of drawing liquid compensation box 27 is connected with the bottom of drawing liquid and dissolve case 23 by compensation box import electrically operated valve 26, draws in liquid compensation box 27 and is provided with compensation box ionometer 28.The bottom of molten medicine-chest 30 is connected with the bottom of drawing liquid compensation box 27 by molten medicine outlet electric valve door 29, and molten medicine-chest 30 is connected with water supply pipe 44, and is provided with molten medicine agitator 31 in it and draws liquid ionometer 32.Multiple-effect evaporator is general-purpose equipment.
Clean water device comprises filtered water tank 34, fresh water pump 35 and clear water pipe, filtered water tank 34 with draw liquid multiple-effect evaporator 21 and be connected, clear water pipe is connected with filtered water tank 34, and fresh water pump 35 is connected on clear water pipe.Clear water pipe is connected with molten medicine-chest 30 by valve, to utilize the clear water drawing liquid multiple-effect evaporator 21 generation.
Infiltration energy utilization device, comprise airtight rotor casing 16 and turbine generation unit 18, be provided with turbine wheel 17 in rotor casing 16, turbine wheel 17 is connected with turbine generation unit 18, and the bottom of rotor casing 16 is provided with rotor casing electric-powered air release valve 46.Rotor casing 16 by rotor casing water inlet electrically operated valve 47 with draw liquid commuting case 13 and be connected, while also with draw liquid intermediate box 19 and be connected.
The operational process of said system, as described below.
Before operation, first determine following several important parameters:
1, the osmotic pressure π (petrochemical wastewater) of the front petrochemical wastewater of process
First carry out detection to petrochemical wastewater before process to analyze, calculate amount concentration (the ionic state amount of substance molecular state amount of substance sum in the solution) (S of permeate substance wherein
1, with molL
-1meter), adopt Fan Tuofu (van ' t Hoff) formulae discovery to draw the osmotic pressure π (petrochemical wastewater) of petrochemical wastewater before process:
π (petrochemical wastewater)=c
brT ≈ S
1rT
Wherein: π (petrochemical wastewater) is the osmotic pressure of petrochemical wastewater before process;
Concerning electrolyte solution, c
bsolute molecule and the total amount of substance of ion that osmotic effect in 1L solution, can be produced, c herein
b≈ S
1, be called the amount concentration of permeate substance;
R is gas law constant;
T is absolute temperature.
In operational process, the amount concentration of the permeate substance in FO films at different levels airtight commuting case mother liquor district (or claiming concentrated liquid zone) is by the approximate conversion of the waste water COD on-line computing model display data that it is arranged;
2, the airtight commuting case of first step FO film draws the ionic concn J of liquid
1
According to required permeable pressure head (△ π by whether determines for the actual demand such as to generate electricity), adopt Fan Tuofu (van ' t Hoff) formula π=c
brT calculates the ionic concn J that the airtight commuting case of required first step FO film draws liquid
1:
J
1≈ c
b=π (drawing liquid)/RT
π (drawing liquid)=π (petrochemical wastewater)+△ π
π (petrochemical wastewater) ≈ S
1rT
Wherein, π (drawing liquid) for drawing the osmotic pressure of liquid, the osmotic pressure that π (petrochemical wastewater) is petrochemical wastewater;
Concerning electrolyte solution, c
bsolute molecule and the total amount of substance of ion that osmotic effect in 1L solution, can be produced, c herein
b≈ J
1, be called the amount concentration of permeate substance;
R is ideal gas constant;
T is absolute temperature.
In operational process, the airtight commuting case of FO films at different levels draws the amount concentration of the permeate substance of liquid zone by the waste water ionometer display data proximate calculation that it is arranged;
For raising the efficiency, generally adopting and drawing liquid close to saturation concentration.
3, the progression n (serial number) of the airtight commuting case of FO film
To draw the ionic concn J of liquid
1for the saturation concentration drawing liquid solute under normal temperature and pressure conditions is example, its osmotic pressure is definite value π (drawing liquid)
saturated;
Due to the effect of agitator and recycle pump, with the airtight commuting case of one-level FO film mother liquor (or claiming concentrated solution) concentration and draw liquid concentration and can think homogeneous;
When system is normally run, along with constantly concentrating of mother liquor (or claiming concentrated solution), the amount concentration of the mother liquor district permeate substance of the airtight commuting case of FO film not at the same level can be more and more higher, and S
n+1> S
n(S
nbe the amount concentration of permeate substance in the mother liquor of n-th grade of airtight commuting case of FO film, n is the progression of the airtight commuting case of FO film), it also can reduce gradually with the permeable pressure head △ π drawing liquid, in theory, works as S
nclose to the saturation concentration of mother liquor solute, close to when drawing liquid ionic concn J1 and equal to draw liquid ionic concn J1, the mother liquor of FO film both sides and draw liquid and there is not permeable pressure head △ π, now the progression of the airtight commuting case of FO film is the greatest measure of n.
The reduction of permeable pressure head △ π can affect membrane flux and osmotic efficiency, the work of generator also can be affected during for generating electricity, for this reason, the practical factor such as pressure needed for membrane flux, osmotic efficiency and generator impeller, comprehensively determines the progression n of the airtight commuting case of FO film usually.
4, the number i (quantity in parallel) of every grade of airtight commuting case of FO film
The number i of every grade of airtight commuting case of FO film is estimated by following formula:
i＝Q/(Q’·S)。
Wherein: Q is wastewater treatment scale (m
3s
-1);
Q ' is FO membrane flux (m
3s
-1m
-2);
S is effective forward osmosis membrane area (m of the airtight commuting case of single FO film
2).
Determine above-mentioned important parameter, mean the configuration of the system of determining.
Open water supply pipe 44, make to add tap water in molten medicine-chest 30, and in molten medicine-chest 30, pouring liquid drawing liquor into, (the amount concentration of permeate substance is J
0, J
0> J
1, market purchasing) or solid draw liquid solute powder (market purchasing), stirred by molten medicine agitator 31, preparation ionic concn is J
1draw liquid, by draw liquid ionometer 32 detect preparation draw liquid ionic concn.Open molten medicine outlet electric valve door 29, make to draw liquid inflow and draw liquid compensation box 27, then the liquid that draws opening the first step successively compensates electrically operated valve 42 and draws liquid compensated pump 41, make to draw liquid and be full of the airtight commuting case 2 of first step FO film, then successively close draw liquid compensated pump 41, the first step draw liquid compensate electrically operated valve 42, molten medicine outlet electric valve door 29 and molten medicine agitator 31, check simultaneously and determine that all the other electrically operated valves are all in closing condition, each vent valve is in opened condition, finally carries out the process preparation work before system cloud gray model.
After above-mentioned job done, open petrochemical wastewater water inlet electrically operated valve 1, petrochemical wastewater flows into the mother liquor district of the airtight commuting case 2 of first step FO film, because the ionic concn (J of liquid zone is drawn in membrane element 6 side
1) be greater than the amount concentration (S of the permeate substance in mother liquor district
1) permeable pressure head (△ π) that formed, water molecules in mother liquor district petrochemical wastewater is freely reached through membrane element 6 and draws liquid zone, be closed structure owing to drawing liquid zone, what after dilution, volume increased draw liquid can enter and airtight draws liquid commuting case 13 by drawing liquid offsetting pipe.Draw after liquid commuting case 13 is full of, close commuting case electric-powered air release valve 45.Draw liquid as utilized to generate electricity, then close commuting case and surmount pipe electrically operated valve 43, open rotor casing water inlet electrically operated valve 47, rare after dilution draws liquid, and (ionic concn is J
1', J
1' < J
1) enter airtight rotor casing 16, promote turbine wheel 17 and do work, export electric energy by turbine generation unit 18, rare after generating draws liquid and enters and draw liquid intermediate box 19.As without the need to generating, then close rotor casing water inlet electrically operated valve 47, open commuting case and surmount pipe electrically operated valve 43, make rare liquid that draws enter and draw liquid intermediate box 19, then enter and draw liquid multiple-effect evaporator 21.By multiple-effect evaporator 21, being separated of liquid solute (being generally gas) and water (solvent) is drawn in realization, solute wherein enters and draws liquid dissolving case 23, open and dissolve box mixer 24, utilize dissolving case ionometer 25 to control strength of solution, realize the recovery and reuse of drawing liquid solute; Unnecessary water enters filtered water tank 34, is delivered to molten medicine-chest 30 or is back to plant area that other is arranged with water by fresh water pump 35, realizes the recycling of water resources.
Petrochemical wastewater after concentrated enters the airtight commuting case of FO film of next stage step by step by discharge opeing electrically operated valve 37, by above-mentioned process flow operation.Every grade of airtight commuting case of FO film utilizes the temperature control equipment 9 bottom it, the temperature of conservative control petrochemical wastewater, the saturation concentration under making its concentration reach this temperature.Finally cannot reconcentration or enter mother liquor incinerator 40 without the need to the mother liquor of concentrated when more than 600000mg/L (general COD) further as required and carry out burning disposal.
Claims (10)
1. an energy-saving petroleum chemical wastewater treatment system, comprise forward osmosis membrane concentrating unit and mother liquor incinerator, it is characterized in that: forward osmosis membrane concentrating unit comprises the airtight commuting case of FO film, draw liquid recycle device and clean water recovery device, the airtight commuting case of FO film at least arranges one-level, draw liquid recycle device to be connected respectively by electrically operated valve with the airtight commuting case of FO films at different levels, clean water recovery device with draw liquid recycle device and be connected, the airtight commuting case of FO films at different levels is connected by discharge opeing electrically operated valve successively, and be all connected with mother liquor incinerator by surmounting electrically operated valve.
2. energy-saving petroleum chemical wastewater treatment system according to claim 1, it is characterized in that: the inside of the airtight commuting case of described FO film arranges membrane element, airtight for FO film commuting case inside is divided into mother liquor district and draws liquid zone by membrane element, the top in mother liquor district is provided with water inlet pipe, this water inlet pipe is provided with into water electrically operated valve; In the airtight commuting case of upper level FO film, the bottom in mother liquor district is connected with the top in mother liquor district in the airtight commuting case of next stage FO film by discharge opeing electrically operated valve, and in every airtight commuting case of one-level FO film, the bottom in mother liquor district is all connected with mother liquor incinerator by surmounting electrically operated valve simultaneously; The top of drawing liquid zone in the airtight commuting case of every one-level FO film is connected with the liquid commuting case that draws drawn in liquid recycle device respectively by drawing liquid transfer lime, respective draw liquid transfer lime is provided with draw liquid outlet electric valve door; The bottom of drawing liquid zone in the airtight commuting case of every one-level FO film is provided with draws liquid compensation electrically operated valve, and with draw drawing between liquid compensation box in liquid recycle device and be connected by drawing liquid offsetting pipe, draw liquid offsetting pipe is connected with and draw liquid compensated pump.
3. energy-saving petroleum chemical wastewater treatment system according to claim 2, is characterized in that: described in draw liquid zone outer setting have connect draw upper and lower, liquid zone draw liquid circulation tube, draw liquid circulation tube is provided with and draw liquid recycle pump.
4. energy-saving petroleum chemical wastewater treatment system according to claim 2, is characterized in that: described mother liquor district is provided with agitator and temperature control equipment with drawing in liquid zone; Mother liquor district is provided with COD on-line computing model, draws liquid zone and is provided with ionometer.
5. energy-saving petroleum chemical wastewater treatment system according to claim 1, it is characterized in that: described in draw liquid recycle device comprise draw liquid commuting case, draw liquid intermediate box, draw liquid multiple-effect evaporator, draw liquid dissolve case, draw liquid compensation box and molten medicine-chest, draw liquid commuting case top and be provided with commuting case electrically operated valve and commuting case electric-powered air release valve, and by commuting case electrically operated valve with draw liquid intermediate box and be connected; The bottom of drawing liquid commuting case is surmounted pipe electrically operated valve by commuting case and is drawn liquid intermediate box and be connected; Draw liquid intermediate box top and be provided with intermediate box electric-powered air release valve, draw liquid intermediate box and draw liquid multiple-effect evaporator and be connected; Draw liquid to dissolve case and draw liquid multiple-effect evaporator and be connected; The bottom of drawing liquid compensation box is connected with the bottom of drawing liquid and dissolve case by compensation box import electrically operated valve; The bottom of molten medicine-chest is connected with the bottom of drawing liquid compensation box by molten medicine outlet electric valve door.
6. energy-saving petroleum chemical wastewater treatment system according to claim 5, is characterized in that: described in draw liquid and dissolve in case and molten medicine-chest and be provided with agitator and ionometer.
7. energy-saving petroleum chemical wastewater treatment system according to claim 5, is characterized in that: described in draw in liquid compensation box and be provided with ionometer.
8. energy-saving petroleum chemical wastewater treatment system according to claim 1, it is characterized in that: described clean water device comprises filtered water tank, fresh water pump and clear water pipe, filtered water tank with draw liquid multiple-effect evaporator and be connected, clear water pipe is connected with filtered water tank, fresh water pump is connected on clear water pipe, and clear water pipe is connected with molten medicine-chest.
9. energy-saving petroleum chemical wastewater treatment system according to claim 1, it is characterized in that: also comprise infiltration energy utilization device, this device comprises airtight rotor casing and turbine generation unit, turbine wheel is provided with in rotor casing, turbine wheel is connected with turbine generation unit, the bottom of rotor casing is provided with rotor casing electric-powered air release valve, rotor casing by rotor casing water inlet electrically operated valve with draw liquid commuting case and be connected, while rotor casing also with draw liquid intermediate box and be connected.
10. a treatment process for energy-saving petroleum chemical wastewater treatment system described in claim 1, is characterized in that:
First the amount concentration S1 of the permeate substance of analytical calculation petrochemical wastewater, show that the airtight commuting case of required first step FO film draws the amount concentration J1 of the permeate substance of liquid according to required seepage water pressure, J1 is greater than S1, and draws the number i of the airtight commuting case of sum of series every grade FO film of the airtight commuting case of FO film of needs; Then by draw liquid recycle device preparation ionic concn J1 draw liquid, make to draw liquid and be full of the airtight commuting case of first step FO film; Open petrochemical wastewater water inlet electrically operated valve, petrochemical wastewater flows in the airtight commuting case of first step FO film, with draw liquid and exchange, water molecules in petrochemical wastewater is freely reached and draws liquid, what after dilution, volume increased draw liquid realizes drawing being separated of liquid solute and water by drawing multiple-effect evaporator in liquid recycle device, realize the recovery and reuse of drawing liquid solute, unnecessary water enters clean water device, realizes the recycling of water resources; Petrochemical wastewater is concentrated by the airtight commuting case of FO film step by step, finally cannot reconcentration or enter mother liquor incinerator without the need to mother liquor concentrated further as required and carry out burning disposal.
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