Fuel-free incineration zero-emission system and process for high-salt bromine condensed ring organic sewage

Abstract

The application provides a high-salt bromine condensed ring organic matter sewage fuel-free incineration zero-emission system and process, which comprises, in sequence, a raw material tank, a first multi-effect evaporation system, an incinerator, a furnace salt dissolving device, a furnace salt filtering device, a second multi-effect evaporation system, a first centrifugal separation device, a sodium bromide evaporator and a second centrifugal separation device, wherein the evaporation water of the first multi-effect evaporation system, the second multi-effect evaporation system and the sodium bromide evaporator is treated by a reverse osmosis membrane recovery system to obtain recycled water; the emission system can effectively treat PTA oxidation residue sewage of high-salt bromine condensed ring organic matter, wherein the treated evaporation water is recycled as circulating water, and a mixture of sodium carbonate and cobalt carbonate, a mixture of sodium bromide and sodium carbonate are recovered, in addition, the heat generated by the fuel-free incineration is used to produce high-pressure steam for PTA device, zero-emission of sewage is realized, the influence on the environment is reduced, and economic benefits are generated.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of PTA oxidation residue sewage treatment, in particular to a high-salt bromine condensed ring organic sewage fuel-free incineration zero-emission system and process. BACKGROUND

[0002] Purified terephthalic acid (PTA) is an important polyester production raw material, mainly using xylene air catalytic oxidation method. First, the crude terephthalic acid produced by PX oxidation is dissolved in water at 250-300 DEG C, and through palladium-carbon catalytic hydrogenation, multi-stage crystallization mother liquor separation and other processes, purified terephthalic acid is obtained. This brings great difficulty to the comprehensive utilization of PTA oxidation residue sewage. Initially, PTA oxidation residue sewage adopts incineration method, which is qualified for emission, but the device is unstable and causes resource waste. Later, it is sent to an anaerobic reactor for treatment to produce biogas, etc., but due to the presence of bromide and inorganic salt in these residues, the anaerobic impact is large. Extraction, filtration and distillation technology are used to obtain organic substances such as isophthalic acid, phthalic acid and benzoic acid, which can be sold. However, due to the improvement of environmental protection requirements, the national standards for these products have also been improved, and now these organic substances are also difficult to sell. Therefore, how to treat PTA oxidation residue sewage is very urgent.

[0003] In view of this, the present application is proposed. SUMMARY

[0004] The purpose of the present application is to provide a high-salt bromine condensed ring organic sewage fuel-free incineration zero-emission system and process. The emission system can effectively treat PTA oxidation residue sewage with high-salt bromine condensed ring organic matter through ingenious process design. The treated evaporation water is recycled as circulating water, and the sodium carbonate and cobalt carbonate mixture, sodium bromide and sodium carbonate mixture are recovered. In addition, the heat generated by fuel-free incineration is used to produce high-pressure steam for PTA device, achieving zero emission of sewage, reducing the impact on the environment and generating economic benefits.

[0005] In order to achieve the above purpose, the present application provides the following technical scheme:

[0006] The present application provides a high-salt bromine condensed ring organic sewage fuel-free incineration zero-emission system, comprising a raw material tank, a first multi-effect evaporation system, an incinerator, a furnace salt dissolving device, a furnace salt filtering device, a second multi-effect evaporation system, a first centrifugal separation device, a sodium bromide evaporator and a second centrifugal separation device connected in sequence, wherein

[0007] The raw material tank is used for receiving high-salt bromine condensed ring organic sewage;

[0008] The first multi-effect evaporation system is used for multi-effect evaporation of the sewage from the raw material tank to concentrate the sewage;

[0009] a furnace for incinerating the concentrated liquid from the first multi-effect evaporation system to obtain a furnace slag containing salt and flue gas, respectively;

[0010] a furnace salt dissolving device for dissolving the furnace slag from the furnace to obtain a furnace slag feed liquid;

[0011] a furnace salt filtering device for filtering the furnace slag feed liquid from the furnace salt dissolving device to remove undissolved waste slag;

[0012] a second multi-effect evaporation system for evaporating the filtrate from the furnace salt filtering device;

[0013] a first centrifugal separation device for solid-liquid separation of the concentrated liquid from the second multi-effect evaporation system to obtain a mixture of cobalt carbonate and sodium carbonate and a first centrifugal mother liquor;

[0014] a sodium bromide evaporator for further evaporating the first centrifugal mother liquor;

[0015] a second centrifugal separation device for solid-liquid separation of the concentrated liquid from the sodium bromide evaporator to obtain a mixture of sodium bromide and sodium carbonate and a second centrifugal mother liquor;

[0016] and the first multi-effect evaporation system, the second multi-effect evaporation system and the sodium bromide evaporator are connected with a reverse osmosis membrane recovery system, which performs reverse osmosis treatment on the evaporated water from the first multi-effect evaporation system, the second multi-effect evaporation system and the sodium bromide evaporator to obtain recycled water;

[0017] The furnace is further provided with a flue gas outlet connected with a first inlet of a steam generator, and the steam generator is further provided with a second inlet for feeding steam condensate, and the steam generator uses the heat of flue gas to heat the fed steam condensate to obtain high-pressure steam.

[0018] Further, a tail gas treatment unit is further included, which is connected with the flue gas outlet of the steam generator and used for purifying the flue gas discharged from the steam generator to reach the emission standard;

[0019] Preferably, the tail gas treatment unit includes dust removal equipment, denitration equipment, acid removal equipment and activated carbon adsorption device connected in sequence.

[0020] Further, the first multi-effect evaporation system includes a one-effect falling film evaporator and a two-effect forced evaporator connected in sequence;

[0021] And / or, the furnace salt filtering device is a flat sheet membrane filter;

[0022] And / or, the concentrated water outlet of the reverse osmosis membrane recovery system is connected with the first multi-effect evaporation system, so that the concentrated water discharged by the reverse osmosis membrane recovery system is returned to the first multi-effect evaporation system for evaporation and concentration;

[0023] And / or, the centrifugal mother liquor outlet of the second centrifugal separation device is connected with the sodium bromide evaporator, so that the second centrifugal mother liquor from the second centrifugal separation device is transported to the sodium bromide evaporator for re-evaporation;

[0024] And / or, the raw material tank is connected with the lye tank, so that the lye in the lye tank is transported to the raw material tank and the sewage in the raw material tank is neutralized.

[0025] In addition, the application also provides a fuel-free incineration zero-emission process for high-salt bromine condensed ring organic sewage, which comprises the following steps:

[0026] (1) Alkali neutralization: the high-salt bromine condensed ring organic sewage and the sodium hydroxide solution are mixed in a mass ratio of 8-10:1 for neutralization reaction, iron and nickel ions are removed by precipitation, and a residue mother liquor containing sodium bromide is obtained;

[0027] (2) First multi-effect evaporation: the residue mother liquor containing sodium bromide is evaporated to obtain concentrated residue mother liquor, and the evaporated water is sent to the reverse osmosis membrane recovery system for treatment to obtain recycled water;

[0028] (3) Incineration: the concentrated residue mother liquor is sent to an incinerator for incineration to obtain slag containing sodium carbonate, cobalt carbonate and sodium bromide; the flue gas generated by incineration enters a steam generator to heat the steam condensate into high-pressure steam as heat energy;

[0029] (4) Slag dissolution preparation: the slag is dissolved in steam condensate or water to obtain a slag feed liquid;

[0030] (5) Slag feed liquid filtration: the slag feed liquid is filtered to remove undissolved slag, and the filtrate is heated to 90-100 DEG C;

[0031] (6) Second multi-effect evaporation: the heated filtrate is evaporated to obtain concentrated liquid containing crystalline cobalt carbonate and sodium carbonate; at the same time, the evaporated water is sent to the reverse osmosis membrane recovery system for treatment to obtain recycled water;

[0032] (7) First centrifugation: the concentrated liquid is centrifuged to obtain a first centrifugal mother liquor and a mixture of sodium carbonate and cobalt carbonate;

[0033] (8) Sodium bromide and sodium carbonate evaporation: the first centrifugal mother liquor is sent to a sodium bromide evaporator for evaporation to obtain a mixed concentrated liquid of sodium bromide and sodium carbonate, and at the same time, the evaporated water is sent to the reverse osmosis membrane recovery system for treatment to obtain recycled water;

[0034] (9) Secondary centrifugation: the mixed concentrated solution of sodium bromide and sodium carbonate is centrifuged to obtain a mixture of sodium bromide and sodium carbonate.

[0035] Further, the high-salt bromine dense ring organic sewage fuel-free incineration zero-emission process is realized by the high-salt bromine dense ring organic sewage fuel-free incineration zero-emission system.

[0036] Further, in the alkali neutralization process of step (1),

[0037] The mass concentration of the sodium hydroxide solution is 3%; and / or the feed flow rate of the sewage is 40,000-50,000 kg / h.

[0038] Further, in the primary multi-effect evaporation process of step (2),

[0039] The heating evaporation temperature is 77-138℃;

[0040] And / or the heating pressure is 20-300 KPa;

[0041] And / or the feed flow rate is 40,000-50,000 kg / h;

[0042] Preferably, the primary multi-effect evaporation process includes first falling film evaporation and then forced evaporation.

[0043] Further, in the incineration process of step (3),

[0044] The feed concentration of the incinerator is 45-70%;

[0045] And / or the feed temperature is 90-100℃;

[0046] And / or the incinerator temperature is 900-1200℃;

[0047] And / or the air and residue mother liquor ratio in the incinerator is 9:1, and the residence time is 2-3 seconds;

[0048] And / or the combustion air pressure in the incinerator is 0.6-0.7 MPa, and the combustion air temperature is 90-100℃; the atomizing air pressure is 0.6-0.8 MPa, and the atomizing air temperature is 90-100℃;

[0049] And / or the relative pressure of the incinerator hearth is -20-50 Pa.

[0050] Further, in the secondary multi-effect evaporation process of step (6), the heating evaporation temperature is 101-146℃;

[0051] And / or the heating pressure is 28-192 KPa;

[0052] And / or, the feed flow rate is 9036-10200 kg / h;

[0053] And / or, the solid content of the concentrated liquid after secondary multiple-effect evaporation is 17-38%.

[0054] Further, the heating evaporation temperature during the evaporation of sodium bromide and sodium carbonate in the step (8) is 102-118 DEG C.

[0055] And / or, the heating pressure is 32-103 KPa.

[0056] And / or, the feed flow rate is 1-2 T / h.

[0057] Further, the tail gas treatment is also included: the tail gas is discharged after dust removal, denitration, acid removal and activated carbon adsorption;

[0058] And / or, the reverse osmosis pressure of the reverse osmosis membrane recovery system is 3-5 MPa.

[0059] And / or, the moisture content of the sodium bromide and sodium carbonate mixture obtained in the step (9) is 10%.

[0060] Compared with the prior art, the technical scheme of the present application has at least the following technical effects:

[0061] The present application can effectively treat the PTA oxidation residue sewage of high-salt bromine condensed ring organic matter through ingenious process design, the evaporated water is recycled as circulating water after treatment through multiple-effect evaporation, and the molten residue is sent to a incinerator for fuel-free combustion to generate a large amount of heat, the temperature is as high as 900-1200 DEG C, and the high-pressure steam can be obtained through the calculation of the residue calorific value, enthalpy and exergy value, the high-pressure steam is used for PTA device, the important feature of the present application is fuel-free combustion, but the benzene ring and condensed ring organic matter in the sewage is used as fuel, compared with the incinerator of the same device which needs to add natural gas or biogas, a large amount of cost is saved, and the sodium carbonate and sodium bromide mixture is recycled, the recovery rate is more than 99%, the sewage zero discharge is realized, the influence on the environment is reduced, and economic benefits are generated. BRIEF DESCRIPTION OF DRAWINGS

[0062] The drawings accompanying the specification of the present application are used to provide further understanding of the present application, the schematic embodiments of the present application and the description thereof are used to explain the present application, and do not constitute improper limitation on the present application. Among them:

[0063] Figure 1 The flow chart of the fuel-free incineration zero discharge process of high-salt bromine condensed ring organic matter sewage and the schematic diagram of the discharge system are provided for the present application.

[0064] The reference signs are explained as follows: 1, raw material tank; 2, first multi-effect evaporation system; 3, incinerator; 4, furnace salt dissolving device; 5, furnace salt filtering device; 6, second multi-effect evaporation system; 7, first centrifugal separation device; 8, sodium bromide evaporator; 9, second centrifugal separation device; 10, reverse osmosis membrane recovery system; 11, steam generator; 12, dust removal equipment; 13, denitration equipment; 14, acid removal equipment; 15, activated carbon adsorption device. DETAILED DESCRIPTION

[0065] In order to make the objectives, technical solutions and advantages of the present application clearer, the technical solutions in the embodiments of the present application will be described clearly and completely below in combination with the embodiments of the present application. It should be appreciated by those skilled in the art that the embodiments are only used for understanding the present application and should not be regarded as specific limitations on the present application. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work should fall within the scope of protection of the present application. The process parameters not specified in the following embodiments are usually according to the conventional conditions.

[0066] The endpoints of the ranges and any values disclosed in the present application are not limited to the precise values stated. The ranges or values should be interpreted as being approximate, meaning values near the stated values are also intended to be within the scope of the present application. For numeric values, the endpoints of each range, the endpoints of each range and individual point values, and individual point values can be combined with each other to obtain one or more new numeric ranges, which should be regarded as being specifically disclosed in the present application.

[0067] According to a first aspect of the present application, a high-salt bromine condensed ring organic sewage fuel-free incineration zero-emission system is provided, comprising a raw material tank 1, a first multi-effect evaporation system 2, an incinerator 3, a furnace salt dissolving device 4, a furnace salt filtering device 5, a second multi-effect evaporation system 6, a first centrifugal separation device 7, a sodium bromide evaporator 8 and a second centrifugal separation device 9 connected in sequence, wherein,

[0068] The raw material tank 1 is used for receiving high-salt bromine condensed ring organic sewage;

[0069] The first multi-effect evaporation system 2 is used for multi-effect evaporation of the sewage from the raw material tank 1 to concentrate the sewage;

[0070] The incinerator 3 is used for incineration treatment of the concentrated liquid from the first multi-effect evaporation system 2 to obtain a furnace slag containing salt and flue gas, respectively;

[0071] The furnace salt dissolving device 4 is used for dissolving the furnace slag from the incinerator 3 to obtain a furnace slag liquid;

[0072] A furnace salt filtering device 5 is used to filter the slag liquid from the furnace salt dissolving device 4 to remove the undissolved waste slag.

[0073] A second multi-effect evaporation system 6 is used to evaporate and concentrate the filtrate from the furnace salt filtering device 5.

[0074] A first centrifugal separation device 7 is used to separate the concentrated liquid from the second multi-effect evaporation system 6 to obtain a mixture of cobalt carbonate and sodium carbonate and a first centrifugal mother liquor.

[0075] A sodium bromide evaporator 8 is used to further evaporate and concentrate the first centrifugal mother liquor.

[0076] A second centrifugal separation device 9 is used to separate the concentrated liquid from the sodium bromide evaporator 8 to obtain a mixture of sodium bromide and sodium carbonate and a second centrifugal mother liquor.

[0077] The first multi-effect evaporation system 2, the second multi-effect evaporation system 6 and the sodium bromide evaporator 8 are connected with a reverse osmosis membrane recovery system 10, which is used to treat the evaporated water from the first multi-effect evaporation system, the second multi-effect evaporation system and the sodium bromide evaporator by reverse osmosis to obtain recycled water.

[0078] The incinerator 3 is also provided with a flue gas outlet connected with the inlet of a steam generator 11, and the steam generator 11 is also provided with a second inlet for feeding steam condensate, and the steam generator 11 uses the heat of flue gas to heat the fed steam condensate to obtain high-pressure steam.

[0079] The following will describe the components of the discharge system and the specific connection relationship in detail.

[0080] A raw material tank 1 is used to store the oxidation residue sewage generated in the process of preparing PTA by oxidation method, and the neutralization treatment of the sewage is completed by alkali in the raw material tank to remove the iron ions and nickel ions in the sewage by precipitation. The oxidation residue sewage contains condensed ring organic matter, benzene ring organic matter, high salt and bromide ions, etc. In the optional embodiment, the raw material tank is connected with an alkali tank to realize the neutralization reaction by feeding the alkali tank to the raw material tank at a certain flow rate while feeding the sewage to the raw material tank.

[0081] A first multi-effect evaporation system 2 is connected with the outlet of the raw material tank 1 to evaporate and concentrate the neutralized liquid to produce evaporated condensate which can be used as a heat source to heat the neutralized liquid in the first multi-effect evaporation system; the concentrated liquid enters the subsequent incinerator.

[0082] The incinerator 3 is connected with the outlet of the first multi-effect evaporation system 2, and is used for incinerating the concentrated liquid to obtain salt-containing slag and flue gas. The flue gas can be used as heat source for other devices, such as high-pressure steam generated by heating steam condensate or water produced by other devices. The slag is sent to the subsequent salt dissolving device 4. The incinerator can burn the condensed polycyclic compound completely, remove the condensed polycyclic compound, produce carbon dioxide, and produce carbon dioxide and cobalt ions to form cobalt carbonate. At the same time, heat is generated by combustion to produce high-temperature flue gas.

[0083] The salt dissolving device 4 is connected with the outlet of the incinerator 3, and is used for dissolving the soluble salt in the slag. For example, the water used for dissolving the slag is steam condensate produced by the evaporation device in the system, such as steam condensate produced by the first multi-effect evaporation system 2, the second multi-effect evaporation system 6 or the sodium bromide evaporator 8. The steam condensate has a certain temperature, and is more suitable for dissolving the salt in the slag.

[0084] The salt filtering device 5 is connected with the outlet of the salt dissolving device 4, and is used for filtering the liquid to remove the insoluble slag in the liquid.

[0085] The second multi-effect evaporation system 6 is connected with the outlet of the salt filtering device 5, and is used for multi-effect evaporation treatment of the filtered liquid to evaporate and concentrate the salt. The evaporated steam condensate can be used as heat source of the multi-effect evaporation system, or can be sent to the reverse osmosis membrane recovery system 10 to obtain recycled water after treatment. The concentrated liquid or the slurry with crystals is sent to the centrifugal device for solid-liquid separation.

[0086] The first centrifugal separation device 7 is connected with the outlet of the second multi-effect evaporation system 6, and is used for separating solid sodium carbonate and cobalt carbonate salt. The liquid after centrifugation (or referred to as first centrifugal mother liquor) is sent to the sodium bromide evaporator 8.

[0087] The sodium bromide evaporator 8 is connected with the outlet of the first centrifugal separation device 7, and is used for further concentrating the liquid separated by the first centrifugal separation device 7 to crystallize sodium bromide and sodium carbonate. The steam produced by evaporation is condensed to obtain steam condensate, which can be used as heat source of the sodium bromide evaporator 8, or can be sent to the reverse osmosis membrane recovery system 10 to obtain recycled water after treatment.

[0088] The second centrifugal separation device 9 is connected with the outlet of the sodium bromide evaporator 8, and is used for separating solid sodium carbonate and sodium bromide salt. The liquid after centrifugation (or referred to as second centrifugal mother liquor) can be sent to the sodium bromide evaporator 8 for further evaporation.

[0089] A steam generator 11, a first inlet of which is connected with the flue gas outlet of the incinerator, and a steam condensate enters the steam generator through a second inlet, the flue gas produced by the combustion of the incinerator enters the steam generator, the flue gas carries a large amount of heat, and the heat energy is used to heat the steam condensate entering the steam generator into high-pressure steam, and the generated high-pressure steam is used by the PTA device. The steam generator 11 can be a conventional heat exchanger. It should be noted that the steam condensate used in the process of the present application is preferably evaporated water generated by the first multi-effect evaporation system 2, the second multi-effect evaporation system 6 and the sodium bromide evaporator 8, thereby saving energy consumption.

[0090] In the above-mentioned high-salt bromine thick ring organic sewage fuel-free incineration zero-emission system, as a preferred embodiment, the treatment system further comprises a tail gas treatment unit connected with the flue gas outlet of the steam generator for purifying the flue gas discharged from the steam generator to meet the emission standard; wherein the tail gas treatment unit comprises dust removal equipment 12, denitration equipment 13, acid removal equipment 14 and activated carbon adsorption device 15 connected in sequence. The flue gas from the steam generator 11 is dusted by the dust removal equipment 12 and then enters the denitration equipment 13, in which the nitrogen oxides in the flue gas are converted into nitrogen (such as by passing in ammonia or using urea to convert nitrogen oxides into nitrogen), then the flue gas enters the acid removal equipment 14, which removes sulfuric acid and nitric acid in the flue gas by adding sodium hydroxide, and finally the flue gas after acid removal enters the activated carbon adsorption device 15, which removes dioxins in the flue gas by activated carbon adsorption, and then the purified flue gas is discharged into the atmosphere.

[0091] In the above-mentioned high-salt bromine thick ring organic sewage fuel-free incineration zero-emission system, the first multi-effect evaporation system 2 comprises a one-effect falling film evaporator and a two-effect forced evaporator connected in sequence.

[0092] The one-effect falling film evaporator realizes efficient falling film evaporation of concentrated liquid in the evaporator through a circulation process and optimal distribution of liquid, the liquid residence time of the falling film evaporator is short, which can reduce the degradation of heat-sensitive materials and the scaling of materials with structural tendency on the heat exchanger tube wall, the liquid in the tube flows under the action of gravity, which can realize boiling heat transfer at a low temperature difference, the heat transfer coefficient is high, and the two-effect forced evaporator can control the outlet concentration by controlling the outlet flow, and high flow circulation is adopted to prevent scaling due to high outlet concentration.

[0093] The second multi-effect evaporation system 6 has the same structure as the first multi-effect evaporation system 2.

[0094] As a preferred embodiment, the furnace salt filtration device 5 is a flat membrane filter.

[0095] As a preferred embodiment, the concentrated water outlet of the reverse osmosis membrane recovery system 10 is connected with the first multi-effect evaporation system 2, so as to return the concentrated water discharged from the reverse osmosis membrane recovery system 10 to the first multi-effect evaporation system for evaporation and concentration.

[0096] As a preferred embodiment, the centrifugal mother liquor outlet of the second centrifugal separation device 9 is connected with the sodium bromide evaporator 8, so as to transport the second centrifugal mother liquor from the second centrifugal separation device 9 to the sodium bromide evaporator 8 for re-evaporation.

[0097] As a preferred embodiment, the raw material tank 1 is connected with an alkali tank, so as to transport the alkali in the alkali tank to the raw material tank 1 and neutralize the sewage in the raw material tank 1.

[0098] According to the second aspect of the present application, a fuel-free incineration zero-emission process for high-salt bromine condensed ring organic sewage is also provided, which comprises the following steps:

[0099] (1) Alkali neutralization: the high-salt bromine condensed ring organic sewage and the sodium hydroxide solution are mixed in a mass ratio of 8-10:1 for neutralization reaction, and the iron and nickel ions are removed by precipitation to obtain a residue mother liquor containing sodium bromide;

[0100] (2) First multi-effect evaporation: the residue mother liquor containing sodium bromide is evaporated to obtain a concentrated residue mother liquor, and at the same time, the evaporated water is sent to the reverse osmosis membrane recovery system 10 for treatment to obtain recycled water;

[0101] (3) Incineration: the concentrated residue mother liquor is sent to an incinerator for incineration to obtain a slag containing sodium carbonate, cobalt carbonate and sodium bromide; the flue gas generated by incineration enters a steam generator to heat the steam condensate into high-pressure steam as heat energy;

[0102] (4) Slag dissolution and preparation: the slag is dissolved and prepared in steam condensate (such as steam condensate generated from the multi-effect evaporator) or water (preferably, the mass ratio of slag to steam condensate or water is 1:4) to obtain a slag feed liquid;

[0103] (5) Slag feed liquid filtration: the slag feed liquid is filtered to remove undissolved slag, and the filtrate is heated to 90-100°C;

[0104] (6) Second multi-effect evaporation: the heated filtrate is evaporated to obtain a concentrated liquid containing crystalline cobalt carbonate and sodium carbonate; at the same time, the evaporated water is sent to the reverse osmosis membrane recovery system for treatment to obtain recycled water;

[0105] (7) First centrifugation: the concentrated liquid is centrifuged to obtain a first centrifugal mother liquor and a mixture of sodium carbonate and cobalt carbonate;

[0106] (8) Sodium bromide and sodium carbonate evaporation: the first centrifugal mother liquor is sent to a sodium bromide evaporator for evaporation to obtain a sodium bromide and sodium carbonate mixed concentrated solution, and the evaporated water is sent to a reverse osmosis membrane recovery system for treatment to obtain recycled water;

[0107] (9) Secondary centrifugation: the sodium bromide and sodium carbonate mixed concentrated solution is subjected to centrifugal separation to obtain a sodium bromide and sodium carbonate mixture.

[0108] In a specific embodiment of the present application, the high-salt bromine thick ring organic sewage fuel-free incineration zero-emission process is completed by using the above-mentioned high-salt bromine thick ring organic sewage fuel-free incineration zero-emission system.

[0109] In the above-mentioned high-salt bromine thick ring organic sewage fuel-free incineration zero-emission process, as a preferred embodiment, in the alkali neutralization process of step (1), the liquid alkali is added in the form of a sodium hydroxide solution, wherein the mass concentration of the sodium hydroxide solution is 3%; and the feed flow rate of the sewage into the raw material tank is 40,000-50,000 kg / h.

[0110] The sewage itself contains bromine, and the addition of the 3% sodium hydroxide solution can generate sodium bromide, which can further generate sodium carbonate with carbon dioxide produced by combustion in the subsequent incineration step.

[0111] The sewage and the concentrated alkali are mixed in a mass ratio of 8-10:1 for neutralization reaction. If the ratio is too high, the iron and nickel content is unqualified, and if the ratio is too low, resources are wasted. After the neutralization reaction, mainly iron hydroxide and nickel hydroxide precipitates are generated, and the iron and nickel are removed. In order to increase the feed temperature of the primary multi-effect evaporation, steam condensate (such as steam condensate generated during the evaporation process) is used to heat the sewage in the raw material tank, and the temperature is controlled at 60-70℃, and the pressure is controlled between 0.5-0.7 MPa.

[0112] In the above-mentioned high-salt bromine thick ring organic sewage fuel-free incineration zero-emission process, as a preferred embodiment, in the primary multi-effect evaporation process of step (2), the heating evaporation temperature is 77-138℃.

[0113] Preferably, the heating pressure is 20-300 KPa.

[0114] Preferably, the feed flow rate is 40,000-50,000 kg / h.

[0115] Preferably, the primary multi-effect evaporation process includes first performing falling film evaporation and then performing forced evaporation, and the heating evaporation temperature of both times of evaporation is controlled at 77-138℃, and the heating pressure of both times of evaporation is controlled at 20-300 KPa; the salt concentration of the feed before the falling film evaporation is about 7-9%, and after the falling film evaporation, forced evaporation is performed, and the final control outlet solid content is about 45-70%.

[0116] In the above-mentioned high-salt bromine thick ring organic sewage fuel-free incineration zero-emission process, as a preferred embodiment, the incinerator feed concentration in the incineration process of step (3) is 45-70% (i.e. the feed solid content);

[0117] Preferably, the feed temperature is 90-100℃;

[0118] Preferably, the incinerator temperature is 900-1200℃;

[0119] Preferably, the air and residue mother liquor ratio in the incinerator is 9:1, and the residence time is 2-3 seconds;

[0120] Preferably, the combustion air pressure in the incinerator is 0.6-0.7MPa, and the combustion air temperature is 90-100℃; the atomizing air pressure is 0.6-0.8MPa, and the atomizing air temperature is 90-100℃;

[0121] Preferably, the relative pressure of the incinerator hearth is -20-50Pa.

[0122] When the incinerator feed concentration (the solid content of the outlet material liquid after multiple-effect evaporation) is less than 45%, explosion is prone to occur, and when the feed concentration is higher than 70%, combustion is not complete, so it is necessary to control the incinerator feed concentration within the range of the present application.

[0123] In addition, when the incinerator feed concentration is 65%, the incinerator exhaust gas index is relatively good, which can ensure complete combustion of thick ring organic matter, safety, economic effect, steam quality, sodium carbonate and sodium bromide, and good safety of the incinerator.

[0124] When the incinerator temperature is lower than 900℃, a large amount of dioxin will be produced, which will exceed the standard when discharged, and when the incinerator temperature is higher than 1250℃, the gas consumption will increase, so it is necessary to control the incinerator temperature within the range of the present application. In addition, in order to control the concentration of emission pollutants, the energy consumption also needs to be controlled, so the air and residue mother liquor ratio in the incinerator needs to be controlled within the range of the present application.

[0125] At least two reactions occur in the incinerator:

[0126] C8H8O4+O2+N2===CO2+NO X +H2O+heat value+dioxin;

[0127] NaOH+CO2==NaCO3+H2O;

[0128] In addition, the carbon dioxide also reacts with cobalt ions to form cobalt carbonate; the combustion reaction in the incinerator also produces a large amount of heat, and the inventor has found that the combustion heat of terephthalic acid and other organic matters is about 4638 kcal / kg through research on the combustion value of the feed composition, so that the heat generated by the incinerator can be used to produce high-pressure steam for the PTA production device.

[0129] In the above high-salt bromine thick ring organic sewage fuel-free incineration zero-emission process, as a preferred embodiment, in the slag dissolving and preparing process of step (4), about 2T / H of slag is prepared by adding 8T / H of steam condensate at a mass ratio of slag to steam condensate of 1:4. It should be noted that the steam condensate used in the process of the embodiment of the present application is the evaporation water generated by the first multi-effect evaporation system, the second multi-effect evaporation system and the sodium bromide evaporator, which saves energy consumption. The temperature of the steam condensate is 50-60℃, and the concentration of the prepared slag is about 20% or so. According to the standard dissolving and preparing of the present application, inorganic soluble salts can be effectively dissolved, and the purpose of cleaning and purifying can be achieved.

[0130] In the slag liquid filtration process of step (5), 12t / h of slag liquid enters the flat plate membrane for filtration, the recovery rate is about 95%, about 500kg / h of waste slag is removed, the filtration temperature is 50-60℃, and the filtrate is heated and then enters the secondary multi-effect evaporation. Heating can reduce the heat source in the subsequent evaporation process, and the waste slag is transported out for treatment.

[0131] In the above high-salt bromine thick ring organic sewage fuel-free incineration zero-emission process, as a preferred embodiment, the heating evaporation temperature in the secondary multi-effect evaporation process of step (6) is 101-146℃.

[0132] Preferably, the heating pressure is 28-192KPa;

[0133] Preferably, the feed flow rate is 9036-10200kg / h;

[0134] Preferably, after secondary multi-effect evaporation, the solid content of the concentrated liquid is 17-38%.

[0135] The heating evaporation temperature and heating pressure of the secondary multi-effect evaporation are related to the solubility of sodium carbonate and sodium bromide, which can be adjusted as needed. It should be noted that by controlling the solubility, the mixture of sodium carbonate and cobalt carbonate obtained after the secondary multi-effect evaporation does not contain sodium bromide.

[0136] In the above-mentioned high-salt bromine thick ring organic sewage fuel-free incineration zero-emission process, as a preferred embodiment, the feed quantity in the primary centrifugation process of step (7) is 3000-5000 kg / h, the water content of the obtained sodium carbonate and cobalt carbonate mixture is 10%, the output is 2-3 t / h, and the mother liquor enters the sodium bromide evaporator. The sodium carbonate and cobalt carbonate can return to the cobalt-manganese recovery unit and then be used in the PTA oxidation reactor.

[0137] In the above-mentioned high-salt bromine thick ring organic sewage fuel-free incineration zero-emission process, as a preferred embodiment, the heating evaporation temperature in the sodium bromide and sodium carbonate evaporation process of step (8) is 102-118℃.

[0138] Preferably, the heating pressure is 32-103 KPa.

[0139] Preferably, the feed flow rate is 1-2 T / h.

[0140] It should be noted that the heating evaporation temperature and the heating pressure herein can be adjusted as needed to obtain sodium bromide and sodium carbonate in different mixing proportions. According to the heating evaporation temperature and the heating pressure of the present application, a mixed concentrated solution of sodium bromide with a concentration of 10-20% and sodium carbonate with a concentration of 40-50% can be obtained.

[0141] In the above-mentioned high-salt bromine thick ring organic sewage fuel-free incineration zero-emission process, as a preferred embodiment, the moisture content of the obtained sodium bromide and sodium carbonate mixture in step (9) is 10%, and the mixture flow rate is 1-2 tons / h.

[0142] In the above-mentioned high-salt bromine thick ring organic sewage fuel-free incineration zero-emission process, as a preferred embodiment, the reverse osmosis pressure of the reverse osmosis membrane recovery system is 3-5 MPa; the material is PVDF, and the pore size is 0.001 μm. The reverse osmosis pressure has a greater impact on the quality of the reclaimed water. If the pressure is too low, the water quality of the reclaimed water will be affected, and if the pressure is too high, the energy consumption will increase. Therefore, the reverse osmosis pressure needs to be controlled within the range of the present application.

[0143] It should be noted that in the high-salt bromine condensed ring organic sewage fuel-free incineration zero-emission process of the present application, the water sent to the reverse osmosis membrane recovery system for treatment includes three parts: one part is the evaporation water (including twice evaporation water of falling film evaporation and forced evaporation) 43T / h produced after the PTA oxidation residue sewage is subjected to one multi-effect evaporation, at this time the COD is relatively high, about 2000PPM, another part is the evaporation water 7T / h produced after the secondary multi-effect evaporation, and the last part is the evaporation water about 1T / h produced by the evaporation of sodium bromide, a total of 51T / h, the three parts of water are treated by the reverse osmosis membrane recovery system, the recovery rate is 95%, and the 48T / h of the produced recycled water is used as the circulating water make-up water, and the concentrated water about 3T / h is sent to the first multi-effect evaporation system for further treatment.

[0144] In the above high-salt bromine condensed ring organic sewage fuel-free incineration zero-emission process, as a preferred embodiment, the treatment process further includes tail gas treatment: the tail gas, i.e. the flue gas, is treated by dust removal, denitration, acid removal and activated carbon adsorption to meet the standard for discharge;

[0145] The flue gas from the incinerator is subjected to heat exchange in the steam generator, and then sequentially enters the dust removal equipment, denitration equipment, acid removal equipment and activated carbon adsorption device for tail gas treatment.

[0146] In the dust removal step, the filter wind speed of the dust remover is 0.6m / min, the resistance is <1.3KPa, the inlet air temperature is <220℃, and the air volume is <40000m 3 / h;

[0147] In the denitration step, the treatment air volume is <40000m 3 / h, the reducing agent such as urea is used in an amount of 45kg / h, the design temperature is 200℃, and the denitration efficiency is 50%;

[0148] In the acid removal step, the treatment air volume is <40000m 3 / h, the alkali flow is 100kg / h, and after reaching the normal acidity, it is discharged into the wastewater pool;

[0149] In the activated carbon adsorption step, the activated carbon mainly removes dioxin, the treatment air volume is <40000m 3 / h, and the activated carbon filling amount is 20m 3 .

[0150] The present application will be further described in detail below in combination with specific examples and comparative examples.

[0151] Example 1

[0152] (1) Alkali neutralization: Wastewater (specific components are shown in Tables 1 and 2) and sodium hydroxide solution (mass concentration 3%) are mixed in the raw material tank at a mass ratio of 10:1 to carry out the neutralization reaction. Ferric hydroxide is reduced from 5 mg / kg to 1 mg / kg and nickel hydroxide is reduced from 3 mg / kg to 0.5 mg / kg, resulting in a residual mother liquor containing sodium bromide. The feed flow rate is 50,000 kg / h.

[0153] To increase the feed temperature into the multi-effect evaporator, condensate steam is used to heat the sodium bromide-containing wastewater in the raw material tank, controlling the temperature at 60-70℃ and the pressure at 0.5-0.7MPa.

[0154] (2) Single-stage multi-effect evaporation: The residual mother liquor containing sodium bromide enters the first multi-effect evaporation system with a feed salt concentration of 8% and a feed flow rate of 50,000 kg / h. Falling film evaporation is performed first, followed by forced evaporation to obtain a concentrated residual mother liquor. The heating evaporation temperature is controlled at 120℃, and the heating pressure at 200 kPa. The outlet concentration is controlled by adjusting the outlet flow rate, requiring a solids content of 65% at the outlet. Due to the high outlet concentration, high-flow-rate circulation is used to prevent scaling. Simultaneously, 43 T / h of evaporation water generated from falling film evaporation and forced evaporation is sent to the reverse osmosis membrane recovery system for treatment.

[0155] (3) Incineration: The concentrated residue mother liquor is sent to an incinerator for incineration. The feed concentration of the incinerator is...

[0156] The concentration is 65%, the feed temperature is 90-100℃, the air-to-concentrated residue-to-mother liquor ratio is 9:1, the incinerator temperature is controlled at 1000℃, the combustion air pressure in the incinerator is 0.6-0.7MPa, and the combustion air temperature is 90-100℃; the atomizing air pressure is 0.6-0.8MPa, and the atomizing air temperature is 90-100℃; the residence time is 2-3 seconds, yielding slag containing sodium carbonate, cobalt carbonate, and sodium bromide. The flue gas generated from incineration enters a steam generator, where it is used as thermal energy to heat the steam condensate into high-pressure steam; the generated high-pressure steam is used by the PTA unit. The composition and standards of the flue gas generated from incineration, i.e., the tail gas produced by the incinerator, are shown in Table 3.

[0157] (4) Slag dissolution and preparation: Approximately 2T / h of slag enters the slag dissolution device, and 8T / h of steam condensate is added at a mass ratio of 1:4 to prepare slag slurry at a temperature of 50-60℃ and a concentration of approximately 20%.

[0158] (5) Slag liquid filtration: 12T / h of slag liquid enters the flat plate membrane filter for filtration. The pressure of the flat plate membrane in the filter is 0.5MPa, the recovery rate is 95%, and about 500kg / h of waste residue is removed. The filtration temperature is 50-60℃, the filtrate is heated to 90-100℃, and the waste residue is transported off-site for treatment.

[0159] (6) Secondary multiple-effect evaporation: the filtrate after heating enters the second multiple-effect evaporation system for evaporation, the heating evaporation temperature is 120℃, the heating pressure is 150KPa, the feeding flow rate is 10200kg / h, and the concentrated solution containing crystallized cobalt carbonate and sodium carbonate with a solid content of 30% is obtained by evaporation. At the same time, 7T / h of evaporated water is sent to the reverse osmosis membrane recovery system for treatment.

[0160] (7) Primary centrifugation: the concentrated solution containing crystallized cobalt carbonate and sodium carbonate enters the first centrifugal separation device, the feeding flow rate is 10000kg / h, and the mixture of sodium carbonate and cobalt carbonate with 10% water is obtained by centrifugal separation, and the yield is 1t / h. The main components in the mixture and their contents are shown in Table 5.

[0161] (8) Sodium bromide and sodium carbonate evaporation: the centrifugal mother liquor in step (7) enters the sodium bromide evaporator, the heating evaporation temperature is 111℃, the heating pressure is 103KPa, the feeding flow rate is 2T / h, and the mixed concentrated solution of sodium bromide with a concentration of 50% and sodium carbonate with a concentration of 10% is obtained, and the discharge amount is 1T / h. At the same time, 1T / h of evaporated water is sent to the reverse osmosis membrane recovery system for treatment.

[0162] (9) Secondary centrifugation: the mixed concentrated solution of sodium bromide and sodium carbonate enters the second centrifugal separation device for centrifugal separation, and the mixture of sodium bromide and sodium carbonate with a moisture content of 10% is obtained, and the mixture flow rate is 0.4T / h.

[0163] In this embodiment, the heat generated by the incinerator in step (3) is converted into high-pressure steam by a steam generator for use in the PTA device, and the composition of the high-pressure steam is shown in Table 4. The tail gas generated by the incinerator is discharged after being treated by dust removal, denitration, acid removal and activated carbon adsorption,

[0164] Dust collector: the filtration air speed is 0.6m / min, the filter has double rows of 4 chambers, the filtration area is 2194m 2 , the resistance is less than 1.3KPa, the inlet air temperature is less than 220℃, the air volume is less than 40000m 3 / h, the inlet dust concentration is 12g / m 3 , the outlet concentration is 5g / m 3 , and the dust removal efficiency is 99.99%.

[0165] Denitration device: the size is 3910*2030mm, the processing air volume is 40000m 3 / h, the urea is 45kg per hour, the design temperature is 200℃, the nitrogen oxide is less than 100mg / m 3 , the ammonia escape control is less than 2.5mg / m 3 , and the denitration efficiency is 50%.

[0166] Acid removal device: the processing air volume is 40000m3 / h, inlet temperature less than 135°C, outlet temperature 60°C, base flow 100 kg / h. After reaching normal acidity, discharge into waste water pool.

[0167] Activated carbon adsorption device: treatment capacity 40000 m 3 / h, size 2*1*1.2 meters, activated carbon filling amount 5 m 3 , dioxin less than 5 mg / m 3 , nitrogen oxides less than 100 mg / m 3 , ammonia escape control 5 mg / m 3 .

[0168] The reverse osmosis membrane recovery system in the embodiment is set to a reverse osmosis pressure of 4 MPa, a material PVDF, and a pore size of 0.001 μm. After the three-part evaporated water is treated by the reverse osmosis membrane recovery system, the recovery rate is 95%, 48 T / h of recycled water is produced as circulating water supplement water, and about 3 T / h of concentrated water is discharged to the first multi-effect evaporation system for further treatment. The COD of the circulating water supplement water or clean water is 20 mg / l. The conditions of the obtained recycled water are shown in Table 6.

[0169] Example 2

[0170] The remaining step parameters are the same as those in Example 1, except for the composition content of the sewage in the alkali neutralization step and the incineration step. The incineration step in the embodiment is as follows:

[0171] (1) In the alkali neutralization step, the composition and content of the sewage are shown in Table 1 and Table 2.

[0172] (3) Incineration: the feeding concentration of the incinerator is 45%, and the feeding temperature is 90-100°C; the temperature of the incinerator is controlled at 950°C. The furnace pressure is changed from -20-50 Pa to 5 Pa, and the furnace pressure alarm is set. The combustion air is 0.6-0.7 MPa, and the temperature is 90-100°C. The atomizing air pressure is 0.6-0.8 MPa, and the temperature is 90-100°C.

[0173] Example 3

[0174] The remaining step parameters are the same as those in Example 1, except for the composition content of the sewage in the alkali neutralization step and the temperature of the incinerator.

[0175] (1) In the alkali neutralization step, the composition and content of the sewage are shown in Table 1 and Table 2.

[0176] (3) Incineration: the feeding temperature is 90-100°C; the temperature of the incinerator is controlled to be lower than 899°C. The combustion air is 0.6-0.7 MPa, and the temperature is 90-100°C. The atomizing air pressure is 0.6-0.8 MPa, and the temperature is 90-100°C. The dioxin is increased from 5 mg / m 3 to 6 mg / m3 Exceeds the standard.

[0177] Example 4

[0178] The rest of the step parameters are the same as in Example 1, except for the composition of the wastewater in the alkali neutralization step and the incinerator temperature.

[0179] (1) In the alkali neutralization step, the composition and content of the wastewater are shown in Table 1 and Table 2.

[0180] (3) Incineration: the feed temperature is 90-100°C; the incinerator temperature is controlled at 1250°C. The emission of dioxin is normal, but the gas needs to be increased. The combustion air pressure is 0.6-0.7 MPa, the temperature is 90-100°C, the atomizing air pressure is 0.6-0.8 MPa, and the temperature is 90-100°C.

[0181] Example 5

[0182] The rest of the step parameters are the same as in Example 1, except for the composition of the wastewater in the alkali neutralization step and the flat membrane filter pressure, as follows:

[0183] (1) In the alkali neutralization step, the composition and content of the wastewater are shown in Table 7 and Table 8.

[0184] (5) Slag solution filtration: 12T / h of slag solution is filtered by a flat filter, about 500kg / h of waste slag is removed, the filtration temperature is 50-60°C, the filtrate is heated to 90-100°C, and the waste slag is sent to the sludge treatment system. Adjust the slag solution flat membrane filter pressure to 0.4Mpa, the recovery rate reaches 90%, and the low pressure results in low recovery rate.

[0185] The conditions of the flue gas or tail gas discharged from the incinerator in this example are shown in Table 9.

[0186] The conditions of the high-pressure steam generated in this example are shown in Table 10.

[0187] The conditions of the cobalt carbonate produced after the first centrifugation in this example are shown in Table 11.

[0188] The conditions of the recycled water treated by the reverse osmosis membrane recovery system in this example are shown in Table 12.

[0189] Example 6

[0190] The rest of the step parameters are the same as in Example 1, except for the heating and evaporation parameters of the secondary multiple-effect evaporation, as follows:

[0191] (6) Secondary multiple-effect evaporation: heating and evaporation temperature 120°C, heating pressure 130KPa, feed flow rate 10000kg / h, the solid content of the concentrated solution containing crystalline cobalt carbonate and sodium carbonate obtained by evaporation changes from 30% to 20%.

[0192] Example 7

[0193] The remaining step parameters are the same as those of Example 1, except that the heating evaporation parameters of sodium bromide and sodium carbonate evaporation are different, and are as follows:

[0194] (8) Sodium bromide and sodium carbonate evaporation: heating evaporation temperature 112℃, heating pressure 35KPa. The mixed concentrated solution of 45% sodium bromide and 15% sodium carbonate is changed to a mixed concentrated solution of 40% sodium bromide and 25% sodium carbonate.

[0195] Example 8

[0196] The remaining step parameters are the same as those of Example 1, except that the reverse osmosis pressure of the reverse osmosis membrane recovery system is different, and is as follows:

[0197] The reverse osmosis pressure of the reverse osmosis membrane recovery system is set to 2MPa. The COD of the membrane recovery water is changed from 20mg / l to 26PPM.

[0198] Among them, the components of the PTA oxidation residue wastewater of Examples 1-4 are analyzed, and the results are shown in Tables 1 and 2:

[0199] Table 1

[0200]

[0201]

[0202] As can be seen from Table 1, there are more condensed ring substances, and the above substances are analyzed by chromatography.

[0203] Table 2

[0204] Item Indicator Run 1 Run 2 Run 3 Run 4 Acetic acid w / w % 0.5-1 0.7 0.1 1.2 0.9 Iron mg / kg 0.1-0.2 0.12 0.1 0.1 0.1 Sodium mg / kg 2000-5000 4510 4100 2000 4300 Chromium mg / kg 0-10 12 6 11 8 Nickel mg / kg 0-10 0.1 0.1 0.1 0.1 Bromine mg / kg 2000-5000 2300 4100 5000 4500 Cobalt mg / kg 1000-2000 1500 1600 1650 1600

[0205] The iron, sodium, chromium, nickel and cobalt in Table 2 are analyzed by ICP, and the bromide ion is analyzed by X fluorescence, among which the value of cobalt is the highest. The present application recovers 2500 tons of carbon dioxide per year, and the recovery of carbon dioxide is reflected in sodium carbonate and cobalt carbonate. The recovery water is 40-50T / H, and the effect is remarkable.

[0206] The tail gas emission conditions and standards of the incinerator of Examples 1-4 are shown in Table 3:

[0207] Table 3

[0208] Item Indicator Run 1 Run 2 Run 3 Run 4 Dioxin mg / m 3 ]]> 5 5.0 4.8 5.1 5 Nitrogen oxides mg / m 3 ]]> 100 100. 99 98 98 ammonia slip mg / m 3 ]]> 5 5.0 4.9 4.8 4.9

[0209] The self-produced high-pressure steam conditions and standards of the incinerator of Examples 1-4 are shown in Table 4:

[0210] Table 4

[0211] Item Indicator Run 1 Run 2 Run 3 Run 4 Pressure MPa 9.8 9.8 9.8 9.8 9.8 Temperature °C 310 310 310 310 310 Sodium Ug / kg 10 10 10 10 10 Silica Ug / kg 20 20 20 20 20 Iron Ug / kg 20 20 20 20 20 Copper Ug / kg 5 5 5 5 5 Conductivity Ug / kg 0.3 0.3 0.3 0.3 0.3

[0212] The situation and standard of the cobalt carbonate produced after once centrifugation of Examples 1-4 are shown in Table 5:

[0213] Table 5

[0214] Item Indicator Unit Run 1 Run 2 Run 3 Run 4 Cobalt carbonate 6-10 wt % 7.5 7.6 7.7 7.5 Particle size 1-10 um 9 8 9 8 Iron 1-2 PPM 1 1 1 1 Sulfate 0.05 wt % 0.045 0.043 0.046 0.045 Nickel 0.5 wt % 0.46 0.47 0.48 0.49

[0215] The situation and standard of the reclaimed water of Examples 1-4 treated by reverse osmosis membrane recovery system are shown in Table 6:

[0216] Table 6

[0217]

[0218]

[0219] The analysis components of the PTA oxidation residue wastewater of Examples 5-8 are shown in Table 7 and Table 8:

[0220] Table 7

[0221]

[0222] Table 8

[0223]

[0224]

[0225] The situation and standard of the tail gas emission of the incinerator of Examples 5-8 are shown in Table 9:

[0226] Table 9

[0227] Item Indicator Run 5 Run 6 Run 7 Run 8 Dioxin mg / M 3 ]]> 5 5.0 4.8 4.9 5 Nitrogen oxides mg / M 3 ]] 100 100 99 98 98 Ammonia slip mg / M 3 ]]> 5 5.0 4.9 4.8 4.9

[0228] The situation and standard of the high pressure steam produced by the incinerator of Examples 5-8 are shown in Table 10:

[0229] Table 10

[0230] Item Indicator Run 5 Run 6 Run 7 Run 8 Pressure MPa 9.8 9.8 9.8 9.8 9.8 Temperature °C 310 310 310 310 310 Sodium Ug / kg 10 10 10 10 10 Silica Ug / kg 20 20 20 20 20 Iron Ug / kg 20 20 20 20 20 Copper Ug / kg 5 5 5 5 5 Conductivity Ug / kg 0.3 0.3 0.3 0.3 0.3

[0231] The situation and standard of the cobalt carbonate produced after once centrifugation of Examples 5-8 are shown in Table 11:

[0232] Table 11

[0233]

[0234]

[0235] The reuse water conditions and standards of the reverse osmosis membrane recovery system of Examples 5-8 after treatment are shown in Table 12:

[0236] Table 12

[0237] Item Indicator Unit Run 5 Run 6 Run 7 Run 8 PH value 6-9 Dimensionless 7.5 7.6 7.7 7.5 Suspended solids 10 mg / L 9 8 9 8 TDS 600 mg / L 165 166 167 168 Hardness 20 mg / L 2 2 1 1 Alkalinity 200 mg / L 18 19 18 19 Ammonia nitrogen 5 mg / L 1 2 1 2 Total phosphorus 0.5 mg / L 0.3 0.3 0.3 0.2 COD 20 mg / L 20 19 20 26

[0238] The above descriptions are only the preferred embodiments of the present application, and are not intended to limit the present application. For those skilled in the art, the present application can have various modifications and changes. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. A high-salt bromine condensed ring organic matter sewage fuel-free incineration zero-emission system, characterized in that, The system comprises a raw material tank, a first multi-effect evaporation system, a incinerator, a furnace salt dissolving device, a furnace salt filtering device, a second multi-effect evaporation system, a first centrifugal separation device, a sodium bromide evaporator and a second centrifugal separation device, wherein, The raw material tank is used for receiving high-salt bromine thick ring organic sewage; The raw material tank is connected with the lye tank to transport the lye in the lye tank to the raw material tank and neutralize the sewage in the raw material tank; The first multi-effect evaporation system is used for multi-effect evaporation of the sewage from the raw material tank to concentrate the sewage; The incinerator is used for incineration treatment of the concentrated liquid from the first multi-effect evaporation system to obtain the furnace slag containing salt and the flue gas respectively; The furnace salt dissolving device is used for dissolving the furnace slag from the incinerator to obtain the furnace slag liquid; The furnace salt filtering device is used for filtering the furnace slag liquid from the furnace salt dissolving device to remove the undissolved waste slag; The second multi-effect evaporation system is used for evaporation of the filtrate from the furnace salt filtering device; The first centrifugal separation device is used for solid-liquid separation of the concentrated liquid after concentration of the second multi-effect evaporation system to obtain the mixture of cobalt carbonate and sodium carbonate and the first centrifugal mother liquor; The sodium bromide evaporator is used for further evaporation concentration of the first centrifugal mother liquor; The second centrifugal separation device is used for solid-liquid separation of the concentrated liquid after concentration of the sodium bromide evaporator to obtain the mixture of sodium bromide and sodium carbonate and the second centrifugal mother liquor; And the first multi-effect evaporation system, the second multi-effect evaporation system and the sodium bromide evaporator are connected with the reverse osmosis membrane recovery system, and the reverse osmosis membrane recovery system performs reverse osmosis treatment on the evaporation water from the first multi-effect evaporation system, the second multi-effect evaporation system and the sodium bromide evaporator to obtain the recycled water; The incinerator is also provided with a flue gas outlet connected with the first inlet of the steam generator, and the steam generator is also provided with a second inlet for introducing steam condensate, and the steam generator uses the heat of flue gas to heat the introduced steam condensate to obtain high-pressure steam.

2. The high salinity bromine condensed ring organic waste water fuel-free incineration zero emission system according to claim 1, characterized in that, It also includes a tail gas treatment unit connected with the flue gas outlet of the steam generator for purifying the flue gas discharged from the steam generator to reach the emission standard.

3. The high salinity bromine condensed ring organic waste water fuel-free incineration zero emission system according to claim 2, characterized in that, The tail gas treatment unit comprises dust removal equipment, denitration equipment, acid removal equipment and activated carbon adsorption device connected in sequence.

4. The high salinity bromine condensed ring organics sewage non-fuel incineration zero emission system according to claim 1, characterized in that, The first multi-effect evaporation system comprises a one-effect falling film evaporator and a two-effect forced evaporator connected in sequence; And / or, the furnace salt filtering device is a flat membrane filter; And / or, the concentrated water outlet of the reverse osmosis membrane recovery system is connected with the first multi-effect evaporation system to return the concentrated water discharged from the reverse osmosis membrane recovery system to the first multi-effect evaporation system for evaporation concentration; And / or, the centrifugal mother liquor outlet of the second centrifugal separation device is connected with the sodium bromide evaporator to transport the second centrifugal mother liquor from the second centrifugal separation device to the sodium bromide evaporator for re-evaporation.

5. A high-salt bromine condensed ring organic matter sewage fuel-free incineration zero-emission process, characterized in that, The system comprises the following steps: (1)alkali neutralization: high-salt bromine condensed ring organic wastewater and sodium hydroxide solution are mixed in a mass ratio of 8-10:1 to carry out neutralization reaction, iron and nickel ions are removed by precipitation to obtain a residue mother liquor containing sodium bromide; (2) primary multi-effect evaporation: the residue mother liquor containing sodium bromide is evaporated to obtain concentrated residue mother liquor, and the evaporated water is sent to a reverse osmosis membrane recovery system for treatment to obtain recycled water; (3) incineration: the concentrated residue mother liquor is sent to an incinerator for incineration to obtain furnace slag containing sodium carbonate, cobalt carbonate and sodium bromide; the flue gas generated by incineration enters a steam generator to heat the steam condensate into high-pressure steam as heat energy; (4) furnace slag dissolution preparation: the furnace slag is dissolved in steam condensate or water to obtain a furnace slag liquor; (5) furnace slag liquor filtration: the furnace slag liquor is filtered to remove undissolved furnace slag, and the filtrate is heated to 90-100℃; (6) secondary multi-effect evaporation: the heated filtrate is evaporated to obtain concentrated liquid containing crystalline cobalt carbonate and sodium carbonate; at the same time, the evaporated water is sent to a reverse osmosis membrane recovery system for treatment to obtain recycled water; wherein the heating evaporation temperature is 101-146℃; the heating pressure is 28-192KPa; (7) primary centrifugation: the concentrated liquid is centrifuged to obtain a first centrifugal mother liquor and a mixture of sodium carbonate and cobalt carbonate; (8) sodium bromide and sodium carbonate evaporation: the first centrifugal mother liquor is sent to a sodium bromide evaporator for evaporation to obtain a mixed concentrated liquid of sodium bromide and sodium carbonate, and the evaporated water is sent to a reverse osmosis membrane recovery system for treatment to obtain recycled water; wherein the heating evaporation temperature is 102-118℃; the heating pressure is 32-103KPa; (9) secondary centrifugation: the mixed concentrated liquid of sodium bromide and sodium carbonate is centrifuged to obtain a mixture of sodium bromide and sodium carbonate.

6. The high-salt bromine condensed ring organic wastewater fuel-free incineration zero-emission process according to claim 5, wherein the high-salt bromine condensed ring organic wastewater fuel-free incineration zero-emission process is realized by the high-salt bromine condensed ring organic wastewater fuel-free incineration zero-emission system of any one of claims 1-4; and / or, in the alkali neutralization process of step (1), the mass concentration of the sodium hydroxide solution is 3%; and / or, the feed flow rate of the wastewater is 40,000-50,000 kg / h. In the primary multi-effect evaporation process of step (2), the heating evaporation temperature is 77-138℃; and / or, the heating pressure is 20-300 KPa; and / or, the feed flow rate is 40,000-50,000 kg / h. The primary multi-effect evaporation process includes first falling film evaporation and then forced evaporation. In the incineration process of step (3), the feed concentration of the incinerator is 45-70%; and / or, the feed temperature is 90-100℃; and / or, the incinerator temperature is 900-1,200℃; and / or, the air to residue mother liquor ratio in the incinerator is 9:1, and the residence time is 2-3 seconds. ​ 7. The high salinity bromine condensed ring organics sewage fuel-free incineration zero emission process of claim 5, wherein, ​ ​ ​ 8. The high salinity bromine condensed ring organics sewage fuel-free incineration zero emission process of claim 7, wherein, ​ 9. The high salinity bromine condensed ring organics sewage fuel-free incineration zero emission process of claim 5, wherein, ​ ​ ​ ​ And / or, the combustion air pressure in the incinerator is 0.6-0.7MPa, the combustion air temperature is 90-100℃; the atomizing air pressure is 0.6-0.8MPa, the atomizing air temperature is 90-100℃; And / or, the relative pressure of the furnace of the incinerator is -20-50Pa.

10. The high salinity bromine condensed ring organics sewage fuel-free incineration zero emission process of claim 5, wherein, The secondary multiple-effect evaporation process of the step (6) has a feed flow rate of 9036-10200kg / h; And / or, after the secondary multiple-effect evaporation, the solid content of the concentrated liquid is 17-38%.

11. The high salinity bromine condensed ring organics sewage fuel-free incineration zero emission process of claim 5, wherein, The sodium bromide and sodium carbonate evaporation process of the step (8) has a feed flow rate of 1-2T / h.

12. The high salinity bromine condensed ring organics sewage fuel-free incineration zero emission process of claim 5, wherein, It also includes tail gas treatment: the tail gas is treated by dust removal, denitration, acid removal and activated carbon adsorption and then discharged in compliance with the standards; And / or, the reverse osmosis pressure of the reverse osmosis membrane recovery system is 3-5MPa; And / or, the moisture content of the sodium bromide and sodium carbonate mixture obtained in the step (9) is 10%.

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