A kind for the treatment of process of G salt mother liquor
Technical field
The invention belongs to technical field of waste water processing, be specifically related to a kind of recycling processing method of G salt mother liquor.
Background technology
Beta naphthal-6.8-disulfonic acid dipotassium, also known as G salt, as matching stain intermediate, can make food dye.By ethyl naphthol (beta naphthal) for raw material is through sulfonation reaction, can obtain after saltouing.First sulfuric acid is added in sulfidation pan, by ice water circulation, make temperature be down to below room temperature, drop into beta naphthal, reacted for 5 ~ 20 times under maintaining certain temperature condition, after having reacted, add Repone K and saltout; G salt finished product is obtained finally by filtering, washing, be filtered dry.Be separated in the spent acid after G salt containing R salt.
G salt belongs to aromatic sulphonate, its factory effluent pollutent water-soluble large, concentration is high, complicated component, the organic concentration in waste water can reach several ten thousand to hundreds of thousands of mg/L, and containing a large amount of inorganic salt; Waste water is generally strongly-acid, and Waste Sulfuric Acid concentration reaches 10 ~ 40%; Color and luster is dark, and colourity is 800 ~ 2000 times; Toxicity is large, and naphthalene series compound belongs to condensed-nuclei aromatics, has larger harm to human body.Stability Analysis of Structures, is difficult to biological degradation.Therefore, the BOD/COD of this kind of waste water is extremely low, biochemical extreme difference, and toxic to microorganism, is difficult to, with general biochemical method process, also be difficult to effective process by general flocculation, extraction and absorption method.Such waste water is a difficult problem for industrial wastewater treatment always.
The technique of industrial dye wastewater treatment has several as follows:
1. the Waste Sulfuric Acid of dye industry massfraction about 10% is obtained after multi-effect evaporation system concentrate the sulfuric acid of about massfraction 45%.React with industrial table salt, through absorb after manufacture hydrochloric acid, filtrate through liquid caustic soda neutralization, cooling, crystallization, refine after the bright powder of manufacture.
2. advanced oxidation processes strengthens the treatment effect of conventional oxidation method by number of ways, improves the efficiency of degradation of organic substances, but required oxygenant or catalyzer often price is more expensive, cause control expense higher.
3. because high density aromatic sulphonic acid class organic industrial sewage is of a great variety, complicated component, be difficult to effectively administer such waste water by a kind of method, advanced oxidation processes, complexing abstraction, emulsion liquid membrane extraction and resin adsorption method can be used as the preprocessing means that aromatic sulphonic acid class organic industrial sewage complements one another, but to such process means, often working cost is high, produces the shortcomings such as secondary pollution.
G salt mother liquor belongs to high density, highly acidity, high salinity, high chroma organic wastewater with difficult degradation thereby, can not adopt the method process such as traditional biochemistry and materialization.All contain a large amount of useful resources in most dye wastewater with high concentration, comprehensive utilization waste water can reduce the processing cost of waste water, can reduce the waste of resource simultaneously.
Summary of the invention
In order to overcome above-mentioned the deficiencies in the prior art, the invention provides a kind of G salt mother liquid disposal and realize the treatment process of resource utilization, this treatment process effectively can not only reduce organic concentration in waste water, organism wherein can also be isolated, reach resource utilization to reclaim, realize the zero release of waste water and waste gas.
Technical conceive of the present invention is as follows: because waste water is that intermittence is collected, the water yield is concentrated, and arranges G salt mother liquid tank, is then promoted to crystallisation by cooling tank with pump, utilize the cold energy of LNG to make its freezing and crystallizing, and recycling vacuum filter realizes solid-liquid separation; Filter cake main component is R salt, sells after storage and dry (utilizing LNG heat energy); Filtrate is Waste Sulfuric Acid, about sulfur acid 30 ~ 40%; Waste Sulfuric Acid pumps into gypsum reactor, and the Wingdale after thin with powder reacts, and generates carbonic acid gas and calcium sulfate; Owing to being exothermic reaction, in tail gas, removing carbon dioxide is outward also containing a large amount of steam; The gypsum produced is sold as commodity gypsum after roasting together with natural gas (utilizing LNG heat energy); Tail gas is made liquid carbon dioxide and is sold after dehydration (utilizing LNG cold energy), purification and liquefaction (utilizing LNG cold energy).The principle of overall improvement is: as far as possible reduce gross investment and running expense, realizes waste water and exhaust-gas resource and zero release.
Use a kind of G salt mother liquid disposal system to process in treatment process of the present invention, this G salt mother liquid disposal system comprises G salt mother liquor storagetank 1, crystallisation by cooling tank 2, equipment for separating liquid from solid 3, filter cake storage area 4, filtrate hold tank 5, gypsum reactor 6, gypsum calciner 7, gypsum storage area 8, CO
2hold tank 9, CO
2purification system 10, CO
2liquefaction system 11, lime mill 12 and Wingdale storage area 13.
Concrete technical scheme is as follows:
A treatment process for G salt mother liquor, comprises the steps:
The G salt mother liquor be stored in G salt mother liquor storagetank 1 is separated through equipment for separating liquid from solid 3 and obtains filter cake and filtrate after flowing into the cooling of crystallisation by cooling tank 2; Described filter cake is placed in filter cake storage area 4, described filtrate is placed in filtrate hold tank 5 and enters gypsum reactor 6 to be reacted, gained reaction product enters gypsum calciner 7 roasting, and the gypsum after roasting is placed in gypsum storage area 8, and the tail gas of gypsum calciner 7 connects CO
2hold tank 9, CO
2liquid carbon dioxide is made into through purification system 10 and liquefaction system 11;
The lime mill 12 connecting Wingdale storage area 13 provides the raw material powder Wingdale of reaction for gypsum reactor 6.
Described crystallisation by cooling tank 2 is continuity crystallizer or batch-type crystallizer, and feed temperature wherein maintains between 5 DEG C to-20 DEG C.
Described equipment for separating liquid from solid 3 is separating centrifuge or pressure filter.
Positive beneficial effect of the present invention: the present invention is by various physicochemical treatment unit organic assembling; can by G salt mother liquor (complicated; belong to high COD, high salt, high chroma, high toxicity sewage) the rear recovery of process wherein most of organism and inorganics; realize wastewater zero discharge and zero waste gas emission (comprising the zero release of carbonic acid gas); reach the object of environment protection; its economic benefit, social benefit and environmental benefit are remarkable, and technology occupies domestic pharmaceutical industry industry advanced level.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet for the treatment of process of the present invention.
Nomenclature:
1G salt mother liquor storagetank; 2 crystallisation by cooling tanks; 3 equipment for separating liquid from solid; 4 filter cake storage areas;
5 filtrate hold tanks; 6 gypsum reactors; 7 gypsum calciners; 8 gypsum storage areas;
9CO
2hold tank; 10CO
2purification system; 11CO
2liquefaction system; 12 lime mills;
13 Wingdale storage areas.
Embodiment
Below in conjunction with accompanying drawing, the present invention is further illustrated.
A kind of G salt mother liquor processing method of the present invention, uses a kind for the treatment of unit comprised as lower component: G salt mother liquor storagetank 1, crystallisation by cooling tank 2, equipment for separating liquid from solid 3, filter cake storage area 4, filtrate hold tank 5, gypsum reactor 6, gypsum calciner 7, gypsum storage area 8, CO
2hold tank 9, CO
2purification system 10, CO
2liquefaction system 11, lime mill 12 and Wingdale storage area 13.
As shown in Figure 1, G salt mother liquor storagetank 1 connects crystallisation by cooling tank 2, crystallisation by cooling tank 2 connects equipment for separating liquid from solid 3, the filter cake that equipment for separating liquid from solid 3 produces is placed in filter cake storage area 4, the filtrate that equipment for separating liquid from solid 3 produces is placed in filtrate hold tank 5, and filtrate hold tank 5 connects gypsum reactor 6, and gypsum reactor 6 gained reaction product enters gypsum calciner 7, gypsum after roasting is placed in gypsum storage area 8, and gypsum calciner 7 tail gas connects CO
2hold tank 9, CO
2make liquid carbon dioxide through purification system 10 and liquefaction system 11 to sell.Lime mill 12 connects Wingdale storage area 13, for gypsum reactor 6 provides the raw material powder Wingdale of reaction.
Described crystallisation by cooling tank 2 can be continuity crystallizer, also can batch-type crystallizer.
Described equipment for separating liquid from solid 3 can be separating centrifuge, also can be pressure filter.
Embodiment 1
The principal pollutant composition of G salt mother liquor is G salt, R acid, sulfuric acid, hydrochloric acid and sal enixum.Simulated wastewater contains G salt 20 grams/L, R acid 5 grams/L, sulfuric acid 20%, sal enixum 20/L.The COD of simulated wastewater is 100000 ~ 120000mg/L.After-8 DEG C, freezing 12 hours, after centrifuging, filtration cakes torrefaction; Filtrate adds powdered form Wingdale, roasting 3 hours under 600 DEG C of conditions, must contain the blended solid 28 grams of G salt and R salt, dehydrated gyp-430 grams.
Embodiment 2
The composition of the G salt mother liquor that certain Production in Chemical Plant G salt process produces is mainly G salt and R acid, and sulfuric acid, Na
2sO
4and KHSO
4in inorganic salt, stoste COD is 240000 ~ 280000mg/L.After-12 DEG C, freezing 12 hours, through centrifuging, produce 8.9 grams of organic solids (containing G salt and R salt), filtrate adds powdered form Wingdale, and roasting 3 hours under 600 DEG C of conditions, obtains dehydrated gyp-426 grams.