[background technology]
In recent years, semi-coke industry has become Shaanxi, Inner Mongol, Ningxia, Xinjiang etc. and has saved one of main coal conversion industry, the industrial chain based on semi-coke has been formed in each region, such as carbide, polrvinyl chloride chemical industrial chain, tail of semi coke, magnesium metal, reduced iron, electric power carry energy industrial sector chain, tail of semi coke hydrogen manufacturing, coal tar hydrogenating oil product industrial chain.Meanwhile, the sound development of the industries such as the carbide of the biggest domestic number, ferroalloy, chemical fertilizer is supported.At present, semi-coke industry is faced with and is produced conversion process by extensive production to cleaning.Wherein semi-coke produce that wastewater discharge (indirectly discharge) is big, toxic pollutant content is high, in waste water containing many can not biologicallydegraded effluent or to amicine, thus difficulty of governance is big.
Semi-coke produces Wastewater Pretreatment and typically uses oil removing unit, extracting and dephenolizing unit, ammonia still process unit etc. to process, wherein extracting and dephenolizing unit produces sodium phenolate solution, sodium phenolate solution reforms into micro-waste if the most effectively processed, the crude phenols product that added value is high can be produced as effectively processed, i.e. increase the economic benefit of semi-coke wastewater processing system, be again that whole semi-coke industry increases economic benefit.
At present, sodium phenolate crude phenols method mainly has sulfuric acid decomposition method and CO2Decomposition method, the sulfuric acid concentration that general sulfuric acid decomposition method uses is 70-75%, and product is difficult to sulfonation compared with concentrated sulphuric acid, and it is the fiercest to react, and decomposes completely, and smog effusion is less, and operating environment is preferable, but equipment is the most serious with corrosive pipeline;Carbon dioxide decomposition method, without discharging of waste liquid, alkali liquor reusable edible, also makes full use of flue gas and gas-fired waste gas etc. simultaneously, but process route is longer, and the content decomposing crude phenols is relatively low.And produce the sodium phenolate production crude phenols that waste water extracting and dephenolizing produces, the most domestic the most reasonably process technique and successful case history from semi-coke.To this end, be badly in need of a kind of sodium phenolate production crude phenols device producing removing phenol in waste water generation from semi-coke of exploitation.
[summary of the invention]
The purpose of this utility model is to provide a kind of device utilizing sodium phenolate to produce crude phenols, greatly reduces the sulphuric acid corrosiveness to pipeline, and technique is simple, and route is short, substantially increases the production efficiency of crude phenols.
A kind of device utilizing sodium phenolate to produce crude phenols, including: pretreatment system: reduce and produce the dustiness the sodium phenolate solution that waste water extracting and dephenolizing is produced and oil content from semi-coke;Acid out system: with pretreated sodium phenolate solution as main fluid, with sulfuric acid solution as secondary fluid, be used for extracting crude phenols;Cleaning system: for purifying the crude phenols extracted, removes the free acid in crude phenols.
Condenser that described pretreatment system includes being sequentially connected with, filter, vaporizer, and sodium phenolate medial launder, produce, from semi-coke, the sodium phenolate solution that waste water extracting and dephenolizing produces and be connected to the entrance of condenser.
Described vaporizer is further provided with steam (vapor) outlet and sodium phenolate outlet, and described steam (vapor) outlet is connected to condenser inlet, and the outlet of described sodium phenolate connects sodium phenolate medial launder.
Described acid out system includes jet mixer and acid precipitation reaction still, described jet mixer is provided with sodium phenolate entrance and sulphuric acid entrance, the outlet of described jet mixer connects acid precipitation reaction still entrance, and the outlet of described acid precipitation reaction still connects further crude phenols medial launder.
Described acid precipitation reaction still is further provided with steam (vapor) outlet, and this steam (vapor) outlet connects acid out gas disposal unit.
Described a kind of device utilizing sodium phenolate to produce crude phenols farther includes to process the acid out gas disposal unit of acid out gas, including Venturi scrubber and washing liquid bath, the steam that described acid out system produces is connected to Venturi scrubber, the outlet of Venturi scrubber connects washing liquid bath, is filled with alkaline solution in described Venturi scrubber.
Described washing liquid bath is further provided with alkaline solution outlet, and the outlet of this alkaline solution is connected to the entrance of Venturi scrubber.
Compared with prior art, this utility model at least has the advantages that the sodium phenolate solution that this utility model is produced with semi-coke production waste water extracting and dephenolizing carries out producing crude phenols for raw material, described sodium phenolate solution is merely through i.e. can get crude phenols after pretreatment, acid out, a small amount of sulphuric acid is only used during whole, therefore, greatly reduce the sulphuric acid corrosiveness to pipeline, and the application technique is simple, route is short, substantially increases the production efficiency of crude phenols.
[detailed description of the invention]
Seeing Fig. 1, this utility model includes that the pretreatment system of sodium phenolate solution, acid out system, clean unit, acid out gas disposal unit form.
The pretreatment system of described sodium phenolate solution, including the sodium phenolate storage tank 1 being sequentially connected with, 1# booster pump 2, condenser 3, filter 4, vaporizer 5.Described vaporizer 5 includes steam (vapor) outlet and sodium phenolate outlet, and described steam (vapor) outlet is connected to condenser 3 through vacuum pump 6, and the outlet of described condenser is further provided with condensing liquid bath 7, and the outlet connection of described sodium phenolate has sodium phenolate medial launder 8.
Described acid out system, including the 2# booster pump 9 being sequentially connected with, sodium phenolate cooler 10, jet mixer 11, acid precipitation reaction still 12,1# separator 13.Described sodium phenolate medial launder outlet is connected to 2# booster pump 9, and described jet mixer is further provided with sulphuric acid entrance, and the outlet of described 1# separator 13 includes two, is respectively connecting to metabisulfite solution groove 14 and crude phenols medial launder 15.
Described clean unit, including the 3# booster pump 16 being sequentially connected with, crude phenols scrubber 17,2# separator 18.Described crude phenols medial launder is connected to crude phenols scrubber 17 by 3# booster pump, it addition, this crude phenols scrubber is further provided with fresh water inlet, the outlet of described 2# separator has two, is connected to type washing trough 19 and crude phenols groove 20.
Described acid out gas disposal unit, including Venturi scrubber 23, the steam (vapor) outlet of described acid precipitation reaction still is connected to this Venturi scrubber 23, the outlet of this Venturi scrubber connects washing liquid bath 21, and the alkaline solution outlet of this washing liquid bath 21 is connected to Venturi scrubber by cleaning mixture feed pump 22 and is circulated use.
Sodium phenolate produces crude phenols method:
(1) pretreatment of sodium phenolate solution: owing to producing in the sodium phenolate solution that waste water extracting and dephenolizing is produced containing impurity such as oils from semi-coke, impurity can affect the product quality of phenol treating, therefore need before acid out sodium phenolate solution is heated to 60 DEG C, by dust content removing in sodium phenolate solution less than 0.01% after being filtered, subsequently into evaporator evaporation, vaporizer is heated to 90 DEG C and carries out stripping, by oil content removing in sodium phenolate solution less than 0.05%.
Specifically, the sodium phenolate solution produced from semi-coke production waste water extracting and dephenolizing is stored in sodium phenolate storage tank 1, by heat exchange to 60 DEG C in 1# booster pump 2 supercharging entrance condenser 3, enter filter 4 and carry out the removal of float, then sodium phenolate solution entrance vaporizer 5 evaporates, and mainly reaches two purposes: one, being condensed into by sodium phenolate solution containing sodium phenolate mass content is 20%;Two, oil content removing in sodium phenolate solution will be less than 0.05% by sodium phenolate solution.It is extracted into condenser 3 condensation, the condensed water condensed out and oily substance from vaporizer 5 top steam out by vacuum pump 6 and enters condensation liquid bath 7.The sodium phenolate solution of vaporizer 5 evaporation and concentration enters sodium phenolate medial launder 8.
(2) acid out: use continuous acid-precipitation method, it is with clean sodium phenolate solution as main fluid, volume fraction be the sulphuric acid of 70%~75% be secondary fluid, it is simultaneously fed into jet mixer, enters back into acid precipitation reaction still, under not higher than 90 DEG C of reaction temperatures, through acid precipitation reaction pH value till 7.7-7.5 is reaction end, standing 4h again, decompose the crude phenols generated and be layered on upper strata, the metabisulfite solution that density is big is layered in lower floor.Acid precipitation reaction equation is as follows:
2C6H5ONa+H2SO4→2C6H5OH+Na2SO4
2C6H4CH3ONa+H2SO4→2C6H5CH3OH+Na2SO4
Detailed process is: enter sodium phenolate medial launder 8 through the pretreated sodium phenolate of sodium phenolate solution, after 2# booster pump 9 supercharging, enter sodium phenolate cooler 10 be cooled to 37 DEG C, use continuous acid-precipitation method, it is with clean sodium phenolate solution as main fluid, volume fraction be the sulphuric acid of 70%~75% be secondary fluid, it is simultaneously fed into jet mixer 11, enter back into acid precipitation reaction still 12, under not higher than 90 DEG C of reaction temperatures, through acid precipitation reaction pH value till 7.7-7.5 is reaction end, enter and 1# separator 13 stands 4h, decompose the crude phenols generated to be layered on 1# separator 13 top, crude phenols enter crude phenols medial launder 15, the metabisulfite solution that density is big is layered in 1# separator 13 bottom, enter metabisulfite solution groove 14.
(3) crude phenols purify: containing either with or without reacting free acid completely from the crude phenols that acid precipitation reaction bottom portion discharges, crude phenols add a certain proportion of fresh water and enters in sink, wash away the free acid in crude phenols, the crude phenols washed out can be as product, and the acid water washed out returns semi-coke water treatment system.
Detailed process is: enter in the crude phenols of crude phenols medial launder 15 containing either with or without reacting free acid completely, crude phenols together enter in sink 17 with a certain proportion of fresh water of addition after 3# booster pump 16 supercharging, crude phenols after washing enter and stand 2h in 2# separator 18, crude phenols are layered on 2# separator 18 top, after washing pH value be 6 crude phenols enter crude phenols groove 20, the washings that density is big are layered in 2# separator 18 bottom, being drained into type washing trough 19, the acid water that this part washes out returns semi-coke water treatment system.
(4) acid out gas disposal: during acid precipitation reaction, the steam dripped containing volatile phenol, acid mist that acid precipitation reaction still is discharged, as entered in air without process, can cause serious air pollution.The technical program uses the steam dripped containing volatile phenol, acid mist that alkaline detergent solution is discharged through Venturi scrubber washing acid out reactor, because steam etc. is condensable gas, will condense on high-speed jet surface, together with cleaning mixture in anemostat, acid mist drips and then neutralizes with alkaline detergent solution.
Detailed process is: during acid precipitation reaction, the steam dripped containing volatile phenol, acid mist that acid precipitation reaction still 5 is discharged will condense on high-speed jet surface with neutralizing treatment liquid through Venturi scrubber 23, together with cleaning mixture in anemostat, acid then neutralizes with alkaline detergent solution, and the cleaning mixture after neutralization is returned washing liquid bath 21 by Venturi scrubber 23.Alkaline detergent solution is entered Venturi scrubber 23 by washing liquid bath 21 scrubbed liquid feed pump 22 supercharging.