Background technology
Ground such as China Henan, the Inner Mongol and Jilin are distributed with the urao resource, and it can process goods such as soda ash, caustic soda, sodium bicarbonate according to the difference of forming with suitable working method.It is a very sophisticated technological process that natural alkali causticization method is produced sodium hydroxide, and it utilizes the low advantage of natural alkali lye cost, the caustic soda that production prices are higher relatively.But causticizing process is produced caustic soda and is existed the comparison serious environmental problem at present; One ton of caustic soda of every production; The lime mud of by-product more than 2 tons can't be handled; Because lime mud contains strong alkaline substances such as a large amount of caustic soda, soda ash and calcium hydroxide, the mode that can only take builds a dam stores up has caused huge threat to environment.
The technological process of causticizing process hydrogen manufacturing sodium oxide generally is used in the recovery of alkali in the black liquid.But after handling the black liquor problem, the processing of lime mud becomes the another severe problem that paper industry faces again.The treatment technology progress of causticization legal system caustic soda and lime mud mainly comprises three kinds of modes: first kind is the quality of strict control lime in the causticization process, the temperature of reaction of control causticization, the growth of regulation and control calcium carbonate crystal; To obtain qualified calcium carbonate product; Present method requires the causticizing reaction temperature low; Reaction efficiency is relatively low, and simultaneously the calcium carbonate crystal particle is little, makes impurity such as its contained caustic soda be difficult to washes clean; The second way is that other technological process is constant in the control lime quality, through the mode of wet-milling or dry grinding lime carbonate is carried out grain refine, and outsourcing simultaneously or lime calcining reclaim carbonic acid gas and remove alkali.Present method is revised existing technology, existing at present the application, but cost is higher relatively.The third method promptly is that the lime carbonate of by-product is calcined, and the output quicklime recycles, but present method is higher to equipment requirements, and fuel cost is high simultaneously, is difficult to promote the use of.
Summary of the invention
The object of the invention has provided a kind of method of utilizing natural alkali lye causticizing process to produce caustic soda and paper filler-calcium carbonate.This method reclaims solvable compositions such as caustic soda to greatest extent, has improved the quality product of lime carbonate simultaneously, and whole process does not have discharge of wastewater, is the cleaning procedure that a causticizing process is produced caustic soda and lime carbonate.
In order to realize above-mentioned purpose, the present invention adopts following steps:
A. at first total alkali is carried out thermolysis at the natural alkali lye of 150~180g/L in the pyrolysis tower; 90~110 ℃ of decomposition temperatures; Utilize alkali lye after the pyrolysis in limeslaker with contain calcium oxide content and reach that unslaked lime more than 90% digests, two reactions of causticization, causticizing efficiency reaches 75%;
B. step a is obtained continuing causticization in the postdigestive solution entering one-level causticization reactor, 80~90 ℃ of causticization temperature, 2 hours causticization time, causticizing efficiency reaches more than 85%;
C. the causticization liquid that step b is obtained gets into the first grade subsides groove, carries out solid-liquid separation, and liquid gets into smart filtering system and obtains the caustic soda refined liquid; Devaporation concentrates, and obtains required caustic soda product, and solid slurry gets into the secondary causticization reactor; Add natural alkali lye, carry out the secondary causticization, 80~90 ℃ of causticization temperature; 2 hours causticization time, causticizing efficiency reaches more than 90%;
D. secondary causticization liquid among the step c is got into three subsiders, carry out three grades of solid-liquid separation, three grades of subsiders are realized countercurrent washings simultaneously, and wherein caustic soda is reclaimed, and obtain the calcium carbonate slurry of remaining caustic soda content below 0.1mol/L simultaneously;
E. the lime carbonate after settlement separate in the steps d is got in the continuous carbonization tower and carry out carbonation reaction; PH is reduced to below 11; After flue gas after being purified, its carbon dioxide content is 10~15% from the dry device of follow-up lime carbonate or other fuel combustions for wherein required carbonic acid gas;
F. the slurries with step e output get into the process that reeling mill carries out calcium carbonate granule expansion and refinement, make the settling volume of lime carbonate bring up to more than the 2.2ml/g;
G. the calcium carbonate serosity behind the step f expansion is got in the vacuum filter and filter, filter lime carbonate drying and dehydrating in solids dryer of back moisture 30%, the back gets into beater and breaks up, and obtains the calcium carbonate product of polymolecularity.
The main elder generation of technology of the present invention has carried out pre-treatment to natural alkali lye and has reduced the lime consumption, takes the mode of countercurrent washing, reclaims solvable compositions such as caustic soda to greatest extent; Improved the quality product of lime carbonate simultaneously; Take the mode of flue gas continuous carbonization to reduce lime carbonate pH value, utilize reeling mill that the particle of lime carbonate is modified, improve the settling volume of lime carbonate; Liquid is got back to settling separation system; Get into caustic soda product prepn flow process, the calcium carbonate content in the prepared calcium carbonate product that goes out more than 93%, whiteness more than 90, pH value be below 11, more than the settling volume 2.2ml/g, other indexs reach the requirement of paper filler-calcium carbonate.Whole process does not have discharge of wastewater, is the cleaning procedure that a causticizing process is produced caustic soda and lime carbonate.
Embodiment
Embodiment
With natural alkali lye (total alkali 160g/L, sodium hydrogencarbonate content 100g/L) 7m
3/ h carries out pyrolysis, and 100 ℃ of pyrolysis temperatures make NaHCO in the solution
350g/L mixes at digestive organ with 1400kg/h unslaked lime (CaO content is greater than 90%) then, and reaction conversion ratio reaches 76%, gets into causticization reactor then, adds 2m
3The natural alkali lye of/h, reaction back liquid gets into the first grade subsides groove, liquid-solid separation, solid gets into the secondary causticization reactor, adds 1m
3The natural alkali lye of/h, reaction conversion ratio reaches 90%, gets into three grades of subsiders then, and countercurrent washing finally obtains the sodium hydroxide solution 11m of 105g/L
3/ h is as product.Caustic soda content gets into the continuous carbonization tower then and carries out carbonization at 0.1mol/L in the lime carbonate after the washing, and carbonic acid gas is from the flue gas of pan dryer; Gas concentration lwevel 13% is reduced to the pH value about 10.8, gets into expansion in the reeling mill; Make settling volume greater than more than the 2.2ml/g, carry out vacuum filtration then, cake moisture is 30%; Get into pan dryer and carry out drying, acquisition lime carbonate is 2250kg/h, breaks up then; Obtain calcium carbonate product, wherein calcium carbonate content is greater than 93% in the product, and whiteness is greater than 90; Settling volume is greater than 2.2ml/g, and other indexs meet national light calcium carbonate salable product standard, adapts to the needs of paper industry filler.