CN101693542A - Production method of 4-A molecular sieve - Google Patents
Production method of 4-A molecular sieve Download PDFInfo
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- CN101693542A CN101693542A CN200910024207A CN200910024207A CN101693542A CN 101693542 A CN101693542 A CN 101693542A CN 200910024207 A CN200910024207 A CN 200910024207A CN 200910024207 A CN200910024207 A CN 200910024207A CN 101693542 A CN101693542 A CN 101693542A
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- sodium aluminate
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Abstract
A production method of 4-A molecular sieve is disclosed, wherein raw materials comprise sodium silicate solution which is obtained through resolving intermediate product sodium silicate solution or product white carbon black in alkaline solution or sodium silicate solution with low modulus and low concentration in the manufacturing process of silicon dioxde which is extracted by adopting the coal ash alkali-soluble method, intermediate product sodium aluminate solution or product aluminum hydroxide, and aluminum oxide solution which are obtained in the production process of aluminum oxide through the coal ash desiliconisation sintering method, sodium-hydroxide and water, the components satisfy the following mole proportion conditions: SiO2: Al2O3=1.5-2.5, Na2O: SiO2=1-10, and filled water H2O: Na2O=10-80, the raw materials are mixed, are stirred into glue, and are added with guiding agent, the temperature rises to 70-100 DEG C, the mixed solution is stationarily placed for crystallization, then the soultion is led out, filtered and washed until the pH value is smaller than 11, and finally the solution is dried in 70-80 DEG C for abtaining 4-A molecular sieve.
Description
Technical field
The present invention relates to a kind of production method of 4A molecular sieve, be particularly related to a kind of flyash that utilizes, by aluminium sources such as silicon source such as the product water glass that obtains in the dissolving-out process behind the pre-desilication process of flyash and flyash or its desiliconization ash sintering and sodium aluminates is raw material, with the synthetic method of producing the 4A molecular sieve of proper amount of sodium hydroxide.
Background technology
The crystal that adsorbs or repel the molecule of different substances according to the size in crystals hole, be called " molecular sieve ", molecular sieve is pressed the different generation with shape of bulk of molecule selective adsorption effect, molecular diameter can enter molecular sieve crystal less than the material of molecular sieve crystal hole diameter, thereby be adsorbed, otherwise be ostracised.Molecular sieve only adsorbs those molecules less than molecular sieve bore diameter, and also can determine the order of preferentially adsorbed according to the polarity of different substances molecule.Molecular sieve has the selection absorption property for little polar molecule and unsaturated molecule, and polarity is big more, degree of unsaturation is high more, and it selects adsorptivity strong more.A type molecular sieve belongs to a kind of of molecular sieve, and its structure is very similar to NaCl's, belongs to isometric system.The 4A molecular sieve is a kind of alkali metal aluminosilicate with microporous type cubic(al)grating of synthetic, because the effective pore radius of 4A molecular sieve is 0.4nm, so be called the 4A molecular sieve, it has, and surface-area is big, hydrothermal stability is high, micropore enriches equal first-class performance.
4A sieve is widely used in national economic development all departments, as fields such as catalysis, sewage disposal and washing composition, especially in the synthetic detergent field.The 4A molecular sieve is as washing auxiliary detergent, is to have utilized sodium in its skeleton structure to be exchanged for the character of calcium, plays the effect that softening water increases scourability.Detergent builder are the important component in the synthetic detergent, generally account for the 15%-45% of synthetic detergent, can strengthen the wash characteristics of main ingredient aspect cleaning function.The soil removability of detergent builder own is less, but adds main component--the tensio-active agent that can cooperate effectively behind the washing composition in the washing composition, to reach best washing clean effect, make the washing composition performance be improved significantly and the use level of tensio-active agent reduce.
The 4A molecular sieve has as the major function of auxiliary agent: (1) softening water effect, from washings, remove Ca
2+, Mg
2+, the activity of raising tensio-active agent; (2) alkaline shock absorption even a small amount of acidic substance exist, by the effect of auxiliary agent, also can make the alkalescence of washings that noticeable change does not take place, and keeps very strong soil-removing action; Effects such as (3) wetting, emulsification, suspension, dispersion suspend dirt and disperse in solution, prevent the deposition again of pollutent.As seen, auxiliary agent is one of important component that improves washing effect, assurance washing composition performance, and under some situation, the consumption of the consumption of washing auxiliary detergent even specific activity composition is also big; The quality of detergent builder quality and performance directly influences the clean effect of washing composition.
Because the shortage of natural mineral and kind is relative dull, the natural molecule sieve does not satisfy the requirement in market far away, and therefore generally adopting sodium aluminate, water glass and clay quasi-mineral at present is the synthetic molecular sieve of producing of raw material.According to raw-material situation, synthetic method is divided into industrial chemicals method, kaolin method and swelling local method, wherein the industrial chemicals method obtain best in quality, but raw materials cost is also the highest; Though both cost of material of back are cheap, complex manufacturing, quality product is relatively poor, seldom can be up to state standards.Suitability for industrialized production 4A molecular sieve general using water glass, sodium aluminate, wilkinite and kaolin etc. are as raw material at present; water glass and sodium aluminate hydrothermal synthesis method are produced the technology comparative maturity of 4A molecular sieve; but raw material is non-regeneration Mineral resources; therefore destroy the resource and the eubiosis; though there be the production and the application of mass-producing in China at present; but efficient is lower mostly, and economy is poor.
Present domestic ordinary method is produced the 4A molecular sieve and is had following two technical problems:
1, in the conventional production process of 4A molecular sieve, a large amount of sodium hydroxide (caustic alkali) that use, therefore the synthetic 4A molecular sieve basicity without before the washing reduction PH that obtains is too high, and general pH value will consume a large amount of water and reduce pH value all greater than 14 in the final wash process.The pH value of detergent builder requirement 4A molecular sieve should be less than 11, reach this level, the liquid-solid ratio of water loss is greater than 3 in the common process washing process, have in addition reach more than 10 times, these simultaneously also will be to a large amount of depleted alkali lye of environmental emission with the mass consumption water resources.Therefore, above-mentioned conventional washing methods has also increased production cost in contaminate environment.Domestic also have producer in the middle of washing process 4A molecular sieve and washing lotion to be mixed making beating, feeds CO again
2Make sodium hydroxide become yellow soda ash to reduce pH value, the method for washing then reduces the pH value of product.But this method is ventilated in the common system of 4A molecular sieve and water, not only need very big air demand, also to overcome very big resistance, and in the middle of this outstanding turbid mixed solution, also be difficult to make the gas of feeding to reach uniform distribution, be difficult to the pH value of accurate online detection suspension liquid in the venting process, operability and cost are higher.
2, the producer of domestic production 4A molecular sieve has individual common characteristic mostly: be exactly a kind of in silicon source in the synthetic 4A molecular sieve desired raw material of only producing or the aluminium source, and the method that another synthesis material adopts outside enterprise or producer to buy obtains.With aluminum oxide enterprise is example, in the process of alumina producing, produce a large amount of aluminium sources such as sodium aluminate solution, and when synthetic 4A molecular sieve, need buy another important material to other enterprises--the silicon source, what this type of enterprise bought mostly is silicon sources such as service water glass.Because half will rely on extraneous buying the raw material of enterprise, not only can not guarantee the stability of outsourcing raw material supply amount and the unity of quality thus, and as an important production cost of product, can not effectively control, therefore the 4A molecular sieve manufacturing enterprise by outsourcing silicon source or aluminium source all is faced with institute's raw material of purchasing and can not keeps the stable difficult problem of raw materials quality with unstable the reaching of market fluctuation price with manufacturer's technical problem like this, thereby can not better controlled turnout and production cost and quality product.
Flyash is the main waste of firepower electrical plant, and its quantity discharged increases year by year, the serious harm environment.How to make full use of flyash, it is turned waste into wealth, become an important problem on industry and the environmental protection battle line.In recent years, the technique means of China's Comprehensive Utilization Power Plant waste flyash improves constantly, the goods and materials product that utilizes flyash production to help national economy becomes the dominant ideas of using flyash, the developing direction that prospect flyash and intermediate product thereof utilize is that high added value, environmental friendly product such as the similar 4A molecular sieve of raw material production are that the Application and Development of guiding is the ultimate aim of flyash future development with flyash.Present stage utilizes flyash to produce white carbon black, the aluminum oxide road that moved towards the industrialization, and utilize flyash and utilize the technology such as intermediate product production 4A molecular sieve in the process also to be in the industrial stage of fumbling, as application number is the production method that 200810080297.1 application for a patent for invention discloses a kind of 4A molecular sieve, and the intermediate product water glass that this method is utilized flyash to extract to obtain in the production process of silicon-dioxide and aluminum oxide and sodium aluminate or final product white carbon black or aluminium hydroxide, aluminum oxide become production 4A molecular sieve with alkali with hydration.But this method still has the following disadvantages:
1) the reaction soln concentration according to this method metering ratio is low excessively, wherein the SiO in the silicon source
2Content generally is no more than 50g/L, and the aluminium in aluminium source is according to Al
2O
3Meter also is no more than 45g/L, so low material concentration is not suitable for the hydrothermal synthesis reaction of 4A molecular sieve substantially, even react, the solid-liquid ratio will inevitably be very high, need to consume a large amount of water like this, cause the filtration washing difficulty, energy consumption increases, but also can reduce reaction efficiency, synthetic ratio and product yield;
2) this method runs into problems such as cost and equipment in order to solve in the impurity removing process, adopted additional technology with silicon source or aluminium source Hui Rong, but this technology just directly is dissolved in silicon or aluminium in the alkali lye, can cause the waste of finished silicon and aluminium, and also unworkable from cost consideration;
3) this method reaction times long, increase energy consumption, reduced production efficiency, prolonged the production cycle;
4) crystallization temperature of this method is generally too high, and about 90 ℃, such temperature is easy to produce stray crystal substantially, influences the quality of product.
Summary of the invention
The production method that the purpose of this invention is to provide a kind of 4A molecular sieve, present method are raw material with flyash, with its recycling final production washing auxiliary detergent 4A molecular sieve.
In order to solve the problems of the technologies described above, the invention provides following technical scheme:
A kind of production method of 4A molecular sieve, its raw material is: the flyash alkali solution technique extracts the intermediate product sodium silicate solution that obtains in the silicon-dioxide production process or product white carbon black and returns the sodium silicate solution that the sodium silicate solution that is dissolved in alkali lye or low modulus lower concentration obtains; Intermediate product sodium aluminate solution that obtains in the flyash desiliconization ash sintering process oxygenerating aluminium production process or product aluminium hydroxide, alumina solution; Sodium hydroxide and water;
May further comprise the steps:
Step 1, raw material is carried out pre-treatment: the molten and sintering of coal ash alkali obtains sodium silicate solution and sodium aluminate solution; The sodium silicate solution that obtains is carried out removal of impurities;
Step 2, sodium aluminate solution is placed reactor, adjust temperature at 70～100 ℃, add proper amount of sodium hydroxide, stir it is dissolved each other and fully be dissolved in reactor or unlimited system reaction vessel in, in above-mentioned solution, add the sodium silicate solution that step 1 obtains then, mix; Wherein, sodium aluminate solution that is added and sodium silicate solution satisfy following molar ratio condition: SiO
2: Al
2O
3Be 1.5～2.5, Na
2O: SiO
2Be 1～10, amount of water satisfies following molar ratio condition: H
2O: Na
2O is 10～80;
Step 3, pulp process: the material after mixing mixes it, and when block gel conversion is the emulsion of resemble cows milk, the stirring velocity that slows down or stop to stir kept under 60～100 ℃ temperature condition 1～2.5 hour;
Step 4, add an amount of directed agents to improve speed of response, the collocation method of this directed agents is as follows: with the aluminium in the solution with Al
2O
3Meter concentration is SiO in the sodium aluminate solution of 30～50g/L and the solution
2Concentration is that the sodium silicate solution of 100～300g/L mixes the SiO of mixed solution
2: Al
2O
3Metering is than being 3～10, and according to metering input sodium hydroxide, makes Na in the solution
2O: SiO
2Be 5～10;
Step 5, crystallization process: the oyster white emulsion behind the pulp end of processing is warming up to 70～100 ℃, and constant temperature leaves standstill or slowly stirs and carry out crystallization, keeps under this state 1.5～2 hours, and crystallization is finished;
Step 6, finished product are handled: the emulsion in the reaction vessel is derived, filter, wash, up to being washed till PH less than 11, dry under 70～80 ℃ of temperature then, dry 12～18 hours, its loss on ignition of 800 ℃ of the dried control of product was 19～21%, obtains the 4A molecular sieve.
As known from the above, intermediate product in Comprehensive Utilization Power Plant waste pollutant flyash of the present invention and the recycling process thereof, and can effectively remove and influence synthetic impurity, utilization and synthetic ratio have been improved, technological process is simple, save industrial chemicals and energy consumption, advantage such as raw material sources are extensive, cheap simultaneously; And solved long problem of reaction times by adding directed agents; The inventive method is also carried out refinement regulation to the exsiccant condition, and the loss on ignition of 800 ℃ of control products is 19～21% to reach the requirement of detergent builder in drying process.
Description of drawings
Fig. 1 is according to schema of the present invention.
Below in conjunction with accompanying drawing the specific embodiment of the present invention is done explanation in further detail.
Embodiment
The effective pore radius of 4A molecular sieve is 0.4nm, and it is linked to six similar holes by an octatomic ring, and the free diameter in the hole that this octatomic ring structure forms is
So be called
Molecular sieve.Its spacial framework is by silicon-oxy tetrahedron unit [SiO
4] and aluminum-oxygen tetrahedron [AlO
4] unit is staggered and forms, and is the crystalline compound with Al--O and the tetrahedral three-dimensional framework structure of Si--O, its chemical constitution general formula is Na
2OAl
2O
32SiO
25H
2O belongs to isometric system.The 4A molecular sieve can planar water, NH
3, H
2S, sulfurous gas, carbonic acid gas, C
2H
5OH, C
2H
6, C
2H
4Be not more than the molecule of 4A Deng critical diameter.4A molecular sieve hole is to Ca
2+, H
2Small molecules such as O have good exchange and adsorptive power, and 4A sieve is widely used in fields such as catalysis, sewage disposal and washing composition.Especially in the synthetic detergent field, the 4A molecular sieve is as washing auxiliary detergent, utilized sodium in its skeleton structure to be exchanged for the character of calcium exactly, and its theoretical cation exchange capacity is 352mgCaCO3/g, play transforming the effect that water increases washing, so at the industrial washing auxiliary detergent that is widely used as.
The present invention uses power plant's waste--and flyash is raw material, being the silicon source through soda boiling, dilution, washing and the sodium silicate solution after carbonation decompsition process is removed impurity in the flyash desilication process, with the sodium aluminate solution produced in flyash or its desiliconization ash sintering process oxygenerating aluminium technology is the aluminium source, and an amount of sodium hydroxide is that raw material is produced the 4A molecular sieve by hydrothermal synthesis method.
With reference to Fig. 1, production method of the present invention specifically comprises the following steps:
Step 1, raw material is carried out pre-treatment: with flyash soda boiling, dilution, filtration, washing, obtain sodium silicate solution and desiliconization ash, the stripping of desiliconization ash sintering is obtained sodium aluminate solution; Owing to contain the more impurity that comprises iron, titanium etc. in the washing and filtering liquid after the flyash soda boiling, the sodium silicate solution that obtains need be carried out removal of impurities, impurity in the solution is occurred with the form of solid precipitation, refilter impurity is leached, obtain the more purified sodium silicate solution of liquid phase;
Step 2, the sodium aluminate solution that step 1 was handled place reactor, adjust temperature at 70～100 ℃, add proper amount of sodium hydroxide, stirring it is dissolved each other and fully be dissolved in reactor or unlimited system reaction vessel in, in above-mentioned solution, add the sodium silicate solution that step 1 obtains continuously then by the conveying pump housing, mix, sodium aluminate that is added in this step and sodium silicate solution satisfy following molar ratio condition: SiO
2: Al
2O
3Be 1.5～2.5, Na
2O: SiO
2Be 1～10, amount of water satisfies following molar ratio condition: H
2O: Na
2O is 10～80;
Step 3, pulp process: solution is mixed quick stirring of mixed material, beginning pulp process; Begin to occur the block gels of a large amount of white solids in mixing process, along with the carrying out of quick stirring, block gel conversion is the emulsion of resemble cows milk, when reaching this state, the stirring velocity that slows down or stop to stir kept under 60～100 ℃ temperature condition 1～2.5 hour;
Step 4, finish substantially in pulp, before crystallization begins, add an amount of directed agents to improve speed of response, the collocation method of this directed agents is as follows: solid sodium aluminate slowly is dissolved in the boiling water, the solid sodium aluminate of being thrown in according to the aluminium in the solution of dissolving back with Al
2O
3Meter solubility is 30～50g/L, simultaneously SiO in the prep solution
2Concentration is the sodium silicate solution of 100～300g/L, and above-mentioned two kinds of solution are mixed the SiO of mixed solution
2: Al
2O
3Metering is than being 3～10, and according to metering input sodium hydroxide, makes Na in the solution
2O: SiO
2Be 5～10; By adding directed agents was controlled in 2 hours the time of next step crystallization process in the step 4, generally between 1.5 hours to 2 hours;
Step 5, crystallization process: the oyster white emulsion behind the pulp end of processing is warming up to 70～100 ℃, and constant temperature leaves standstill or slowly stirs and carry out crystallization, keeps under this state 1.5～2 hours, makes its sufficient crystallising, and crystallization is finished; In addition, the present invention can also adopt following method to judge finishing of crystallization further: after stopping stirring, when having tangible solid-liquid separation phenomenon, the oyster white emulsion in the reaction vessel can judge tentatively that the reaction crystallization finishes, just getting simultaneously, the emulsion in whipping process is placed under 1000 times of opticmicroscopes, if can observe the neat crystallization of similar frog ovum shape arranges, illustrate that then crystallization finishes, reaction finishes; Judge in this step that the method that crystallization is finished can solve in the process of synthetic 4A molecular sieve, infer and rely on knowhow to judge that crystallization finishes by detection indexs such as conventional on-line monitoring method detection reaction temperature, strength of solution, solution pH values, so just can accurately not hold reaction terminating constantly, cause reaction not finish easily and make product defective, perhaps long generation stray crystal of reaction times and increase energy consumption and may cause and not finish the underproof problem of product that makes;
Step 6, finished product are handled: the emulsion in the reaction vessel is derived filter, wash, up to being washed till PH less than 11, place drying plant to carry out drying then, drying temperature is controlled at about 70～80 ℃, dry 12～18 hours, its loss on ignition of 800 ℃ of the dried control of product is about 19～21%, obtains can be used as washing auxiliary detergent or the 4A molecular sieve of adsorption function requirement is arranged.
Removal of impurities in the step 1 of the present invention can be by feeding CO in impure sodium silicate solution
2, the control solution PH is 11～11.2, CO
2Concentration makes that impurity occurs with sedimentary form in the solution about 38%～45%, filter impurity is leached, and obtains more purified sodium carbonate solution, is a carbon and divides impurity removal process.Perhaps can also by add to impure sodium silicate solution milk of lime etc. make the impurity flocculation sediment then other method such as filtering separation carry out effective removal of impurities, removing wherein influences synthetic impurity.The step of milk of lime removal of impurities is specific as follows among the present invention: with SiO among every 100L
2Concentration is 80～150g/L, modulus is that 1～3 sodium silicate solution places subsider, in subsider, add 500g quickened lime breast again, make it even then with the abundant coagulation of impurity in the solution, about standing sedimentation 6 hours, sank to the subsider bottom land with rear impurity with precipitation forms in 6 hours, take out supernatant liquor or by filter method filtrate is collected this moment, promptly obtains utilizing the pure sodium silicate solution that does not contain the synthetic impurity of influence after the milk of lime removal of impurities.
As mentioned above, the raw material of synthetic 4A molecular sieve extensively is easy to get among the present invention, and the mature production technology of raw material is stable.And the impurity removal process of raw material can remove effectively that to influence 4A molecular sieve synthetic assorted as matter such as iron, titaniums, and time molten technology of raw material can effectively improve the concentration and the modulus of synthesis material effective constituent, thereby provides good raw material supply for 4A molecular sieve synthetic.
In addition, cross low or modulus is crossed when low when in the removal of impurities process, running into reaction vessel or technology and economy problems or reaction raw materials concentration, can also be by with intermediate state in the flyash sintering process oxygenerating aluminium production technique or final state, as aluminium hydroxide, aluminum oxide, sodium aluminate, Tai-Ace S 150 etc., and intermediate state or final state in the silicon production white carbon black production technology are put forward in the flyash soda boiling, as white carbon black etc., return molten processing, to obtain to satisfy sodium aluminate solution and the sodium silicate solution of producing required concentration and modulus.At this moment, the silicon source of being adopted is the aluminium hydroxide solution after the removal of impurities, and the aluminium source is to return the sodium silicate solution of resultant high-module in the sodium silicate solution that is dissolved in low modulus by the finished product white carbon black after the removal of impurities, and all the other steps are identical with preceding method.
Hui Rong joins dissolving again in a certain amount of sodium hydroxide solution with white carbon black, Hui Rong among the present invention is without washing exsiccant work in-process white carbon black test water ratio in the first dialogue manufacturing technologies of carbon black, use quality divided by its water ratio then, calculate water-free SiO
2Amount, promptly measure SiO in the white carbon black
2Content; The requirement of the aimed concn that obtains as required and the sodium silicate solution of modulus, existing SiO in the sodium silicate solution of the low modulus of deduction lower concentration
2Amount, after aforementioned calculation, being added to without washing exsiccant work in-process white carbon black of adding of needs after the metering is heated to 80-120 ℃, needs to improve dissolving again in the sodium silicate solution of low modulus lower concentration of concentration or modulus, stir simultaneously, after the work in-process white carbon black that adds fully dissolves, carry out removal of impurities by carbonation decompsition process or the method that adds milk of lime sedimentation removal of impurities again, and the basicity in the adjustment solution, finally obtain water glass liquid as the high-module high density that meets stoichiometric ratio in silicon source; The Hui Rong in aluminium source is earlier to its water ratio of substance testing such as the aluminium hydroxide produced in flyash or its desiliconization ash sintering process oxygenerating aluminium technology, sodium aluminate, aluminum oxide among the present invention, uses quality divided by its water ratio then, calculates water-free Al
2O
3Amount, the requirement of the sodium aluminate solution of the aimed concn that obtains as required, existing Al in the pre-lower concentration sodium aluminate solution that improves of deduction
2O
3Amount, after aforementioned calculation, materials such as the aluminum oxide that adds of needs after the metering, sodium aluminate, aluminum oxide are added to are heated in 80-120 ℃, the sodium aluminate solution of lower concentration, stir simultaneously, after materials such as the aluminum oxide that adds, sodium aluminate, aluminum oxide fully dissolve, finally obtain sodium aluminate liquid as the high density that meets stoichiometric ratio in aluminium source.
By returning in the material solution that is dissolved in the low modulus of lower concentration, improved the concentration and the modulus of raw material, thereby improved the efficient of reaction.Aluminium hydroxide solution after the removal of impurities adds proper amount of sodium hydroxide and stirs, it is dissolved each other and fully dissolve and place reactor or unlimited system reaction vessel, return the sodium silicate solution of in the sodium silicate solution that be dissolved in low modulus resultant high-module by the finished product white carbon black by carrying pump housing successive to add after the removal of impurities of metering in the above-mentioned solution then, proportioning adding sodium hydroxide according to synthetic needs is regulated its basicity, makes the mol ratio of this mixture satisfy following ratio condition: SiO
2: Al
2O
3Be 1.5～2.5, Na
2O: SiO
2Be 1～10, the control water yield satisfies H
2O: Na
2O is 10～80, can add an amount of directed agents simultaneously.Stir then and solution is mixed begin to carry out the pulp process, this mixing process begins to occur the block gel of a large amount of white solids, along with the carrying out that stirs, this bulk gel can change the emulsion of resemble cows milk into, when reaching this state, the stirring velocity that slows down or stop to stir, under 60～100 ℃ temperature condition, kept 1～2.5 hour, add directed agents then, then this oyster white emulsion is warming up to 70～100 ℃, constant temperature leaves standstill or slowly stirs and carry out crystallization process, this process kept under this state 1.5～2 hours, make its sufficient crystallising with this understanding, when the oyster white emulsion that stops to stir in the afterreaction container has tangible solid-liquid separation phenomenon, get the emulsion in whipping process just simultaneously and be placed on the neat crystallization that can observe similar frog ovum shape under 1000 times of opticmicroscopes and arrange, then the explanation reaction finishes.Can derive the emulsion in the reaction vessel and filter, wash this moment, up to being washed till PH less than 11, place drying plant to carry out drying then, dry 12～18 hours, its loss on ignition of 800 ℃ of the dried control of product is about 19～21%, and the finished product are exactly the 4A molecular sieve that can be used as washing auxiliary detergent or the adsorption function requirement is arranged.
Synthetic whole process of the present invention is the liquid phase reaction under the alkaline environment, does not need to add acid; Reaction conditions is a normal temperature and pressure, and temperature is controlled within 100 ℃, and pressure requires to be normal pressure, and is therefore lower to the reaction vessel requirement, and Working environment is nontoxic.And, this method also can solve equipment and the economic problems and the low excessively problem of material concentration of removal of impurities by the Hui Rong that carries aluminium and carry the finished product of silicon process, make the synthetic reaction efficiency than higher, and when reaction is initial, add effective directed agents and improve the reaction times, thereby the raising speed of response is saved energy consumption.The proportioning of each reactant of the present invention can detect in real time and adjust in reaction process by artificial or self-reacting device, and the terminating point of reaction can effectively be measured by macroscopic observation and micrometer microscope observation.The technology of entire reaction is simple, and equipment requirements is low, and process is directly perceived, and correlation parameter can be surveyed in real time.
The present invention is in the process of using flyash as the synthetic 4A molecular sieve of raw material, and the control of the pre-treatment of raw material, pulp and crystallization process, the drying process of product are three committed steps of producing the 4A molecular sieve.It is generally acknowledged that raw material through the molten technology of returning that a carbon of the present invention divides removal of impurities and silicon raw material and aluminum feedstock, can reach the good raw material pretreating effect, stoichiometric ratio is controlled at SiO in the reaction process
2: Al
2O
3Be 1.5～2.5, Na
2O: SiO
2Be 1.0～10, H
2O: Na
2O (basicity) is 10～80, stir mixing is even fast under 60～100 ℃ temperature, keep carrying out in 1～2.5 hour the pulp process under the condition stirring at a slow speed or leave standstill then, after the pulp process is finished, stirred or leave standstill under the condition crystallization at a slow speed 1.5～2 hours under 70～100 ℃ of temperature, in the sample drying process, drying temperature is controlled at about 70～80 ℃, dry 12～18 hours, its loss on ignition of 800 ℃ of the dried control of product was about 19～21%.The synthetic molecular sieve has the performance of washing auxiliary detergent requirements such as comparatively ideal calcium exchange capacity under this condition, and utilization rate of raw materials is increased substantially.Can make reaction reduce to 2～4 hours total time after before reaction beginning, adding directed agents, thereby effectively reduce the reaction times, cut down the consumption of energy, enhance productivity and reduce the products production cost.
According to technological line of the present invention: flyash of the present invention is carried silicon and is carried in the process of the intermediate product water glass of aluminium and the synthetic 4A molecular sieve of sodium aluminate, presses SiO at reaction vessel mesosilicic acid sodium and sodium aluminate
2: Al
2O
3Mol ratio is 1.5～2.5, and solid caustic soda and silicon oxide proportioning are according to Na
2O: SiO
2Mol ratio is 1～10 uniform mixing, control H
2O: Na
2The O mol ratio is 10～80; 60～100 ℃ of pulps 1～2.5 hour, be warming up to then and stir at a slow speed under 70～100 ℃ or left standstill crystallization 3～6 hours, the reaction back suction filtration that finishes, washing leaching cake to 4A molecular sieve pH value less than 11, then sample drying is pulverized, promptly get the 4A molecular sieve.
Below be several specific embodiments that the contriver provides:
Embodiment 1:
The sodium aluminate solution 100L of the 96.8g/L of removal of impurities in the flyash production process, solution temperature is risen to 75 ℃, then dividing the sodium silicate solution 100L of the 108g/L of removal of impurities to join in the reaction vessel continuously by a carbon, under 75 ℃ of temperature, stirred 15 minutes fast, make mixing of materials even, macro manifestations is uniform oyster white emulsion, and the mol ratio of present embodiment batching is respectively SiO
2: Al
2O
3=1.5, Na
2O: SiO
2=1.67, H
2O: Na
2O=75.3; Other puts a 1L beaker, with an amount of Al
2O
3Concentration is sodium aluminate solution and the SiO of 30g/L
2Concentration is that the sodium silicate solution of 150g/L mixes, and mixes the back and adds a certain amount of sodium hydroxide, makes last mixed solution Na
2O: SiO
2Be 5, this mixed solution is a directed agents, add in the middle of the above-mentioned oyster white emulsion this moment, reduce stirring velocity then or leave standstill and carried out the pulp reaction in 2 hours, be warming up to 80 ℃ of constant temperature after time is up and left standstill crystallization 1.5 hours, mixed solution is stirring the solid-liquid layering rapidly of end back, get under the opticmicroscope that mixed solution that firm stirring finishes is positioned over 1000 times and observe, can observe the neat crystallization of similar frog ovum shape arranges, illustrate that reaction finishes, then oyster white emulsion is derived reactor and carries out suction filtration, wash with water crystal to PH less than 11, in baking oven with 80 ℃, carry out drying under the situation that air blast is opened, dry 10 hours, keeping the gained dry sample was best at 800 ℃ of loss on ignition 19～21%, promptly gets the 4A zeolite product with this understanding.Prove that after tested the 4A molecular sieve of this embodiment, calcium exchange quantity are 318.5mg CaCO
3/ g, whiteness is 95.6, median size be 2.85 μ m (wherein, less than 4 μ m be 93%, greater than 10 μ m is 0.74%), Al
3+(butt) is 20.15%, and aerated density is 285mg/ml, and the slope of repose is 62 °.The detection of each parameter index of 4A molecular sieve is tested according to the method among the GB GB/T 1768-2003 among the present invention.
Embodiment 2:
The sodium aluminate solution 100L of the 120g/L of removal of impurities in the flyash production process is placed reaction vessel, adding the 34.2kg industrial sodium hydroxide after solution temperature risen to 75 ℃ fully dissolves, also add the 34.2kg industrial sodium hydroxide among the sodium silicate solution 100L of 223.14g/L of removal of impurities and fully dissolve dividing by carbon then, join in the reaction vessel continuously then, under 80 ℃ of conditions, stirred 10 minutes fast, make mixing of materials even, macro manifestations is uniform oyster white emulsion, and the mol ratio of preparing burden in the present embodiment is respectively SiO
2: Al
2O
3=2.5, Na
2O: SiO
2=6.07, H
2O: Na
2O=10.0; Other puts a 1L beaker, with an amount of Al
2O
3Concentration is sodium aluminate solution and the SiO of 40g/L
2Concentration is that the sodium silicate solution of 200g/L mixes, and mixes the back and adds a certain amount of sodium hydroxide, makes last mixed solution Na
2O: SiO
2Be 7, this mixed solution is a directed agents, add in the middle of the above-mentioned oyster white emulsion this moment, reduce stirring velocity then or leave standstill and carried out the pulp reaction in 1 hour, be warming up to 85 ℃ of constant temperature after time is up and left standstill crystallization 2 hours, solid-liquid layering rapidly afterwards after mixed solution is stirring end, and get under the opticmicroscope that mixed solution that firm stirring finishes is positioned over 1000 times and observe, can observe the neat crystallization of similar frog ovum shape arranges, illustrate that reaction finishes, then oyster white emulsion is derived reactor and carries out suction filtration, wash with water crystal to PH less than 11, in baking oven with 75 ℃, carry out drying under the situation that air blast is opened, dry 12 hours, keeping the gained dry sample was best at 800 ℃ of loss on ignition 19～21%, promptly gets the 4A zeolite product with this understanding.Prove that after tested the 4A molecular sieve of this embodiment, calcium exchange quantity are 309.4mg CaCO
3/ g, whiteness is 98.6, median size be 2.64 μ m (wherein, less than 4 μ m be 94%, greater than 10 μ m is 0.63%), Al
3+(butt) is 19.83%, and aerated density is 307mg/ml, and the slope of repose is 61 °.
Embodiment 3:
The sodium aluminate solution 100L of the 95g/L of removal of impurities in the flyash production process is placed reaction vessel, solution temperature is risen to 75 ℃, then the SiO after the flyash soda boiling washing
2Be 40g/L, Na
2O is that the sodium silicate solution 100L of 85g/L adds continuously without washing and exsiccant work in-process white carbon black 20kg (water ratio is 50%), again through adding milk of lime sedimentation removal of impurities, makes SiO in the sodium silicate solution
2Rise to about 140g/L, the modulus of solution is about 1, join the sodium silicate solution behind this Hui Rong in the reaction vessel continuously then, under 75 ℃ of conditions, stirred 15 minutes fast, make mixing of materials even, macro manifestations is uniform oyster white emulsion, and the mol ratio of preparing burden in the present embodiment is respectively SiO
2: Al
2O
3=2.0, Na
2O: SiO
2=1.50, H
2O: Na
2O=64.3; Other puts a 1L beaker, with an amount of Al
2O
3Concentration is sodium aluminate solution and the SiO of 50g/L
2Concentration is that the sodium silicate solution of 300g/L mixes, and mixes the back and adds a certain amount of sodium hydroxide, makes last mixed solution Na
2O: SiO
2Be 10, this mixed solution is a directed agents, add in the middle of the above-mentioned oyster white emulsion this moment, reduce stirring velocity then or leave standstill and carried out the pulp reaction in 1 hour, be warming up to 80 ℃ of constant temperature after time is up and left standstill crystallization 2 hours, mixed solution is solid-liquid layering rapidly after stirring end, and get under the opticmicroscope that mixed solution that firm stirring finishes is positioned over 1000 times and observe, can observe the neat crystallization of similar frog ovum shape arranges, illustrate that reaction finishes, then oyster white emulsion is derived reactor and carry out suction filtration, wash with water crystal to PH less than 11, in baking oven at 80 ℃, carry out drying under the situation that air blast is opened, dry 10 hours, keeping the gained dry sample is best at 800 ℃ of loss on ignition 20～21%, promptly gets the 4A zeolite product with this understanding.Prove that after tested the 4A molecular sieve of this embodiment, calcium exchange quantity are 312.7mg CaCO
3/ g, whiteness is 99.6, median size be 2.59 μ m (wherein, less than 4 μ m be 92%, greater than 10 μ m is 0.83%), Al
3+(butt) is 20.04%, and aerated density is 318mg/ml, and the slope of repose is 63 °.
Embodiment 4:
The Al of removal of impurities in the flyash production process
2O
3Concentration is among the sodium aluminate solution 100L of 40g/L, adds the intermediate product Al (OH) in the flyash production process
37.8kg fully dissolving, the lysate removal of impurities is placed in the reaction vessel, and solution temperature is risen to 75 ℃.Then the SiO that passes through to add milk of lime sedimentation removal of impurities
2Content is 85g/L, Na
2O content is that the sodium silicate solution 100L of 80g/L joins in the reaction vessel continuously, stirs 10 minutes fast under 80 ℃ of conditions, makes mixing of materials even, and macro manifestations is uniform oyster white emulsion, and the mol ratio of preparing burden in the present embodiment is respectively SiO
2: Al
2O
3=1.60, Na
2O: SiO
2=1.54, H
2O: Na
2O=50.92; Other puts a 1L beaker with an amount of Al
2O
3Concentration is sodium aluminate solution and the SiO of 40g/L
2Concentration is that the sodium silicate solution of 160g/L mixes, and mixes the back and adds a certain amount of sodium hydroxide, makes last mixed solution Na
2O: SiO
2Be 6, this mixed solution is a directed agents, add in the middle of the above-mentioned oyster white emulsion this moment, reduce stirring velocity then or leave standstill and carried out the pulp reaction in 1.5 hours, be warming up to 75 ℃ of constant temperature after time is up and left standstill crystallization 2.5 hours, solid-liquid layering rapidly afterwards after mixed solution is stirring end, and get under the opticmicroscope that mixed solution that firm stirring finishes is positioned over 1000 times and observe, can observe the neat crystallization of similar frog ovum shape arranges, illustrate that reaction finishes, then oyster white emulsion is derived reactor and carries out suction filtration, wash with water crystal to PH less than 11, in baking oven with 85 ℃, carry out drying under the situation that air blast is opened, dry 8 hours, keeping the gained dry sample was best at 800 ℃ of loss on ignition 20～21%, promptly gets the 4A zeolite product with this understanding.Prove that after tested the 4A molecular sieve of this embodiment, calcium exchange quantity are 308.9mg CaCO
3/ g, whiteness is 98.7, median size be 2.77 μ m (wherein, less than 4 μ m be 93%, greater than 10 μ m is 0.74%), Al
3+(butt) is 21.03%, and aerated density is 324mg/ml, and the slope of repose is 62 °.
Embodiment 5:
The sodium aluminate solution 100L of the 120g/L of removal of impurities in the flyash production process is placed reaction vessel, solution temperature is risen to 75 ℃, flyash is produced the finished product white carbon black 9kg that produces in the white carbon black technique be dissolved in fully dissolving in the 100L alkali lye that naoh concentration is 116g/L, after white carbon black dissolving fully, join in the reaction vessel continuously, under 80 ℃ of conditions, stirred 10 minutes fast, make mixing of materials even, macro manifestations is uniform oyster white emulsion, and the mol ratio of preparing burden in the present embodiment is respectively SiO
2: Al
2O
3=2.05, Na
2O: SiO
2=1.73, H
2O: Na
2O=42.71; Other puts one 11 beakers with an amount of Al
2O
3Concentration is sodium aluminate solution and the SiO of 35g/L
2Concentration is that the sodium silicate solution of 140g/L mixes, and mixes the back and adds a certain amount of sodium hydroxide, makes last mixed solution Na
2O: SiO
2Be 4.5, this mixed solution is a directed agents, add in the middle of the above-mentioned oyster white emulsion this moment, reduce stirring velocity then or leave standstill and carried out the pulp reaction in 1 hour, be warming up to 75 ℃ of constant temperature after time is up and left standstill crystallization 2 hours, solid-liquid layering rapidly afterwards after mixed solution is stirring end, and get under the opticmicroscope that mixed solution that firm stirring finishes is positioned over 1000 times and observe, can observe the neat crystallization of similar frog ovum shape arranges, illustrate that reaction finishes, then oyster white emulsion is derived reactor and carries out suction filtration, wash with water crystal to PH less than 11, in baking oven with 75 ℃, carry out drying under the situation that air blast is opened, dry 12 hours, keeping the gained dry sample was best at 800 ℃ of loss on ignition 20～21%, promptly gets the 4A zeolite product with this understanding.Prove that after tested the 4A molecular sieve of this embodiment, calcium exchange quantity are 317.6mg CaCO
3/ g, whiteness is 97.8, median size be 2.53 μ m (wherein, less than 4 μ m be 93%, greater than 10 μ m is 0.78%), Al
3+(butt) is 19.93%, and aerated density is 326mg/ml, and the slope of repose is 62 °.
The 4A molecular sieve of method preparation of the present invention has the following advantages:
1. synthetic used raw silicon source and the aluminium source of 4A molecular sieve, pass through an impurity removal process such as carbonation decompsition process and carried out removal of impurities, effectively remove in the raw material and influence 4A molecular sieve synthetic impurity such as iron, titanium etc., thereby obtain clean silicon source and aluminium source, the rational index of washing auxiliary detergents such as this exchange capacity of sintetics, whiteness is good, and quality product is better.
2. when lower or modulus is low when the concentration in silicon source that produces with flyash and aluminium source, utilize white carbon black to join dissolving again in a certain amount of sodium hydroxide solution, or dissolve again joining in the sodium silicate solution of a certain amount of low modulus and lower concentration without washing and exsiccant work in-process white carbon black in the white carbon black production technology, carry out removal of impurities by a carbonation decompsition process then, and the alkali lye in the adjustment solution, the water glass liquid that finally obtains meeting stoichiometric ratio is the silicon source; In like manner flyash and desiliconization thereof ash sintering process being carried materials such as the aluminium hydroxide produced in the aluminium technology, sodium aluminate, aluminum oxide adds soda boiling and separates, perhaps materials such as aluminium hydroxide, sodium aluminate are joined in the sodium aluminate solution of a certain amount of lower concentration, making it be converted into the purified sodium aluminate solution that measures ratio that meets is the process in aluminium source.So just solved by the silicon source of flyash direct production gained and aluminium source concentration and modulus lowly excessively, be not suitable for the directly problem of synthetic 4A molecular sieve.
3. the sodium silicate raw material that contains impurity is carried out after a carbon divides removal of impurities, caustic soda in the water glass is converted into the yellow soda ash form, clean water glass PH after the removal of impurities is controlled at about 11, when containing a certain proportion of yellow soda ash in as silicon source synthetic 4A molecular sieve with this raw material, and contain the caustic soda concentration of guaranteed reaction requirement in the aluminium source, therefore not only quality is unaffected for the 4A molecular sieve before present method not washing of producing, can also control lower basicity, 4A molecular sieve PH before the washing is about 12～13, be lower than the pH value that does not wash the 4A molecular sieve that traditional technology is produced, therefore in washing process, the washing water yield significantly reduces, and washing water yield control liquid-solid ratio is below 3.In the washing process, divide and wash for two to three times, and the washings after will filtering reclaims, and be recycled to produce in the washing process next time and serve as washing lotion, after washing lotion increases through alkali concn after repeatedly circulating, use raw material return molten process or turn back to the silicon source and the metering batch mixing process in aluminium source in, to put forward highly basic concentration and to improve H
2O: Na
2The ratio of O.Reduced a large amount of water yields than conventional washing method like this, not only the conserve water resource reduces the discharging of discarded alkali lye simultaneously.
4. present method required main raw material water glass (silicon source) and sodium aluminate (aluminium source) when synthetic 4A molecular sieve all is to be initial raw materials with the fly ash in electric power plant, utilizes flyash to produce soda boiling in the white carbon black process, solid-liquid separation, carbon and grades and carry the sodium silicate solution that silicon technology produces (or be dissolved in sodium silicate solution etc. that the sodium silicate solution that hang down modulus obtain high-module with returning without washing and exsiccant work in-process white carbon black in the white carbon black production technology) as the silicon source; Sodium aluminate in the flyash sintering process for alumina production process (or aluminium hydroxide etc.) solution is as the aluminium source, above-mentioned silicon source and aluminium source be need not to introduce or buy by technology involved in the present invention production supply voluntarily.
5. present method is finished substantially in pulp reaction, can make reaction reduce to 2～4 hours total time after adding directed agents before crystallization process is about to begin, thereby effectively reduce the reaction times, cuts down the consumption of energy, and enhances productivity and reduces the products production cost.
6. the present invention can effectively carry out online detection to the crystallization terminal point, detection method is as follows: have tangible solid-liquid separation phenomenon can judge tentatively that promptly the reaction crystallization finishes when stopping to stir oyster white emulsion in the afterreaction container, just getting simultaneously, the emulsion in whipping process is placed on the neat crystallization arrangement that can observe similar frog ovum shape under 1000 times of opticmicroscopes, illustrate that then crystallization finishes, reaction finishes, present method can accurately be determined the time of reaction terminating, can save energy consumption of reaction and time, thereby enhance productivity, reduce product cost, can guarantee quality product simultaneously.
The above is the preferred embodiments of the present invention only, is not limited to the present invention, and for a person skilled in the art, the present invention can have various changes and variation.Within the spirit and principles in the present invention all, any modification of being made, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (5)
1. the production method of a 4A molecular sieve, its raw material is: the flyash alkali solution technique extracts the intermediate product sodium silicate solution that obtains in the silicon-dioxide production process or product white carbon black and returns the sodium silicate solution that the sodium silicate solution that is dissolved in alkali lye or low modulus lower concentration obtains; Intermediate product sodium aluminate solution that obtains in the flyash desiliconization ash sintering process oxygenerating aluminium production process or product aluminium hydroxide, aluminum oxide return the sodium aluminate solution that the sodium aluminate solution that is dissolved in low modulus lower concentration obtains; Sodium hydroxide and water;
It is characterized in that: may further comprise the steps:
Step 1, raw material is carried out pre-treatment: molten and sintering obtains sodium silicate solution and sodium aluminate solution with coal ash alkali, and sodium silicate solution and sodium aluminate solution are carried out removal of impurities;
Step 2, sodium aluminate solution is placed reactor, adjust temperature at 70～100 ℃, add proper amount of sodium hydroxide, stir it is dissolved each other and fully be dissolved in reactor or unlimited system reaction vessel in, in above-mentioned solution, add the sodium silicate solution that step 1 obtains then, mix; Wherein, sodium aluminate solution that is added and sodium silicate solution satisfy following molar ratio condition: SiO
2: Al
2O
3Be 1.5～2.5, Na
2O: SiO
2Be 1～10, amount of water satisfies following molar ratio condition: H
2O: Na
2O is 10～80;
Step 3, pulp: stir material it is mixed, when block gel conversion is an emulsion, the stirring velocity that slows down or stop to stir kept under 60～100 ℃ temperature condition 1～2.5 hour;
Step 4, interpolation directed agents are to improve speed of response, and described directed agents configuration is as follows: with Al in the solution
2O
3Concentration is SiO in the sodium aluminate solution of 30～50g/L and the solution
2Concentration is that the sodium silicate solution of 100～300g/L mixes the SiO of mixed solution
2: Al
2O
3Mol ratio is 3～10, and throws in sodium hydroxide according to metering, makes Na in the solution
2O: SiO
2Mol ratio is 5～10;
Step 5, crystallization: the oyster white emulsion after the pulp end is warming up to 70～100 ℃, and constant temperature leaves standstill or slowly stirs and carry out crystallization, keeps under this state 1.5～2 hours, and crystallization is finished;
Step 6, finished product are handled: the emulsion in the reaction vessel is derived, filter, wash, up to being washed till PH less than 11, dry under 70～80 ℃ of temperature then, dry 12～18 hours, its loss on ignition of 800 ℃ of the dried control of product was 19～21%, obtains the 4A molecular sieve.
2. the production method of a kind of 4A molecular sieve according to claim 1 is characterized in that: adopt in the described step 1 to add the removal of impurities of milk of lime subsidence style: with SiO among every 100L
2Concentration is 80～150g/L, modulus is that 1～3 sodium silicate solution places subsider, in subsider, add 500g quickened lime breast again, make the abundant coagulation of impurity in itself and the solution even then, about 6 hours of standing sedimentation, sank to the subsider bottom land with rear impurity with precipitation forms in 6 hours, take out supernatant liquor or with filter method filtrate is collected this moment, obtains purified sodium silicate solution.
3. the production method of a kind of 4A molecular sieve according to claim 1 is characterized in that: the step of described white carbon black Hui Rong is as follows: measure in the white carbon black production technology without water-free SiO in the washing exsiccant work in-process white carbon black
2Amount, according to the requirement of the sodium silicate solution of required aimed concn and modulus, existing SiO in the sodium silicate solution of the low modulus of deduction lower concentration
2Amount, being added to without washing exsiccant work in-process white carbon black of adding of needs after the metering is heated to 80～120 ℃, needs to improve dissolving again in the sodium silicate solution of low modulus lower concentration of concentration or modulus, stir simultaneously, after the work in-process white carbon black that adds fully dissolves, carry out removal of impurities, and the basicity in the adjustment solution, promptly obtain meeting the water glass liquid of the high-module high density of stoichiometric ratio.
4. the production method of a kind of 4A molecular sieve according to claim 1 is characterized in that: the step of described aluminium hydroxide, aluminum oxide Hui Rong is as follows: the water-free Al that measures aluminium hydroxide, sodium aluminate, aluminum oxide
2O
3Amount, the requirement of the sodium aluminate solution of the aimed concn that obtains as required, existing Al in the pre-lower concentration sodium aluminate solution that improves of deduction
2O
3Amount, materials such as the aluminum oxide that adds of needs after the metering, sodium aluminate, aluminum oxide are added in the sodium aluminate solution of the lower concentration that is heated to 80～120 ℃, stir simultaneously, after materials such as the aluminum oxide that adds, sodium aluminate, aluminum oxide fully dissolve, promptly obtain meeting the sodium aluminate liquid of the high density of stoichiometric ratio.
5. the production method of a kind of 4A molecular sieve according to claim 1, it is characterized in that: can adopt following method to judge finishing of crystallization in the described step 5: after stopping to stir, when having tangible solid-liquid separation phenomenon, the emulsion in the reaction vessel can judge tentatively that the reaction crystallization finishes, just getting simultaneously, the emulsion in whipping process is placed under 1000 times of opticmicroscopes, if can observe neat crystallization arranges, illustrate that then crystallization finishes, reaction finishes.
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