CN108658091A

CN108658091A - Flyash acid system residue of aluminum-extracted prepares the method for NaY types molecular sieve and high silicon mordenite and the utilization method of flyash

Info

Publication number: CN108658091A
Application number: CN201710196582.9A
Authority: CN
Inventors: 刘汇东; 孙琦; 王宝冬; 张中华; 徐文强; 李歌; 肖永丰
Original assignee: Shenhua Group Corp Ltd; National Institute of Clean and Low Carbon Energy
Current assignee: China Energy Investment Corp Ltd; National Institute of Clean and Low Carbon Energy
Priority date: 2017-03-29
Filing date: 2017-03-29
Publication date: 2018-10-16
Anticipated expiration: 2037-03-29
Also published as: CN108658091B

Abstract

Field is utilized the present invention relates to flyash acid system residue of aluminum-extracted and flyash, a kind of flyash acid system residue of aluminum-extracted is disclosed and prepares the method for NaY types molecular sieve and high silicon mordenite and the utilization method of flyash.This method includes：(1) flyash acid system residue of aluminum-extracted is subjected to alkaline process roasting, obtains roasting slag charge；The roasting slag charge carries out high temperature water logging successively and heat preservation is filtered, and obtains the first filtrate；(2) first filtrate is subjected to NaY type zeolite-water thermal crystallisations, obtains NaY types molecular sieve and molecular sieve filtrate；(3) the molecular sieve filtrate and sodium fluoride are subjected to high silicon mordenite hydrothermal crystallizing, obtain high silicon mordenite and the second filtrate.It realizes consumption flyash acid system residue of aluminum-extracted, improves the utilization rate of flyash acid system residue of aluminum-extracted and the utilization of flyash.

Description

Flyash acid system residue of aluminum-extracted prepares the side of NaY types molecular sieve and high silicon mordenite The utilization method of method and flyash

Technical field

The present invention relates to the utilization fields that flyash acid system carries aluminium slag and flyash, and in particular, to a kind of flyash acid Method residue of aluminum-extracted prepares the method for NaY types molecular sieve and high silicon mordenite and the utilization method of flyash.

Background technology

Aluminous fly-ash is a kind of novel bauxite resource specific to China, about 10,000,000,000 tons of aluminium oxide of Prospective resources.And China's bauxite resource reserves that it has been established that only have 3,200,000,000 tons, and by current exploitation Quantity customizing, the resource guarantee time limit is only about 20 years, the current external dependence degree of bauxite resource was up to 55%.Therefore, the utilization of aluminous fly-ash are for alleviating China's alumina Ore resources shortage ensures that China's aluminium Industrial Security and the enhancing aluminium industry capability of sustainable development have realistic meaning.

Existing developed aluminum-extracted pulverized fuel ash technique is broadly divided into three acid system, alkaline process and acid and alkali combination method major class, Qualified alumina product is produced, but is all faced with that residue of aluminum-extracted discharge capacity is big, the problem of cannot effectively dissolving in various degree. By taking Shenhua Group " one step acid extracting of joint removal of impurities " aluminium oxide extraction process as an example, 100 tons of Al are often produced₂O₃About 130 tons will be discharged Residue of aluminum-extracted.The residue that alkaline process puies forward aluminium technique discharges ratio then higher.And promulgated within 2013 according to Ministry of Industry and Information《Aluminium industry is accurate Enter condition》Relevant regulations, the newly-built solid waste comprehensive utilization ratio using aluminous fly-ash production alumina system must reach 96% or more.Thus, it would be highly desirable to it develops the high level of residue of aluminum-extracted pulverized fuel ash, efficiently dissolve technology.

One of residue of aluminum-extracted pulverized fuel ash is noteworthy characterized by Silicon-rich (calcium) poor aluminium.Utilizing for residue of aluminum-extracted pulverized fuel ash is led at present Concentrate on silicon systems product (waterglass, white carbon, silicon powder etc.) preparation, basic building materials (cement, ceramic tile, steam-pressing brisk etc.) are made It makes, and for producing the fields such as heat preservation, refractory material.Use above direction all exist in various degree product economy added value, The contradiction of market capacity and residue utilization rate causes current residue of aluminum-extracted pulverized fuel ash overall utilization rate relatively low, and then directly limits Application and popularization that aluminous fly-ash carries aluminum technology are made.

Molecular sieve is a kind of material for having uniform cell structure.Due to high with adsorption capacity, thermal stability waits by force it The unexistent advantage of its adsorbent, molecular sieve many application scenarios such as catalysis, adsorbing separation, ion exchange obtain it is important and It is widely applied.

NaY type molecular sieves are a kind of artificial synthesized molecular sieve with faujasite structure, channel diameter 0.74nm, with it High-temperature stability and good catalytic activity, are hydrocracked, the fields such as desulfurization have a wide range of applications, synthetic detergent field Pay attention to using people are increasingly subject to, demand is continuously increased.

Modenite (Mordenite) is another common alumino-silicate matter molecular sieve, with a large amount of five-membered ring knot Structure and in pairs it is parallel with one another, main aperture road be straight-cylindrical twelve-ring, aperture ellipsoidal cross section, size be 0.65nm × 0.68nm.Conventional modenite silica alumina ratio=9~11, chemical formula are Na [Al₈Si₄₀O₉₆]·24H₂O.With more high silica alumina ratio The modenite of (such as 17 or more) is known as high silicon mordenite, is used to be alkylated, alkane isomerization, is hydrocracked, modifies, taking off When the synthetic reaction of wax and dimethylamine, the more conventional MOR types molecular sieve of catalytic activity, selectivity and thermal stability significantly improves, Application prospect is extensive.

The industrial chemicals such as industrial synthesis zeolite generally use waterglass, sodium aluminate or aluminium hydroxide, cost It is relatively high.Many scholars have carried out with same type raw material (including flyash, gangue, kaolin etc.) hydrothermal synthesis molecule The research of sieve.

CN102658194B discloses a kind of method by coal ash for manufacturing for NaY type molecular sieves：Flyash it is fired except carbon, The NaY type molecular sieves containing P zeolite stray crystals have been made after adding NaOH high-temperature fusions, aging and hydrothermal crystallizing.This method can only profit NaY type molecular sieves are produced with flyash, silicon and aluminium in flyash cannot be fully utilized.

CN101928010A discloses a kind of preparation method of NaY types molecular sieve, and step includes：A. aluminous fly-ash extracts The desiliconization liquid that alumina technology pre-desiliconizing process generates is mixed to prepare mother liquor with silicon source；B. mother liquor and directed agents are mixed to form silicon Aluminum sol；C. silicon-aluminum sol carries out aging, is carrying out crystallization, is being filtered, washed and dried to obtain NaY type molecular sieves, wherein is described Na in mother liquor₂O、Al₂O₃、SiO₂With H₂The molar ratio of O is 4-18：1：5-15：100-420.

CN1230518A discloses a kind of method of synthesizing high silicon content mordenite, SiO₂/Al₂O₃Molecular proportion is 15-30, Using waterglass, inorganic acid, inorganic base and aluminium salt or aluminate as raw material, the molecular proportion in reaction mixture is Na₂O/Al₂O₃= 1-10；SiO₂/Al₂O₃=10-30；H₂O/Al₂O₃=200-1000, crystallization temperature be 120-240 DEG C, complete crystallization needed for when Between be 6-360h, high silicon mordenite is made through filtering, washing, drying in mixture obtained by crystallization, it is characterised in that in crystallization mistake Using anion surface active as additive reagent in journey, the addition of anion surfactant is final modenite products weight 0.1-10%.

CN101804995A discloses the method for preparing high silicon mordenite using raw mineral materials, it is characterised in that it includes Following steps：1) according to the SiO in silicon source₂:Al in silicon source₂O₃:Inorganic base:Fluoride:Template：H₂The molar ratio of O= (20~50):1:(2~5):(5~10)：(1.5~6):(300~600) choose silicon source, silicon source, inorganic base, fluoride, mould Plate agent and water；Source of aluminium is gangue or kaolin；The silicon source is kaolin, gangue, non-hydrate sodium metasilicate, activation two The mixture of any one or any two or more of silica powder, Ludox is arbitrary proportioning when any two is mixed above； 2) silicon source, silicon source, inorganic base, fluoride, template and water are mixed, mashing, in room temperature to plastic is stirred at 80 DEG C, is obtained To initial gel mixture；It is 11-13 that initial gel mixture, which adjusts pH value, in a kettle hydrothermal crystallizing synthetic reaction, water The condition of thermal crystallisation synthetic reaction is crystallization 48~70 hours at 160~180 DEG C, obtains crystallization product；Crystallization product passes through Filter, wash to pH be 7-8, drying, 500 DEG C roasting 5-10h, after demoulding, obtain high silicon mordenite (silica alumina ratio=12~20).

The method of the prior art will cause a side of the aluminium in flyash acid system residue of aluminum-extracted or silicon superfluous, need by outer Silicon source or silicon source is added to be allocated, but this mode is unfavorable for the efficient consumption of flyash acid system residue of aluminum-extracted.

Therefore, have and prepare molecular sieve by using flyash acid system residue of aluminum-extracted to realize flyash acid system residue of aluminum-extracted The technology of consumption, which cannot be met the requirements, makes full use of sial in flyash acid system residue of aluminum-extracted, needs more effectively to utilize powder Coal ash acid system residue of aluminum-extracted prepares molecular sieve and realizes the method that flyash acid system residue of aluminum-extracted efficiently dissolves.

Invention content

The purpose of the present invention is to solve how by prepare molecular sieve improve flyash be acidified residue of aluminum-extracted consumption Efficiency, coproduction high-silicon type and low silicon type molecular sieve, and the problem of how to utilize flyash, a kind of flyash acid system is provided and carries aluminium Residue prepares the method for NaY types molecular sieve and high silicon mordenite and the utilization method of flyash.

The present inventor has found that the material composition of flyash acid system residue of aluminum-extracted has compared with flyash under study for action Its particularity：Silicone content is more enriched with compared with ordinary fly ash, and aluminium content significantly reduces, and the acid-soluble element such as Fe, Mg is carried in acid system It is largely removed during aluminium, wherein SiO₂With Al₂O₃Molar ratio (can be expressed as silica alumina ratio or SiO₂/Al₂O₃) it is about 10： 1.Silica alumina ratio cannot be exactly matched with high-silicon type molecular sieve, low silicon type molecular sieve in flyash acid system residue of aluminum-extracted, such as When fruit powder coal ash acid system residue of aluminum-extracted is directly used in synthesizing low silicon molecular sieve (such as Y type molecular sieve, silica alumina ratio are about 3~5), Si It is significantly excessive, need additional silicon source；And when being used for synthesizing high-silicon type molecular sieve (such as high silicon mordenite of silica alumina ratio ＞ 18), Al members It is plain excessive, and need additional silicon source.Obviously external silicon source or silicon source are introduced, needs additionally to consume other resources, can not effectively carry High fly-ash is acidified the utilization rate of residue of aluminum-extracted.On the other hand, in flyash acidification residue of aluminum-extracted, mullite, quartz, anatase Equal low activities component is further enriched with compared with original powder coal ash, and the utilization rate that Ash Conveying is acidified residue of aluminum-extracted improves.Therefore how Silicon, the bauxite resource in flyash acidification residue of aluminum-extracted are utilized rationally and preferably, additional silicon or aluminium is not necessarily to, needs to consider State factor.The present invention is proposed to improve the consumption efficiency that flyash is acidified residue of aluminum-extracted with regard to the invention people, realizes flyash acidification The efficient consumption of residue of aluminum-extracted, and realize coproduction NaY types molecular sieve and high silicon mordenite.

To achieve the goals above, a kind of flyash acid system residue of aluminum-extracted of present invention offer prepares NaY types molecular sieve and height The method of silicon content mordenite, including：

(1) flyash acid system residue of aluminum-extracted is subjected to alkaline process roasting, obtains roasting slag charge；The roasting slag charge carries out successively High temperature water logging and heat preservation are filtered, and the first filtrate is obtained；

(2) first filtrate is subjected to NaY type zeolite-water thermal crystallisations, obtains NaY types molecular sieve and molecular sieve filtrate；

(3) the molecular sieve filtrate and sodium fluoride are subjected to high silicon mordenite hydrothermal crystallizing, obtain high silicon mordenite With the second filtrate.

The present invention also provides a kind of utilization method of flyash, this method includes：Flyash progress acid system is carried aluminium to obtain To flyash acid system residue of aluminum-extracted and aluminium oxide；NaY is prepared in the method for flyash acid system residue of aluminum-extracted through the invention Type molecular sieve and high silicon mordenite.

Through the above technical solutions, the method for the present invention can be realized to the silicon in flyash acid system residue of aluminum-extracted, aluminium money The more preferable utilization in source realizes effective consumption to flyash acid system residue of aluminum-extracted, generates considerable environmental benefit；Realize powder simultaneously High level, the high-efficiency resource recycling of coal ash acid system residue of aluminum-extracted.

Utilization method provided by the invention to flyash acid system residue of aluminum-extracted, not needing separation and Extraction part silicon can profit Zeolite product is produced with silicon therein and aluminium, it is convenient to omit extracts the operation of separation.In addition, method provided by the invention can be with Without additionally introducing external silicon source, you can utilize the abundant and efficient consumption of flyash acid system residue of aluminum-extracted.

The method of the present invention is to realize the more preferable utilization of flyash acid system residue of aluminum-extracted, is particularly limited to and first uses low silica-alumina ratio The synthesis of molecular sieve can not only obtain NaY type molecular sieves, but also can adjust through synthesizing in the filtrate that NaY type molecular sieves generate Silicon, aluminium ratio, to be appropriate for again synthesizing high-silicon aluminium than high silicon mordenite, make silicon in flyash acid system residue of aluminum-extracted, Bauxite resource is fully used.The present invention dexterously using the synthesis that flyash acid system residue of aluminum-extracted is carried out to multiple molecular sieve, And first synthesizing low silicon aluminium is limited than molecular sieve, then synthesizing high-silicon aluminium realizes efficiently consumption flyash acid system and carries aluminium than molecular sieve Residue and the purpose for producing high value added product again.

Method provided by the invention can also carry out flyash to utilize production aluminium oxide, NaY types molecular sieve and high silicon silk Geolyte makes flyash be fully used, and there is no waste sludge discharges.

Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.

Description of the drawings

Attached drawing is to be used to provide further understanding of the present invention, an and part for constitution instruction, with following tool Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：

Fig. 1 is the flow chart of method provided by the invention；

Fig. 2 is the XRD spectra of the NaY type molecular sieves prepared by the present invention；

Fig. 3 is the XRD spectra of the high silicon mordenite prepared by the present invention.

Specific implementation mode

The specific implementation mode of the present invention is described in detail below.It should be understood that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.

The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more New numberical range, these numberical ranges should be considered as specific open herein.

The first object of the present invention provides a kind of flyash acid system residue of aluminum-extracted preparation NaY types molecular sieve and high silicon mercerising The method of zeolite, as shown in Figure 1, including：

(1) flyash acid system residue of aluminum-extracted is subjected to alkaline process roasting, obtains roasting slag charge；Then high temperature water logging is carried out successively It is filtered with heat preservation, obtains the first filtrate；

In the present invention, flyash acid system residue of aluminum-extracted mainly contains：SiO₂、Al₂O₃And TiO₂, SiO₂Content be about 70~ 80 weight %, Al₂O₃Content be about 10~15 weight % and TiO₂Content be about 3~8 weight %.Such as the Shenhua Inner Mongol Quasi- Ge Er flyash acid system residue of aluminum-extracted, wherein SiO₂Content be about 78.7 weight %, Al₂O₃Content be about 13.4 weights Measure % and TiO₂Content be about 5.2 weight %.Moreover, further flyash acid system residue of aluminum-extracted progress XRD analysis is shown Show, Al₂O₃Substantially with mullite (3Al₂O₃·SiO₂) form exist, TiO₂Carrier is anatase and rutile；There are about 85% Si exist as an amorphous form, remaining Si preservations in mullite and quartz in.The low activities group such as mullite, quartz, anatase Point be further enriched with compared with original powder coal ash, silicon, aluminium element poor activity, be unfavorable for flyash acidification residue of aluminum-extracted utilizes production point Son sieve.

According to the present invention, step (1) has both made the flyash for handling the flyash acid system residue of aluminum-extracted Silicon, aluminium element in acid system residue of aluminum-extracted can activate, and the synthesis that can more effectively participate in molecular sieve utilizes, and can be reasonable Adjust silicon in first filtrate made, the content of aluminium element meets synthesizing low silicon aluminium than the reaction raw materials of molecular sieve It asks.In step (1), the alkaline process roasting purpose is there is the mineral constituent of stable crystal structure to exist mullite, quartz etc. It is fully decomposed under lower calcination temperature, wherein Si, Al element is made fully to be activated.By being acidified residue of aluminum-extracted to flyash Middle addition alkaline matter is roasted together, and the activation of Si, Al element may be implemented.Under preferable case, in step (1), institute Stating the process that alkaline process roasts includes：By the flyash acid system residue of aluminum-extracted of 100 parts by weight and containing for 100~130 parts by weight Sodium carbonate material carries out mixed grinding, and obtained grinding product roasts after 60min~120min powder again at 830 DEG C~890 DEG C 200 mesh are broken to hereinafter, obtaining the roasting slag charge.

In the present invention, in step (1), after completing the roasting, the product for being quickly cooled down roasting can be carried out with air, Cooling obtains the roasting slag charge.

In the present invention, the containing sodium carbonate material can directly use sodium carbonate solid powder, can also be as shown in Figure 1 It is the part reuse for second filtrate for obtaining step (3).Main component is sodium carbonate in second filtrate, by part The sodium carbonate solid that second filtrate obtains after evaporative crystallization can be utilized.The flyash acid system residue of aluminum-extracted It can be mixed with from the heat preservation and be obtained by filtration and the first filter residue of reuse.

According to the present invention, in step (1), the high temperature water logging can further leach silicon, aluminium in the roasting slag charge Element, specifically can with it is water-soluble go out it is described roasting slag charge in Na₂SiO₃And NaAlSiO₄.Under preferable case, in step (1), The process of the high temperature water logging includes：Progress water logging is mixed with water after the roasting slag charge is removed iron, obtains water logging product；Water It is 95 DEG C~105 DEG C to soak temperature, and the water logging time is 15min~20min；Relative to the roasting slag charge of 100g, the dosage of water For 150~200ml.Wherein roasting slag charge removing iron can be realized by using the mode of dry magnetic separation.The high temperature Water logging process can carry out under normal pressure or self-generated pressure.The water logging product is solidliquid mixture, and solid is the fired slags Material is flooded dissolution Na₂SiO₃And NaAlSiO₄Resultant product afterwards, the mineral phase composition of the product be amorphous aluminosilicates and A small amount of crystalline state NaAlSiO₄；Liquid is to contain Na₂SiO₃And NaAlSiO₄Solution.

It is further filtered by the heat preservation according to the present invention, in step (1) and is separated by solid-liquid separation the water logging product, And obtain first filtrate.Under preferable case, in step (1), the process of the heat preservation filtering includes：The water logging is produced Object is diluted, filters and is rinsed with second filtrate of part, and obtained slurries are filtered to obtain the first filter residue and institute State the first filtrate；Filtration temperature is maintained at 60 DEG C~80 DEG C.

In the case of, according to the invention it is preferred to, relative to the roasting slag charge of 100g, the dosage of second filtrate is 250~350ml.

In a kind of preferred embodiment of the present invention, alkaline process roasting, high temperature water logging and the three of dilute filtration is kept the temperature During a, the conditional parameter that is related to while when within above-mentioned limited range, first filter residue that can be obtained With minimum yield (i.e. the ratio between the first filter residue and drying matrix amount and flyash acid system residue of aluminum-extracted dry matrices amount used).Such as This can be when not introducing external silicon and aluminum source, and flyash acid system residue of aluminum-extracted will have highest primary consumption efficiency μ.Flyash The primary consumption efficiency μ of acid system residue of aluminum-extracted can be calculate by the following formula：

μ=[(M-M₁)/(M+M_out)] × 100%；

Wherein, μ is the primary consumption efficiency of flyash acid system residue of aluminum-extracted；

M is the dry matrices amount of the flyash acid system residue of aluminum-extracted for alkaline process roasting in step (1)；

M₁For the dry matrices amount of the first filter residue of gained in step (1)；

M_outDry matrices amount for the external silicon and aluminum source introduced in total overall reaction system.

Introducing without external silicon and aluminum source in the present invention, so M_out=0.

The primary consumption efficiency μ and the first filter residue M₁Quality and external silicon and aluminum source M_outThe inversely proportional relationship of quality, with Flyash acid system residue of aluminum-extracted finally dissolves efficiency direct proportionality.

In the present invention, is filtered by above-mentioned alkaline process roasting, high temperature water logging and heat preservation, flyash acid system can be made to carry aluminium residual Silicon, aluminium element in slag switch to active component, with Na₂SiO₃And NaAlSiO₄Form extract, and adjust the ratio of silicon and aluminium Example, to adapt to the needs of follow-up Zeolite synthesis.Preferably, SiO in first filtrate₂With Al₂O₃Molar ratio be (10~ 25)：1.It is preferred that SiO in first filtrate₂With Al₂O₃Molar ratio be (12~20)：1；More preferably (13~16.5)：1.

In the present invention, the chemical composition (molar ratio) that can control first filtrate is SiO₂:Al₂O₃:Na₂O:CO₃ ^2-: H₂O=(12~17):1:(11~20):(6~10):(390~430).

Existing conventional techniques usually allocate the silica alumina ratio in hydrothermal crystallizing mother liquor in synthesizing low silicon molecular sieve analog NaY It is limited to (3~6)：1 or so；And in synthesizing high-silicon molecular sieve analog high silicon mordenite, it usually will be in hydrothermal crystallizing mother liquor Silica alumina ratio allotment is limited to 20:1 or more.It is easier to synthesize pure NaY type molecular sieves under the conditions of the silica alumina ratio of above-mentioned mother liquor Or high silicon mordenite.

But method provided by the invention is used to improve the consumption efficiency of flyash acid system residue of aluminum-extracted.For flyash acid The material properties of method residue of aluminum-extracted needs to add respectively if producing NaY types molecular sieve or high silicon mordenite according to routine techniques Enter external silicon source to turn down silica alumina ratio to (2~3)：1, or external silicon source is added so that silica alumina ratio is turned up to 20:1 or more.And it is external Silicon, silicon source (i.e. M_out) introducing will result directly in the reduction that flyash acid system residue of aluminum-extracted once dissolves efficiency μ, and then influence The consumption efficiency of flyash acid system residue of aluminum-extracted entirety prepares the flyash acid system residue of aluminum-extracted that unit mass product is dissolved Quality will reduce.

In second filtrate that the present invention obtains, the concentration of sodium carbonate can be 15~25 weight %.By described second Filtrate can reduce filtration system concentration while inhibit in the water logging product for water logging product described in dilution and filtration and washing The hydrolysis of sodium metasilicate can improve filter efficiency, reduce filter loss, reduce the first filter residue yield, help to improve fine coal The primary consumption efficiency of grey acid system residue of aluminum-extracted.At the same time, sodium carbonate recycling in systems is realized.The filtering Suction filtration or press filtration mode may be used.

In the case of, according to the invention it is preferred to, this method further comprises：By first filter residue, reuse walks after drying Suddenly (1) is added in the flyash acid system residue of aluminum-extracted.

In the present invention, first filter residue is rinsed with 80~90 DEG C of water before can also drying.

According to the present invention, step (2) synthesizes NaY type molecular sieves using first filtrate that step (1) obtains.And it closes At condition make in the molecular sieve filtrate obtained after synthesis, silicon, aluminium element composition be suitble to further synthesizing high-silicon silk Geolyte.Under preferable case, in step (2), the process of the NaY types zeolite-water thermal crystallisation includes：A) directed agents are added Enter configuration NaY molecular sieve mother liquor in first filtrate, and the composition for adjusting the NaY molecular sieve mother liquor meets Na₂O:Al₂O₃: SiO₂:H₂O=(11.1~23.7)：1：(12.9~18.4)：(380~550)；B) product for obtaining step a) 95 DEG C~ 18~36h of hydrothermal crystallizing is carried out at 105 DEG C, obtains NaY type molecular sieve water heat crystallization products；C) by the NaY types zeolite-water Thermal crystallisation product is filtered, and obtains the second filter residue and the molecular sieve filtrate；It is dried second filter residue to obtain institute State NaY type molecular sieves.The XRD spectra of finally obtained solid product, such as Fig. 2 can be measured by XRD (X-ray diffraction) method It is shown, and compared with standard spectrogram, determination obtains NaY type molecular sieves.

In the present invention, the directed agents can be commercially available, can also be prepared by following method：By sodium metaaluminate, hydrogen Sodium oxide molybdena, waterglass and deionized water, by Na₂O:Al₂O₃:SiO₂:H₂O=10.66:1:9.8:215 molal weight match into Row batch mixing, and be aged at 35 DEG C and obtain NaY molecular sieve directed agents for 24 hours.The adjustment can pass through CO₂Gaseous carbon point Mode adjusts mother liquor sodium-silicon-rate value, finally to make the forming for NaY types molecular sieve mother liquor meet above-mentioned restriction.

It can be obtained pure by the restriction to NaY type molecular sieve water heat crystallization conditions in step (2) according to the present invention NaY types molecular sieve and chemical composition be suitable for the molecular sieve filtrate of high silicon mordenite hydrothermal crystallizing in step (3).Step (2) in the molecular sieve filtrate generated, silicon, aluminium content first filtrate in generation significant changes, it is preferably described SiO in molecular sieve filtrate₂With Al₂O₃Molar ratio be (35~45)：1, more preferably (30~45)：1.The molecular sieve filtrate In chemical composition (molar ratio) can be SiO₂:Al₂O₃:Na₂O:CO₃ ^2-:H₂O=(30~45):1:(59~95):(27~ 47):(1610~2260).

In the case of, according to the invention it is preferred to, in step (3), the process of the high silicon mordenite hydrothermal crystallizing includes： I) sodium fluoride solid is added into the molecular sieve filtrate, obtains Synthesis liquid；Ii) CO is passed through into the Synthesis liquid₂Carry out carbon Point, it is 11~14 to make the pH of the Synthesis liquid；Iii) by step ii) obtained product carries out hydro-thermal crystalline substance at 140 DEG C~190 DEG C Change 15~72h, obtains high silicon mordenite hydrothermal crystallizing product；Iv) the high silicon mordenite hydrothermal crystallizing product is carried out Filtering, obtains third filter residue and second filtrate；The third filter residue washed, dry and roasting obtains the high silicon silk Geolyte.It can determine that finally obtained solid is high silicon mordenite by XRD (X-ray diffraction) method, as shown in Figure 3.

In the case of, according to the invention it is preferred to, the addition of the sodium fluoride solid is SiO in the Synthesis liquid₂10~ 20mol%.The sodium fluoride solid is top pure grade, the weight % of purity >=99, available commercially from Shanghai Hu Shi companies top pure grade (>= 99%) NaF.

According to the present invention, second filtrate, which can be improved, to be utilized, under preferable case, by the one of second filtrate During the heat preservation of part reuse to step (1) is filtered；Another part of second filtrate is evaporated crystallization After obtaining sodium carbonate, during the alkaline process roasting of reuse to step (1).To which flyash acid system residue of aluminum-extracted can be complete Portion is utilized, and is generated without waste.

The second object of the present invention, provides a kind of utilization method of flyash, and this method includes：Flyash is subjected to acid system It carries aluminium and obtains flyash acid system residue of aluminum-extracted and aluminium oxide；The method of flyash acid system residue of aluminum-extracted through the invention is prepared into To NaY types molecular sieve and high silicon mordenite.

Wherein, flyash can be the fine ash that catching is got off from the flue gas after the coal combustion that coal-burning power plant is discharged.It can be with It is to mainly contain SiO₂、Al₂O₃And TiO₂。SiO₂Content be about 20~40 weight %, Al₂O₃Content be about 45~60 weights Measure % and TiO₂Content be about 1.5~4.5 weight %.Such as the flyash of power plant of China of Inner Mongol ancient country of Shenhua discharge, wherein SiO₂Content be about 32.43 weight %, Al₂O₃Content be about 50.42 weight % and TiO₂Content be about 2.14 weights Measure %.

Heretofore described acid system carries aluminium and method well known in the art may be used, and details are not described herein.

In the present invention, the silica alumina ratio for the high silicon mordenite that can be obtained is 24 or more, preferably 24.4~33.5.

The present invention will be described in detail by way of examples below.

In following embodiment, by XRD (X-ray diffraction) method, penetrated using German Bruker companies D8ADVANCE types X Line diffractometer, under the conditions of 40Kv-40mA scan 4 °~75 ° of (2 θ), scanning result by with 43-0168 standard cards (PDF2004 editions) comparisons determine that obtained substance is NaY type molecular sieves；

By XRD (X-ray diffraction) method, using German Bruker companies D8ADVANCE type X-ray diffractometers, 4 °~75 ° of (2 θ) is scanned under the conditions of 40Kv-40mA, scanning result is compared by (PDF2004 editions) with 29-1257 standard cards It is right, determine that obtained substance is modenite.

By SEM-EDS (scanning electron microscope with energy disperse spectroscopy) method, simultaneously using 50 type EDS of Oxford companies of Britain X-man Arrange in pairs or groups 450 type SEM of FEI Co. of U.S. Navo NanoSEM, and modenite sample chemical ingredient letter is acquired under 15Kv voltages Number, the silica alumina ratio of high silicon mordenite is calculated.

The computational methods of the primary consumption efficiency μ of flyash acid system residue of aluminum-extracted are as previously described.

Flyash comes from power plant of China of Inner Mongol ancient country of Shenhua, and concrete composition content is as shown in table 1,

Table 1

Composition	Al₂O₃	SiO₂	P₂O₅	SO₃	K₂O	CaO	TiO₂	Fe₂O₃	MgO	Na₂O
											Content, weight %	50.42	32.43	0.19	4.0	0.37	3.03	2.14	1.71	0.18	0.03

Flyash acid system residue of aluminum-extracted comes autocollimatic Ge Er limited energies responsible company alumina producer, concrete composition content such as table Shown in 2.

Table 2

Composition	Al₂O₃	SiO₂	P₂O₅	SO₃	K₂O	CaO	TiO₂	Fe₂O₃	ZrO₂	Na₂O
											Content, weight %	13.4	78.7	0.14	0.35	0.16	0.37	5.2	0.45	0.29	-

Preparation example 1

This preparation example illustrates that flyash acid system residue of aluminum-extracted is prepared in flyash.

Flyash 100g is taken, 5mol/L hydrochloric acid solutions are added, 30min is stirred to react at 150 DEG C, filtering obtains after rinsing Rich aluminum solutions and flyash acid system residue of aluminum-extracted.

Flyash acid system residue of aluminum-extracted chemical composition is as shown in table 2.

Preparation example 2

This preparation example illustrates the preparation of NaY directed agents.

By sodium metaaluminate, sodium hydroxide, waterglass and deionized water, by Na₂O:Al₂O₃:SiO₂:H₂O=10.7:1:9.8: 215 molal weight proportioning carries out batch mixing, and is aged for 24 hours at 35 DEG C, obtains NaY directed agents.

SiO in directed agents₂Content is 152.6g/L.

Embodiment 1

(1) Na is added in flyash acid system residue of aluminum-extracted 50g₂CO₃Solid powder 60g is roasted at 860 DEG C after mixed grinding 90min, Quick air cools down after roasting, and is crushed to about 200 mesh hereinafter, obtaining roasting slag charge；

(2) after roasting slag charge progress dry magnetic separation being removed iron, take 70g that the 140ml deionized water (roastings relative to 100g are added The dosage of slag material, water is 200ml), water logging 20min is carried out under 100 DEG C and normal pressure, leaching dissolves out in roasting slag charge Na₂SiO₃And NaAlSiO₄, obtain the water logging product of solid-liquid mixing；Wherein solid is dissolution Na₂SiO₃And NaAlSiO₄Afterwards surplus Remaining product；Liquid is to contain Na₂SiO₃And NaAlSiO₄Solution；

(3) under high-speed stirred state, whole water logging product 100g (the equivalent slag charge 70g containing roasting) is taken, are added thereto Sodium carbonate liquor (reuse from the second filtrate of step (6), 15 weight % of concentration) 100ml is diluted, and is kept the temperature at 60 DEG C Filtered, add above-mentioned sodium carbonate liquor 100ml be rinsed (be equivalent to the roasting slag charge relative to 100g, above-mentioned Total dosage of two filtrates is 286ml)；It adds a certain amount of hot water (about 80 DEG C) to be rinsed, obtains first that volume is 400ml Filtrate, for synthesizing NaY type molecular sieves；The the first filter residue oven-dried weight 6.05g that will be obtained simultaneously, reuse to step (1) flyash In the alkaline process roasting of acid system residue of aluminum-extracted；

The chemical composition (molar ratio) of first filtrate is SiO₂:Al₂O₃:Na₂O:CO₃ ^2-:H₂O=16.5:1:17.1:9.9: 424。

(4) it takes the first filtrate 100ml that 3g directed agents (carrying out ester from preparation 2) are added, and passes through CO₂The mode tune of gaseous carbon point Sodium-silicon-rate value is saved, in this, as NaY molecular sieve synthesis mother liquid.The NaY molecular sieve mother liquor chemical composition is Na₂O:Al₂O₃: SiO₂:H₂O=16.9：1：16.3：420；

The NaY molecular sieve mother liquor is subjected to hydrothermal crystallizing for 24 hours at 95 DEG C, and obtained hydrothermal crystallizing product is passed through The second filter residue and molecular sieve filtrate are obtained after filter；Further the second filter residue is rinsed, drying, obtained product is obtained through XRD analysis To spectrogram as shown in Fig. 2, being compared with standard card, it is determined as NaY type molecular sieves；

The chemical composition (molar ratio) of molecular sieve filtrate is SiO₂:Al₂O₃:Na₂O:CO₃ ^2-:H₂O=30.2:1:65.2:37: 1610；

(5) to obtained molecular sieve filtrate about 100ml be added 1.05g NaF solids (GR top pure grades, >=99.0%, Shanghai Try in Shanghai), obtaining Synthesis liquid, (addition of NaF is about SiO in Synthesis liquid₂15mol%)；

CO is passed through into Synthesis liquid under stirring₂Carbon point is carried out to pH=11.03；Then at a temperature of 180 DEG C into Row hydrothermal crystallizing 40h, and by obtained hydrothermal crystallizing product through third filter residue and the second filtrate is obtained by filtration；Further by third Residue washing, drying, roasting, obtained product obtain spectrogram as shown in Figure 3 through XRD analysis, are compared with standard card, determine For high silicon mordenite；It is analyzed through EDS, gained modenite silica alumina ratio=24.4；

(6) by the second filtrate, (main component is Na₂CO₃, contain a small amount of Si, Al) part reuse be added step (3) sodium carbonate Solution, the dilution for water logging product and filtration and washing；The remainder of second filtrate obtains Na after evaporative crystallization₂CO₃Gu Body, in the alkaline process roasting of reuse to step (1) flyash acid system residue of aluminum-extracted.

The primary consumption efficiency μ of flyash acid system residue of aluminum-extracted is 87.90%；First filter residue can be recognized after recycling It is approximately 100% for the whole consumption efficiency of flyash acid system residue of aluminum-extracted；Na₂CO₃、CO₂, NaF realizes and recycles.

Embodiment 2

(1) Na is added in flyash acid system residue of aluminum-extracted 50g₂CO₃Solid powder 65g is roasted at 890 DEG C after mixed grinding 60min, Quick air cools down after roasting, and is crushed to about 200 mesh hereinafter, obtaining roasting slag charge；

(2) after roasting slag charge progress dry magnetic separation being removed iron, take 70g that the 105ml deionized water (roastings relative to 100g are added The dosage of slag material, water is 150ml), water logging 18min is carried out under 95 DEG C and normal pressure, leaching dissolves out in roasting slag charge Na₂SiO₃And NaAlSiO₄, obtain the water logging product of solid-liquid mixing；Wherein, solid is dissolution Na₂SiO₃And NaAlSiO₄Afterwards surplus Remaining product；Liquid is to contain Na₂SiO₃And NaAlSiO₄Solution.

(3) under high-speed stirred state, whole water logging product 93g (the equivalent slag charge 70g containing roasting) is taken, carbon is added thereto Acid sodium solution (reuse from the second filtrate of step (6), 20 weight % of concentration) 100ml is diluted, and keep the temperature at 80 DEG C into Row filters, add above-mentioned sodium carbonate liquor 100ml be rinsed (be equivalent to the roasting slag charge relative to 100g, above-mentioned second Total dosage of filtrate is 286ml) it adds a certain amount of hot water (about 90 DEG C) and is rinsed, obtain the first filter that volume is 400ml Liquid, for synthesizing NaY type molecular sieves；The the first filter residue oven-dried weight 6.93g that will be obtained simultaneously, reuse to step (1) flyash acid In the alkaline process roasting of method residue of aluminum-extracted；

The chemical composition (molar ratio) of first filtrate is SiO₂:Al₂O₃:Na₂O:CO₃ ^2-:H₂O=15.2:1:14.9:7.2: 428。

(4) it takes the first filtrate 100ml that 5g directed agents (carrying out ester from preparation 2) are added, and passes through CO₂The mode tune of gaseous carbon point Sodium-silicon-rate value is saved, in this, as NaY molecular sieve synthesis mother liquid.The NaY molecular sieve mother liquor chemical composition is Na₂O:Al₂O₃: SiO₂:H₂O=14.7：1：14.9：418；

The NaY molecular sieve mother liquor is subjected to hydrothermal crystallizing 36h at 100 DEG C, and obtained hydrothermal crystallizing product is passed through The second filter residue and molecular sieve filtrate is obtained by filtration；Further the second filter residue is rinsed, drying, obtained product is obtained through XRD analysis It is compared to spectrogram and standard card, is determined as NaY type molecular sieves；

The chemical composition (molar ratio) of molecular sieve filtrate is SiO₂:Al₂O₃:Na₂O:CO₃ ^2-:H₂O=33.4:1:59.1: 27.6:1680；

(5) the NaF solids of 0.7g are added to obtained molecular sieve filtrate 100ml, obtaining Synthesis liquid, (addition of NaF is about For SiO in Synthesis liquid₂10mol%)；

CO is passed through into Synthesis liquid under stirring₂Carbon point is carried out to pH=12.0；Then it is carried out at a temperature of 150 DEG C Hydrothermal crystallizing 36h, and by obtained hydrothermal crystallizing product through third filter residue and the second filtrate is obtained by filtration；Further third is filtered Wash heat is washed, dries, is roasted, and obtained product obtains spectrogram and compared with standard card through XRD analysis, is determined as high silicon mercerising boiling Stone is analyzed through EDS, gained modenite silica alumina ratio=24.7；

The primary consumption efficiency μ of flyash acid system residue of aluminum-extracted is 86.14%；First filter residue can be recognized after recycling It is approximately 100% for the whole consumption efficiency of flyash acid system residue of aluminum-extracted；Na₂CO₃、CO₂, NaF realizes and recycles.

Embodiment 3

(1) Na is added in flyash acid system residue of aluminum-extracted 50g₂CO₃Solid powder 50g is roasted at 830 DEG C after mixed grinding 120min, Quick air cools down after roasting, and is crushed to about 150 mesh hereinafter, obtaining roasting slag charge；

(2) after roasting slag charge progress dry magnetic separation being removed iron, take 70g that the 130ml deionized water (roastings relative to 100g are added The dosage of slag material, water is 186ml) water logging 15min is carried out under 105 DEG C and normal pressure, leaching dissolves out in roasting slag charge Na₂SiO₃And NaAlSiO₄, obtain the water logging product of solid-liquid mixing；Wherein solid is dissolution Na₂SiO₃And NaAlSiO₄Afterwards surplus Remaining product；Liquid is to contain Na₂SiO₃And NaAlSiO₄Solution；

(3) under high-speed stirred state, to the water logging product (the equivalent slag charge 70g containing roasting) of 100g, carbon is added thereto Acid sodium solution (reuse from the second filtrate of step (6), 25 weight % of concentration) 100ml is diluted, and keep the temperature at 70 DEG C into Row filters；Add nearly saturated sodium carbonate solution 100ml be rinsed (be equivalent to the roasting slag charge relative to 100g, above-mentioned Total dosage of two filtrates is 286ml), it adds a certain amount of hot water (about 70 DEG C) and is rinsed, obtain first that volume is 400ml Filtrate, for synthesizing NaY type molecular sieves；The the first filter residue oven-dried weight 6.60g that will be obtained simultaneously, reuse to step (1) flyash In the alkaline process roasting of acid system residue of aluminum-extracted；

The chemical composition (molar ratio) of first filtrate is SiO₂:Al₂O₃:Na₂O:CO₃ ^2-:H₂O=13.2:1:11.2:6.5: 399。

(4) it takes the first filtrate 100ml that 7g directed agents (carrying out ester from preparation 2) are added, and passes through CO₂The mode tune of gaseous carbon point Sodium-silicon-rate value is saved, in this, as NaY molecular sieve synthesis mother liquid.The NaY molecular sieve mother liquor chemical composition is Na₂O:Al₂O₃: SiO₂:H₂O=11.2：1：13.0：387；

The NaY molecular sieve mother liquor is subjected to hydrothermal crystallizing 28.0h, and the hydrothermal crystallizing product that will be obtained at 105 DEG C Through the second filter residue and molecular sieve filtrate is obtained by filtration；Further the second filter residue is rinsed, drying, obtained product through XRD analysis, It obtains spectrogram to compare with standard card, is determined as NaY type molecular sieves；

The chemical composition (molar ratio) of molecular sieve filtrate is SiO₂:Al₂O₃:Na₂O:CO₃ ^2-:H₂O=41:1:62.2:38.8: 2155；

(5) the NaF solids of 1.4g are added to obtained molecular sieve filtrate 100ml, obtaining Synthesis liquid, (addition of NaF is about For SiO in Synthesis liquid₂20mol%)；

CO is passed through into Synthesis liquid under stirring₂Carbon point is carried out to pH=13.838；Then at a temperature of 190 DEG C into Row hydrothermal crystallizing 15h, and by obtained hydrothermal crystallizing product through third filter residue and the second filtrate is obtained by filtration；Further by third Residue washing, drying, roasting, obtained product obtain spectrogram and are compared with standard card, be determined as high silicon mercerising through XRD analysis Zeolite is analyzed through EDS, gained modenite silica alumina ratio=33.5；

(6) by the second filtrate, (main component is Na₂CO₃, contain a small amount of Si, Al) part reuse be added step (3) the carbon Acid sodium solution, the dilution for water logging product and filtration and washing；The remainder of second filtrate obtains Na after evaporative crystallization₂CO₃ Solid, in the alkaline process roasting of reuse to step (1) flyash acid system residue of aluminum-extracted.

The primary consumption efficiency μ of flyash acid system residue of aluminum-extracted is 86.80%；First filter residue can be recognized after recycling It is approximately 100% for the whole consumption efficiency of flyash acid system residue of aluminum-extracted；Na₂CO₃、CO₂, NaF realizes and recycles.

Embodiment 4

(2) roasting slag charge is subjected to dry magnetic separation except after iron, taking 70g that 105ml deionized waters are added under 95 DEG C and normal pressure Carry out water logging 18min, the Na in leaching dissolution roasting slag charge₂SiO₃And NaAlSiO₄, obtain the water logging product of solid-liquid mixing；Its Middle solid is dissolution Na₂SiO₃And NaAlSiO₄Resultant product afterwards；Liquid is to contain Na₂SiO₃And NaAlSiO₄Solution；

(3) under high-speed stirred state, whole water logging product 100g (the equivalent slag charge 70g containing roasting) is taken, are added thereto Sodium carbonate liquor (reuse from the second filtrate of step (6), 20 weight % of concentration) 100ml is diluted, and is kept the temperature at 80 DEG C Filtered, add above-mentioned sodium carbonate liquor 100ml be rinsed (be equivalent to the roasting slag charge relative to 100g, above-mentioned Total dosage of two filtrates is 286ml)；It adds a certain amount of hot water (about 90 DEG C) to be rinsed, obtains first that volume is 400ml Filtrate, for synthesizing NaY type molecular sieves；The the first filter residue oven-dried weight 6.45g that will be obtained simultaneously, reuse to step (1) flyash In the alkaline process roasting of acid system residue of aluminum-extracted；

The chemical composition (molar ratio) of first filtrate is SiO₂:Al₂O₃:Na₂O:CO₃ ^2-:H₂O=13.4:1:15.7:7.8: 420。

(4) it takes the first filtrate 100ml that 10g directed agents (carrying out ester from preparation 2) are added, and passes through CO₂The mode of gaseous carbon point Sodium-silicon-rate value is adjusted, in this, as NaY molecular sieve synthesis mother liquid.The NaY molecular sieve mother liquor chemical composition is Na₂O:Al₂O₃: SiO₂:H₂O=15.2：1：13.1：401；

The chemical composition (molar ratio) of molecular sieve filtrate is SiO₂:Al₂O₃:Na₂O:CO₃ ^2-:H₂O=41:1:85.7:39.9: 2260；

(5) 1.4g NaF solids are added to obtained molecular sieve filtrate 100ml, obtaining Synthesis liquid, (addition of NaF is about SiO in Synthesis liquid₂20mol%)；

CO is passed through into Synthesis liquid under stirring₂Carbon point is carried out to pH=11.03；Then at a temperature of 140 DEG C into Row hydrothermal crystallizing 72h, and by obtained hydrothermal crystallizing product through third filter residue and the second filtrate is obtained by filtration；Further by third Residue washing, drying, roasting, obtained product obtain spectrogram and are compared with standard card, be determined as high silicon mercerising through XRD analysis Zeolite is analyzed through EDS, gained modenite silica alumina ratio=32.9；

The primary consumption efficiency μ of flyash acid system residue of aluminum-extracted is 87.10%；First filter residue can be recognized after recycling It is approximately 100% for the whole consumption efficiency of flyash acid system residue of aluminum-extracted；Na₂CO₃、CO₂, NaF realizes and recycles.

Embodiment 5

(2) roasting slag charge is subjected to dry magnetic separation except after iron, taking 70g that 140ml deionized waters are added under 100 DEG C and normal pressure Carry out water logging 20min, the Na in leaching dissolution roasting slag charge₂SiO₃And NaAlSiO₄, obtain the water logging product of solid-liquid mixing；Its Middle solid is dissolution Na₂SiO₃And NaAlSiO₄Resultant product afterwards；Liquid is to contain Na₂SiO₃And NaAlSiO₄Solution；

(3) under high-speed stirred state, whole water logging product 100g (the equivalent slag charge 70g containing roasting) is taken, are added thereto Sodium carbonate liquor (reuse from the second filtrate of step (6), 25 weight % of concentration) 100ml is diluted, and is kept the temperature at 60 DEG C Filtered, add above-mentioned sodium carbonate liquor 100ml be rinsed (be equivalent to the roasting slag charge relative to 100g, above-mentioned Total dosage of two filtrates is 286ml)；It adds a certain amount of hot water (about 80 DEG C) to be rinsed, obtains first that volume is 400ml Filtrate, for synthesizing NaY type molecular sieves；The the first filter residue oven-dried weight 5.98g that will be obtained simultaneously, reuse to step (1) flyash In the alkaline process roasting of acid system residue of aluminum-extracted；

The chemical composition (molar ratio) of first filtrate is SiO₂:Al₂O₃:Na₂O:CO₃ ^2-:H₂O=16.5:1:19.3:9.6: 430。

(4) it takes the first filtrate 100ml that 7g directed agents (carrying out ester from preparation 2) are added, and passes through CO₂The mode tune of gaseous carbon point Sodium-silicon-rate value is saved, in this, as NaY molecular sieve synthesis mother liquid.The NaY molecular sieve mother liquor chemical composition is Na₂O:Al₂O₃: SiO₂:H₂O=23.7：1：18.4：550；

The NaY molecular sieve mother liquor is subjected to hydrothermal crystallizing for 24 hours at 95 DEG C, and obtained hydrothermal crystallizing product is passed through Filter obtains the second filter residue and molecular sieve filtrate；Further the second filter residue is rinsed, drying, obtained product is obtained through XRD analysis Spectrogram is compared with standard card, is determined as NaY type molecular sieves；

The chemical composition (molar ratio) of molecular sieve filtrate is SiO₂:Al₂O₃:Na₂O:CO₃ ^2-:H₂O=32.2:1:95.1: 46.6:2100。

(5) the NaF solids of 1.05g are added to obtained molecular sieve filtrate 100ml, obtaining Synthesis liquid, (addition of NaF is about For SiO in Synthesis liquid₂15mol%)；

CO is passed through into Synthesis liquid under stirring₂Carbon point is carried out to pH=12.0；Then it is carried out at a temperature of 180 DEG C Hydrothermal crystallizing 44h, and by obtained hydrothermal crystallizing product through third filter residue and the second filtrate is obtained by filtration；Further third is filtered Wash heat is washed, dries, is roasted, and obtained product obtains spectrogram and compared with standard card through XRD analysis, is determined as high silicon mercerising boiling Stone is analyzed through EDS, gained modenite silica alumina ratio=27.8；

The primary consumption efficiency μ of flyash acid system residue of aluminum-extracted is 88.40%；First filter residue can be recognized after recycling It is approximately 100% for the whole consumption efficiency of flyash acid system residue of aluminum-extracted；Na₂CO₃、CO₂, NaF realizes and recycles.

Embodiment 6

(1) Na is added in flyash acid system residue of aluminum-extracted 50g₂CO₃Solid powder 65g is roasted at 890 DEG C after mixed grinding 60min, Quick air cools down after roasting, and is crushed to about 180 mesh hereinafter, obtaining roasting slag charge；

(2) roasting slag charge is subjected to dry magnetic separation except after iron, taking 70g that 105ml deionized waters are added under 100 DEG C and normal pressure Carry out water logging 15min, the Na in dissolution roasting slag charge₂SiO₃And NaAlSiO₄, obtain the water logging product of solid-liquid mixing；It is wherein solid Body is dissolution Na₂SiO₃And NaAlSiO₄Resultant product afterwards；Liquid is to contain Na₂SiO₃And NaAlSiO₄Solution；

(3) under high-speed stirred state, whole water logging product 93g (the equivalent slag charge 70g containing roasting) is taken, carbon is added thereto Acid sodium solution (reuse from the second filtrate of step (6), 20 weight % of concentration) 100ml is diluted, and keep the temperature at 80 DEG C into Row filters, add above-mentioned sodium carbonate liquor 100ml be rinsed (be equivalent to the roasting slag charge relative to 100g, above-mentioned second Total dosage of filtrate is 286ml)；It adds a certain amount of hot water (about 90 DEG C) to be rinsed, obtains the first filter that volume is 400ml Liquid, for synthesizing NaY type molecular sieves；The the first filter residue oven-dried weight 6.21g that will be obtained simultaneously, reuse to step (1) flyash acid In the alkaline process roasting of method residue of aluminum-extracted；

The chemical composition (molar ratio) of first filtrate is SiO₂:Al₂O₃:Na₂O:CO₃ ^2-:H₂O=13.4:1:15.6:7.8: 411。

(4) it takes the first filtrate 100ml that 7g directed agents (carrying out ester from preparation 2) are added, and passes through CO₂The mode tune of gaseous carbon point Sodium-silicon-rate value is saved, in this, as NaY molecular sieve synthesis mother liquid.The NaY molecular sieve mother liquor chemical composition is Na₂O:Al₂O₃: SiO₂:H₂O=15.5：1：13.3：406；

The chemical composition (molar ratio) of molecular sieve filtrate is SiO₂:Al₂O₃:Na₂O:CO₃ ^2-:H₂O=44.1:1:82.7: 40.7:2170；

CO is passed through into Synthesis liquid under stirring₂Carbon point is carried out to pH=13.838；Then at a temperature of 190 DEG C into Row hydrothermal crystallizing 15h, and by obtained hydrothermal crystallizing product through third filter residue and the second filtrate is obtained by filtration；Further by third Residue washing, drying, roasting, obtained product obtain spectrogram and are compared with standard card, be determined as high silicon mercerising through XRD analysis Zeolite is analyzed through EDS, gained modenite silica alumina ratio=31.6；

The primary consumption efficiency μ of flyash acid system residue of aluminum-extracted is 87.12%；First filter residue can be recognized after recycling It is approximately 100% for the whole consumption efficiency of flyash acid system residue of aluminum-extracted；Na₂CO₃、CO₂, NaF realizes and recycles.

Comparative example 1

(2) after roasting slag charge progress dry magnetic separation being removed iron, take 70g that the 700ml deionized water (roastings relative to 100g are added The dosage of slag material, water is 1000ml), water logging 40min is carried out under 100 DEG C and normal pressure, leaching dissolves out in roasting slag charge Na₂SiO₃And NaAlSiO₄, obtain the water logging product of solid-liquid mixing；Wherein solid is dissolution part Na₂SiO₃And NaAlSiO₄Afterwards Resultant product；Liquid is to contain Na₂SiO₃And NaAlSiO₄Solution；

(3) under high-speed stirred state, whole water logging product 650g (the equivalent slag charge 70g containing roasting) is taken, are kept the temperature at 60 DEG C Under filtered, the sodium carbonate liquor 100ml for adding 15 weight % is rinsed and (is equivalent to the fired slags relative to 100g Total dosage of material, sodium carbonate liquor is 286ml)；It adds a certain amount of hot water (about 80 DEG C) to be rinsed, the first obtained filter residue Oven-dried weight 20.08g, is computed, and it is only 59.84% that flyash acid system residue of aluminum-extracted, which once dissolves efficiency μ,.

Comparative example 1 high-temperature water leaching during be added water dosage it is excessive, be more than it is of the invention limit relative to 100g The roasting slag charge, the dosage of water is the liquid-solid ratio range of 150~200ml, causes the basicity of water logging product to reduce, silicon, aluminium Dissolution rate it is seriously relatively low, the first filter residue yield is higher, fails to realize the target that efficiently dissolves of flyash acid system residue of aluminum-extracted.

Comparative example 2

(3) under high-speed stirred state, whole water logging product 100g (the equivalent slag charge 70g containing roasting) is taken, are added thereto Boiling water 100ml is diluted, and keep the temperature filtered at 60 DEG C, add boiling water 100ml be rinsed (be equivalent to relative to The addition total amount of the roasting slag charge of 100g, boiling water is 286ml)；It adds a certain amount of hot water (about 80 DEG C) to be rinsed, obtains body Product is the first filtrate of 400ml, for synthesizing NaY type molecular sieves；The the first filter residue oven-dried weight 18.13g that will be obtained simultaneously, reuse Into the alkaline process roasting of step (1) flyash acid system residue of aluminum-extracted；

The chemical composition (molar ratio) of first filtrate is SiO₂:Al₂O₃:Na₂O:CO₃ ^2-:H₂O=8.9:1:12.2:7.7: 426。

(4) after taking the first filtrate 100ml that 3g directed agents (carrying out ester from preparation 2) are added, hydro-thermal is brilliant directly at 95 DEG C Change and synthesize NaY type molecular sieves for 24 hours, and solid product is obtained by filtration in obtained hydrothermal crystallizing product.

Obtained solid product detects the mixture consisting of amorphous aluminosilicate and multiple types molecular sieve through XRD, Pure NaY type molecular sieves can not be obtained.

Using boiling water water logging product is diluted in comparative example 2 and filtration and washing, and does not use sodium carbonate liquor, caused Si elements are diluting and the highly hydrolyzed hydrated SiO 2 for generating solid phase occur in filter process in water logging product liquid phase, to Serious filter loss is generated, the first filter residue yield is caused to be sharply increased, flyash acid system residue of aluminum-extracted once dissolves efficiency μ drops Down to 63.74%.Meanwhile hydrothermal synthesis is directly carried out according to conventional hydrothermal synthesis condition using the first filtrate, fail to obtain pure Net NaY type molecular sieves.

In addition, step (1)-(3) can not also obtain the synthesis mother liquid for being suitable for synthesizing high silicon content mordenite, cannot get pure High silicon mordenite.Tail washings or molecular sieve filtrate main component after synthesis NaY molecular sieve are sodium carbonate only containing micro- Si, Al of amount cannot act as silicon and aluminum source and further synthesize any other types of molecules sieve.

Comparative example 3

(3) under high-speed stirred state, whole water logging product 100g (the equivalent slag charge 70g containing roasting) is taken, are added thereto Sodium carbonate liquor (reuse from the second filtrate of step (5), 15 weight % of concentration) 100ml is diluted, and is kept the temperature at 60 DEG C Filtered, add above-mentioned sodium carbonate liquor 100ml be rinsed (be equivalent to the roasting slag charge relative to 100g, above-mentioned Total dosage of two filtrates is 286ml)；It adds a certain amount of hot water (about 80 DEG C) to be rinsed, obtains first that volume is 400ml Filtrate, for synthesizing NaY type molecular sieves；The the first filter residue oven-dried weight 6.13g that will be obtained simultaneously, reuse to step (1) flyash In the alkaline process roasting of acid system residue of aluminum-extracted；

The chemical composition (molar ratio) of first filtrate is SiO₂:Al₂O₃:Na₂O:CO₃ ^2-:H₂O=13.0:1:12.5:9.5: 424。

(4) take the first filtrate whole 400ml that sodium metaaluminate (NaAlO is added₂) 26.25g solids and 325ml deionized waters, NaY molecular sieve synthesis mother liquid is prepared, chemical composition (molar ratio) is SiO₂:Al₂O₃:Na₂O:CO₃ ^2-:H₂O=4:1:5.8: 3.0:240。

12g directed agents (carrying out ester from preparation 2) are added into the NaY synthesis mother liquids again and synthesize NaY type molecular sieves, at 95 DEG C For 24 hours, and solid product is obtained by filtration in obtained hydrothermal crystallizing product by lower hydrothermal crystallizing.Obtained solid product is detected through XRD, really Its fixed object phase composition is pure NaY type molecular sieves.

(main component is Na to (5) second filtrates₂CO₃, only contain a small amount of Si, Al) part reuse be added step (3) carbonic acid Sodium solution, the dilution for water logging product and filtration and washing；The remainder of second filtrate obtains Na after evaporative crystallization₂CO₃Gu Body, in the alkaline process roasting of reuse to step (1) flyash acid system residue of aluminum-extracted.

According to being formulated conventionally NaY type molecular sieve synthesis mother liquids in comparative example 3, but need additional silicon source sodium metaaluminate (M_out =26.25g) adjustment silica alumina ratio, as a result the primary consumption efficiency μ of flyash acid system residue of aluminum-extracted is only 57.16%；And it obtains The second filtrate main component be sodium carbonate, only contain micro sial, also can not further be prepared as silicon and aluminum source ZSM-5 or It is a kind of that other any types molecular sieves, i.e. products obtained therefrom only have NaY types molecular sieve.

Comparative example 4

(1) Na is added in flyash acid system residue of aluminum-extracted 50g₂CO₃Solid powder 60g is roasted at 890 DEG C after mixed grinding 60min, Quick air cools down after roasting, and is crushed to about 200 mesh hereinafter, obtaining roasting slag charge；

(3) under high-speed stirred state, whole water logging product 100g (the equivalent slag charge 70g containing roasting) is taken, are added thereto Sodium carbonate liquor (reuse from the second filtrate of step (6), 15 weight % of concentration) 100ml is diluted, and is kept the temperature at 60 DEG C Filtered, add above-mentioned sodium carbonate liquor 100ml be rinsed (be equivalent to the roasting slag charge relative to 100g, above-mentioned Total dosage of two filtrates is 286ml)；It adds a certain amount of hot water (about 80 DEG C) to be rinsed, obtains first that volume is 400ml Filtrate, for synthesizing NaY type molecular sieves；The the first filter residue oven-dried weight 6.25g that will be obtained simultaneously, reuse to step (1) flyash In the alkaline process roasting of acid system residue of aluminum-extracted；

The chemical composition (molar ratio) of first filtrate is SiO₂:Al₂O₃:Na₂O:CO₃ ^2-:H₂O=12.6:1:19:9:440.

(4) it takes the first filtrate whole 400ml (the equivalent slag charge 70.0g containing roasting) that 866ml deionized waters are added to be hydrolyzed (relative to the roasting slag charge of 100g, the total volume of hydrolysate is 1237ml)；Sodium metasilicate (Na is added again₂SiO₃) solid 122.07g, as the hydrothermal crystallizing mother liquor of high silicon mordenite after being completely dissolved, chemical composition (molar ratio) is SiO₂: Al₂O₃:Na₂O:CO₃ ^2-:H₂O=32.6:1:39:9:1402.

(5) the NaF solids of 1.4g are added to obtained hydrothermal crystallizing mother liquor 100ml, obtain the Synthesis liquid (addition of NaF About SiO in Synthesis liquid₂20mol%)；

CO is passed through into Synthesis liquid under stirring₂Carbon point is carried out to pH=12.0；Then it is carried out at a temperature of 180 DEG C Hydrothermal crystallizing 36h, and by obtained hydrothermal crystallizing product through third filter residue and the second filtrate is obtained by filtration；Further third is filtered Wash heat is washed, dries, is roasted, and for obtained product through XRD analysis, it is similar to that shown in Fig. 3 to obtain spectrogram, is determined as high silicon mercerising boiling Stone is analyzed through EDS, gained modenite silica alumina ratio=27.6；

The composition that the first filtrate is adjusted in comparative example 4 is used for synthesizing high silicon content mordenite, needs additional silicon source sodium metasilicate (M_out=122.07g), high silicon mordenite as a result can only be produced, and lead to the primary consumption of flyash acid system residue of aluminum-extracted Efficiency μ is only 25.43%.And the second obtained filtrate main component is sodium carbonate, only contains micro sial, can not also make NaY or other any types molecular sieves are further prepared for silicon and aluminum source；I.e. products obtained therefrom only has high silicon mordenite one kind.

From above-described embodiment as can be seen that method provided by the invention need not can additionally add silicon source or silicon source Under the conditions of, realize making full use of for flyash acid system residue of aluminum-extracted.It, can while efficiently consumption flyash acid system residue of aluminum-extracted To produce the NaY types molecular sieve and high silicon mordenite that obtain high added value simultaneously.

In addition, method provided by the invention can also realize making full use of for flyash, without additional addition silicon source or aluminium Realize flyash conversion production aluminium oxide, NaY types molecular sieve and high silicon mordenite in source.

Claims

1. a kind of method that flyash acid system residue of aluminum-extracted prepares NaY types molecular sieve and high silicon mordenite, including：

(1) flyash acid system residue of aluminum-extracted is subjected to alkaline process roasting, obtains roasting slag charge；The roasting slag charge carries out high temperature successively Water logging and heat preservation are filtered, and the first filtrate is obtained；

(3) the molecular sieve filtrate and sodium fluoride are subjected to high silicon mordenite hydrothermal crystallizing, obtain high silicon mordenite and the Two filtrates.

2. according to the method described in claim 1, wherein, in step (1), the process of the alkaline process roasting includes：By 100 weights The containing sodium carbonate material of the flyash acid system residue of aluminum-extracted and 100~130 parts by weight of measuring part carries out mixed grinding, obtains Grinding product is crushed to 200 mesh hereinafter, obtaining the roasting slag charge after roasting 60min~120min at 830 DEG C~890 DEG C.

3. according to the method described in claim 1, wherein, in step (1), the process of the high temperature water logging includes：It will be described Roasting slag charge mixes progress with water after removing iron, obtains water logging product；Water soaking temperature is 95 DEG C~105 DEG C, and the water logging time is 15min~20min；

Preferably, relative to the roasting slag charge of 100g, the dosage of water is 150~200ml.

4. according to the method described in claim 3, wherein, in step (1), the process of the heat preservation filtering includes：It will be described Water logging product is diluted, filters and is rinsed with second filtrate of part, obtains the first filter residue and first filtrate；It crosses Filter temperature is maintained at 60 DEG C~80 DEG C；

Preferably, relative to the roasting slag charge of 100g, the dosage of second filtrate is 250~350ml；

Preferably, SiO in first filtrate₂With Al₂O₃Molar ratio be (10~25)：1.

5. according to the method described in claim 4, wherein, this method further comprises：By first filter residue after drying Reuse step (1) is added in the flyash acid system residue of aluminum-extracted.

6. according to the method described in claim 1, wherein, in step (2), the process of the NaY types zeolite-water thermal crystallisation Including：

A) configuration NaY molecular sieve mother liquor in first filtrate is added in directed agents, and adjusts the group of the NaY molecular sieve mother liquor At meeting Na₂O:Al₂O₃:SiO₂:H₂O=(11.1~23.7)：1：(12.8~18.4)：(386~550)；

B) product for obtaining step a) carries out 18~36h of hydrothermal crystallizing at 95 DEG C~105 DEG C, obtains NaY type zeolite-waters Thermal crystallisation product；

C) the NaY types molecular sieve water heat crystallization product is filtered, obtains the second filter residue and the molecular sieve filtrate；By institute The second filter residue is stated to be dried to obtain the NaY types molecular sieve；

Preferably, SiO in the molecular sieve filtrate₂With Al₂O₃Molar ratio be (30~45)：1.

7. according to the method described in claim 1, wherein, in step (3), the process of the high silicon mordenite hydrothermal crystallizing Including：

I) sodium fluoride solid is added into the molecular sieve filtrate, obtains Synthesis liquid；

Ii) CO is passed through into the Synthesis liquid₂Carbon point is carried out, it is 11~14 to make the pH of the Synthesis liquid；

Iii) by step ii) obtained product carries out 15~72h of hydrothermal crystallizing at 140 DEG C~190 DEG C, obtain high silicon mercerising boiling Stone hydrothermal crystallizing product；

Iv) the high silicon mordenite hydrothermal crystallizing product is filtered, obtains third filter residue and second filtrate；It is described Third filter residue washed, dry and roasting obtains the high silicon mordenite.

8. according to the method described in claim 7, wherein, the addition of the sodium fluoride solid is SiO in the Synthesis liquid₂'s 10~20mol%.

9. according to the method described in claim 1, wherein, this method further comprises：

During the heat preservation of a part of reuse of second filtrate to step (1) is filtered；By second filtrate Another part be evaporated after crystallization obtains sodium carbonate, during the alkaline process roasting of reuse to step (1).

10. the utilization method of flyash, this method include：Flyash progress acid system is carried into aluminium and obtains flyash acid system residue of aluminum-extracted And aluminium oxide；NaY types are prepared by the method described in any one of claim 1-9 in flyash acid system residue of aluminum-extracted Molecular sieve and high silicon mordenite.