CN106587098B

CN106587098B - Flyash acid system residue of aluminum-extracted prepares the method for 13X type molecular sieve and type ZSM 5 molecular sieve and the utilization method of flyash

Info

Publication number: CN106587098B
Application number: CN201611091098.1A
Authority: CN
Inventors: 刘汇东; 孙琦; 王宝冬; 徐文强; 张中华; 肖永丰; 李歌
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: 2016-12-01
Filing date: 2016-12-01
Publication date: 2018-11-20
Anticipated expiration: 2036-12-01
Also published as: CN106587098A

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 13X type molecular sieve and type ZSM 5 molecular sieve 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 successively carries out high temperature water logging and heat preservation filtering, obtains the first filtrate；(2) first filtrate is subjected to 13X type zeolite-water thermal crystallisation, obtains 13X type molecular sieve and molecular sieve filtrate；(3) the molecular sieve filtrate is subjected to type ZSM 5 molecular sieve hydrothermal crystallizing, obtains type ZSM 5 molecular sieve 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 13X type molecular sieve and type ZSM 5 molecular sieve The utilization method of method and flyash

Technical field

The present invention relates to the utilization fields of flyash acid system residue of aluminum-extracted and flyash, and in particular, to a kind of flyash Acid system residue of aluminum-extracted prepares the method for 13X type molecular sieve and type ZSM 5 molecular sieve and the utilization method of flyash.

Background technique

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 development and 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 amount 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 of every production₂O₃About 130 tons will be discharged Residue of aluminum-extracted.The residue discharge ratio that alkaline process proposes aluminium technique is then higher.And promulgated within 2013 according to Ministry of Industry and Information《Aluminium industry is quasi- 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 black, 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 mentions 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 applications such as catalysis, adsorbing separation, ion exchange obtain it is important and It is widely applied.

13X type is a kind of common molecular sieve, and any molecule of aperture 1.0nm, adsorbable 0.364nm~1.0nm can be used Carrier, water and carbon dioxide eutectoid content, water and hydrogen sulfide gas eutectoid content are assisted in catalyst, is mainly used in medicine and air pressure The drying of compression system, the market price is at 10,000 yuan/ton or more.ZSM-5 molecular sieve is a kind of height with special intersection cellular structure Silicon type molecular sieve, channel diameter about 0.5nm have good thermal stability, hydrothermal stability and shape selective catalysis efficiency, at present It is widely used in the fields such as petrochemical industry.Type ZSM 5 molecular sieve, which is ten thousand yuan/ton of 30-50 according to its different price of silica alumina ratio, to be differed. Industrial synthesis zeolite generallys use the industrial chemicals such as waterglass, sodium aluminate or aluminium hydroxide, and cost is also relatively high. Many scholars have carried out with the research of same type raw material (including flyash, gangue, kaolin etc.) hydrothermal synthesis molecular sieve.

CN101734683A discloses a kind of method for preparing 13X molecular sieve as silicon source by aluminous fly-ash desiliconization liquid： The silicon sources such as aluminum sulfate or aluminium chloride are incorporated into desiliconization liquid, in SiO₂/Al₂O₃=3~5, Na₂O/SiO₂=1.0~1.5, H₂O/ Na₂The 13X molecular sieve of high-crystallinity has been synthesized under the system of O=35~60 through aging, crystallization.This method needs additional addition aluminium Source is not complete efficiently consumption flyash.

《Utilize the experimental study of flyash synthesis 13X zeolite molecular sieve》(Zhang Xihuan etc., Chinese non-metallic mineral industry are led Periodical, the 2nd phase in 2003,13X.23-35) use flyash for raw material, a certain proportion of sodium metasilicate tune is incorporated after sodium carbonate roasting Section silica alumina ratio is added prefabricated amorphous state 13X crystal seed, adds a certain amount of sodium hydroxide and water carries out hydrothermal crystallizing and synthesizes Include the amorphous 13X molecular sieve in part.This method is raw material using flyash, is not complete efficiently consumption flyash,

《The research of 13X type zeolite molecular sieve is prepared by the tailings after coal ash lifting calcium iron》(Wang Minghua etc., material and metallurgy Journal, the 1st phase of volume 14, in March, 2015,13X.58-61) utilize flyash acid system to remove the acid sludge of de-iron calcium for raw material, first Sodium carbonate roasting, water logging dissolution, then addition directed agents and template (CTAB), 100 DEG C of hydrothermal crystallizing 20h are synthesized into slurry 13X molecular sieve, wherein there are apparent noncrystalline sial.This method is raw material using the acid sludge that flyash acid system removes de-iron calcium, 13X type molecular sieve can only be produced, and waste material can be generated, cannot be fully utilized flyash acid system except de-iron calcium acid sludge in silicon and Aluminium.

CN103435064A discloses a kind of method using coal ash for manufacturing for nanoscale ZSM-5 molecular sieve, including：Fine coal Ash pretreatment；Using coal ash for manufacturing for aluminium hydroxide and sodium metasilicate；By aluminium hydroxide and sodium metasilicate and water, template tetrapropyl hydrogen Amine-oxides mixing, microwave heating carry out hydrothermal synthesis ZSM-5 molecular sieve.The process route of the method is first to be prepared into from flyash To aluminium hydroxide and sodium metasilicate, then synthesis of molecular sieve again, step is complicated, and can only be produced to obtain ZSM-5 type point by flyash Son sieve.

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 deployed, but this mode is unfavorable for the efficient consumption of flyash acid system residue of aluminum-extracted.

Therefore, have by preparing molecular sieve 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.

Summary of the invention

The purpose of the present invention is to solve the consumptions how to be acidified residue of aluminum-extracted by preparing molecular sieve raising flyash Efficiency, coproduction high-silicon type and low silicon type molecular sieve, and the problem of how to utilize flyash, provide a kind of flyash acid system and mention Residue of aluminum prepares the method for 13X type molecular sieve and type ZSM 5 molecular sieve 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 compared with ordinary fly ash, and aluminium content significantly reduces, and the acid-soluble element such as Fe, Mg is mentioned in acid system It is largely removed during aluminium, wherein SiO₂With Al₂O₃Molar ratio (can be expressed as silica alumina ratio or SiO below₂/Al₂O₃) 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, If flyash acid system residue of aluminum-extracted is directly used in synthesizing low silicon molecular sieve (such as 13X type molecular sieve, silica alumina ratio are about 2~3), Si is significantly excessive, needs additional silicon source；And it is used for synthesizing high-silicon type molecular sieve (silica alumina ratio is about > 30, such as type ZSM 5 molecular sieve) When, Al element is excessive, and needs additional silicon source.Obviously external silicon source or silicon source are introduced, needs additionally to consume other resources, it can not Effectively improve the utilization rate of flyash acidification residue of aluminum-extracted.On the other hand, flyash acidification residue of aluminum-extracted in, mullite, quartz, The low activities such as anatase 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.Cause How this is not necessarily to additional silicon or aluminium, needs integrate rationally and preferably using silicon, the bauxite resource in flyash acidification residue of aluminum-extracted Consider above-mentioned factor.The present invention is proposed to improve the consumption efficiency of flyash acidification residue of aluminum-extracted with regard to the invention people, realizes fine coal The efficient consumption of ash acidification residue of aluminum-extracted, and realize coproduction 13X type molecular sieve and type ZSM 5 molecular sieve.

To achieve the goals above, the present invention provide a kind of flyash acid system residue of aluminum-extracted preparation 13X type molecular sieve and The method of type ZSM 5 molecular sieve, including：

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

(2) first filtrate is subjected to 13X type zeolite-water thermal crystallisation, obtains 13X type molecular sieve and molecular sieve filtrate；

(3) the molecular sieve filtrate is subjected to type ZSM 5 molecular sieve hydrothermal crystallizing, obtains type ZSM 5 molecular sieve and second Filtrate.

The present invention also provides a kind of utilization method of flyash, this method includes：Flyash progress acid system is mentioned aluminium to obtain To flyash acid system residue of aluminum-extracted and aluminium oxide；13X is prepared in flyash acid system residue of aluminum-extracted by means of the present invention Type molecular sieve and type ZSM 5 molecular sieve.

Through the above technical solutions, method of the 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；Powder is realized 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 benefit 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, i.e., using the abundant and efficient consumption of flyash acid system residue of aluminum-extracted.

Method of the invention is to realize the more preferable utilization of flyash acid system residue of aluminum-extracted, is particularly limited to first using low silica-alumina ratio The synthesis of molecular sieve can not only obtain in 13X type molecular sieve, but also the adjustable filtrate generated through synthesis 13X type molecular sieve Silicon, aluminium ratio, to be appropriate for the type ZSM 5 molecular sieve of synthesizing high-silicon aluminium ratio again, 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 mention 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, 13X type molecular sieve and ZSM-5 type Molecular sieve makes flyash be fully used, and there is no waste sludge discharges.

Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.

Detailed description of the invention

The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, 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 13X type molecular sieve prepared by the present invention；

Fig. 3 is the XRD spectra of type ZSM 5 molecular sieve prepared by the present invention.

Specific embodiment

Detailed description of the preferred embodiments 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 13X type molecular sieve and ZSM-5 type point The method of son sieve, including：

In the present invention, flyash acid system residue of aluminum-extracted is mainly contained：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 preservation in mullite and quartz in.The low activities group such as mullite, quartz, anatase Divide and be further enriched with compared with original powder coal ash, the poor activity of silicon, aluminium element, be unfavorable for flyash acidification residue of aluminum-extracted utilizes production point Son sieve.

According to the present invention, step (1) makes the flyash acid for handling the flyash acid system residue of aluminum-extracted Silicon, aluminium element in method residue of aluminum-extracted can activate, and the synthesis that can more effectively participate in molecular sieve utilizes, and can rationally adjust The content reaction raw materials requirement that meets synthesizing low silicon aluminium than molecular sieve of silicon in whole first filtrate made, aluminium element. In step (1), the alkaline process roasting purpose is have the mineral constituent of stable crystal structure lower in mullite, quartz etc. Maturing temperature under sufficiently decompose, make wherein Si, Al element sufficiently activated.Added by being acidified in residue of aluminum-extracted to flyash Enter alkaline matter to be roasted together, the activation of Si, Al element may be implemented.Under preferable case, in step (1), the alkali Method roasting process include：The flyash acid system residue of aluminum-extracted of 100 parts by weight and 100~130 parts by weight are contained into carbonic acid Sodium material carries out mixed grinding, and obtained grinding product is crushed to again after roasting 60min~120min at 830 DEG C~890 DEG C 200 mesh are hereinafter, obtain the roasting slag charge.

In the present invention, in step (1), after completing the roasting, the product of roasting can be rapidly cooled with air, Cooling obtains the roasting slag charge.

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

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 be with the Na in the water-soluble roasting slag charge described out₂SiO₃And 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 Soaking temperature is 95 DEG C~105 DEG C, 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.

According to the present invention, it is further filtered by the heat preservation 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 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 being located within above-mentioned limited range, first filter residue that can be obtained With the smallest 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 in step (1) for the flyash acid system residue of aluminum-extracted of alkaline process roasting；

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 mention aluminium residual Silicon, aluminium element in slag switch to active component, and with Na₂SiO₃And NaAlSiO₄Form be extracted into first filtrate.Institute State SiO in the first filtrate₂With Al₂O₃Molar ratio be (10~25)：1.It is preferred that SiO in first filtrate₂With Al₂O₃Mole Than for (12~20)：1；More preferably (12~15)：1.

In the present invention, the chemical composition (molal weight ratio) that can control first filtrate is SiO₂:Al₂O₃:Na₂O: CO₃ ^2-:H₂O=(10~25):1:(13~20):(3.5~11):(340~430).

Existing conventional techniques usually deploy the silica alumina ratio in hydrothermal crystallizing mother liquor in synthesizing low silicon molecular sieve analog 13X It is limited to (3~5)：1 or so；And in synthesizing high-silicon molecular sieve analog ZSM-5, usually by the silica alumina ratio tune in hydrothermal crystallizing mother liquor With being limited to 30:1 or more.It is easier to synthesize pure 13X type or ZSM-5 type molecule under the conditions of the silica alumina ratio of above-mentioned mother liquor Sieve.

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 be separately added into outside if producing 13X type or type ZSM 5 molecular sieve according to routine techniques Silicon source is to turn down silica alumina ratio to (3~5)：1, or external silicon source is added so that silica alumina ratio is turned up to 30:1 or more.And external silicon, silicon source (i.e. M_out) introducing will result directly in flyash acid system residue of aluminum-extracted once dissolve efficiency μ reduction so that influence flyash acid The consumption efficiency of method residue of aluminum-extracted entirety, that is, preparing the flyash acid system residue of aluminum-extracted quality that unit mass product is dissolved will drop It is low.

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 be improved filter efficiency, reduce filter loss, reduce the first filter residue yield, helps 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 It can be using suction filtration or filters pressing mode.

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

According to the present invention, first filtrate synthesis 13X type molecular sieve that step (2) is obtained using step (1).And it closes At condition make after synthesis in the obtained molecular sieve filtrate, silicon, aluminium element composition be suitble to further synthesize ZSM-5 type Molecular sieve.Under preferable case, in step (2), the process of the 13X type zeolite-water thermal crystallisation includes：A) by the filtrate Add water to be hydrolyzed, obtains hydrolysate；The additional amount of water meets the roasting slag charge relative to 100g, the hydrolysate Total volume be 850~1000ml；B) CO is passed through into the hydrolysate₂Carbon point is carried out, the pH of the hydrolysate is made 13~15；C) 13X type molecular sieve seed is added or is added without in the product obtained to step b), then at 90 DEG C~110 DEG C 15~30h of hydrothermal crystallizing is carried out, 13X type molecular sieve water heat crystallization product is obtained；The dosage of the 13X type molecular sieve seed is institute State 0~10 weight % of roasting slag charge；D) the 13X type molecular sieve water heat crystallization product is filtered, obtains the second filter residue With the molecular sieve filtrate；Second filter residue is dried to obtain the 13X type molecular sieve.It is described in above-mentioned synthesis process 13X type molecular sieve seed is known substance, can be synthesized by laboratory according to conventional method, and synthetic method is known no longer superfluous It states, SiO₂With Al₂O₃Molar ratio be (2~3)：1.It can be measured by XRD (X-ray diffraction) method finally obtained solid The XRD spectra of body product, and compared with standard spectrogram, determination obtains 13X type molecular sieve.

According to the present invention, it by the restriction in step (2) to 13X type molecular sieve water heat crystallization condition, can obtain pure 13X type molecular sieve and chemical composition be suitable for the molecular sieve filtrate of type ZSM 5 molecular sieve 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 (40~45)：1.The molecular sieve filtrate In chemical composition (molal weight ratio) can be SiO₂:Al₂O₃:Na₂O:CO₃ ^2-:H₂O=(35~45):1:(65~90):(60 ~85):(1900~2300).

In the case of, according to the invention it is preferred to, in step (3), the process packet of the type ZSM 5 molecular sieve hydrothermal crystallizing It includes：I) organic formwork agent and/or type ZSM 5 molecular sieve crystal seed are added into the molecular sieve filtrate, obtains Synthesis liquid；Ii) to CO is passed through in the Synthesis liquid₂Carbon point is carried out, the pH 9~12 of the Synthesis liquid is made；Iii) the obtained product of step ii) is existed 15~48h of hydrothermal crystallizing is carried out at 150 DEG C~190 DEG C, obtains type ZSM 5 molecular sieve hydrothermal crystallizing product；Iv) by the ZSM- 5 type molecular sieve water heat crystallization products are filtered, and obtain third filter residue and second filtrate；The third filter residue is washed It washs, dry and roasting obtains the type ZSM 5 molecular sieve.Second filter residue can be determined by XRD (X-ray diffraction) method The substance being dried to obtain is type ZSM 5 molecular sieve.

In the case of, according to the invention it is preferred to, the additional amount of the organic formwork is SiO in the Synthesis liquid₂3~ 10mol%；The organic formwork is selected from tetrapropylammonium hydroxide (TPAOH), 4-propyl bromide (TPABr), n-propylamine and just At least one of butylamine.In the present invention, the process of hydrothermal crystallizing can be elder generation in step (iii) when the organic formwork is added In 120 DEG C~150 DEG C progress 2~12h of hydrothermal crystallizing, 150 DEG C~190 DEG C 5~48h of progress hydrothermal crystallizing are then heated to.

In the case of, according to the invention it is preferred to, the additional amount of the type ZSM 5 molecular sieve crystal seed is SiO in the Synthesis liquid₂ 3~15mol%, the SiO of the type ZSM 5 molecular sieve crystal seed₂With Al₂O₃Molar ratio=(50~400)：1.The ZSM-5 type Molecular sieve seed can be known substance, and due to alumina content highest only 3% in crystal seed, calculating the molecular weight of crystal seed influences Little, it is 60 that the molecular weight that can be approximately considered crystal seed, which is the molecular weight of silica, is calculated with this and determines the ZSM-5 type point The additional amount of son sieve crystal seed is SiO in the Synthesis liquid₂3~15mol%.The type ZSM 5 molecular sieve crystal seed can be commercially available The type ZSM 5 molecular sieve that the trade mark produced from Catalyst Factory, Nankai Univ is NKF-5 is crystal seed.

According to the present invention, second filtrate, which can be improved, is 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 mentions aluminium and obtains flyash acid system residue of aluminum-extracted and aluminium oxide；Flyash acid system residue of aluminum-extracted is prepared by means of the present invention To 13X type molecular sieve and type ZSM 5 molecular sieve.

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 mentions aluminium and can adopt with method known in this field, and details are not described herein.

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 company D8 ADVANCE type X Line diffractometer, under the conditions of 40Kv-40mA scan 4 °~75 ° of (2 θ), scanning result by with 38-0284 standard card (PDF2004 editions) comparisons determine that obtained substance is 13X type molecular sieve；

By XRD (X-ray diffraction) method, using German Bruker company D8 ADVANCE type X-ray diffractometer, 4 °~75 ° of (2 θ) is scanned under the conditions of 40Kv-40mA, scanning result with 44-0003 standard card (PDF2004 editions) by comparing It is right, determine that obtained substance is type ZSM 5 molecular sieve.

The calculation method of the primary consumption efficiency μ of flyash acid system residue of aluminum-extracted is as previously described.

Flyash comes from Shenhua Inner Mongol power plant of China of ancient country, 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 energy 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 solution is 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 component is as shown in table 2.

Preparation example 2

This preparation example illustrates the preparation of 13X type molecular sieve seed.

It is silicon source by silicon source, sodium aluminate of sodium metasilicate, water is added to configure 13X type molecular sieve water heat crystallization mother liquor hydrothermal crystallizing The composition (molal weight ratio) of mother liquor is SiO₂:Al₂O₃:Na₂O:H₂O=5:1:1.5:50.

Above-mentioned mother liquor is transferred in hydrothermal reaction kettle, hydro-thermal reaction 20h is stood at 95 DEG C.

Product after reaction is filtered, washed, is dried, and is obtained pure 13X type molecular sieve solid powder, is used as 13X type molecular sieve seed in the present invention..

The average grain diameter of 13X type molecular sieve seed is 1~3 μm, silica alumina ratio 3.

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 is cooling 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 (roasting relative to 100g of 140ml deionized water is added Slag material, the dosage of water are 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, is added thereto Sodium carbonate liquor (second filtrate of the reuse from step (6), 15 weight % of concentration) 100ml is diluted, and is kept the temperature at 60 DEG C It is filtered；Add above-mentioned second filtrate 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 80 DEG C) to be rinsed, obtains the first filter that volume is 400ml Liquid, for synthesizing 13X type molecular sieve；The the first filter residue oven-dried weight 6.30g 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 (molal weight ratio) of first filtrate is SiO₂:Al₂O₃:Na₂O:CO₃ ^2-:H₂O=12:1:18:9.5: 430。

(4) it takes the first filtrate 120ml (the equivalent slag charge 21.0g containing roasting) that 50ml deionized water is added to be hydrolyzed (relatively In the roasting slag charge of 100g, the total volume of hydrolysate is 714ml)；It is passed through under stirring into obtained hydrolysate Carbon dioxide carries out carbon point to pH=13.455；Then the hydrolysate after carbon point is subjected to hydrothermal crystallizing 15.5h at 95 DEG C, And the second filter residue and molecular sieve filtrate is obtained by filtration in obtained hydrothermal crystallizing product；Further the second filter residue is rinsed, is dried Dry, obtained product is analysed through XRD, obtains spectrogram as shown in Figure 2, is compared with standard card, is determined as 13X type molecular sieve；

The chemical composition (molal weight ratio) of molecular sieve filtrate is SiO₂:Al₂O₃:Na₂O:CO₃ ^2-:H₂O=37.2:1: 72.7:68.2:1910；

(5) to obtained molecular sieve filtrate 100ml be added 0.7g ZSM-5 crystal seed (Catalyst Factory, Nankai Univ, NKF-5, SiO₂/Al₂O₃=200, molecular weight is about that 60), obtaining Synthesis liquid, (additional amount of ZSM-5 crystal seed is SiO in Synthesis liquid₂'s 10mol%)；

CO is passed through into Synthesis liquid under stirring₂Carbon point is carried out to pH=10.447；Then at a temperature of 180 DEG C into Row hydrothermal crystallizing 21h, and third filter residue and the second filtrate is obtained by filtration in obtained hydrothermal crystallizing product；Further by third Residue washing, drying, roasting, obtained product obtain spectrogram as shown in Figure 3 through XRD analysis, compare with standard card, determine For type ZSM 5 molecular sieve；

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

The primary consumption efficiency μ of flyash acid system residue of aluminum-extracted is 87.4%；First filter residue is after recycling, it is believed that The whole consumption efficiency of flyash acid system residue of aluminum-extracted is approximately 100%.

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 is cooling after roasting, and is crushed to about 180 mesh hereinafter, obtaining roasting slag charge；

(2) after roasting slag charge progress dry magnetic separation being removed iron, take 70g that the (roasting relative to 100g of 105ml deionized water is added Slag material, the dosage of water are 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 100g (the equivalent slag charge 70g containing roasting) is taken, is added thereto Sodium carbonate liquor (second filtrate of the reuse from step (6), 20 weight % of concentration) 100ml is diluted, and is kept the temperature at 80 DEG C It is filtered；Add above-mentioned second filtrate 100ml be rinsed (be equivalent to the roasting slag charge relative to 100g, above-mentioned second Total dosage of filtrate adds a certain amount of hot water (about 90 DEG C) for 286ml) and is rinsed, and obtains the first filter that volume is 400ml Liquid, for synthesizing 13X type molecular sieve；The the first filter residue oven-dried weight 6.63g 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 (molal weight ratio) of first filtrate is SiO₂:Al₂O₃:Na₂O:CO₃ ^2-:H₂O=13.4:1:18: 9.5:420。

(4) 50ml deionized water water is added in the first filtrate 120ml (the equivalent slag charge 21.0g containing roasting) and (phase is hydrolyzed For the roasting slag charge of 100g, the total volume of hydrolysate is 857ml)；Lead under stirring into obtained hydrolysate Enter CO₂Carbon point is carried out to pH=13.59；Then hydrolysate after carbon point is added to the 13X type molecular sieve seed (preparation of 0.2g Example 2), then hydrothermal crystallizing 20h is carried out at 110 DEG C, and the second filter residue is obtained by filtration in obtained hydrothermal crystallizing product and is divided Sub- sieving liquid；Further the second filter residue is rinsed, drying, obtained product obtains spectrogram and standard card pair through XRD analysis Than being determined as 13X type molecular sieve；

The chemical composition (molal weight ratio) of molecular sieve filtrate is SiO₂:Al₂O₃:Na₂O:CO₃ ^2-:H₂O=38.1:1: 77.5:66:1960；

(5) ZSM-5 crystal seed (Catalyst Factory, Nankai Univ, the NKF- of 0.43g are added to obtained molecular sieve filtrate 100ml 5, SiO₂/Al₂O₃=400, molecular weight is about that 60), obtaining Synthesis liquid, (additional amount of ZSM-5 crystal seed is SiO in Synthesis liquid₂'s 6mol%)；

CO is passed through into Synthesis liquid under stirring₂Carbon point is carried out to pH=10.447；Then at a temperature of 150 DEG C into Row hydrothermal crystallizing 48h, and third filter residue and the second filtrate is obtained by filtration in obtained hydrothermal crystallizing product；Further by third Residue washing, drying, roasting, obtained product obtain spectrogram and standard card compare, be determined as ZSM-5 type point through XRD analysis Son sieve；

The primary consumption efficiency μ of flyash acid system residue of aluminum-extracted is 84.74%；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.

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 is cooling 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 (roasting relative to 100g of 130ml deionized water is added Slag material, the dosage of water are 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 (second filtrate of the reuse from step (6), 25 weight % of concentration) 100ml is diluted, and keep the temperature at 70 DEG C into Row filters；It adds above-mentioned second filtrate 100ml and is rinsed and (be equivalent to the roasting slag charge relative to 100g, above-mentioned second filter Total dosage of liquid is 286ml), it adds a certain amount of hot water (about 70 DEG C) and is rinsed, obtain the first filter that volume is 400ml Liquid, for synthesizing 13X type molecular sieve；The the first filter residue oven-dried weight 6.50g 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 (molal weight ratio) of first filtrate is SiO₂:Al₂O₃:Na₂O:CO₃ ^2-:H₂O=14.6:1:21.4: 11.3:361。

(4) 50ml deionized water is added in the first filtrate 120ml (the equivalent slag charge 18.0g containing roasting) to be hydrolyzed (relatively In the roasting slag charge of 100g, the total volume of hydrolysate is 960ml)；It is passed through under stirring into obtained hydrolysate CO₂Carbon point is carried out to pH=12.96；Then hydrolysate after carbon point is added to the 13X type molecular sieve seed (preparation of 0.45g Example 2), then hydrothermal crystallizing 18h is carried out at 95 DEG C, and the second filter residue and molecule is obtained by filtration in obtained hydrothermal crystallizing product Sieving liquid；Further the second filter residue being rinsed, drying, obtained product obtains spectrogram and standard card compares through XRD analysis, It is determined as 13X type molecular sieve；

The chemical composition (molal weight ratio) of molecular sieve filtrate is SiO₂:Al₂O₃:Na₂O:CO₃ ^2-:H₂O=43.3:1:66: 83:2035；

(5) to obtained molecular sieve filtrate 100ml be added 0.7g ZSM-5 crystal seed (Catalyst Factory, Nankai Univ, NKF-5, SiO₂/Al₂O₃=50, molecular weight is about that 60), obtaining Synthesis liquid, (additional amount of ZSM-5 crystal seed is SiO in Synthesis liquid₂'s 10mol%)；

CO is passed through into Synthesis liquid under stirring₂Carbon point is carried out to pH=9.5；Then it is carried out at a temperature of 190 DEG C Hydrothermal crystallizing 15h, and third filter residue and the second filtrate is obtained by filtration in obtained hydrothermal crystallizing product；Further third is filtered Wash heat is washed, dries, is roasted, and obtained product obtains spectrogram and standard card compares, be determined as ZSM-5 type molecule through XRD analysis Sieve；

The primary consumption efficiency μ of flyash acid system residue of aluminum-extracted is 87.0%；First filter residue is after recycling, it is believed that The whole consumption efficiency of flyash acid system residue of aluminum-extracted is approximately 100%.

Embodiment 4

(2) roasting slag charge is subjected to dry magnetic separation except after iron, taking 70g that 105ml deionized water is 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, is added thereto Sodium carbonate liquor (second filtrate of the reuse from step (6), 20 weight % of concentration) 100ml is diluted, and is kept the temperature at 80 DEG C It is filtered；Above-mentioned second filtrate 100ml is added to be rinsed；Relative to the roasting slag charge of 100g, total use of the second filtrate Amount is 286ml)；It adds a certain amount of hot water (about 90 DEG C) to be rinsed, the first filtrate that volume is 400ml is obtained, for closing At 13X type molecular sieve；The the first filter residue oven-dried weight 6.84g that will be obtained simultaneously, reuse to step (1) flyash acid system residue of aluminum-extracted Alkaline process roasting in；

The chemical composition (molal weight ratio) of first filtrate is SiO₂:Al₂O₃:Na₂O:CO₃ ^2-:H₂O=13.6:1:17.8: 9.75:426。

(4) take the first filtrate 120ml (containing roasting slag charge 21.0g) be added 80ml deionized water be hydrolyzed (relative to The roasting slag charge of 100g, the total volume of hydrolysate are 952ml)；CO is passed through into obtained hydrolysate under stirring₂ Carbon point is carried out to pH=13.59；Then hydrolysate after carbon point is added to the 13X type molecular sieve seed (preparation example 2) of 0.2g, Hydrothermal crystallizing 20h is carried out at 110 DEG C again, and the second filter residue and molecule sieving is obtained by filtration in obtained hydrothermal crystallizing product Liquid；Further the second filter residue is rinsed, drying, obtained product obtains spectrogram and standard card compares, determine through XRD analysis For 13X type molecular sieve；

The chemical composition (molal weight ratio) of molecular sieve filtrate is SiO₂:Al₂O₃:Na₂O:CO₃ ^2-:H₂O=40.4:1: 89.7:72:2235；

(5) TPAOH (25 weight % aqueous solution) template (traditional Chinese medicines of 10.0g are added to obtained molecular sieve filtrate 100ml Group's reagent) and 0.2g ZSM-5 crystal seed (Catalyst Factory, Nankai Univ, NKF-5, SiO₂/Al₂O₃=50,60) molecular weight is about Obtaining Synthesis liquid, (additional amount of TPAOH is SiO in Synthesis liquid₂2.5mol%, the additional amount of ZSM-5 crystal seed is in Synthesis liquid SiO₂3mol%)；

CO is passed through into Synthesis liquid under stirring₂Carbon point is carried out to pH=10.10；Then at a temperature of 140 DEG C into Row hydrothermal crystallizing 2h is warming up to 180 DEG C of progress hydrothermal crystallizing 16h again, and by obtained hydrothermal crystallizing product through third is obtained by filtration Filter residue and the second filtrate；Further by third residue washing, drying, roasting, obtained product through XRD analysis, obtain spectrogram with Standard card comparison, is determined as type ZSM 5 molecular sieve；

The primary consumption efficiency μ of flyash acid system residue of aluminum-extracted is 86.32%；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.

Embodiment 5

(2) roasting slag charge is subjected to dry magnetic separation except after iron, taking 70g that 140ml deionized water is 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, is added thereto Sodium carbonate liquor (second filtrate of the reuse from step (6), 25 weight % of concentration) 100ml is diluted, and is kept the temperature at 60 DEG C It is filtered；Add above-mentioned second filtrate 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 80 DEG C) to be rinsed, obtains the first filter that volume is 400ml Liquid, for synthesizing 13X type molecular sieve；The the first filter residue oven-dried weight 6.44g 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 (molal weight ratio) of first filtrate is SiO₂:Al₂O₃:Na₂O:CO₃ ^2-:H₂O=12.5:1:17.5: 9.2:428。

(4) 60ml deionized water is added in the first filtrate 120ml (the equivalent slag charge 21.0g containing roasting) to be hydrolyzed (relatively In the roasting slag charge of 100g, the total volume of hydrolysate is 857ml)；It is passed through under stirring into obtained hydrolysate Carbon dioxide carries out carbon point to pH=13.455；Then the hydrolysate after carbon point is subjected to hydrothermal crystallizing 15.5h at 95 DEG C, And the second filter residue and molecular sieve filtrate is obtained by filtration in obtained hydrothermal crystallizing product；Further the second filter residue is rinsed, is dried Dry, obtained product is analysed through XRD, obtains spectrogram and standard card compares, be determined as 13X type molecular sieve；

The chemical composition (molal weight ratio) of molecular sieve filtrate is SiO₂:Al₂O₃:Na₂O:CO₃ ^2-:H₂O=35:1:86:71: 2140。

(5) ZSM-5 crystal seed (Catalyst Factory, Nankai Univ, the NKF- of 1.05g are added to obtained molecular sieve filtrate 100ml 5, SiO₂/Al₂O₃=200, molecular weight is about that 60), obtaining Synthesis liquid, (additional amount of ZSM-5 crystal seed is SiO in Synthesis liquid₂'s 15mol%)；

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 20h, and third filter residue and the second filtrate is obtained by filtration in obtained hydrothermal crystallizing product；Further by third Residue washing, drying, roasting, obtained product obtain spectrogram and standard card compare, be determined as ZSM-5 type point through XRD analysis Son sieve；

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.

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 is cooling after roasting, and is crushed to about 200 mesh hereinafter, obtaining roasting slag charge；

(2) roasting slag charge is subjected to dry magnetic separation except after iron, taking 70g that 105ml deionized water is added under 95 DEG C and normal pressure Carry out water logging 20min, 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 (second filtrate of the reuse from step (6), 20 weight % of concentration) 100ml is diluted, and keep the temperature at 80 DEG C into Row filters；It adds above-mentioned second filtrate 100ml and is rinsed and (be equivalent to the roasting slag charge relative to 100g, above-mentioned second filter Total dosage of liquid 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 13X type molecular sieve；The the first filter residue oven-dried weight 6.90g 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 (molal weight ratio) of first filtrate is SiO₂:Al₂O₃:Na₂O:CO₃ ^2-:H₂O=13.6:1:18.6: 10.5:441。

(4) it takes the first filtrate 120ml (the equivalent slag charge 21.0g containing roasting) that 60ml deionized water is added to be hydrolyzed (relatively In the roasting slag charge of 100g, the total volume of hydrolysate is 857ml)；It is passed through under stirring into obtained hydrolysate CO₂Carbon point is carried out to pH=13.59；Then hydrolysate after carbon point is added to the 13X type molecular sieve seed (preparation example of 0.2g 2) hydrothermal crystallizing 20h, then at 110 DEG C is carried out, and the second filter residue and molecule is obtained by filtration in obtained hydrothermal crystallizing product Sieving liquid；Further the second filter residue being rinsed, drying, obtained product obtains spectrogram and standard card compares through XRD analysis, It is determined as 13X type molecular sieve；

The chemical composition (molal weight ratio) of molecular sieve filtrate is SiO₂:Al₂O₃:Na₂O:CO₃ ^2-:H₂O=37.7:1: 86.5:63:1970；

(5) to the cetyl trimethylammonium bromide of obtained molecular sieve filtrate 100ml addition 1.0g, (25 weight % are water-soluble Liquid) template (Chinese medicines group reagent) obtain Synthesis liquid (additional amount of cetyl trimethylammonium bromide be Synthesis liquid in SiO₂ 2.8mol%)；

CO is passed through into Synthesis liquid under stirring₂Carbon point is carried out to pH=10.565；Then at a temperature of 120 DEG C into Row hydrothermal crystallizing 76h, and third filter residue and the second filtrate is obtained by filtration in obtained hydrothermal crystallizing product；Further by third Residue washing, drying, roasting, obtained product obtain spectrogram and standard card compare, be determined as ZSM-5 type point through XRD analysis Son sieve；

The primary consumption efficiency μ of flyash acid system residue of aluminum-extracted is 86.2%；First filter residue is after recycling, it is believed that The whole consumption efficiency of flyash acid system residue of aluminum-extracted is approximately 100%.

Comparative example 1

(2) after roasting slag charge progress dry magnetic separation being removed iron, take 70g that the (roasting relative to 100g of 700ml deionized water is added Slag material, the dosage of water are 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, is kept the temperature at 60 DEG C Under filtered, the sodium carbonate liquor 100ml for adding 15 weight %, which is rinsed, (is equivalent to the fired slags relative to 100g Material, total dosage of above-mentioned sodium carbonate liquor are 286ml)；A certain amount of hot water (about 80 DEG C) is added to be rinsed, first obtained Filter residue oven-dried weight 21.62g, is computed, and it is only 56.76% 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, is not able to achieve the target that flyash acid system residue of aluminum-extracted efficiently dissolves.

Comparative example 2

(3) under high-speed stirred state, whole water logging product 100g (the equivalent slag charge 70g containing roasting) is taken, is 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 roasting slag charge of 100g, the addition total amount of boiling water are 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 13X type molecular sieve；The the first filter residue oven-dried weight 16.53g that will be obtained simultaneously, reuse Into the alkaline process roasting of step (1) flyash acid system residue of aluminum-extracted；

The chemical composition (molal weight ratio) of first filtrate is SiO₂:Al₂O₃:Na₂O:CO₃ ^2-:H₂O=8.2:1:12.5: 7.8:450。

(4) 13X type molecular sieve is directly synthesized using first filtrate, the hydrothermal crystallizing 15.5h at 95 DEG C, and will obtain Hydrothermal crystallizing product solid product is obtained by filtration.

Obtained solid product detects the mixture consisting of amorphous aluminosilicate and multiple types molecular sieve through XRD, Pure 13X type molecular sieve 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 The highly hydrolyzed hydrated SiO 2 for generating solid phase occurs in dilution and filter process for Si element in water logging product liquid phase, thus 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 drop Down to 66.94%.Meanwhile hydrothermal crystallizing is directly carried out according to conventional hydrothermal crystallization condition using the first filtrate, fail to obtain pure Net 13X type molecular sieve.

In addition, step (1)-(3) can not also obtain the synthesis mother liquid for being suitable for synthesizing type ZSM 5 molecular sieve, cannot get pure Net type ZSM 5 molecular sieve.Tail washings or molecular sieve filtrate main component after synthesis 13X type molecular sieve are sodium carbonate, only Containing micro Si, Al, it cannot act as silicon source or silicon 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, is added thereto Sodium carbonate liquor (second filtrate of the reuse from step (5), 15 weight % of concentration) 100ml is diluted, and is kept the temperature at 60 DEG C Filtered, add above-mentioned second filtrate 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 80 DEG C) to be rinsed, obtains the first filter that volume is 400ml Liquid, for synthesizing 13X type molecular sieve；The the first filter residue oven-dried weight 6.52g 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 (molal weight ratio) of first filtrate is SiO₂:Al₂O₃:Na₂O:CO₃ ^2-:H₂O=14.5:1:21.2: 11.5:366。

(4) it takes the first filtrate whole 400ml (the equivalent slag charge 70.0g containing roasting) that 200ml deionized water is added to be hydrolyzed (relative to the roasting slag charge of 100g, the total volume of hydrolysate is 857ml)；Sodium metaaluminate (NaAlO is added again₂) solid 31.44g, is configured to 13X type molecular sieve synthesis mother liquid, and chemical composition (molal weight ratio) is SiO₂:Al₂O₃:Na₂O:CO₃ ^2-: H₂O=12:4:115.5:46:487.

CO is passed through into obtained hydrolysate under stirring₂Carbon point is carried out to pH=13.455；Then by carbon point Hydrolysate afterwards carries out hydrothermal crystallizing 15.5h at 95 DEG C, and the second filter is obtained by filtration in obtained hydrothermal crystallizing product Slag and the second filtrate；Further the second filter residue is rinsed, drying, obtained product obtains spectrogram and standard card through XRD analysis Comparison, is determined as 13X type molecular sieve；

(main component is Na to (5) second filtrates₂CO₃, only it is the carbon that step (3) are added containing a small amount of Si, Al) part reuse Acid sodium solution, dilution and filtration and washing for water logging product；The remainder of second filtrate obtains Na after evaporative crystallization₂CO₃ Solid, reuse to step (1) flyash acid system residue of aluminum-extracted alkaline process roasting in.

According to being formulated conventionally 13X type molecular sieve synthesis mother liquid in comparative example 3, but need additional silicon source sodium metaaluminate (M_out =31.44g) adjustment silica alumina ratio, as a result the primary consumption efficiency μ of flyash acid system residue of aluminum-extracted is only 53.39%；And it obtains The second filtrate can not also continue to prepare type ZSM 5 molecular sieve, only product 13X type molecular sieve.

Comparative example 4

(3) under high-speed stirred state, whole water logging product 100g (the equivalent slag charge 70g containing roasting) is taken, is added thereto Sodium carbonate liquor (second filtrate of the reuse from step (6), 15 weight % of concentration) 100ml is diluted, and is kept the temperature at 60 DEG C Filtered, add above-mentioned second filtrate 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 80 DEG C) to be rinsed, obtains the first filter that volume is 400ml Liquid, for synthesizing 13X type molecular sieve；The the first filter residue oven-dried weight 6.79g 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 (molal weight ratio) of first filtrate is SiO₂:Al₂O₃:Na₂O:CO₃ ^2-:H₂O=13.5:1:17.6: 9.7:425。

(4) it takes the first filtrate whole 400ml (the equivalent slag charge 70.0g containing roasting) that 1500ml deionized water is added to be hydrolyzed (relative to the roasting slag charge of 100g, the total volume of hydrolysate is 2143ml)；Sodium metasilicate (Na is added again₂SiO₃) solid 161.65g, as the hydrothermal crystallizing mother liquor of type ZSM 5 molecular sieve after being completely dissolved, chemical composition (molal weight ratio) is SiO₂:Al₂O₃:Na₂O:CO₃ ^2-:H₂O=40:1:44.1:9.7:2092.

CO is passed through into Synthesis liquid under stirring₂Carbon point is carried out to pH=10.10；Then at a temperature of 140 DEG C into Row hydrothermal crystallizing 2h is warming up to 180 DEG C of progress hydrothermal crystallizing 16h again, and by obtained hydrothermal synthesis product through third is obtained by filtration Filter residue and the second filtrate；Further by third residue washing, drying, roasting, obtained product through XRD analysis, obtain spectrogram with Standard card comparison, is determined as type ZSM 5 molecular sieve；

(6) by the second filtrate, (main component is Na₂CO₃, only it is that step (3) are added containing a small amount of Si, Al) part reuse Sodium carbonate liquor, dilution and filtration and washing for water logging product；The remainder of second filtrate obtains after evaporative crystallization Na₂CO₃Solid, reuse to step (1) flyash acid system residue of aluminum-extracted alkaline process roasting in.

The composition of the first filtrate is adjusted in comparative example 4 for synthesizing type ZSM 5 molecular sieve, needs additional silicon source sodium metasilicate (M_out=161.65g), type ZSM 5 molecular sieve 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 20.42%.And the second obtained filtrate also can not further be prepared as silicon source or silicon source 13X type or other Any type molecular sieve；I.e. products obtained therefrom only has type ZSM 5 molecular sieve one kind.

From above-described embodiment as can be seen that method provided by the invention can not need additionally to 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 13X type molecular sieve and type ZSM 5 molecular sieve 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, 13X type molecular sieve and type ZSM 5 molecular sieve in source.

Claims

1. a kind of method that flyash acid system residue of aluminum-extracted prepares 13X type molecular sieve and type ZSM 5 molecular sieve, including：

Wherein, 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 Soak product；Relative to the roasting slag charge of 100g, the dosage of water is 150~200mL；

It is described heat preservation filtering process include：The water logging product is diluted with second filtrate of part, filter and It rinses, obtains the first filter residue and first filtrate；Main component is sodium carbonate in second filtrate；

(2) first filtrate is subjected to 13X type zeolite-water thermal crystallisation, obtains 13X type molecular sieve and molecular sieve filtrate；It is described The molal weight ratio of the chemical composition of first filtrate is SiO₂:Al₂O₃:Na₂O:CO₃ ^2-:H₂O=(10~25):1:(13~20): (3.5~11):(340~430)；

(3) the molecular sieve filtrate is subjected to type ZSM 5 molecular sieve hydrothermal crystallizing, obtains type ZSM 5 molecular sieve and the second filtrate； The molal weight ratio of the chemical composition of the molecular sieve filtrate is SiO₂:Al₂O₃:Na₂O:CO₃ ^2-:H₂O=(35~45):1:(65 ~90):(60~85):(1900~2300)；

This method does not need additionally to add silicon source or silicon source.

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 fired slags after roasting 60min~120min at 830 DEG C~890 DEG C again Material.

3. according to the method described in claim 2, wherein, during the high temperature water logging, water soaking temperature is 95 DEG C~105 DEG C, the water logging time is 15min~20min.

4. according to the method described in claim 3, wherein, during the heat preservation filtering, filtration temperature be maintained at 60 DEG C~ 80℃。

5. according to the method described in claim 1, wherein, during the heat preservation filtering, the roasting relative to 100g Slag charge, the dosage of second filtrate are 250~350mL.

6. according to the method described in claim 1, wherein, SiO in first filtrate₂With Al₂O₃Molar ratio be (10~ 25)：1.

7. according to the method described in claim 1, 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.

8. according to the method described in claim 1, wherein, in step (2), the process of the 13X type zeolite-water thermal crystallisation Including：

A) add water to be hydrolyzed first filtrate, obtain hydrolysate；The additional amount of water meets relative to described in 100g Slag charge is roasted, the total volume of the hydrolysate is 850~1000mL；

B) CO is passed through into the hydrolysate₂Carbon point is carried out, the pH 13~15 of the hydrolysate is made；

C) 13X type molecular sieve seed is added or be added without in the product obtained to step b), is then carried out at 90 DEG C~110 DEG C 15~30h of hydrothermal crystallizing obtains 13X type molecular sieve water heat crystallization product；The dosage of the 13X type molecular sieve seed is the roasting 0~10 weight % of slag material；

D) the 13X type molecular sieve water heat crystallization product is filtered, obtains the second filter residue and the molecular sieve filtrate；It is described Second filter residue is dried to obtain the 13X type molecular sieve.

9. according to the method described in claim 1, wherein, SiO in the molecular sieve filtrate₂With Al₂O₃Molar ratio be (35~ 45)：1.

10. according to the method described in claim 1, wherein, in step (3), the mistake of the type ZSM 5 molecular sieve hydrothermal crystallizing Journey includes：

I) organic formwork agent and/or type ZSM 5 molecular sieve crystal seed are added into the molecular sieve filtrate, obtains Synthesis liquid；

Ii) CO is passed through into the Synthesis liquid₂Carbon point is carried out, the pH 9~12 of the Synthesis liquid is made；

Iii) product for obtaining step ii) carries out 15~48h of hydrothermal crystallizing at 150 DEG C~190 DEG C, obtains ZSM-5 type point Son sieve hydrothermal crystallizing product；

Iv) the type ZSM 5 molecular sieve hydrothermal crystallizing product is filtered, obtains third filter residue and second filtrate；Institute Third filter residue is stated to be washed, dried and roasting obtains the type ZSM 5 molecular sieve.

11. according to the method described in claim 10, wherein, the additional amount of the organic formwork is SiO in the Synthesis liquid₂3 ~10mol%；The organic formwork in tetrapropylammonium hydroxide, 4-propyl bromide, n-propylamine and n-butylamine at least It is a kind of.

12. according to the method described in claim 10, wherein, the additional amount of the type ZSM 5 molecular sieve crystal seed is the synthesis SiO in liquid₂3~15mol%, the molar ratio of the Si and Al of the type ZSM 5 molecular sieve crystal seed is (50~400)：1.

13. 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).

14. a kind of utilization method of flyash, this method include：Flyash progress acid system is mentioned aluminium and obtains flyash acid system and mentions aluminium Residue and aluminium oxide；Flyash acid system residue of aluminum-extracted is prepared by method described in any one of claim 1-13 13X type molecular sieve and type ZSM 5 molecular sieve.