CN107265472A

CN107265472A - A kind of modified clay and preparation method thereof

Info

Publication number: CN107265472A
Application number: CN201710735295.0A
Authority: CN
Inventors: 于向真
Original assignee: Individual
Current assignee: Individual
Priority date: 2017-08-24
Filing date: 2017-08-24
Publication date: 2017-10-20

Abstract

The present invention relates to a kind of modified clay and preparation method thereof, it is characterised in that：It is 1 that clay and liquid caustic soda or sodium carbonate/bicarbonate are pressed into butt part by weight：0.01 0.8 ratio is mixed and made into clay slurry, and powdery particles, and the calcination activation at 250 DEG C 850 DEG C is made in then drying, is then added in deionized water the pulp at 60 DEG C 120 DEG C, is passed through after cooling containing CO₂It is drying to obtain after gas reaction, control pH value, heating aging, filtration washing at 60 DEG C ~ 500 DEG C.Instant invention overcomes being modified the sticky poor, production process of clay in the prior art to have the shortcomings that waste residue, the waste liquid of its filtration washing can be reclaimed after processing to be used, production process clean environment firendly.

Description

A kind of modified clay and preparation method thereof

Technical field

The invention belongs to clay-like material field, available for fields such as manufacture catalyst, adsorbent, drying and dehydrating agent.

Background technology

Clay is a kind of important raw mineral materials, is aoxidized by a variety of hydrosilicates and a certain amount of aluminum oxide, alkali metal Thing and alkaline earth oxide composition, and contain the impurity such as quartz, feldspar, mica and sulfate.The particle of clay mineral is tiny, Often in the range of colloid size, in crystal or noncrystal, most of is sheet, and minority is tubulose, bar-shaped.Clay mineral is wet with water There is plasticity after profit, can deform and can maintain the original state for a long time under smaller pressure, and specific surface area is big, is carried on particle Elecrtonegativity, therefore have good physical adsorbability and chemical mobility of the surface, it is industrial with the ability with other cation exchanges Clay pit has kaolin, bentonite（Main composition is montmorillonite）, atlapulgite（Composition is indefinite）, diatomite etc..

Just because of clay has good physical adsorbability and chemical mobility of the surface, it is manufacture catalyst, adsorbent, done The main raw material(s) of drying prescription etc., the country is only used for the clay consumption of catalyst manufacture more than 100,000 tons；It is preferably anti-to obtain Performance is answered, is often further modified clay.

A kind of modified kaolins of USP4843052, by kaolin fine powder in 700 DEG C ~ 910 DEG C roastings, then with acidic materials (such as hydrochloric acid) reacts, washing and filtering, obtains average pore size and is more than 150m for 2 ~ 4nm, than surface²/ g sour modified kaolin, is used In preparing FCC catalyst.But it is more with the removing of its alumina amount, it is bigger than surface, while its caking property is also poor, the production of its process Raw soluble aluminum salt waste.

A kind of modified clays of CN101590432A and preparation method thereof, clay is small in 800 DEG C ~ 1100 DEG C roastings 0.3 ~ 10 When, the clay after roasting is mixed with deionized water, add concentration be 0.5 ~ 15 mole of hydroxide ion/liter inorganic base (such as NaOH etc.) solution, reacted 0.1 ~ 5 hour at 50 DEG C ~ 100 DEG C, material filtering uses inorganic acid elution, then to impregnate upper 0.1 ~ 3.0% P, 0.1 ~ 4% rare earth, filtration drying obtain being modified clay, applied to preparing FCC catalyst.But because being stripped of part Aluminum oxide, its bad adhesion, while the aluminum soluble salt that its process is produced is through filtering emission, yield is low.

CN1420082 is related to a kind of preparation method of activated alumina, is configured to aluminium hydrate powder and sodium hydroxide dense Spend for 15~75gAl₂O₃L-1 sodium aluminate solution, is passed through CO₂The CO of content >=90% (V)₂Gaseous mixture, controls plastic 20~70 DEG C of temperature, when pH value is 9~11, reaction product is filtered, filter cake is washed, dry cake is obtained at 60~100 DEG C To boehmite, and in 500~700 DEG C of roastings, activated alumina is produced, its porosity is more than 0.85mlg-1, compares surface In 260m²/ more than g.

USP60/267,469 there is provided the preparation method of an anionic clay-containing and boehmite composition, in preparation process In, by containing divalent metal source and trivalent metal source predecessor at least through twice-aged step, and in twice-aged step At least plus a silicon source；Product structure is actually the composition of houghite and boehmite, it can also be used to prepare catalyst.

A kind of modified clay new materials of CN102091609B and preparation method thereof, by clay first with acid or alkali 40 DEG C ~ Reacted 10 minutes to 48 hours at 600 DEG C, then add perforating agent, then reacted with alkaline matter or acidic materials, control ph 6 ~ 12, then 60 ~ 200 DEG C of agings 0.2 ~ 24 hour are warming up to, filtration washing obtains product after drying；There is also can for its production process Soluble emission problem.

The content of the invention

It is an object of the invention to overcome the sticky poor, production process for being modified clay in the prior art to have the shortcomings that waste residue, A kind of modified clay and preparation method thereof is provided.

The technical scheme is that：A kind of modified clay, it is characterised in that：Its main component is silica and oxidation Aluminium, BET is than 120 ~ 600m of surface²/ g, nitrogen absorption under low temperature pore volume is 0.2 ~ 2.5ml/g；Its preparation method, including following step Suddenly：

(1) it is 1 by butt part by weight by clay and liquid caustic soda or sodium carbonate/bicarbonate：0.01-0.8 ratio mixing, system It is 10 ~ 60% slurries into clay mass concentration；

(2) and then above-mentioned slurries are dried and is prepared into powdery particles, be calcined 0.2-8 hours at 250 DEG C -850 DEG C；

(3) in the deionized water for being then added to 5-20 times (weight ratio), pulp 0.5-4 hours at 60 DEG C -120 DEG C, cooling, Temperature is controlled to 10 ~ 80 DEG C；

(4) CO containing 8 ~ 100% volumetric concentrations is then passed to₂Gas reaction, controls 6-11pH, then be warming up to 60 DEG C ~ 150 DEG C always Change 0.5 ~ 8 hour；

(5) it is drying to obtain after filtration washing at 60 DEG C ~ 500 DEG C.

Described step (5) filtration washing contain Na₂CO₃、NaHCO₃Concentrating filter liquor processing or milk of lime processing after can Used with returning in step (1).

Described clay is kaolin, bentonite, galapectite, montmorillonite, sepiolite, rectorite, attapulgite, diatomite One or more in.

Described CO₂The excellent control of content is in 30% ~ 100% (volume).

Described filtrate milk of lime processing is that filtrate is concentrated by evaporation into finite concentration, then with lime reaction, generates carbonic acid Calcium precipitate and sodium hydroxide liquid, calcium carbonate can be sold as light sodium carbonate byproduct, and sodium hydroxide liquid can be with reuse Used to step (1).

The processing of concentration and milk of lime is conventional technique, but it is combined herein after, realize the circulation of Na materials Utilize, without the discharge of waste.

Embodiment

The following examples will be to further instruction of the present invention, but the present invention is not limited to these embodiments.

Embodiment 1：

By 200 grams of kaolin (Chinese kaolin industrial group (Suzhou) produces, solids content 72%) and 120g deionization water slurrys Change, and add the NaOH solution that 42g concentration is 30%, be well mixed, slurries are dried 6 hours and clayed into power at 120 DEG C, It is calcined 2 hours at 300 DEG C, material adds 1000ml deionized waters stirring to pulp 60 minutes at 80 DEG C after roasting, and slurries are cooled to After 30 DEG C, the CO of 40% volume content is passed through₂Then gas, control slurry pH value is warming up to 90 DEG C of agings 2 hours, thing to 10.5 Material filtering, then collected with 4 washing and filtering filter cakes of 3000ml deionizations moisture, filtrate and cleaning solution, filter cake is dried at 120 DEG C 8 hours, sample A is obtained, nitrogen absorption under low temperature analysis obtains its pore volume for 0.23ml/g, and BET is 265m than surface²/g。

Embodiment 2：

By 200 grams of kaolin (Chinese kaolin industrial group (Suzhou) produces, solids content 72%) and 150g deionization water slurrys Change, and add 18g solids Na₂CO₃, it is well mixed, slurries are spray dried to powder shape at 300 DEG C, 2 is calcined at 800 DEG C small When, material adds 800ml deionized waters stirring to pulp 60 minutes at 110 DEG C after roasting, and slurries are cooled to after 40 DEG C, are passed through 40% The CO of volume content₂Then gas, control slurry pH value is warming up to 90 DEG C of agings 2 hours, material filtering, then use to 10.5 4 washing and filtering filter cakes of 3000ml deionizations moisture, filtrate is collected with cleaning solution, and filter cake is dried 8 hours at 120 DEG C, is obtained Sample B, nitrogen absorption under low temperature analysis obtains its pore volume for 0.26ml/g, and BET is 225m than surface²/g。

Embodiment 3：

The filtrate collected in embodiment 1 and cleaning solution are concentrated by evaporation and arrive 200ml, by (the Chinese kaolin industry of 200 grams of kaolin Company (Suzhou) produces, solids content 72%) it is added thereto, pulp is carried out, after being well mixed, slurries are spray-dried at 300 DEG C Into powdered, it is calcined 2 hours at 800 DEG C, material adds 1200ml deionized waters 60 points of stirring to pulp at 110 DEG C after roasting Clock, slurries add 2000ml deionized waters and are cooled to after 35 DEG C again, are passed through the CO of 100% volume content₂Gas, control slurries pH It is worth 9.5, is then warming up to 90 DEG C of agings 2 hours, material filtering, then with 5 washing and filtering filter cakes of 3000ml deionizations moisture, Filtrate is collected with cleaning solution, and filter cake is dried 8 hours at 120 DEG C, obtains sample C, and nitrogen absorption under low temperature analysis obtains its pore volume For 0.36ml/g, BET is 435m than surface²/g。

Embodiment 4：

By 200 grams of kaolin (Chinese kaolin industrial group (Suzhou) produces, solids content 72%) and 150g deionization water slurrys Change, and add the NaOH solution that 61g concentration is 30%, be well mixed, slurries are spray dried to powder at 350 DEG C, at 500 DEG C Lower roasting 2 hours, material adds 1000ml deionized waters stirring to pulp 60 minutes at 90 DEG C after roasting, then, and slurries are added 2000ml deionized waters are simultaneously cooled to after 30 DEG C, are passed through the CO of 40% volume content₂Gas, control slurry pH value to 7.0, then It is warming up to 90 DEG C of agings 4 hours, material filtering, then with 4 washing and filtering filter cakes of 4000ml deionizations moisture, filtrate and cleaning solution Collect, filter cake is dried 8 hours at 120 DEG C, obtain sample D, nitrogen absorption under low temperature analysis obtains its pore volume for 0.81ml/g, BET is 568m than surface²/g。

Claims

1. a kind of preparation method of modified clay, it is characterised in that：The main component of clay is modified for silica and aluminum oxide, BET is than 120 ~ 600m of surface²/ g, nitrogen absorption under low temperature pore volume is 0.2 ~ 2.5ml/g；Its preparation method is comprised the steps of：

（1）It is 1 that clay and liquid caustic soda or sodium carbonate/bicarbonate are pressed into butt part by weight：0.01-0.8 ratio is mixed, is made Clay mass concentration is 10 ~ 60% slurries；

（2）Then above-mentioned slurries are dried and is prepared into powdery particles, be calcined 0.2-8 hours at 250 DEG C -850 DEG C；

（3）In the deionized water for being then added to 5-20 times (weight ratio), pulp 0.5-4 hours at 60 DEG C -120 DEG C is cooled down, control Temperature processed is to 10 ~ 80 DEG C；

（4）Then pass to the CO containing 8 ~ 100% volumetric concentrations₂Gas reaction, controls 6-11pH, then be warming up to 60 DEG C ~ 150 DEG C agings 0.5 ~ 8 hour；

（5）It is drying to obtain after filtration washing at 60 DEG C ~ 500 DEG C.

2. the preparation method of modified clay according to claim 1, it is characterised in that：Step (5) filtration washing contains Na₂CO₃、NaHCO₃Concentrating filter liquor processing or milk of lime processing after may return to and used in step (1).

3. the preparation method of modified clay according to claim 1, it is characterised in that described clay is kaolin, swelling One or more in soil, galapectite, montmorillonite, sepiolite, rectorite, attapulgite, diatomite etc..

4. the preparation method of modified clay according to claim 1, it is characterised in that described CO₂The excellent control of content 30% ~ 100% (volume).