阅读说明：本技术 应用于大水灰比硫铝酸盐水泥基材料中的锂铝类水滑石衍生物的制备方法 (Preparation method applied to the lithium aluminium houghite derivative in big ratio of mud sulphoaluminate cement base material ) 是由 李海艳 杨阔 黄远征 王蒙蒙 杨新银 付鑫 闫鹏举 于 2019-09-11 设计创作，主要内容包括：本发明提供一种应用于大水灰比硫铝酸盐水泥基材料中的锂铝类水滑石衍生物的制备方法,首先将配制的混合盐溶液和混合碱溶液,在反应器中迅速反应得到混合浆液,混合浆液加热回流晶化后处理得到锂铝类水滑石,然后高温焙烧或水合制得焙烧态和水合态的锂铝类水滑石衍生物。锂铝类水滑石衍生物在大水灰比硫铝酸盐水泥基材料中的掺入量按硫铝酸盐水泥基材料的0.2％～5％添加,所制备的水泥材料的水灰比为0.4～3.0。本发明中锂铝类水滑石衍生物的制备方法易于工业化,操作简单,锂铝类水滑石衍生物作为晶核材料来促进水泥水化产物的生成,大水灰比条件下,显著提高硫铝酸盐水泥基材料早期的抗压强度,28天抗压强度不发生倒缩现象。(The present invention provides a kind of preparation method applied to the lithium aluminium houghite derivative in big ratio of mud sulphoaluminate cement base material, first by the mixing salt solution of preparation and mixed ammonium/alkali solutions, reaction obtains mixed serum rapidly in the reactor, mixed serum is heated to reflux crystallization and post-processes to obtain lithium aluminium houghite, and then the lithium aluminium houghite derivative of roasting state and hydrated state is made in high-temperature roasting or hydration.For incorporation of the lithium aluminium houghite derivative in big ratio of mud sulphoaluminate cement base material by 0.2%~5% addition of sulphoaluminate cement base material, the ratio of mud of prepared cement material is 0.4~3.0.The preparation method of lithium aluminium houghite derivative is easy to industrialize in the present invention, it is easy to operate, lithium aluminium houghite derivative promotes the generation of hydrolysis product of cement as host material, under the conditions of the big ratio of mud, the compression strength of sulphoaluminate cement base material early stage is significantly improved, retraction phenomenon does not occur for compression strength within 28 days.)

1. a kind of preparation method of lithium aluminium houghite derivative, which is characterized in that the preparation method comprises the following steps:

S1, weighs lithium salts respectively and aluminium salt is dissolved in deionized water, is configured to mixing salt solution；Then bases hydrogen is weighed respectively again Oxide, alkali carbonate are dissolved in deionized water, are configured to mixed ammonium/alkali solutions；

The mixing salt solution being configured in step S1, mixed ammonium/alkali solutions are added into reactor S2, mixing salt solution and mixing Aqueous slkali, which reacts rapidly, obtains mixed serum；

S3 after being heated to reflux crystallization, is centrifuged mixed serum transposition is in reaction kettle obtained in step S2 by deionized water Washing obtains lithium aluminium houghite to neutrality；

S4 lithium aluminium houghite obtained in step S3 is dried, grind into powder, then high-temperature roasting and keeps the temperature, and makes State lithium aluminium houghite derivative must be roasted.

2. the preparation method of lithium aluminium houghite derivative as described in claim 1, which is characterized in that described in step S4 It roasts state lithium aluminium houghite derivative to be hydrated by soluble salt solutions, obtains hydrated state lithium aluminium houghite derivative；

Preferably, the soluble salt solutions are one in sodium carbonate, sodium sulphate, potassium carbonate, potassium nitrate, calcium nitrate and magnesium nitrate Kind.

3. the preparation method of lithium aluminium houghite derivative as claimed in claim 1 or 2, which is characterized in that institute in step S1 Stating lithium salts is LiNO₃Or Li₂CO₃, the aluminium salt is Al (NO₃)₃﹒ 9H₂O or Al₂(SO₄)₃﹒ 18H₂O；

Bases hydroxide described in step S1 is alkali metal hydroxide or alkaline earth metal hydroxide；Preferably, the alkali Metal hydroxides is sodium hydroxide, potassium hydroxide；The alkaline earth metal hydroxide is calcium hydroxide；

Alkali carbonate described in step S1 is sodium carbonate or potassium carbonate.

4. the preparation method of lithium aluminium houghite derivative as claimed in claim 3, which is characterized in that the lithium salts and aluminium salt Molal weight ratio be (0.1~30): 1, the molal weight ratio of the bases hydroxide and alkali carbonate be (5~ 20): 1.

5. the preparation method of lithium aluminium houghite derivative as claimed in claim 3, which is characterized in that mixed described in step S2 Close salting liquid, the mixed ammonium/alkali solutions are added with identical rate of addition into reactor.

6. the preparation method of lithium aluminium houghite derivative as claimed in claim 3, which is characterized in that add described in step S3 The temperature of heat reflux crystallization is 50 DEG C~120 DEG C, and the time for being heated to reflux crystallization is 2h~6h；

Preferably, the temperature for being heated to reflux crystallization is 95 DEG C, and the time for being heated to reflux crystallization is 5h.

7. the preparation method of lithium aluminium houghite derivative as claimed in claim 3, which is characterized in that height described in step S4 The temperature of temperature roasting is 400 DEG C~1000 DEG C, and the high-temperature roasting soaking time is 2h~6h.

8. lithium aluminium class water prepared by a kind of preparation method of lithium aluminium houghite derivative as described in claim 1~7 is any Talcum derivative is applied to big ratio of mud sulphoaluminate cement base material, which is characterized in that the sulphoaluminate cement base material Including Huang material and white material, the white material includes gypsum and lime；

Preferably, the mass ratio of the yellow material and white material is 1:(0.8~1), the mass ratio of the gypsum and lime is (1~3): 1；

Preferably, the lithium aluminium houghite derivative be incorporated into the incorporation in big ratio of mud sulphoaluminate cement base material by 0.2%~5% addition of sulphoaluminate cement base quality of materials.

9. lithium aluminium houghite derivative as claimed in claim 8 is applied to big ratio of mud sulphoaluminate cement base material, It is characterized in that, the lithium aluminium houghite derivative in the big ratio of mud sulphoaluminate cement base material is in 100W~200W Ultrasound 2min~10min is scattered in outer water mixing under power.

10. lithium aluminium houghite derivative as claimed in claim 8 is applied to big ratio of mud sulphoaluminate cement base material, It is characterized in that, the lithium aluminium houghite derivative is applied to institute in big ratio of mud sulphoaluminate cement base material as early strength agent The ratio of mud of the cement material of preparation is 0.4~3.0.

Technical field

The invention belongs to the field of building materials, and in particular to one kind is applied in big ratio of mud sulphoaluminate cement base material Lithium aluminium houghite derivative preparation method.

Background technique

Sulphoaluminate cement base material (CBGM) is with aluminium sulfate (CSA) clinker, gypsum and lime for main group The inorganic material of part has the characteristics that corrosion-resistant, morning is high-strength, impervious, in salvaging, mine high water base material infilling work etc. Aspect has preferable application.In slip casting application process, in order to guarantee slurry mobility with higher and permeability, usually select It selects and constructs in the big ratio of mud or mix additive under conditions of, but the early anti pressured intension of slurry is not able to satisfy work under above-mentioned condition The demand of journey.

Concern using the modified sulphoaluminate cement base material of nanotechnology by more and more scholars, nano material partial size Small, large specific surface area promotes the generation of hydrolysis product of cement to be very effective as host material, by nano material Cement-based material is added, to attempt to change its mechanics, condensation, endurance quality etc..

Houghite also known as layered double hydroxide are a kind of layered anionic clay, the hydrated product of cement AFm phase belongs to houghite family.Theoretically promote the aquation of CBGM, tool using lithium aluminium houghite derivative as seed crystal material There is preferable effect.Lithium aluminium houghite is roasted by different temperatures, and veneer structure can be destroyed, but under suitable conditions, roasting Product after burning can restore layer structure again.

Know by inspection information and document, is there is no at present about lithium aluminium class neatly derivative in big ratio of mud aluminium sulfate water The relevant report applied in cement-based material.

Summary of the invention

The object of the present invention is to provide a kind of lithium aluminium class neatlys applied in big ratio of mud sulphoaluminate cement base material The preparation method of stone derivative, lithium aluminium houghite derivative prepared by the present invention are applied in big ratio of mud sulphoaluminate cement base In material, the compression strength of cement-based material early stage is not only significantly improved, and retraction phenomenon does not occur for 28 days intensity, solve sulphur aluminium Acid salt cement the problem of compression strength cannot be met the requirements under the conditions of the big ratio of mud.

To achieve the goals above, the invention provides the following technical scheme:

A kind of preparation method of lithium aluminium houghite derivative, the preparation method comprises the following steps:

S1, weighs lithium salts respectively and aluminium salt is dissolved in deionized water, is configured to mixing salt solution；Then alkali is weighed respectively again Hydroxide, alkali carbonate are dissolved in deionized water, are configured to mixed ammonium/alkali solutions；

The mixing salt solution being configured in step S1, mixed ammonium/alkali solutions are added in reactor S2, and reaction is mixed rapidly Close slurries；

S3 after being heated to reflux crystallization, passes through deionized water for mixed serum transposition is in reaction kettle obtained in step S2 Centrifuge washing obtains lithium aluminium houghite to neutrality；

S4 lithium aluminium houghite obtained in step S3 is dried, grind into powder, then high-temperature roasting and protects Roasting state lithium aluminium houghite derivative is made in temperature.

The preparation method of lithium aluminium houghite derivative as described above, it is preferable that the roasting state lithium aluminium in step S4 Houghite derivative is hydrated by soluble salt solutions, obtains hydrated state lithium aluminium houghite derivative；

Preferably, the soluble salt solutions are in sodium carbonate, sodium sulphate, potassium carbonate, potassium nitrate, calcium nitrate and magnesium nitrate One kind.

The preparation method of lithium aluminium houghite derivative as described above, it is preferable that lithium salts described in step S1 is LiNO₃Or Li₂CO₃, the aluminium salt is Al (NO₃)₃﹒ 9H₂O or Al₂(SO₄)₃﹒ 18H₂O；

Bases hydroxide described in step S1 is alkali metal hydroxide or alkaline earth metal hydroxide；Preferably, institute Stating alkali metal hydroxide is sodium hydroxide, potassium hydroxide；The alkaline earth metal hydroxide is calcium hydroxide；

Alkali carbonate described in step S1 is sodium carbonate or potassium carbonate.

The preparation method of lithium aluminium houghite derivative as described above, it is preferable that the molal weight of the lithium salts and aluminium salt Than for (0.1~30): 1, the molal weight of the alkali metal hydroxide or alkaline earth metal hydroxide and alkali carbonate Than for (5~20): 1.The preparation method of lithium aluminium houghite derivative as described above, it is preferable that salt-mixture described in step S2 Solution, the mixed ammonium/alkali solutions are added with identical rate of addition into reactor.

The preparation method of lithium aluminium houghite derivative as described above, it is preferable that be heated to reflux crystallization described in step S3 Temperature be 50 DEG C~120 DEG C, the time for being heated to reflux crystallization be 2h~6h；

It is furthermore preferred that the temperature for being heated to reflux crystallization is 95 DEG C, the time for being heated to reflux crystallization is 5h.

The preparation method of lithium aluminium houghite derivative as described above, it is preferable that the temperature of high-temperature roasting described in step S4 Degree is 400 DEG C~1000 DEG C, and the high-temperature roasting soaking time is 2h~6h.

The lithium aluminium houghite derivative of the preparation method preparation of lithium aluminium houghite derivative as described above is applied to Big ratio of mud sulphoaluminate cement base material, it is preferable that the sulphoaluminate cement base material includes yellow material and white material, the white material Including gypsum and lime, the mass ratio of the yellow material and white material is 1:(0.8~1), the mass ratio of the gypsum and lime is (1 ~3): 1；

Preferably, the lithium aluminium houghite derivative is incorporated into the incorporation in big ratio of mud sulphoaluminate cement base material Amount is added by the 0.2%~5% of sulphoaluminate cement base quality of materials.

Lithium aluminium houghite derivative as described above is applied to big ratio of mud sulphoaluminate cement base material, it is preferable that institute It is ultrasonic under the power of 100W~200W for stating the lithium aluminium houghite derivative in big ratio of mud sulphoaluminate cement base material 2min~10min is scattered in outer water mixing.

Lithium aluminium houghite derivative as described above is applied to big ratio of mud sulphoaluminate cement base material, it is preferable that institute State prepared cement when lithium aluminium houghite derivative is applied to big ratio of mud sulphoaluminate cement base material as early strength agent The ratio of mud of material is 0.4~3.0.

Compared with the immediate prior art, technical solution provided by the invention has following excellent effect:

1, the present invention is mixed by salt-mixture and mixed ammonium/alkali solutions, is prepared after being heated to reflux crystallization using roasting, hydration The lithium aluminium houghite derivative of state and hydrated state is roasted out, and the preparation method is easy to operate, reproducible.

2, lithium aluminium houghite derivative prepared in the present invention is added to big ratio of mud aluminium sulfate as early strength agent The ratio of mud of prepared cement grout is 0.4~3.0 in cement-based material, and lithium aluminium houghite derivative is as host material Promote the generation of hydrolysis product of cement, sulphoaluminate cement base material early stage can be significantly improved under the conditions of the big ratio of mud Compression strength, when the ratio of mud is 0.8, the compression strength of cement-based material early stage improves 262.7%, and 28 days compression strength is not Retraction phenomenon occurs, solves the problems, such as that existing cement-based material compression strength under the conditions of the big ratio of mud cannot be met the requirements, And the blank that lithium aluminium houghite derivative is applied to building field as early strength agent has been filled up, lithium aluminium houghite derivative is made The effect that generates in sulphoaluminate cement base material is added than effect that lithium aluminium houghite is generated as early strength agent for early strength agent More preferably, early anti pressured intension improves 42.15%.

Detailed description of the invention

The accompanying drawings constituting a part of this application is used to provide further understanding of the present invention, and of the invention shows Examples and descriptions thereof are used to explain the present invention for meaning property, does not constitute improper limitations of the present invention.Wherein:

Fig. 1 be the lithium aluminium houghite prepared under difference maturing temperatures in reference examples 5 of the present invention and Examples 1 to 6 and its The XRD diagram of derivative.

Specific embodiment

The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation Example is only a part of the embodiments of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is general Logical technical staff's every other embodiment obtained, shall fall within the protection scope of the present invention.

The present invention will be described in detail below with reference to the accompanying drawings and embodiments.It should be noted that in the feelings not conflicted Under condition, the feature in embodiment and embodiment in the present invention be can be combined with each other.

The preparation method of lithium aluminium houghite derivative provided by the invention is to prepare mixing salt solution respectively and mix first Aqueous slkali is closed, is reacted rapidly after the two mixing, then by being heated to reflux crystallization, post-processing obtains lithium aluminium houghite, Roasting state lithium aluminium houghite derivative finally is obtained by high-temperature roasting, hydrated state lithium aluminium houghite is made using being hydrated Derivative, the preparation method is easy to operate, reproducible；The present invention is added to using lithium aluminium houghite derivative as early strength agent In big ratio of mud sulphoaluminate cement base material, sulphoaluminate cement base material can be significantly improved under the conditions of the big ratio of mud The compression strength of early stage, retraction does not occur for compression strength within 28 days, solves existing cement-based material and resists under the conditions of the big ratio of mud The problem of Compressive Strength cannot be met the requirements.

The present invention provides a kind of preparation method of lithium aluminium houghite derivative, comprising the following steps:

S1, weighs lithium salts respectively and aluminium salt is dissolved in deionized water, is configured to mixing salt solution；Weigh bases hydrogen respectively again Oxide, alkali carbonate are dissolved in deionized water, are configured to mixed ammonium/alkali solutions.

In the specific embodiment of the invention, the water solubility of lithium salts is solvable or slightly soluble in step S1, and the water solubility of aluminium salt is Solvable or slightly soluble；Preferably, lithium salts LiNO₃Or Li₂CO₃, the aluminium salt is Al (NO₃)₃﹒ 9H₂O or Al₂(SO₄)₃﹒ 18H₂O；

Bases hydroxide is alkali metal hydroxide in step S1 or alkaline earth metal hydroxide is sodium hydroxide, hydrogen-oxygen Change in potassium or calcium hydroxide；

Alkali carbonate is sodium carbonate or potassium carbonate in step S1.

In the specific embodiment of the invention, the molal weight ratio of lithium salts and aluminium salt is (0.1~30): 1 (such as 0.1:1, 0.5:1,1:1,3:1,5:1,7:1,9:1,12:1,14:1,16:1,18:1,20:1,23:1,25:1,27:1,30:1), alkali gold The molal weight ratio for belonging to hydroxide or alkaline earth metal hydroxide and alkali carbonate is (5~20): 1 (such as 5:1,6: 1、7:1、8:1、9:1、10:1、11:1、12:1、13:1、14:1、15:1、16:1、17:1、18:1、19:1、20:1)。

The mixing salt solution being configured in step S1, mixed ammonium/alkali solutions are rapidly added full back-mixing explosion type and are nucleated instead by S2 It answers in device, violent circulation stirring, which reacts rapidly, obtains mixed serum.

In the specific embodiment of the invention, mixing salt solution, mixed ammonium/alkali solutions are added in step S2 with identical rate of addition Enter in reactor.

S3 after being heated to reflux crystallization, passes through deionized water for mixed serum transposition is in reaction kettle obtained in step S2 Centrifuge washing obtains lithium aluminium houghite (LiAl-LDH) to neutral (pH value is between 7~8).

In the specific embodiment of the invention, the temperature that crystallization is heated to reflux in step S3 is 50 DEG C~120 DEG C (such as 50 ℃、52℃、55℃、58℃、60℃、62℃、65℃、68℃、70℃、72℃、75℃、78℃、80℃、82℃、85℃、88 DEG C, 90 DEG C, 92 DEG C, 95 DEG C, 98 DEG C, 100 DEG C, 105 DEG C, 110 DEG C, 112 DEG C, 114 DEG C, 116 DEG C, 118 DEG C, 120 DEG C), heating Flow back crystallization time be 2h~6h (such as 2h, 2.2h, 2.4h, 2.8h, 3h, 3.2h, 3.6h, 3.8h, 4h, 4.2h, 4.4h, 4.6h,4.8h,5h,5.2h,5.4h,5.6h,5.8h,6h)；

Preferably, the temperature for being heated to reflux crystallization is 95 DEG C, and the time for being heated to reflux crystallization is 5h.

S4 lithium aluminium houghite obtained in step S3 is dried, grind into powder, then high-temperature roasting and protects Roasting state lithium aluminium houghite derivative is made in temperature.

Preferably, step S4 high temperature roasting temperature be 400 DEG C~1000 DEG C (such as 400 DEG C, 420 DEG C, 450 DEG C, 480℃、500℃、520℃、550℃、580℃、600℃、620℃、650℃、680℃、700℃、720℃、750℃、780 DEG C, 800 DEG C, 820 DEG C, 850 DEG C, 880 DEG C, 900 DEG C, 920 DEG C, 950 DEG C, 970 DEG C, 1000 DEG C), high-temperature roasting soaking time is 2h~6h (such as 2h, 2.2h, 2.4h, 2.8h, 3h, 3.2h, 3.6h, 3.8h, 4h, 4.2h, 4.4h, 4.6h, 4.8h, 5h, 5.2h、5.4h、5.6h、5.8h、6h)。

Preferably, the temperature of step S4 high temperature roasting is 450 DEG C, 650 DEG C and 850 DEG C, and high-temperature roasting soaking time is 3h。

It is the roasting state LiAl- that will be prepared the present invention also provides the preparation method of another lithium aluminium houghite derivative LDH derivative is hydrated by soluble salt solutions, obtains hydrated state lithium aluminium houghite derivative；Preferably, soluble-salt is molten Liquid is one of sodium carbonate, sodium sulphate, potassium carbonate, potassium nitrate, calcium nitrate and magnesium nitrate.

It is applied to greatly in addition, the present invention also provides a kind of lithium aluminium houghite derivatives produced as described above as early strength agent In ratio of mud sulphoaluminate cement base material.

In the specific embodiment of the invention, sulphoaluminate cement base material includes yellow material and white material, white material include gypsum and The mass ratio of lime, Huang material and white material is 1:(0.8~1) (such as 1:0.8,1:0.82,1:0.84,1:0.86,1；0.88,1: 0.9,1:0.92,1:0.94,1:0.96,1:0.98:, 1:1), the mass ratio of gypsum and lime is (1~3): 1 (such as 1:1, 1.2:1,1.4:1,1.6:1,1.8:1,2:1,2.2:1,2.4:1,2.6:1,2.8:1,3:1)；

Preferably, lithium aluminium houghite derivative be incorporated into the incorporation in big ratio of mud sulphoaluminate cement base material by Sulphate aluminium cement 0.2%~5% (such as 0.2%, 0.8%, 1.2%, 1.6%, 2.0%, 2.4%, 2.8%, 3%, 3.2%, 3.6%, 4.0%, 4.2%, 4.6%, 5%) addition；

Lithium aluminium houghite derivative in the specific embodiment of the invention, in big ratio of mud sulphoaluminate cement base material It is at 100W~200W (such as 100W, 110W, 120W, 130W, 140W, 150W, 160W, 170W, 180W, 190W, 200W) Ultrasound 2min~10min under power (such as 2min, 2.5min, 3min, 3.5min, 4min, 4.5min, 5min, 5.5min, 6min, 6.5min, 7min, 7.5min, 8min, 8.5min, 9min, 9.5min, 10min) it is scattered in outer water mixing；

Preferably, the lithium aluminium houghite derivative in big ratio of mud sulphoaluminate cement base material is the power in 150W Lower ultrasound 3min is scattered in outer water mixing.

In the specific embodiment of the invention, lithium aluminium houghite derivative is applied to big ratio of mud sulphur aluminic acid as early strength agent When salt water cement-based material the ratio of mud of prepared cement material be 0.4~3.0 (such as 0.4,0.6,0.8,1.0,1.2,1.4, 1.6,1.8,2.0,2.2,2.4,2.6,2.8,3.0), wherein the ratio of mud refers to the weight of the dosage of water and cement consumption in concrete Ratio is measured, the ratio of mud influences the compactness after the rheological property, cement slurry coherent structure and its hardening of concrete；

Raw material as used in the following examples are commercially available.